Bentonite clays have unique properties that determine their use as the main component of engineered barrier systems (EBS) for the isolation of radioactive waste. At present, the Russian Federation is elaborating the concept of deep geological disposal of radioactive waste in crystalline rocks of the Yeniseisky site, where bentonite clays play an important role in ensuring the safety of the repository for a long period of time. This work demonstrates the first results of short-term laboratory experiments (1 and 3 months) on the thermochemical interaction of bentonite and concrete in the presence of synthetic water at an elevated temperature. These experiments will help predict the effect of EBS materials on montmorillonite. Bentonite from the 10th Khutor deposit (Russia) and Portland cement were used in the experiments. At the first stage of the experiments, solutions were obtained after leaching the concrete with a synthetic groundwater solution for 1 month at 90 °C. At the second stage, the interactions of the obtained solutions with bentonite at 90 °C were studied. As a result of the experiments, the processes of concrete leaching were revealed, which changed the composition and acidity (an increase in the pH from 6.1 to 12.1) of the synthetic water and led to an increase in the porosity of the material in contact with the solution. However, no dissolution of montmorillonite was observed, and the changes were quite small. The research results show the high stability of bentonite from the 10th Khutor deposit under model conditions, which was confirmed by modeling. Thus, we can say that at pH ≈ 12 and at elevated temperatures, montmorillonite retains a stable structure for a long time, which is important for ensuring the safety of disposal in general.

In order to enhance the efficiency of heavy metal ion extraction from aqueous medium, new nanocomposite magnetic sorbents were synthesized on the base of natural zeolite (Zt) and nanoparticles of ZnFe₂O₄ (F). The composition, structure and physical–chemical properties of new composites with 2% (Zt-2F), 8% (Zt-8F) and 16% (Zt-16F) of zinc ferrite were characterized by XRD, BET adsorption–desorption of nitrogen, SEM with elemental mapping, TEM and magnetometry. The sorption capacity of materials was assessed towards Cu²⁺ ions in aqueous solutions, for which kinetic and equilibrium features of sorption were established. The maximal sorption capacity (a_max, mg/g) of the studied materials increased in the order: Zt (19.4) < Zt-2F (27.3) < Zt-8F (30.2) < Zt-16F (32.8) < ZnFe₂O₄ (161.3). The kinetics of the sorption process followed a pseudo-second order kinetic model. The sorption equilibrium at zinc ferrite was successfully described by the Langmuir model, while the Freundlich model better fitted the sorption equilibrium on zeolite and composites. The efficiency of Cu²⁺ ion extraction from 320 mg/dm³ aqueous solution was 63% for composite Zt-16F and 100% for a sample of ZnFe₂O₄. It was established that the proposed composite sorbents provide the operation of several cycles without regeneration, they can be easily recycled with 0.1 N HCl solution and are capable of magnetic separation. The advantages of new composites and the proposed method of synthesis allow recommending these materials as effective sorbents of heavy metals from wastewater.

During the development of the disposal concept in a crystalline massif of the Russian Federation, a question arose regarding the selection of the most suitable types of bentonite for a buffer layer. Data on the composition, structure, surface, and adsorption properties of four promising deposits have been obtained. The correlations between genesis and specific surface area (SSA) revealed in this study indicate that bentonites of volcanogenic-sedimentary origin have lower SSA in comparison with those of sedimentary and hydrothermal origin. The main contribution to the charge of the 2:1 layer is made by isomorphic substitutions in the tetrahedral sheet, which directly affects the sorption properties of bentonites. The influence of smectite structure on adsorption properties have been described. In particular, the dependencies between the layer charge and cation exchange capacity (CEC) have been analyzed. At the same time, the research indicates that, unlike the CEC, the specific surface area of a deposit is determined by its geological history. Special attention is being paid to refining methodological approaches for deriving crystal chemical formulae of smectites, which will be needed in the future for modelling changes in bentonite over a long-term perspective.

Synthetic alumosilicates are used in many industrial applications, and the synthesis of clay minerals under different conditions allows us to understand the conditions of their formation. This study examined the impact of varying silica precursors, pH conditions and synthesis durations. Synthetic kaolinite group mineral analogues were investigated by X-ray diffraction, scanning electron microscopy and infrared spectroscopy. Additionally, the crystallinity index was calculated. The impact of using different silica sources on the structural features of synthetic kaolinite group analogues was revealed. The use of a Nanosil precursor resulted in the formation of highly crystalline kaolinite. The most significant alterations in the course of synthesis were observed at different pH values. The formation of various synthetic analogues of minerals from the kaolinite group was observed: at a high pH, the formation of halloysite with a small admixture of kaolinite was observed. Conversely, the synthesis resulted in the formation of ordered kaolinite at a low pH. The crystallinity index of the resulting synthesized kaolinite analogues rises as the synthesis duration increases, while the quantity of non-crystallized material decreases. The changes in the crystallinity of kaolinite when using different silica precursors are related to the different homogenization of the material that occurs at the stage of alumosilica gel formation.

This work is based on a detailed study of samples from three industrial bentonite deposits in Russia (10th Khutor, Zyryanskoe) and Kazakhstan (Taganskoe). The samples of the listed bentonites were undergoing stage-by-stage purification from carbonates, organic matter, and non-clay iron-bearing phase procedures. The conducted research revealed changes in the composition of bentonites already at the first stage of purification, which, however, were not noted for all bentonites, as well as a change in the forms of Fe in smectite structure. The latter is probably associated with changes in cis- and trans-vacant positions. Sorption characteristics with respect to ¹³⁷Cs are determined using the localization and charges in the smectite layer and the slight changes during purification, along with the specific surface area indicators.

Clay minerals may transform in various systems under the influence of geological, biological, or technogenic processes. The most active to the geological environment are technogenic and biochemical processes that, in a relatively short time, can cause transformation of the rocks’ composition and structure and formation of new minerals, especially clay minerals. Isolation of radioactive waste is a complex technological problem. This work considers the influence of alkaline solutions involved in the radioactive waste (RW) disposal process. In the Russian Federation, due to historical reasons, radioactive waste has accumulated in various types of repositories and temporary storages. All these facilities are included in the federal decommissioning program. Solid radioactive wastes in cement slurries at the landfill site of the Angara Electrolysis Chemical Combine are buried in sandstones and currently suffer the influence of a highly alkaline and highly saline groundwater storage area, which leads to a considerable transformation of the sandstones. This influence results in the formation of peculiar "technogenic” illites that have smectite morphology but illite structure which was confirmed by modeling of X-ray diffraction (XRD) patterns. The described transformations will lead to the increase of porosity and permeability of the sandstones. The research results can be used in assessing the potential contamination of the areas adjacent to the disposal site and in planning the decommissioning measures of this facility.