Plutonium diffusivity in compacted bentonite

Measurements on plutonium diffusivity in water-saturated compacted bentonite were carried out. Representative specimens of sodium bentonite were taken from the Tsukinuno and Kuroishi mines situated in northeast Japan. Tsukinuno bentonite was divided into three types: raw type, purified Na-type, and H-type which was prepared by treating Na-type bentonite with hydrochloric acid. Kuroishi bentonite contained chlorite as impurity. H-type bentonite was used as reference for the convenience of profile measurement in bentonite, since plutonium diffusivity in H-type bentonite was considered to be larger than that in Na-type bentonite because of low pH and low swelling pressure of H-type bentonite.

Sampled bentonite was compacted into pellets of 20 mm in diameter and 20 mm in height. Bulk densities of these specimens were 1200–1800 kg/m³ for purified Na-type and H-type bentonite and 1600 kg/m³ for raw type bentonite.

Plutonium profiles obtained in H-type bentonite can be explained by diffusion equation with constant concentration source. Diffusivity ranges from 10^-13 to 10¹² m²/s for H-type and Kuroishi impure sodium bentonite. Diffusivity in both raw type and purified Tsukinuno bentonite was was estimated to less than 10^-14 M²/s. Diffusivity in H-type bentonite showed a tendency to decrease with increasing density. Influence of in bentonite was also studied. Quartz content up to 50% or hematite content up to 1% did not influence diffusivity significantly in H-type bentonite.

The chemical species of plutonium in pore water of Na-type and H-type were estimated Pu(OH)₃^-; and PuO₂^- , respectively.     

Characteristics,modification and environmental application of Yemen’s natural bentonite

The bentonite deposit of Lahij Province, Yemen, has very promising commercial applications due to its mineralogy and physical and chemical properties. It was examined to determine its mineralogical composition, chemical and physical properties of the bentonite deposit, purity and sodium-exchanged bentonite. Modified bentonite was synthesized by exchanging cetyltrimethylammonium cations for inorganic ions on the bentonite and its adsorption properties for ammonium were characterized in batch experiments. Analytical methods were carried out to study the bentonite comprising X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy, chemical analysis and kinetic and isotherm models were also tested. The results have shown that the purification of bentonite resulted in a bentonite fractions of the total sample composed of montmorillonite and <5 % quartz. The XRD data showed that the interlayer spacing (d ₀₀₁) of bentonite decreased from 15.3 to 12.5 Å and then increased to 19.7 Å. Moreover, high cation exchange capacity, good water absorption and high swelling capacity were also obtained. The results have shown that the modified bentonite was more effective than the natural bentonite for ammonium removal. In addition to that, pseudo-second-order kinetic model, Freundlich and the Langmuir models described the adsorption kinetics and isotherm well. It was concluded that Yemen (Alaslef) bentonite can be potential adsorbents for ammonium removal.     

The average molecular weight and shape of the “polymeric acids” found in Black Trona Water from the Green River Basin

Macromolecular organic material, called “polymeric acids”, has been isolated from Black Trona Water by exhaustive dialysis and characterized as the sodium salt in 0.10 M sodium carbonate, pH 10, by several physico-chemical methods. Analysis by gel filtration chromatography on Sepharose-CL 6B indicates that the “polymeric acids” are polydisperse and composed of species of relatively high molecular weight ( 4 × 10⁵, using proteins as standards). With this method, the range of molecular weights appears to be rather narrow. If “polymeric acids” are transferred from sodium carbonate, pH 10, into distilled water, selfassociation occurs and all species elute in the void volume. The weight-average molecular weight determined in 0.10 M sodium carbonate, pH 10, by the light scattering method is 1.7 × 10⁵. Sedimentation velocity analysis at 20°C with the analytical ultracentrifuge gives a value for S_20,w of 5.4 and the shape of the Schlieren patterns suggest a polydisperse sample with a relatively narrow range of sizes. Analysis of the molecular weight distribution by a sedimentation equilibrium method indicates that the range of molecular weights is 8 × 10⁴ to 2.1 × 10⁵. The partial specific volume ( ) of “polymeric acids” is 0.874 ml/g. Viscosity measurements yield a value for [η] of 2.5 ml/g, which indicates that the “polymeric acids” are compact (spherical or ellipsoidal) in shape.     

高庙子膨润土水化膨胀特性及其微观机理研究

膨润土具有遇水膨胀的特性,是高放核废料深地质处置库理想的缓冲回填材料。膨胀特性是其作为缓冲材料最重要的性能之一,同时受多方面因素的影响。本文以我国首选缓冲材料高庙子膨润土为研究对象,以含水率和干密度为控制变量,以恒体积法为试验方法,研究了高压实高庙子膨润土的水化膨胀特性,采用压汞试验法(MIP)对膨润土微观结构进行了研究,并以此对水化膨胀特性进行了解释。膨胀力试验结果表明,高庙子膨润土的膨胀力发展形式和最大膨胀力均受试样含水率和干密度影响,干密度较小时,水化曲线呈明显的双峰结构,干密度较大时,水化曲线形态与含水率相关,随着含水率增大,双峰结构逐渐消失。MIP试验结果表明,高庙子膨润土的孔径分布同样受含水率和干密度影响,随着含水率和干密度降低,集合体间大孔隙体积增多。膨润土的水化膨胀曲线受集合体间大孔隙影响显著。大孔隙较多时,膨润土集合体能迅速膨胀形成临时结构,当膨胀力超过临时结构的极限荷载时发生坍塌,膨胀力回落,内部结构重组后继续水化达到最大膨胀力,因此其水化膨胀曲线呈明显的双峰结构。随着大孔隙量减少,水化膨胀曲线由双峰结构演变成一条平滑曲线。     

Performance evaluation of soil mixtures treated with graphite and used as barrier fill material for high-level radioactive waste repository

Buffer/backfill material is an important engineering barrier in a deep geological repository of high-level radioactive waste (HLW). Its thermo-hydro-mechanical (THM) performance is very important for the safe and stable operation of the HLW repository system. Natural graphite powder mixed with sodium bentonite forms a buffer/backfill material that can dissipate heat quickly and provide strong isolation. In this paper, the THM characteristics of bentonite–sand–graphite–polypropylene fiber (BSGF) mixtures, used as a buffer/backfill material, were studied through a series of laboratory tests. The influence of graphite and polypropylene fiber contents on thermal conductivity, swelling pressure, hydraulic conductivity, and strength properties of BSGF mixtures with different sand contents was analyzed. Experimental results indicated that the graphite content, the maximum graphite mesh number, and the initial dry density of bentonite–graphite mixtures influenced the thermal conductivity of bentonite–graphite mixtures. The addition of polypropylene fiber was found to enhance the shear strength and inhibit cracking without significantly affecting the expansivity, permeability, and thermal conductivity of the BSGF mixtures. This study provides a new buffer/backfill material that can improve the stability, functionality, and thermal efficiency of the HLW repository.

     

碱金属离子及碱溶液对膨润土性能影响的研究进展

基于前人有关膨润土在碱性环境下的室内试验和数值模拟的研究结果 ,重点阐述了碱金属离子及碱溶液对膨润土矿物成分、微观结构、膨胀性和渗透性等方面的影响,讨论了温度、pH值与溶液浓度等对上述过程的影响。碱金属离子及碱性溶液不仅可交换膨润土中蒙脱石层间阳离子,而且可溶解膨润土中的蒙脱石,生成非膨胀性矿物,并随着温度和pH值升高,蒙脱石被溶解程度增加,从而导致了膨润土膨胀力减小,且随着温度、溶液浓度及pH值的增加,膨胀力削弱程度加强;同时,膨润土与碱金属离子及碱溶液接触时孔隙增多,进而渗透性增强,随着温度和溶液浓度增加,渗透性也明显增强。数值模拟可实现膨润土与碱性溶液长期接触时发生的矿物成分及渗透性变化的预测。高温、不同pH值的低碱性溶液及其耦合作用对膨润土的矿物化学成分、微观结构、膨胀力和渗透性的影响及机理研究应该是今后研究的重点。     

Mineralogy, geochemistry and uses of the mordenite–bentonite ash-tuff beds of Los Escullos, Almería, Spain

The mordenite ore deposit of Los Escullos has a surface area of 10⁶ m² with an average thickness of 5 m and estimated reserves of 7,500,000 tons of mordenite–bentonite. It is made up of horizontal layers of interbedded epiclastic tuffs with volcanic bentonitised materials which have been subjected to hydromagmatic activity. The layers are essentially composed of bentonite and mordenite with lesser amounts of quartz, cristobalite, biotite, plagioclase, chlorite, amphiboles, titanomagnetite, ilmenite and calcite. The harder layers display a higher proportion of plagioclase crystals and are enriched in Al₂O₃, CaO, Fe₂O₃, TiO₂, P₂O₅, Cu, Zn, Co, Cr, Ni and V, while the more altered layers contain larger contents of SiO₂, K₂O and Y. The amount of sodium increases (from 2% to 4%) relative to depth. Alteration processes resulted in a reduction in the contents of CaO, K₂O and MnO and increase in Na₂O and MgO. The beds of volcanic ash-tuffs have been devitrified by hydrothermal solutions giving rise to bentonites and sodium- and silica-rich residual fluids which have partly crystallized as mordenite and cristobalite. The raw material (mordenite–bentonite) can be improved removing biotite (magnetic separation) and plagioclase and quartz (by floating methods); however, the mordenite–bentonite mineral assemblage is practically impossible to separate due to the size of the crystals (average 0.5 μm under SEM–EDAX). In turn, this upgraded raw material has very useful properties (total area=520 m²/g and cation exchange capacity=70 meq/100 g) which may make it suitable for use in absorption processes (e.g. deodorization, cationic exchange), catalysis and molecular sieving.     

Effect of alkaline solutions on bentonite properties

The influence of alkaline aqueous solutions on the properties of bentonite was investigated to evaluate the performance of bentonitic engineered barriers when contacted with alkaline groundwater. Batch and hydraulic conductivity tests were conducted on Na-bentonite using six different alkaline aqueous solutions. For the batch tests, almost no change in the montmorillonite fraction of the bentonite was observed after reacting with alkaline solutions (pH = 8.4–13.1), regardless of the solution type. On the other hand, aluminosilicate minerals (e.g., albite) were dissolved and secondary minerals (e.g., anorthite) were formed in alkaline NaOH solutions (pH > 13). The cation (Ca or Na) concentration primarily affected the swelling properties of bentonite rather than the pH of the solution, which was comparable to the results of the hydraulic conductivity tests. For the Ca solutions, the hydraulic conductivity of the bentonite specimen to the 0.02 mol/L Ca(OH)₂ solution (6.5 × 10^?9 cm/s) was approximately an order of magnitude lower than that of the bentonite specimen to the 0.02 mol/L Ca(OH)₂ + 1 mol/L CaCl₂ solution (5.0 × 10^?8 cm/s), whereas the hydraulic conductivity to the 0.02 mol/L Ca(OH)₂ + 1 mol/L CaCl₂ solution (pH = 11.3) (5.0 × 10^?8 cm/s) was slightly higher than that to the 1 mol/L CaCl₂ solution (pH_i = 8.4) (4.4 × 10^?8 cm/s). For the NaOH solutions with pH > 13, the hydraulic conductivity of the bentonite specimen decreased with increasing Na concentration, suggesting that the effect of Na concentration was more dominant than that of permeant pH.     

膨润土加砂混合物膨胀特征试验研究

运用自行研制的膨胀仪对膨润土加砂混合物进行了一系列膨胀力及膨胀应变等膨胀特性的试验研究,分析了膨胀力随时间的变化规律、两向膨胀力之间的关系和膨胀应变与时间及吸水量之间的关系。试验研究表明,膨润土加砂混合物的最大膨胀力以及最大膨胀应变主要取决于混合物的最初干密度和膨润土含量,并且随着二者的增大而增大;膨润土加砂混合物的水平膨胀力与竖向膨胀力之比随着混合物干密度的增大减小,并且与干密度近似成线性关系;不同膨润土含量的膨润土加砂混合物的膨胀应变与时间成双曲线关系,与吸水量近似呈S型曲线关系,并且其最大膨胀应变与膨润土含量存在指数关系。试验结果对高放废物深处置库中的缓冲回填材料设计具有一定的参考价值。     

Minimal alteration of montmorillonite following long-term interaction with natural alkaline groundwater: Implications for geological disposal of radioactive waste

Bentonite is one of the more safety-critical components of the engineered barrier system in the disposal concepts developed for many types of radioactive waste. Bentonite is utilised because of its favourable properties which include plasticity, swelling capacity, colloid filtration, low hydraulic conductivity, high retardation of key radionuclides and stability in geological environments of relevance to waste disposal. However, bentonite is unstable under the highly alkaline conditions induced by Ordinary Portland Cement (OPC: initial porewater pH > 13) and this has driven interest in using low alkali cements (initial porewater pH9-11) as an alternative to OPC. To build a robust safety case for a repository for radioactive wastes, it is important to have supporting natural analogue data to confirm understanding of the likely long-term performance of bentonite in these lower alkali conditions. In Cyprus, the presence of natural bentonite in association with natural alkaline groundwater permits the zones of potential bentonite/alkaline water reaction to be studied as an analogy of the potential reaction between low alkali cement leachates and the bentonite buffer in the repository. Here, the results indicate that a cation diffusion front has moved some metres into the bentonite whereas the bentonite reaction front is restricted to a few millimetres into the clay. This reaction front shows minimal reaction of the bentonite (volumetrically, less than 1% of the bentonite), with production of a palygorskite secondary phase following reaction of the primary smectites over time periods of 10⁵–10⁶ years.     

An upscaling method and a numerical analysis of swelling/shrinking processes in a compacted bentonite/sand mixture

This paper presents an upscaling concept of swelling/shrinking processes of a compacted bentonite/sand mixture, which also applies to swelling of porous media in general. A constitutive approach for highly compacted bentonite/sand mixture is developed accordingly. The concept is based on the diffuse double layer theory and connects microstructural properties of the bentonite as well as chemical properties of the pore fluid with swelling potential. Main factors influencing the swelling potential of bentonite, i.e. variation of water content, dry density, chemical composition of pore fluid, as well as the microstructures and the amount of swelling minerals are taken into account. According to the proposed model, porosity is divided into interparticle and interlayer porosity. Swelling is the potential of interlayer porosity increase, which reveals itself as volume change in the case of free expansion, or turns to be swelling pressure in the case of constrained swelling. The constitutive equations for swelling/shrinking are implemented in the software GeoSys/RockFlow as a new chemo‐hydro‐mechanical model, which is able to simulate isothermal multiphase flow in bentonite. Details of the mathematical and numerical multiphase flow formulations, as well as the code implementation are described. The proposed model is verified using experimental data of tests on a highly compacted bentonite/sand mixture. Comparison of the 1D modelling results with the experimental data evidences the capability of the proposed model to satisfactorily predict free swelling of the material under investigation. Copyright © 2004 John Wiley & Sons, Ltd.     

Swelling characteristics of compacted lateritic soil–bentonite mixtures subjected to municipal waste leachate contamination

Compacted soil–bentonite mixtures are finding wide application as buffer material for waste repositories for their favorable self-sealing qualities. The swelling properties of such materials which serve as a measure of their self-sealing capabilities and, thus, the efficiency of the repository in sealing off their contents from the environment are closely related to the chemistry of the leachate that emanate from the wastes. For this reason, the swelling parameters (namely swelling potential and pressure) of compacted lateritic soil–bentonite mixtures under consideration for use as barrier in municipal waste landfill were evaluated. Series of swelling potential and pressure tests were performed using variable content (0–10 %) of bentonite at predetermined optimum moisture content. Soil mixtures were compacted with British Standard Heavy compactive effort and saturated with processed tap water as well as three leachate solutions of varying ionic strength that were generated in active open dump landfills. Experimental results showed that swelling potential based on the free swell together with the maximum swell pressures of compacted soil mixtures measured at equilibrium increased approximately linearly with increase in the amount of bentonite when inundated with processed tap water and the three leachate solutions. On the other hand, these swelling parameters decreased as the ionic strength of the leachate solutions measured by their electrical conductivity increased for the various soil mixtures. These results provide an insight into the swelling behavior and the possible degradation in the efficiency of the proposed lateritic soil–bentonite mixtures in relation to their use as buffer material in waste landfills.     

Effect of sand grain size and boundary condition on the swelling behavior of bentonite–sand mixtures

Deep geological repository is a favorable choice for the long-term disposal of nuclear wastes. Bentonite–sand mixtures have been proposed as the potential engineered barrier materials because of their suitable swelling properties and good ability to seal under hydrated repository conditions. To investigate the effects of sand grain size on the engineering performance of bentonite–sand mixtures, we prepare five types of bentonite–sand mixtures by mixing bentonite with sand of varying particle size ranges (0.075–0.25 mm, 0.25–0.5 mm, 0.5–1 mm, 1–2 mm and 2–5 mm, respectively). We carry out sequential oedometer tests under different simulated repository conditions, including constant vertical stress (CVS), constant stiffness (CS) and constant volume (CV) conditions. The microstructural heterogeneity and anisotropy of these soil mixtures are characterized through the quantitative analysis of micro-CT scanning results. Experimental results reveal that both sand grain size and boundary condition significantly influence the swelling of soil mixtures. Under three conditions, the temporal evolutions of swelling stress and strain follow similar trends that they increase faster at the beginning and gradually stabilize afterward. Comparing the ultimate values, swelling strains follow CVS?>?CS?>?CV, while swelling stresses follow CV?>?CS?>?CVS. Under CS boundary conditions, as the stiffness coefficient increases, the swelling pressure increases and the swelling strain decreases. CT results further indicate that mixtures with larger sand inclusions are more structurally heterogeneous and anisotropic, resulting in increased inter-particle friction and collision and a higher energy dissipation during the swelling process. Moreover, the non-uniform distribution of bentonite in local zones would be intensified, which plays an important role in compromising swelling behavior. Therefore, soil samples mixed with larger sand particles present a smaller swelling stress and strain values. This study may guide the choice of engineered barrier materials toward an improved design and assessment of geological repository facilities.

     

蒙脱石层电荷与有机改性蒙脱石凝胶性能关系研究

利用自然沉降法提取了山东两不同产地膨润土中的钙基蒙脱石矿物M1和M2,利用结构式推算法计算了两提纯蒙脱石的层电荷:M1单位半晶胞的层电荷为0.38,M2单位半晶胞的层电荷为0.59;利用十八烷基三甲基氯化铵对蒙脱石进行有机改性,并对有机蒙脱石凝胶性能和层电荷的相关关系进行研究。研究发现:蒙脱石单位半晶胞的层电荷越低,在水中的分散性越好,越有利于十八烷基三甲基铵阳离子的插层,相应有机改性蒙脱石在二甲苯和乙醇体系中的凝胶性能越好(如M1);蒙脱石单位半晶胞的层电荷越高,在水中的分散性越差,越不利于十八烷基三甲基铵阳离子的插层,相应有机改性蒙脱石产品的凝胶性能较差(如M2)。     

Effect of wetting–drying cycles on swelling behavior of lime stabilized sand–bentonite mixtures

In the present study, influence of wetting–drying cycles on swelling pressures of sand–bentonite mixtures used in the construction of sanitary landfills to have an impermeable liner was investigated before and after lime treatment of the mixtures. Swelling pressure tests were conducted to see if the swelling pressures were affected by wetting–drying cycles. First series of specimens were prepared as a mixture of sand and bentonite only. In the first series of specimens, sand was mixed with bentonite in various proportions with their optimum water contents and compacted by using standard proctor energy. In the second series of the specimens, lime in various proportions was added to the mixtures of sand–bentonite. Then, the sand–bentonite mixtures stabilized by lime were compacted with the standard proctor energy at their optimum moisture contents. Five wetting–drying cycles were performed on each specimen and values of swelling pressures were measured at the end of each cycle. Results of swelling pressure tests indicated that the swelling pressure is decreased when lime is added to the mixtures. In addition, decrements were observed on swelling pressures by wetting–drying cycles. The results of the experiments of this investigation showed that the beneficial effect of lime stabilization to control the swelling pressures was partly lost by the wetting–drying cycles. However, the test results indicated that the swelling pressures of the specimens made of sand–bentonite mixtures stabilized by lime were lower than the swelling pressures of the specimens made of only sand–bentonite mixtures.     

The effect of iron on montmorillonite stability. (I) Background and thermodynamic considerations

It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al₂O₃-FeO-Fe₂O₃-MgO-Na₂O-SiO₂-H₂O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if f_O2(g) values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If f_O2(g) exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.     

Insights into the water retention behaviour of GMZ bentonite pellet mixture

Bentonite pellets are recognized as good buffer/backfill materials for sealing technological voids in high-level radioactive waste (HLW) repository. Compared to that of a traditional compacted bentonite block, one of the most important particularities of this material is the initially discrete pellets and the inevitable heterogeneous porosity formed, leading to a distinctive water retention behaviour. In this paper, water retention and mercury intrusion porosimetry (MIP) tests were conducted on pellet mixture (constant volume), single pellet (free swelling) and compacted block (constant volume) of GMZ bentonite, water retention properties and pore structure evolutions of the specimens were comparatively investigated. Results show that the water retention properties of the three specimens are almost similar to each other in the high suction range (>?10 MPa), while the water retention capacity of pellet mixture is lower than those of the compacted block and single pellet in the low suction range (<?10 MPa). Based on the capillary water retention theory (the Young–Laplace equation), a new concept ‘saturated void ratio’ that was positively related to water content and dependent on pore size distribution of the specimen was defined. Then, according to the product of saturated void ratio and water density in saturated void, differences of water retention properties for the three specimens at low suctions were explained. Meanwhile, MIP tests indicate that as suction decreases, the micro- and macrovoid ratios of pellet mixture and compacted block decrease as the mesovoid ratio increases, while all the void ratios of single pellets increase. This could be explained that upon wetting, water is successively adsorbed into the inter-layer, inter-particle and inter-pellet voids, leading to the subdivision of particles and swelling of aggregates and pellets. Under constant volume condition, aggregates and pellets tend to swell and fill into the inter-aggregates or inter-pellets voids. While under free swelling condition, the particles and aggregates in a single pellet tend to swell outward rather than squeezing into the inter-aggregate voids, leading to the expansion of the pores and even formation of cracks. Results including the effects of initial conditions (initial dry density and fabric) and constraint conditions (constant volume or free swelling) on the water retention capacity and pore structure evolution reached in this work are of great importance in designing of engineering barrier systems for the HLW repository.

     

A method for predicting swelling pressure of compacted bentonites

An approach for predicting swelling pressure of bentonites based on thermodynamic relationships between swelling pressure and suction is presented in this paper. The proposed method requires sorption isotherm data of the bentonites. A series of swelling pressure tests were performed on compacted specimens of bentonite-sand mixtures with different bentonite contents, water contents, and dry densities. The sorption isotherm of the pure bentonite was measured using a chilled-mirror hygrometer. It is found that the method works well for the bentonite-sand mixtures tested. Several published data on bentonites that have been proposed to be used as buffer and sealing material for nuclear waste repository were collected and used to verify the method. The proposed method is found to be also applicable for other bentonites of different types and therefore, can be used to predict swelling pressure of bentonites.     

Effects of Post-compaction Residual Lateral Stress and Electrolyte Concentration on Swelling Pressures of a Compacted Bentonite

The effects of post-compaction residual lateral stress and salt concentration in the hydrating fluid on swelling pressures of compacted MX80 bentonite is brought out in this paper. In order to release the residual lateral stresses, following the static compaction process during preparation of specimens, compacted bentonite specimens were extruded from the specimen rings and then inserted back prior to testing them for swelling pressures in isochoric condition. The swelling pressure tests were carried out at several dry densities of the bentonite with distilled water and solutions of NaCl (0.1 and 1.0 M) as the hydrating fluids. With water, the test results showed that specimens that underwent extrusion and insertion processes exhibited about 10–15 % greater swelling pressures as compared to the specimens those that were compacted and tested. The influence of saline solutions was found to reduce the swelling pressure of the bentonite, but their impact was less significant at high compaction dry densities.     

The influence of Fe(II) competition on the sorption and migration of Ni(II) in MX-80 bentonite

The results from batch sorption experiments on montmorillonite systems have demonstrated that bivalent transition metals compete with one another for sorption sites. For safety analysis studies of high level radioactive waste repositories with compacted bentonite near fields, the importance of competitive sorption on the migration of radionuclides needs to be evaluated. Under reducing conditions, the bentonite porewater chosen has a Fe(II) concentration of ∼5.3 × 10⁻⁵ M through saturation with siderite. The purpose of this paper is to assess the influence of such high Fe(II) concentrations on the transport of Ni(II) through compacted bentonite, Ni(II) was chosen as an example of a bivalent transition metal. The one-dimensional calculations were carried out at different Ni(II) equilibrium concentrations at the boundary (Ni(II)_EQBM) with the reactive transport code MCOTAC incorporating the two site protolysis non electrostatic surface complexation/cation exchange sorption model, MCOTAC-sorb. At a Ni(II)_EQBM level of 10⁻⁷ M without Fe(II) competition, the reactive transport calculations using a constant K_d approach and the MCOTAC-sorb calculation yielded the same breakthrough curves. At higher Ni(II)_EQBM (10⁻⁵ M), the model calculations with MCOTAC-sorb indicated a breakthrough which was shifted to later times by a factor of ∼5 compared with the use of the constant K_d approach.When sorption competition was included in the calculations, the magnitude of the influence depended on the sorption characteristics of the two competing sorbates and their respective concentrations. At background Fe(II) concentrations of 5.3 × 10⁻⁵ M, and a Ni(II)_EQBM level of 10⁻⁷ M, the Ni(II) breakthrough time was ∼15 times earlier than in the absence of competition. At such Fe(II) concentrations the Ni(II) breakthrough curves at all source concentrations less than 3.5 × 10⁻⁵ M (fixed by the NiCO_3,S solubility limit) are the same i.e. Ni(II) exhibits linear (low) sorption.Competitive sorption effects can have significant influences on the transport of radionuclides through compacted bentonite i.e. reduce the migration rates. Since, for the case considered here, the Fe(II) concentration in the near field of a high-level radioactive waste repository may change in time and space, the transport of bivalent transition metal radionuclides can only be properly modelled using a multi-species reactive transport code which includes a sorption model.