Retention of heavy metal ions in bentonites from Grau Region (Northern Peru)

Experimental studies on the retention of metals (Cu, Co, Ni, and Zn) in bentonite samples from the Grau Region (Northern Peru) have been accomplished using monometallic, bimetallic, trimetallic, and tetrametallic solutions. Parameters such as pH and concentration of dissolved metals and organic compounds have been evaluated by means of batch adsorption experiments. Adsorption rates indicate the suitability of these bentonites in the environmental industry for heavy metals retention purposes. In addition to its quality as physical barrier to avoid the dispersion through the environment of polluted leachates, bentonite, due to its high cation exchange capacity, can act also as a chemical barrier, protecting the quality of surface and groundwater systems, while limiting the migration of heavy metals in solid residues or sludge stocked in security landfills. Adsorption rates of tested bentonites were proved to decrease when concentrations of both metal and organic compounds, as well as the number of ionic species, increase in solution; additionally, lower metal removal rates from solution were obtained when extremely acidic conditions were achieved.     

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.     

Hydromechanical Behaviour of Rock-Bentonite Interfaces Under Compression

Summary Interfaces between geomaterials may be critical for the long term confinement of the engineered barriers of nuclear waste disposals, particularly if there is water flow. Hydromechanical compression tests have been performed on rock-bentonite interfaces representing the contact between a host rock (toarcian argillite) and an engineered barrier within a nuclear waste repository. The results show that there is no major influence of the bentonite fraction or the nature of the additive as long as the additive is inert (sand or crushed rock): all the interfaces are closed for low values of normal stress (about 4 MPa). On the other hand, the hydromechanical behaviour of the interfaces changes when a high fraction of cement is used. Moreover, it has been shown that bentonite is very sensitive to hydraulic erosion, producing flow channels within the interface zone. A numerical study confirms the importance of erosion for the hydromechanical behaviour of the interface. Authors’ address: Olivier Buzzi, Laboratoire Sols, Solides, Structures, Université Joseph Fourier, BP 53, 38041 Grenoble, Cedex 9, France     

Effect of groundwater chemistry on the swelling behavior of a Ca-bentonite for deep geological repository

The swelling properties of buffer material for high level radioactive waste repository in a near-field environment are of particular importance for achieving the low permeability sealing function. In this study, the free swelling behavior of a potential buffer material Zhisin clay is evaluated under simulated groundwater conditions such as immersion in NaCl, CaCl₂, and Na₂SO₄ solutions at various concentrations. Experimental results indicate that Zhisin clay, being a Ca-bentonite, exhibits reduced swelling strain in salt solutions. The amount of decrease in swelling strain upon saline water intrusion is affected by both the type and concentration of electrolyte. At the same concentration, the swelling strains in CaCl₂ solution are lower than those in NaCl solution due to the quasi-crystals formed in the presence of calcium ions. Also, the swells in Na₂SO₄ solution are found to be lower than those in NaCl solution. This is attributed to the precipitation of CaSO₄, which acts as binding agent and results in aggregation of clay particles.     

Mechanisms and Models for Bentonite Erosion Used for Geologic Disposal of High Level Radioactive Waste: A Review

The performance of the bentonite buffer in nuclear waste repository concept relies to a great extent on the buffer surrounding the canister having sufficient dry density. Loss of buffer material caused by erosion remains as the most significant process reducing the density of the buffer. In the worst case, the process is assumed to last as long as the free volume between the pellets in the pellets filled regions is filled with groundwater. Erosion rate and mass erosion are calculated based on the erosion model, and the measures are presented to prevent the geological disaster due to bentonite erosion. The groundwaters may solubilise the smectite particles in the bentonite and carry them away as colloidal particles. A dynamic model is developed for sodium gel expansion in fractures where the gel soaks up groundwater as it expands. The model is based on a force balance between and on smectite particles, which move in the water. Attractive van der Waals forces, repulsive electric diffuse layer (DDL) forces, gravity and buoyancy forces and forces caused by the gradient of chemical potential of the particles act to move the particle in the water. The effect of the fracture width and the frictions between particles and water and surrouding rock is analysed based on erosion model. The DDL forces strongly depend on the type of clay minerals and the type of ion and concentration in the water surrounding the particles. In the designed safe use of nuclear waste disposal (tens of thousands of years to hundreds of thousands of years), the safety of nuclear waste disposal is affected by the hydrodynamic and chemical effects, and bentonite erosion. Due to the bentonite erosion, the buffer/backfill layers become loose, and their permeability increases, which causes the nuclear element diffusion and convection, and even the nuclear disaster. In this paper, the mechanisms, models, experiments and control measures of bentonite erosion were systematically summarized. The current deficiencies of bentonite erosion were pointed out, and new methods were put forward to carry out the research for bentonite erosion. The measures were presented to prevent the geological disaster due to bentonite erosion through changes. The project is not only academic innovation, but also has a large practical significance. The research results of this project can be widely applied to the design, construction and maintenance of the bentonite buffer in nuclear waste repository.     

Large scale buffer material test: Mock-up experiment at CIEMAT

FEBEX is a demonstration and research project, which is being carried out by an international consortium led by the Spanish agency ENRESA and simulates components of the engineering barrier system in accordance with the ENRESA's AGP (Deep Geological Disposal) Granite reference disposal concept. The project includes tests on three scales: an “in situ” test at full scale in natural conditions; a “mock-up” test at almost full scale in controlled conditions; and a series of laboratory test to complement the information from the two large-scale test.The components of the mock-up test are similar to those of the “in situ” test: two electric heaters, a clay barrier consisting of highly compacted bentonite blocks, instrumentation, automatic control of heaters, and a data acquisition system for the data generated. The heterogeneities of the natural system (granite formation) are avoided, the hydration process is controlled with unlimited amount of water at constant pressure, and the boundary conditions are better defined than in the “in situ” test.The operational phase -hydration and heating- started in February 1997. It was initially planned to last for three years, but it has been decided to extend the operational phase to get as close as possible complete saturation of the buffer.Fifty-five months after the start of the operational phase, it can be concluded that the synergy achieved from the simultaneous, integrated performance of tests at different scales, is a valuable approach to establishing the viability of the reference concept, and making progress in the understanding and evaluation of the behaviour in the near field, especially the clay barrier.     

Evaluation of a compacted bentonite/sand seal for underground waste repository isolation

This study investigates the performance of an optimum compacted bentonite/sand mixture seal for the isolation of underground waste repositories. Engineering geological tests such as compaction, flow, swelling, mechanical and shear strength tests have been conducted to select an optimum mixture and to recommend a stable bentonite/sand seal length-to-radius ratio (L/a) as far as the factor of safety (F) is concerned. The results of the compaction permeameter tests led to a recommendation to select an optimum compacted bentonite/sand mixture possessing a bentonite content of about 20% to satisfy the minimum regulatory hydraulic conductivity requirement. Engineering geological analysis of the seal/rock mechanical interaction with regard to reduce the possibility of seal slip led to a recommendation to utilize a seal L/a of at least 25.     

Undrained cyclic behavior of bentonite–sand mixtures and factors affecting it

In this work, the cyclic behavior of bentonite–sand mixtures and factors affecting it were studied by means of a ring-shear apparatus and a scanning electron microscope. It was found that bentonite content had a significant influence on the liquefaction potential of the studied soils. A small amount of bentonite in the mixtures would cause the formation of “loose” microstructures, resulting in the occurrence of rapid liquefaction under cyclic loading, while a high bentonite content would cause the formation of clay matrixes, thus raising the soil resistance to liquefaction. In addition, the effect of pore water chemistry on the cyclic behavior of a high plasticity bentonite–sand mixture was carefully examined. It was also found that the presence of ions in pore water would change the clay microfabric, making it more open and thus more vulnerable to liquefaction. Finally, the effects of loading frequency on the cyclic behavior of mixtures with different amounts of bentonite were investigated. It was found that as the bentonite content increased, the influence became more pronounced.     

Na and HTO diffusion in compacted bentonite: Effect of surface chemistry and related texture

In underground repository concepts for radioactive waste, bentonite is studied as a reference swelling material to be used as an engineered barrier. Under the changing geochemical conditions prevailing within the barrier (saturation with the fluid coming from the host formation, diffusion of various chemical plumes caused by the degradation of some constituents of the barrier-system, etc.), the surface chemistry of the clay particles could evolve. This work aims to characterize the effects of these changes on (i) the microstructure of compacted bentonite samples and (ii) the diffusion properties of HTO and Na in these samples.For this purpose, bentonite sets were equilibrated with different solutions: NaCl, CaCl₂, CsCl solutions as well as an artificial clayey porewater solution. The microstructure of the different samples was characterized by HRTEM and XRD, in a water saturated state. In parallel, effective diffusion coefficients of both HTO and ²²Na were measured for the different samples. The density of the bentonite in the diffusion tests and in the HRTEM observations was set at 1.6 Mg m⁻³.From the microstructural observations and the results of diffusion tests, it is deduced that one key parameter is the occurrence of a gel phase in the material, which is found to depend strongly on the bentonite set: the gel phase dominates in Na-bentonite, while it is lacking in Cs-bentonite. The HTO diffusion coefficients are found to be lower in the samples with high gel phase content. Sodium diffusion does not follow the same trend: when compared with HTO, Na diffuses faster when the gel phase content is high. The latter result could indicate that the “accelerated diffusion mechanism” of cations, already mentioned in the literature, is enhanced in clayey materials that contain a gel phase.