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Bentonite clay is an important natural material, widely used in many industries. The purpose of this article is to analyze the mineral resource base of bentonite clays in Russia. The data on reserves of deposits, the degree of their development and production volumes are given. The composition and uses of the main developed deposits of bentonite clay in Russia are characterized. A comparative analysis of the reserves and production growth of bentonite over the past decade is carried out. A brief description of the world situation is given, and the mineral resource base of the CIS countries is considered. Since the quality of raw materials, its properties and reserves directly depend on the conditions of origin, a characteristic of the geological and tectonic position and genesis of the bentonite clay deposits of Russia is given. Bentonite-bearing provinces with favorable conditions for the formation of bentonite deposits with volcanogenic-sedimentary genesis are considered. The most promising regions are proposed for the purposes of expanding the mineral resource base of bentonite materials. This work is the result of the authors’ own geological works at various deposits of bentonite clays in Russia, the near and far abroad, as well as the study and interpretation of published materials on this subject over the past decades.

Bentonites from the 10th Khutor deposit (Republic of Khakassia, Russia) are considered a potential buffer material for isolation of radioactive waste in the crystalline rocks of Yeniseyskiy site (Krasnoyarskiy region). This study presents the results of a series of permeameter experiments with bentonite compacted to dry densities of 1.4, 1.6, and 1.8 g/cm3, saturated and permeated by the artificial groundwater from Yeniseyskiy Site. Permeation was conducted at hydraulic gradients of 180–80,000 m/m to simulate potential hydraulic conditions in the early post-closure phase of a deep geological repository (DGR). The respective swelling pressures of 0.8 ± 0.3, 2.2 ± 0.6, and 6.3 ± 0.3 MPa and permeabilities of (27 ± 15) × 10−20, (3.4 ± 0.8) × 10−20, and (0.96 ± 0.26) × 10−20 m2 were observed for the hydraulic gradient of 2000 m/m, which is recommended for the determination of undisturbed swelling pressures and permeabilities in permeameter experiments. Upon incremental increases in the hydraulic gradient, swelling pressures at all densities and permeability at the density of 1.8 g/cm3 remained unchanged, whereas permeabilities at 1.4 and 1.6 g/cm3 decreased overall by a factor of approximately 5 and 1.7, respectively. Seepage-induced consolidation and/or reorganisation of bentonite microstructure are considered possible reasons for these decreases.

Clays have been adopted in most nuclear waste producing countries as a key constituent in engineered barrier systems for final disposal facilities at all levels of radioactive wastes (LILW-SL, LILW-LL, and HLW). The following study presents a thorough characterization upon five Brazilian clay-rich deposits, mostly smectite bearing clays, aiming to evaluate their expected performance as barrier under the conditions associated to a Low and Intermediate Level Waste Repository; being the former a matter of national strategic interest. Samples coming from the Brazilian states of Paraná, Bahia, Paraíba, and Maranhão were treated and analyzed by means of X-Ray diffraction as main technique, and complemented by FTIR, LALLS, XRF, and SEM-EDS, in order to establish the mineralogical composition, particle size distribution, and chemical composition. Moreover, several standard clay treatments over the

10th Khutor deposit is located in the Republic of Khakassia and confined to the coal-bearing formation of Carboniferous age within the development of continental tuff-sandy-argillaceous sediments. In terms of mineral composition, bentonites are mainly composed of Al-rich montmorillonite. The content of montmorillonite reaches a maximum of 70-75%, with an average content of 55 to 70%. It is one of the main sources of bentonite for the metallurgical and foundry industries in Russia. One of the distinctive features of bentonites from the 10th Khutor deposit is that despite the age of the deposit, about 350 million years, and the presence of an initial phase of metamorphism, as evidenced by the formation of hard coal, these bentonites retained the ability to swell and have high thermal stability. The formation of bentonites is associated with the decomposition of volcanic ash of rhyodacite and dacite composition in zones of shallow seawater - bays and lagoons. The properties of bentonite were influenced by the initial stage of metamorphism. The main purpose of this work was to establish the conditions for the formation of this deposit, as well as to study the features of the mineral composition and physicochemical properties of these raw materials. In addition to fundamental issues, the aim of the work was applied research on the properties and quality of bentonites.

The sorption of Cu2+ onto bentonite modified with Al Keggin cations and humic acid from CuCl2 solutions at pH 4.5 was studied. Modification of Na-bentonite with Al Keggin cations was found to result in an increase in the basal spacing of montmorillonite from 1.29 nm for N-form to 1.85 and 1.78 nm for HAl13 and Al13 forms respectively, in a reduction of CEC (cation exchange capacity) and in the formation of additional sites with a variable charge with pHPZC 4.2. Al13-bentonite is not affected by heat. Under the conditions of the experiments at pH of 4.5 Na-bentonite adsorbs more Cu2+ from CuCl2 solutions then Al13 forms of bentonites. The main mechanism of copper sorption on Na-bentonite is the cation exchange Cu2+&ndash, Na+. The reduction of CEC of Na-bentonite after modification with Al Keggin cations leads to a decrease in the Cu2+ sorption. pH-dependent sorption sites on Al13-bentonites have a pHPZC of 4.2 and, therefore, under conditions of the experiment have positive charge which prevents Cu2+ sorption. Na-bentonite adsorbs more humic acid solution (HA) then Al13-bentonite and the proportion of adsorbed HA remains constant over the entire concentration range. Treatment of the Al13-bentonite with HA leads to the formation of the additional sorption sites. The amount of sorbed Cu2+ and the percentage of their extraction from solutions by HAAl13-bentonite is similar to those values for Na-bentonite.

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&rsquo, 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&rdquo, 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.

This study is devoted to studying the sorption of 137Cs on mineral sorbents at a wide pH range, from 2 to 10, as well as to studying sorption mechanisms. In order to obtain the most reliable sorption characteristics, samples of high purity were examined as sorbents: bentonite, glauconite, zeolite, and diatomite. A detailed description of their mineral composition, cation exchange capacity and specific surface of sorbents is given. XRD, XRF, FTIR, SEM, and BET adsorption methods were used for assaying. The sorption and desorption values were identified for each sorbent. As a result of the conducted research, it can be concluded that 137Cs sorption mainly occurs through the exchange reaction on zeolite, glauconite and bentonite. The highest cesium Kd was observed on zeolite due to its high CEC and amounted to 4.05 mg/L at pH 7. The higher sorption capacity of glauconite in comparison with bentonite is primarily due to the high layer charge which is mainly localized in tetrahedral sheets, and to the existence of highly selective sorption sites (frayed edge sites) on the glauconite surface. Diatomite showed the lowest sorption capacity provided by the presence of a small quantity of smectite and kaolinite in its composition. The values of desorption increase in the following order: zeolite &lt, bentonite ~ diatomite &lt, glauconite.

This paper presents the results of the first experimental thermochemical investigation of two natural trioctahedral chlorites (clinochlores). The study was performed with the help of a high-temperature heat-flux Tian-Calvet microcalorimeter. The samples were characterized by X-ray spectroscopy analysis, X-ray powder diffraction, thermal analysis, and FTIR spectroscopy. The enthalpies of formation of clinochlores were found using the melt solution calorimetry method to be: −8806 ± 16 kJ/mol for composition ( Mg 4 . 9 Fe 0 . 3 2 + Al 0 . 8 ) [ Si 3 . 2 Al 0 . 8 O 10 ] ( OH ) 8 and −8748 ± 24 kJ/mol for composition ( Mg 4 . 2 Fe 0 . 6 2 + Al 1 . 2 ) [ Si 2 . 8 Al 1 . 2 O 10 ] ( OH ) 8 The experimental data for natural samples allowed calculating the enthalpies of formation for end-members and intermediate members of the clinochlore (Mg 5 Al)[Si 3 AlO 10 ](OH) 8 and chamosite (Fe 5 Al)[Si 3 AlO 10 ](OH) 8 series. An important feature of the clinochlore structure is the presence of two distinct hydroxyl-containing octahedral layers: the interlayer octahedral sheet and octahedral 2:1 layer; the enthalpies of water removal from these positions in clinochlore structure were determined as: 53 ± 20 kJ/(mol·H 2 O) and 131 ± 10 kJ/(mol·H 2 O), respectively. These obtained first thermodynamic characteristics of Mg-Fe clinochlores can be used for quantitative thermodynamic modeling of geological and industrial processes including clinochlores of different composition.

Natural kaolin and the metakaolin obtained by calcination of kaolin at 650 °C were chemically activated using 0.25–3.0 mol/dm3 HCl solutions. Structural and textural properties of samples were characterized by X-ray diffraction, elemental analysis and N2-adsorption/desorption analyses. The amount of Bronsted acid sites (BAS) was determined by infrared spectroscopy using pyridine as probe molecule. The amount of BAS for kaolin rose with increasing HCl concentration up to 1.0 M, and decreased for higher concentrations, that is related with the leaching of Al from the solid. Effect of HCl concentration on amount of BAS was negligible for metakaolin. The catalytic performance of these materials was investigated in the Prins cyclization of (−)-isopulegol with vanillin to form octahydro-2H-chromen-4-ol, carried out in toluene at 50 °C. The reaction rate and the selectivity toward octahydro-2H-chromen-4-ol depended on the Bronsted acidity, structural and textural properties of the catalysts. The reaction rate in the presence of kaolin modified by HCl correlated with the amount of BAS. HCl-kaolin samples were more active compared with HCl-metakaolin, while selectivity reaction toward octahydro-2H-chromen-4-ol was larger in the presence of HCl-metakaolin.

This work considers terrestrial coastal landscapes of Abrosimov and Stepovoi gulfs and Yuzhnii (Southern) Island in the Novaya Zemlya Archipelago in the Kara Sea. These areas are dominated by horizons of slightly acidic leptosols and lithic leptosols of 10 cm thick (Stepovoi Gulf) and those of weak skeleton acidic lithic leptosols of 10–15 cm thick (Abrosimov Gulf) covered by moss–shrub assemblages. Kaolinite is formed in a rhizosphere fine earth layer; illite is formed along the leptosol sequence. The studied coastal landscapes are characterized by low accumulation potential of chemical elements, including radionuclides, at higher contents of them. Elements such as Fe and Ti are dispersed in sols, whereas P, S, Cl, Cu, Pb, and Zn are accumulated in soils in minor amounts. Plants accumulate S, P, Cl, Sr, Zn, and 137Cs in minor amounts as well. Elements such as Ti, Mn, Fe, Cr, V, Co, Ni, Cu, Rb, Zr, Ba, Th, Y, Nb, Pb, and As are attributed to the group of weak biological adsorption. The specific 137Cs activity (Bq kg–1) amounts to 10–150 in plants, 10–300 in moor leptosol horizons, and 1–40 in mull horizons.

Subaerial endolithic systems of the current extreme environments on Earth provide exclusive insight into emergence and development of soils in the Precambrian when due to various stresses on the surfaces of hard rocks the cryptic niches inside them were much more plausible habitats for organisms than epilithic ones. Using an actualistic approach we demonstrate that transformation of silicate rocks by endolithic organisms is one of the possible pathways for the beginning of soils on Earth. This process led to the formation of soil-like bodies on rocks in situ and contributed to the raise of complexity in subaerial geosystems. Endolithic systems of East Antarctica lack the noise from vascular plants and are among the best available natural models to explore organo-mineral interactions of a very old “phylogenetic age” (cyanobacteria-to-mineral, fungi-to-mineral, lichen-to-mineral). On the basis of our case study from East Antarctica we demonstrate that relatively simple endolithic systems of microbial and/or cryptogamic origin that exist and replicate on Earth over geological time scales employ the principles of organic matter stabilization strikingly similar to those known for modern full-scale soils of various climates.

The Prins cyclization of (−)-isopulegol with vanillin to form octahydro-2 H -chromen-4-ol was studied in the presence of natural layered aluminosilicates modified by 0.5 mol/dm 3 HCl, such as montmorillonite, kaolin, and metakaolin obtained by the calcination of kaolin at 650 °C. According to infrared spectroscopy using pyridine as probe molecule, the amount and strength of Bronsted acid sites depend on the type of clay and decrease in the following order HCl-montmorillonite > HCl-kaolin > HCl-metakaolin. The difference in Bronsted acidity and textural properties of clays affected the reaction rate and the selectivity towards octahydro-2 H -chromen-4-ol.

Research on migration of chemical elements (ChEs) in soils is important for the understanding of geochemical processes in polluted and undisturbed landscapes. In this article, we report original data on Anthric Chernozems and Anthric Planosols within a small gully's catchment area in the Trans Urals (Russia). Mean total concentrations of 24 ChEs and content of mobile fractions (F1 – exchangeable, F2 – bound within organo-mineral complexes and F3 – bound with Fe and Mn hydroxides) of 61 ChEs including macro elements (Al, Ca, Fe, K, Mg, Mn, Na, P, Ti, S, Si), heavy metals (Ba, Co, Cr, Cu, Ni, Pb, Rb, Sr, Th, U, V, Zn), trace elements (Ag, As, B, Be, Bi, Br, Cd, Cs, Ge, Hf, Li, Mo, Nb, Pd, Sb, Sc, Se, Sn, Ta, Te, Tl, W, Zr) and rare earth elements (Ce, Er, Eu, Gd, La, Lu, Nd, Pr, Sm, Tb, Tm, Dy, Ho, Y, Yb) are determined from in a total of 60 samples from topsoil and subsoil of Anthric Chernozems and Anthric Planosols. The data obtained also include pH-value, total organic carbon content (TOC), seven particle-size classes (

The effect of acid modification of a natural montmorillonite clay (MM) by HNO3 on the catalytic properties of MM from Dash-Salakhlinsk (Kazakhstan) has been investigated in the synthesis of solketal from glycerol and acetone in solvent free and acetonitrile media. HNO3 concentration allowed to control the chemical composition, the surface acidity, the porous structure of the acid-activated MMs and their catalytic performance. The main reaction product was solketal with 86.6–98% selectivity. Conversion of glycerol depended on the Bronsted acidity. The most active sample, namely, MM activated with 0.5 mol/dm3 HNO3, showed good reusability for 3 catalyst cycles.

The paper discusses the mechanism of montmorillonite structure alteration and bentonites properties modification (on the example of samples from clay deposit Taganka, Kazakhstan) due to the thermochemical treatment (treatment with inorganic acid solutions at different temperatures, concentrations and reaction times). With the use of the suit of methods certain processes were distinguished: transformation of montmorillonite structure, which appears in the leaching of interlayer and octahedral cations, protonation of the interlayer and OH groups at octahedral sheets. Changes in the structure of the 2:1 layer of montmorillonite and its interlayer result in significant changes in the properties – reduction of cation exchange capacity and an increase of specific surface area. The results of the work showed that bentonite clays retain a significant portion of its adsorption properties even after the long term and intense thermochemical treatment (6M HNO3, 60°C, 108 hours)

The aim of this study was to investigate the correlation between the basic and catalytic properties of brucite and Mg,Al-layered double hydroxides (Mg,Al-LDHs) in the reaction of propylene oxide with methanol. The basic properties of the solids were investigated by FT-IR spectroscopy using CDCl3 as probe molecule and Hammett acidity titration with n-butylamine and benzoic acid. Both the increase in the activation temperature and the decrease in Al content favored the increase in the basicity of Mg,Al-LDH. The nature of “Mn+ O2− Lewis acid-base” pairs was a key factor to control the catalytic behavior of the solids. The length of the M-O bond, the basicity of the oxygen ion and the strength of the metal ion on the surface affected the catalytic activity of the solids and their isomer selectivity in the reaction between methanol and propylene oxide to form 1-methoxy-2-propanol. It was demonstrated that brucite(150) can be applied as catalyst for at least four successive cycles without loss of activity.

Two calcium-rich natural layered aluminosilicates containing 90–95 wt.% montmorillonite were chemically activated using 0.125–3.0 M HCl solutions. Structural and textural properties were characterized by X-ray diffraction, elemental analysis and N 2 -adsorption/desorption analyses. According to infrared spectroscopy using pyridine as probe molecule, the amount of Bronsted acid sites increased when increasing HCl concentration. The catalytic performance of these materials was investigated in the Prins cyclization of (−)-isopulegol with vanillin to form octahydro-2 H -chromen-4-ol, carried out in toluene at 35 °C. It was found that the amount of Bronsted acid sites and the microporosity of the catalysts are key factors for the control of the reaction rate and the selectivity towards octahydro-2 H -chromen-4-ol.

This paper discusses the mechanism of montmorillonite structural alteration and modification of bentonites’ properties (based on samples from clay deposits Taganskoye, Kazakhstan and Mukhortala, Buriatia) under thermochemical treatment (treatment with inorganic acid solutions at different temperatures, concentrations and reaction times). Treatment conditions were chosen according to those accepted in chemical industry for obtaining acid modified clays as catalysts or sorbents. Also, more intense treatment was carried out to simulate possible influence at the liquid radioactive site repositories. A series of methods was used: XRD, FTIR, ICP-AES, TEM, nitrogen adsorption, and particle size analysis. It allowed revealing certain processes: transformation of montmorillonite structure which appears in the leaching of interlayer and octahedral cations and protonation of the interlayer and –OH groups at octahedral sheets. In turn, changes in the structure of the 2:1 layer of montmorillonite and its interlayer result in significant alterations in the properties: reduction of cation exchange capacity and an increase of specific surface area. Acid treatment also leads to a redistribution of particle sizes and changes the pore system. The results of the work showed that bentonite clays retain a significant portion of their adsorption properties even after a prolonged and intense thermochemical treatment (1 M HNO3, 60 °C, 108 h).