Search Results (12)

This study examines the formation of the clay mineral simonkolleite (Skl) in bentonites contaminated with zinc(II) chloride (ZnCl₂), a process that has been little documented in heterogeneous systems such as contaminated bentonites. We explain the contamination mechanisms and provide new insights into the mineralogical, structural, and physicochemical transformations occurring within these materials. The objective, explored for the first time, was to assess how the ZnCl₂-induced mineral phase formation influences the properties of bentonites used as sealing materials, particularly regarding changes in specific surface area and porosity. Three bentonites were analyzed: Ca-bentonite from Texas (STx-1b), Na-bentonite from Wyoming (SWy-3), and Ca-bentonite from Jelsovy Potok, Slovakia (BSvk). Treatment with ZnCl₂ solution led to ion exchange and the formation of up to ~30% simonkolleite, accompanied by a concurrent decrease in montmorillonite content by 9–30%. A suite of analytical techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray fluorescence (XRF), and energy-dispersive X-ray spectroscopy (EDS), was employed to characterize these transformations. The contamination mechanism of ZnCl₂ involves an ion exchange of Zn²⁺ within the montmorillonite structure, the partial degradation of specific montmorillonite phases, and the formation of a secondary phase, simonkolleite. These transformations caused a ~50% decrease in specific surface area and porosity as measured by the Brunauer–Emmett–Teller (BET) nitrogen adsorption and Barrett–Joyner–Halenda (BJH) methods. The findings raise concerns regarding the long-term performance of bentonite-based barriers. Further research should evaluate hydraulic conductivity, mechanical strength, and the design of modified bentonite materials with improved resistance to Zn-induced alterations. Full article

Gas extraction from coal seams can significantly mitigate gas accidents and improve resource utilization. The effectiveness of borehole sealing directly determines the concentration and efficiency of gas drainage. In recent years, liquid-phase sealing materials, represented by non-solidifying pastes, gel-based materials, and inorganic retarders, have gradually become a research hotspot. Compared to the traditional solid sealing materials such as cement-based or organic polymers, liquid-phase sealing materials can effectively seal secondary fractures caused by mining vibration through grout replenishment. However, the influence of each component in liquid-phase non-solidified materials on sealing properties such as fluidity, water retention, and permeability remains unclear. To address these issues, a novel liquid-phase non-solidified hole sealing material was developed using bentonite as the base material, sodium dodecyl benzene sulfonate as the dispersant, and sodium carboxymethyl cellulose as the thickener. Initially, single-factor experiments were applied to investigate the effects of material ratios on the fluidity, water retention, and permeability. Subsequently, orthogonal experimental design and response surface methodology were used to establish nonlinear quadratic regression models relating these properties to water–bentonite ratio, dispersant content, and thickener content. The results indicated that an optimal water–bentonite ratio enhances both fluidity and permeability, while dispersants improve water retention and permeability and thickeners primarily boost water retention. Finally, the optimized composition was determined as a water–bentonite ratio of 4.41:1, a dispersant content of 0.38%, and a thickener content of 0.108%. We believe that the developed slurry materials will maintain excellent sealing performance through the entire gas extraction period. Full article

The deep geological repository (DGR) system has been selected by most of the world’s nuclear waste management organizations for the long-term disposal of radioactive wastes. The DGR mainly consists of a multi-barrier system—comprising the natural host rock and an engineered barrier system—to contain and isolate high-level radioactive waste, including used fuel containers (UFCs), to protect humans and the environment. Bentonite materials and host rock are the main components of the DGR’s engineered and natural barrier system, respectively. It is crucial to understand the coupled behavior of bentonite and rock materials under various in situ conditions over long-term durations, as it supports safety assessments and enhances the overall safety level of DGR systems. This study presents a methodology for the numerical modeling of a hypothetical DGR using developed coupled models. The developed model was used to investigate the hydromechanical (HM) and thermomechanical (TM) response within the near-field (the area within a radius of 50 m near the UFC and multiple-barrier system) of a simplified hypothetical DGR, based on the proposed design concept of the Nuclear Waste Management Organization (NWMO) of Canada. The analysis results included the evolution of temperature, thermal stresses, saturation, and swelling pressure at different stages of the DGR system’s lifetime. The results indicated that it could take up to 10,000 years to fully saturate the bentonite materials with a corresponding swelling pressure of 2.7 MPa associated with a decrease in the rock’s strength/stress ratio near the placement room; however, the ratio did not indicate a significant system failure. Sensitivity analysis was also conducted to assess the impact of various parameters on the saturation time and the strength/stress ratio in a DGR. The results highlighted that saturation time was highly influenced by the permeability of both the rock formation and the bentonite, resulting in saturation times ranging from 500 to 20,000 years. Moreover, the strength/stress ratio was found to be sensitive to the model’s parameters, particularly the maximum swelling pressure. The results of the TM analysis show that temperature development around the placement of rooms in a DGR is highly influenced by room spacing, with a lower factor of safety (FOS) as time and temperature progressed due to elevated temperature, while the rock remained stable over the 150-year analysis period. The inclusion of temperature-dependent mechanical properties produced negligible changes to the overall stability of the rock around the placement rooms of the DGR. Full article

Cement grout is traditionally used for treating water leakage distress in tunnels. However, traditional cement grout has the disadvantages of a poor anti-seepage performance, long setting time, and slow strength gain. To this end, a high-performance cement-based capillary crystalline waterproofing (CCCW) grouting material was synthesized using cement, capillary crystalline material, and several admixtures. The influences of the material proportions on the viscosity, bleeding rate, and setting time of the fresh grout, as well as the permeability coefficient of the grouted aggregate and the unconfined compression strength of the hardened grout material, were systematically studied. The mineralogy and microstructure of the CCCW grouting material were examined using X-ray diffraction, industrial computed tomography, and scanning electron microscopy. The results indicated that the capillary crystalline material PNC803 was not suitable for mixing with bentonite, sodium chloride, and triethanolamine in cementitious slurries, but it can produce excellent synergistic effects with sulfate, calcium chloride, and triisopropanolamine. An analysis of the microstructure of the CCCW grouting material showed that the PNC803 and additives can promote the hydration of cement, which yields more hydration products, sealing water passage and filling micro voids and therefore leading to enhanced waterproofing and strengthening effects. These research results could improve the applicability of CCCW material in tunnel engineering. Full article

The buffer material that makes up the geological disposal system of high-level waste swells by contact with groundwater and seals space with rock mass and fractures in rock mass. The buffer material has a function of mechanical buffer with rock pressure, and swelling stress is important in this case. The alteration of bentonite may occur due to the initial replacement of cations (Na⁺ ions) in the interlayer with K⁺ ions upon contact with groundwater, but there are no studies on the swelling stress of K-bentonite. In this study, the author prepared K-montmorillonite samples and obtained thermodynamic data on interlayer water as a function of water content using a relative humidity method. The swelling stress was analyzed based on a thermodynamic model developed in earlier studies and compared with measured data. The activity and the relative partial molar Gibbs free energy of porewater decreased with decreasing water content in the region, below approximately 15%. This behavior significantly differs from that of other ions, such as Na. The swelling stress calculated based on the thermodynamic model and date occurred in the region of high density of 1.9 Mg/m³ with montmorillonite partial density. It was indicated for the first time that K-bentonite scarcely swells under realistic design conditions. Full article

A typical deep geological repository (DGR) design consists of a multi-barrier system, including the natural host rock and the engineered barrier system. Understanding the swelling behavior of bentonite-based sealing materials (BBSM), as a candidate material for the engineered barrier system, is crucial for DGR’s long-term safety. In this study, a hydromechanical (HM) column-type test was designed to model the hydration of BBSM from the underground water and determine the resulting swelling pressure in vertical and radial directions. Five hydration tests were carried out on identical compacted samples of 70% bentonite and 30% sand (70-30 bentonite-sand) mixtures with a dry density of 1.65 g/cm³ for varied durations of hydration, between 1 day and 120 days. The experiments were performed parallel to the compaction direction. Following each HM column-type test, the advancement of the wetting front was determined for each test. After 120 days, 56,339 mm³ of water infiltrated the sample and the wetting front reached over 50% of the sample height. The evolution of axial swelling pressure revealed an initial increase in swelling pressure with time in all tests, followed by a reduction in the rate at later times. After early stages of swelling, radial sensors showed an increase in swelling pressure. After 120 days, the radial pressure sensor closest to the hydration front showed 52% more radial pressure than the axial swelling pressure. Full article

The growing population and urbanization rates in developing countries causes huge pressure on the construction sector to aid the equivalent infrastructure growth. Natural resources are essential to attain the required infrastructure needs. The demand in the construction sector for materials causes significant environmental effects due to the higher consumption rate of finite natural resources. To address such an issue, the study focuses on the landfill capping application demand in Vietnam, based on its extensive landfill presence in its current state and their need to be closed in the years ahead. The study considers utilization of secondary raw materials arising from industrial or anthropogenic waste as an alternative material as a landfill mineral sealing layer, to replace the dependence on conventional clay and bentonite. The selected alternative materials were tested to satisfy the permeability conditions for the landfill sealing layer standards, where results indicated very low permeability values for the mixtures, meeting German quality requirements which require k ≤ 5 × 10⁻⁹ m/s for landfill class I (landfills without further environmental requirements) and k ≤ 5 × 10⁻¹⁰ m/s for class II (conventional landfill for non-hazardous waste) for sealing layers of landfills. Further, the various mixes of alternative mineral layers in a life cycle analysis for a functional unit of one hectare landfill mineral sealing layer resulted in lower environmental footprints than the conventional layer. The results of the mineral sealing layer showed that the higher bentonite composition of about 20% in the mix ratio and transport distance of 65 km for the ashes increased the overall environmental footprint of the mix. In this case, mix 6 and mix 7, having 20% bentonite, tended to possess higher impacts, despite the alternative ashes holding zero allocation, along with the 65 km transportation distance associated with ashes. The avoidance factor over the alternative mixes has an effective approximate 25–50% Global Warming Potential (GWP) impact reduction. There was a significant mineral resource scarcity impact reduction on the use of secondary raw materials. Full article

Compacted bentonite is currently being considered as a suitable backfill material for sealing underground repositories for radioactive waste as part of a multi-barrier concept. Although showing favorable properties for this purpose (swelling capability, low permeability, and high adsorption capacity), the best choice of material remains unclear. The goal of this study was to examine and compare the hydration behavior of a Milos (Greek) Ca-bentonite sample (SD80) in two types of simulated ground water: (i) Opalinus clay pore water, and (ii) a diluted saline cap rock brine using a confined volume, flow-through reaction cell adapted for in situ monitoring by X-ray diffraction. Based on wet-cell X-ray diffractometry (XRD) and calculations with the software CALCMIX of the smectite d(001) reflection, it was possible to quantify the abundance of water layers (WL) in the interlayer spaces and the amount of non-interlayer water uptake during hydration using the two types of solutions. This was done by varying WL distributions to fit the CALCMIX-simulated XRD model to the observed data. Hydrating SD80 bentonite with Opalinus clay pore water resulted in the formation of a dominant mixture of 3- and 4-WLs. The preservation of ca. 10% 1-WLs and the apparent disappearance of 2-WLs in this hydrated sample are attributed to small quantities of interlayer K (ca. 8% of exchangeable cations). The SD80 bentonite of equivalent packing density that was hydrated in diluted cap rock brine also contained ca. 15% 1-WLs, associated with a slightly higher concentration of interlayer K. However, this sample showed notable suppression of WL thickness with 2- and 3-WLs dominating in the steady-state condition. This effect is to be expected for the higher salt content of the brine but the observed generation of CO₂ gas in this experiment, derived from enhanced dissolution of calcite, may have contributed to the suppression of WL thickness. Based on a comparison with all published wet-cell bentonite hydration experiments, the ratio of packing density to the total layer charge of smectite is suggested as a useful proxy for predicting the relative amounts of interlayer and non-interlayer water incorporated during hydration. Such information is important for assessing the subsequent rates of chemical transport through the bentonite barrier. Full article

Shaft seals are geotechnical barriers in nuclear waste deposits and underground mines. The Sandwich sealing system consists of alternating sealing segments (DS) of bentonite and equipotential segments (ES). MiniSandwich experiments were performed with blended Ca-bentonite (90 mm diameter and 125 mm height) to study hydration, swelling, solute transport and cation exchange during hydration with A3 Pearson water, which resembles pore water of Opalinus Clay Formation at sandy facies. Two experiments were run in parallel with DS installed either in one-layer hydrate state (1W) or in air-dry two-layer hydrate (2W) state. Breakthrough at 0.3 MPa injection pressure occurred after 20 days and the fluid inlet was closed after 543 days, where 4289 mL and 2984 mL, respectively, passed both cells. Final hydraulic permeability was 2.0–2.7 × 10⁻¹⁷ m². Cells were kept for another 142 days before dismantling. Swelling of DS resulted in slight compaction of ES. No changes in the mineralogy of the DS and ES material despite precipitated halite and sulfates occurred. Overall cation exchange capacity of the DS does not change, maintaining an overall value of 72 ± 2 cmol(+)/kg. Exchangeable Na⁺ strongly increased while exchangeable Ca²⁺ decreased. Exchangeable Mg²⁺ and K⁺ remained nearly constant. Sodium concentration in the outflow indicated two different exchange processes while the concentration of calcium and magnesium decreased potentially. Concentration of sulfate increased in the outflow, until it reached a constant value and chloride concentration decreased to a minimum before it slightly increased to a constant value. The available data set will be used to adapt numerical models for a mechanism-based description of the observed physical and geochemical processes. Full article

Bentonite is currently proposed as a potential backfill material for sealing high-level radioactive waste in underground repositories due to its low hydraulic conductivity, self-sealing ability and high adsorption capability. However, saline pore waters, high temperatures and the influence of microbes may cause mineralogical changes and affect the long-term performance of the bentonite barrier system. In this study, long-term static batch experiments were carried out at 25 °C and 90 °C for one and two years using two different industrial bentonites (SD80 from Greece, B36 from Slovakia) and two types of aqueous solutions, which simulated (a) Opalinus clay pore water with a salinity of 19 g·L⁻¹, and (b) diluted cap rock solution with a salinity of 155 g·L⁻¹. The bentonites were prepared with and without organic substrates to study the microbial community and their potential influence on bentonite mineralogy. Smectite alteration was dominated by metal ion substitutions, changes in layer charge and delamination during water–clay interaction. The degree of smectite alteration and changes in the microbial diversity depended largely on the respective bentonite and the experimental conditions. Thus, the low charged SD80 with 17% tetrahedral charge showed nearly no structural change in either of the aqueous solutions, whereas B36 as a medium charged smectite with 56% tetrahedral charge became more beidellitic with increasing temperature when reacted in the diluted cap rock solution. Based on these experiments, the alteration of the smectite is mainly attributed to the nature of the bentonite, pore water chemistry and temperature. A significant microbial influence on the here analyzed parameters was not observed within the two years of experimentation. However, as the detected genera are known to potentially influence geochemical processes, microbial-driven alteration occurring over longer time periods cannot be ruled out if organic nutrients are available at appropriate concentrations. Full article

Gases can potentially generate in a deep geological repository (DGR) for the long-term containment of radioactive waste. Natural and engineered barriers provide containment of the waste by mitigating contaminant migration. However, if gas pressures exceed the mechanical strength of these barriers, preferential flow pathways for both the gases and the porewater could form, providing a source of potential exposure to people and the environment. Expansive soils, such as bentonite-based materials, are widely considered as sealing materials. Understanding the long-term performance of these seals as barriers against gas migration is an important component in the design and the long-term safety assessment of a DGR. This study proposes a hydro-mechanical mathematical model for migration of gas through a low-permeable swelling geomaterial based on the theoretical framework of poromechanics. Using the finite element method, the model is used to simulate 1D flow through a confined cylindrical sample of near-saturated low-permeable soil under a constant volume boundary stress condition. The study expands upon previous work by the authors by assessing the influence of heterogeneity, the Klinkenberg “slip flow” effect, and a swelling stress on flow behavior. Based on the results, this study provides fundamental insight into a number of factors that may influence two-phase flow. Full article

Gas generation and migration are important processes that must be considered in a safety case for a deep geological repository (DGR) for the long-term containment of radioactive waste. Expansive soils, such as bentonite-based materials, are widely considered as sealing materials. Understanding their long-term performance as barriers to mitigate gas migration is vital in the design and long-term safety assessment of a DGR. Development and the application of numerical models are key to understanding the processes involved in gas migration. This study builds upon the authors’ previous work for developing a hydro-mechanical mathematical model for migration of gas through a low-permeable geomaterial based on the theoretical framework of poromechanics through the contribution of model verification. The study first derives analytical solutions for a 1D steady-state gas flow and 1D transient gas flow problem. Using the finite element method, the model is used to simulate 1D flow through a confined cylindrical sample of near-saturated low-permeable soil under a constant volume boundary stress condition. Verification of the numerical model is performed by comparing the pore-gas pressure evolution and stress evolution to that of the results of the analytical solution. The results of the numerical model closely matched those of the analytical solutions. Future studies will attempt to improve upon the model complexity and investigate processes and material characteristics that can enhance gas migration in a nearly saturated swelling geomaterial. Full article