Modelling of the physical behaviour of clay barriers close to water saturation

The physical properties of bentonite-based buffer materials for nuclear waste repositories have been investigated by a number of different laboratory tests. These tests have yielded a material model that is valid for conditions close to water saturation and is useful for describing: (a) the stress, strain and volume change behaviour; (b) the pore pressure and flow of water; and (c) the thermal and thermomechanical response.

The material model is based on the Drucker-Prager Plasticity model and a Porous Elastic Model. The effective stress concept and Darcy's law are applied and the swelling/consolidation and thermomechanical processes are coupled according to the separate mechanical properties of the pore water, the solids and the clay skeleton. The model can be used by the finite-element program ABAQUS.

The model has been tested in several laboratory and field verification tests. Comparison between measured and calculated behaviour shows that the general behaviour is described properly and several calculations of different scenarios have been made for the Swedish KBS 3 concept. However, certain processes, like the hysteresis effect at consolidation/swelling, the curved stress-strain relation at shearing, and the curved failure envelope, are not modelled in a perfectly accurate way and an improved material model is proposed here. It combines the behaviour of the Cam-clay model on the wet side with the more relevant plastic behaviour of a modified Drucker-Prager model with a curved failure envelope and the possibility to introduce strain softening after failure.

The paper presents some laboratory results that are the basis of the first model. It also shows the application of the model to finite-element calculations of some laboratory tests. Comparisons between the calculations and measured results expose some disadvantages of the model and a concept for an improved model is suggested.     

Overconsolidation effects of ground freezing

Temporary ground freezing is a valuable technique for stabilizing soft soils during construction. It imparts large increases in strength and bearing capacity to most soils. However, freezing can cause significant changes in soil structure and density which can lead to adverse settlement during thaw.

Settlement of clay soils after freezing and thawing is the result of the suction forces that draw pore water to the freezing front. These suction forces cause an increase in the effective stress on the clay beneath the freezing front, and thus cause an overconsolidation of the clay. As these suction forces often exceed 1 atm, their direct measurement is not easy.

A technique for indirectly determining the maximum suction occurring during freezing is presented which utilizes the apparent memory that clay soils have for maximum past (preconsolidation) pressures. Suctions as large as 532 kN m⁻² were observed after freezing and thawing a clay soil which was initially consolidated to 128 kN m⁻².

The volume changes resulting from the freezing and thawing of clays were related to the plastic limit and were observed in the laboratory to be as high as 25%. If provisions are not made to account for these volume changes in a ground freezing project, considerable damage to structures can occur from settlement and the resulting stresses.     

Size and shape evolution of pores in a viscoplastic matrix under compression

The frequent use of soils and earth materials for hydraulic capping and for geo‐environmental waste containment motivated our interest in detailed modelling of changes in size and shape of macro‐pores to establish links between soil mechanical behaviour and concurrent changes in hydraulic and transport properties. The objective of this study was to use finite element analysis (FEA) to test and extend previous analytical solutions proposed by the authors describing deformation of a single macro‐pore embedded in linear viscoplastic soil material subjected to anisotropic remote stress. The FEA enables to consider more complex pore geometries and provides a detailed picture of matrix yield behaviour to explain shortcomings of approximate analytical solutions. Finite element and analytical calculations agreed very well for linear viscous as well as for viscoplastic materials, only limited for the case of isotropic remote stress due to the simplifications of the analytical model related to patterns and onset of matrix‐yielding behaviour. FEA calculations were compared with experimental data obtained from a compaction experiment in which pore deformation within a uniform modelling clay sample was monitored using CAT scanning. FEA predictions based on independently measured material properties and initial pore geometry provided an excellent match with experimentally determined evolution of pore size and shape hence lending credence to the potential use of FEA for more complex pore geometries and eventually connect macro‐pore deformation with hydraulic properties. Copyright © 2006 John Wiley & Sons, Ltd.     

Isotopic exchange of Zn with stable Zn adsorbed on reference clay minerals

For reference clays of low organic content, Zn adsorbed on the clay minerals is in kinetic equilibrium with ⁶⁵Zn in solution. Thus the specific activity approach applied to the transport of ⁶⁵Zn(II) at the water-reference clay interface is intrinsically valid.     

Investigations of clay colloid aggregates by scanning transmission X-ray microspectroscopy of suspensions

The environmental behaviour of colloidal clay in aquatic systems is linked to the properties of their aggregates. Earlier investigations of clay colloids were performed with electron microscope techniques which caused de-hydration of the particles. Information on the structure of colloid aggregates is needed for understanding their sedimentation behaviour, as well as colloid contaminant transport properties in natural systems. Scanning transmission X-ray microspectroscopy successfully produced images of montmorillonite colloid aggregates in a pseudo-equilibrium state in 1 mM NaCl suspensions equilibrated for more than a year. These clay aggregates were revealed at photon energies below the O absorption edges of clay and water. They were spherical or ellipsoidal with diameters of the order of 100–800 nm. The aggregates are porous and gel like with lower densities than the clay mineral. These investigations are important for modelling the occurrence of clay aggregates in aqueous environments.     

Modelling hygro-thermo-mechanical behaviour of engineered clay barriers — validation phase

The Canadian Nuclear Fuel Waste Management Program (CNFWMP) is evaluating the concept of disposal of nuclear fuel waste in an engineerted vault at a depth of 500 to 1000 m in the plutonic rock of the Canadian Shield. In common with engineered barrier system designs being developed in other countries, the waste would be contained within durable containers that, in turn, would be isolated from the host rock by clay-based materials.

The objective of the CNFWMP is to develop a disposal concept that will protect human health and the natural environment far into the future. Assessments of the conceptual vault designs are based on system theory in which an attempt is made to correlate experiences with theoretical concepts of planned systems in such a way that the resulting coordination is sound and convincing. By necessity, since experiments with a total disposal system can never be performed, both the design and the performance assessment rely on experiments performed on physical models of vault elements over relatively short times and on information inferred from calculations (mathematical models) that simulate the probable behaviour of the system in the space-time domainof interest. For a simulation model to be successful, that is applied within a real world situation, the model must provide information regarding the behaviour of the system of interest that is clearly better, in some way, than the mental image or other abstract model that would be used instead. The results of a series of tests performed within the activity known as validation serve as tangible evidence regarding the success of a model in representing the system of interest.

This paper focusses on the validation of the models that describe the hygro-thermo-mechanical behaviour of the engineered clay-barriers proposed for application in the Canadian disposal system concept. The strategy being used to address the key issues in modelling to minimize the model error and to maximize the usefulness of the simulation model, based on testing procedures, is reviewed. Finally, a concept of the validation of codes/models that describe the unsaturated behaviour of engineered clay barriers, is described.     

Some thermodynamic properties of the Berman and Brown model for CaO-Al2O3-SiO2

The and (1984) excess free energy model (B&B) is extremely convenient to use in modelling multicomponent solutions. However, spinodal calculations reveal that their calibration of this model for CaO-Al₂O₃-SiO₂ produces liquation tielines that do not appear to be in agreement with experimental work. In addition, their calibration contains some strongly negative excess entropy parameters and these permit a most unusual inverted liquation field to start at approximately >2115°C, wt% (SiO₂, Al₂O₃, CaO) = (70, 16, 14). This inverted field expands rapidly to cover most of the ternary for T> 2300°C and continues to expand at all higher temperatures. The Berman and Brown calibration for this system carries these negative excess entropies of mixing because the solution model is very strongly asymmetric as a result of the use of normal oxide mole weights in modelling the configurational entropy of mixing. A suggestion is made for a fairly natural restriction on the relative sizes of empirical models for excess versus configurational entropy.

Expressions are presented for the general consolute condition (all solution models) and for the second and third partials of the B&B G^x model.     

The combined effect of clay and moisture content on the behavior of remolded unsaturated soils

The behavior of unsaturated clayey soil is highly influenced by the coupled interaction between water and clay content. Various aspects of the behavior of artificial clay–sand mixtures with variable water content were experimentally studied. Laboratory tests were utilized for the determination of consistency limits, the stress–strain relationship, strength parameters, hydraulic conductivity, and volume change characteristics for various combinations of water and clay content in soil mixtures.

Results presented for various clay–sand mixtures include: new normalized consistency limits; the combined effect of clay content and water content on the stress–strain relationship and on the strength parameters (c and φ); and the effect of clay content on hydraulic conductivity and swelling potential. The cohesion of clayey sand is found to increase with increasing water content to a certain limit, above which it decreases. The angle of internal friction for clayey sand is found generally to decrease with increasing water content. The degree of saturation is found to be better than the water content in explaining the strength behavior. The hydraulic conductivity sharply decreases with increasing clay content up to 40% beyond which the reduction becomes less significant. Simple empirical equations are proposed for predicting the swelling potential of clayey soils as a function of either the clay content or plasticity index.     

桂中坳陷环江凹陷上古生界海相页岩储层孔隙结构和分形特征研究

通过有机地化分析、全岩X衍射矿物分析、甲烷等温吸附及低压氮气吸附实验,本文对桂中坳陷环江凹陷上古生界页岩样品的孔隙结构及分形特征进行了研究.结果表明:研究区页岩总有机碳含量(TOC)平均为2.40%,热成熟度(Ro)平均为2.65%,处于过成熟演化阶段.页岩主要的矿物组成为石英和黏土.页岩的比表面积平均为5.86 m2/g,孔容平均为0.014 9 mL/g,平均孔径为11.2 nm.页岩中发育大量的中孔,主要呈两端开口的圆筒形孔或四边开放的平行板状孔.页岩中TOC含量和石英含量越多,微-中孔越发育、比表面积和孔容越大,而平均孔径则变小.通过Frenkel-Halsey-Hill (FHH)模型和氮气吸附实验数据计算得到孔隙表面分形维数D1(平均为2.428 4)和孔隙结构分形维数D2(平均为2.622 2),对应的相对压力(P/P0)分别是0~ 0.45和0.45 ~ 0.99.分形维数D1、D2随着比表面积、孔容的增加而增加,而平均孔径随着前者的增加而减小.分形维数D1、D2、TOC含量、石英含量和甲烷吸附量之间呈现较好的正相关性,但随着黏土矿物含量的增多而减小.分形维数D1与Langmuir压力存在弱负相关性,分形维数D2随Langmuir压力增大有变大的趋势.桂中坳陷西北部页岩分形维数越大,孔隙结构越复杂,其对天然气的吸附和存储能力越强.     

利用数字岩心技术评价含黏土砂岩导电模型

黏土附加导电性使得岩石导电机理复杂化,影响了测井解释中饱和度计算的准确性。随着石油勘探的发展,测井解释研究者针对特定地区和储层条件的饱和度求解提出了多种导电模型。本文基于贝雷砂岩的数字岩心,构建多种含黏土的砂岩数字岩心,利用有限元方法模拟岩心饱和水时的电导率C₀,并将数值模拟C₀与5种模型计算C₀对比,分析各种导电模型的适用情况。结果表明,黏土体积分数越小,黏土的阳离子交换容量越小,岩石孔隙度越大,公式计算C₀越接近数值模拟C₀。Doll公式和Indonesia公式计算C₀与数值模拟C₀接近,基本适用于不同孔隙度、黏土体积分数和阳离子交换容量的情况。     

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

The applicability and limitations of thermodynamic geochemical models to simulate trace element behaviour in natural waters. Lessons learned from natural analogue studies

Natural analogue investigations aim to understand key phenomena and processes in natural systems related to those expected to occur in radioactive waste repositories. One of the key applications of natural analogue studies has been the possibility to test the geochemical models to be used to describe the migration of radionuclides in a future radioactive waste repository system. To this end, several geochemical modelling testing exercises (commonly denoted as blind predictive modelling, BPM) have formed an integral part of these studies over the last decade.

We have reviewed, discussed and compared the results obtained from geochemical modelling BPM exercises carried out within six natural analogue studies: Poços de Caldas, Cigar Lake, Maqarin, El Berrocal, Oklo and Palmottu. To make this comparison meaningful, we present the main geochemical characteristics of each site in order to highlight the most relevant mineralogical and hydrochemical differences. The elements selected for discussion are: Sr, Ba, Sn, Pb, Se, Ni, Zn, REEs, Th and U. We have based our discussion on the results obtained from the calculated aqueous speciation as well as by comparing solubility calculations with the actually observed concentrations.

Results can be differentiated into two categories of elemental behaviour:

1. those elements like Th and U under reducing conditions that can be fairly well described by assuming solubility control exerted by pure solid phases as their oxyhydroxides;

2. elements such as Sr, Zn, REEs and U under oxidising conditions for which the association to major geochemical components of the system must be considered in order to explain their concentrations in groundwaters.

Additionally, we discuss the main improvements made to the thermodynamic databases and the geochemical calculation methodologies due to the BPM exercises. Furthermore, the most important characterisation geochemical data needed to complete predictive solubility and speciation calculations are identified.     

GPS-measured land subsidence in Ojiya City, Niigata Prefecture, Japan

Land subsidence caused by compression of clay layers in Ojiya City, Japan was measured by global positioning system (GPS) between 1 April 1996 and 31 December 1998.

Three baselines were selected in and around the city, and height difference on a WGS-84 ellipsoid was measured by GPS on each baseline. The ground at the GPS station in the city subsides and rebounds 7 cm every winter and spring, respectively. Measurement accuracy was 9.5 mm standard deviation. Ground water level was observed at a well near the GPS station. Regression analysis between total strain, calculated as ratio of the height difference displacement to the total thickness of the clay layers, and the layers' effective stress change with ground water level change gave good correlation. The slope of regression line 7.0×10⁻¹¹ m²/N was obtained as an average apparent coefficient of volume compressibility of the layers.     

Numerical simulation of elasto-plastic electro-osmosis consolidation at large strain

In this paper, a numerical solution for the electro-osmosis consolidation of clay in multi-dimensional domains at large strains is presented, with the coupling of the soil mechanical behaviour, pore water transport and electrical fields being considered. In particular, the Modified Cam Clay model is employed to describe the elasto-plastic behaviour of clay, and some empirical expressions are used to consider the nonlinear variation of the hydraulic and electrical conductivities of the soil mass during the consolidation processes. The implementation of the theoretical model in a finite element code allows for analysis of the evolution of the transient response of the clay subjected to electro-osmosis treatment. The proposed model is verified via comparison with data from a large strain electro-osmosis laboratory test, to demonstrate its accuracy and effectiveness. Various numerical examples are also investigated to study the deformation characteristics and time-dependent evolution of the excess pore pressure. Finally, a well-documented field application of electro-osmosis is simulated to provide further verification. The results show that the numerical solution is effective in predicting the nonlinear behaviour of clay during electro-osmosis consolidation.     

Simulation of groundwater flow and contaminant transport at a landfill site using models

Numerical and analytical modelling studies were conducted for the analysis of groundwater flow and contaminant transport at the Innisfil landfill site in the Town of Innisfil, County of Simcoe, in Ontario, Canada. Previously conducted field studies categorized the upper stratigraphy at the site into three units: upper sand unit, upper silt/clay unit and Intermediate Sand unit. Essentially horizontal groundwater movement in the two sand units and vertical downward flow in the silt/clay unit were reported by the field hydrogeologists. In the following, application of three computer models (FLOWPATH, USGS MOC and POLLUTE) for the simulation of the groundwater flow and contaminant transport processes at the Innisfil landfill site is described. The paper focuses on the calibration of groundwater flow and contaminant transport systems, and demonstrates how the insight gained during the contaminant transport calibration was used to improve the initial groundwater flow characterization of the hydrogeological system.     

A coupled non-isothermal reactive transport model for long-term geochemical evolution of a HLW repository in clay

A numerical model of coupled saturated/unsaturated water flow, heat transfer and multi-component reactive solute transport is presented to evaluate the long-term geochemical evolution in bentonite, concrete and clay formation for a potential geological radioactive waste repository. Changes in formation porosity caused by mineral dissolution/precipitation reactions are taken into account. Simulations were carried out with a general-purpose multicomponent reactive transport code, CORE^2D V4. Numerical results show that pH in the bentonite porewater can vary from neutral to up to 13 over a time scale of 1 Ma although dissolution of silica minerals and precipitation of secondary calcium silicate hydrate (CSH) minerals in bentonite buffer the effect of the hyperalkaline plume. Mineral precipitation reduces the volume of pore space in bentonite close to the bentonite–concrete interface due to the precipitation of CSH minerals. Model results indicate that bentonite porosity decreases less than 25%. The hyperalkaline plume from the concrete only extends to a distance of 0.7 m in the clay formation over the time range of 1 Ma.     

电化学循环井驱动模拟含水层化学氧化降解三氯乙烯

传统原位化学氧化地下水修复技术存在氧化剂迁移距离短和利用率低等问题。本研究在双井循环模式促进传质的基础上,通过注水井中的地下水电解原位提供O₂和H₂,配合乙二胺四乙酸(ethylenediamine tetraacetic acid,EDTA)络合溶解出含水层Fe(Ⅱ),活化O₂产生羟基自由基(•OH),实现地下水三氯乙烯(TCE)的氧化降解。在填充了砂土和黏土互层的二维砂槽中,设置电流为0.2 A、流速为72 cm/d、初始TCE浓度为3 mg/L,经过9 d的连续通电处理后,TCE浓度降低到1 mg/L,降解率达到67%。通电前投加0.5 mmol/L EDTA,经过1 d水流循环后含水层中溶解态Fe(Ⅱ)浓度从02 mg/L增加到414 mg/L,黏土区域较高。通电过程中,循环井促进O₂、Fe(Ⅱ)-EDTA和TCE的有效接触与反应,使TCE氧化降解。通电初期,黏土区域Fe(Ⅱ)氧化速率、TCE降解速率较周围慢,后期差异逐渐减小。未通电时加入醋酸钠可促进Fe(Ⅲ)还原,使含水层中铁循环利用。该修复过程通过循环井提升了氧化剂迁移距离,使用源于含水层的Fe(Ⅱ)-EDTA和稳定性较好的O₂提高了氧化剂利用率,有望应用于有机污染地下水修复。     

基于膨润土凝胶分形结构的屈服强度理论

在核废料处置库安全使用的设计年限（数万年至数十万年）内,膨润土遇水侵蚀,导致缓冲/回填层致密性降低、渗透性增加,危及核废料处置库安全。膨润土侵蚀是以膨润土凝胶形式迁移,膨润土凝胶的屈服强度就是侵蚀的临界剪切应力。膨润土凝胶颗粒之间的联结靠颗粒间的长程作用,即van der Waals力,颗粒间的联结作用取决于凝胶的结构。本文基于膨润土凝胶结构的分形模型,假设凝胶的屈服强度等于冲刷面上单位面积的van der Waals力的总和,导出了膨润土凝胶的屈服强度（σ_y）的表达式,表示为凝胶的固体体积率（φ_s）的幂函数,即σ_y=σ_y0φ_sm,幂函数的指数是凝胶结构分维的函数。膨润土凝胶的屈服强度理论得到了试验数据的验证。     

Flow and transport through clay membrane barriers

Flux equations for liquid and solute migration through clay barriers that behave as semi-permeable membranes used in waste containment and remediation applications, known as clay membrane barriers (CMBs), are discussed. The results of a simplified analysis of flow through a geosynthetic clay liner (GCL) using measured values for the chemico-osmotic efficiency coefficient (ω) of the GCL indicate a total liquid flux that counters the outward Darcy (hydraulic) flux due to chemico-osmosis associated with clay membrane behavior of the GCL. Also, the solute (contaminant) flux through the GCL is reduced relative to the solute flux that would occur in the absence of membrane behavior due to chemico-osmotic counter advection and solute restriction. Since diffusion commonly controls solute transport through GCLs and other low-permeability clay barriers, the implicit (empirical) correlation between ω and the effective salt-diffusion coefficient of the migrating contaminant is an important consideration with respect to contaminant restriction in CMBs.     

Contribution à la modélisation des vitesses de propagation des ondes P et S dans les formations sédimentaires argileuses

Acoustic P and S wave propagation in the argillaceous sediments is related to the media porosity as well as on clay-mineral composition. The propagation-velocity prediction of these waves thus requires knowledge of these two parameters and their impact on the velocities. Porosity decreasing with effective pressure increasing, due to the burial, follows an exponential law. We will limit our analysis to the three clays: kaolinite, illite and montmorillonite. The variations of porosity between various clays are strongly reduced with the increase in effective pressure, which tends to minimize the impact of mineralogy with the burial. By integrating these equations in a model of Reuss and Voigt, in which we consider an association mineral argillaceous/fluid, we extract a law of evolution for bulk and shear moduli of clay according to the pressure, for each type of clay. By associating clay moduli calculation results to qualitative and quantitative predictions from spectral nuclear-radiations tools and X-ray-diffraction measurements on cores, it is possible to predict sonic velocities in clays with a given effective pressure. An example of P and S velocity modelling is presented on a well in the deep offshore-turbiditic environment.