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A quantitative understanding of the molecular-scale mechanisms of radionuclide sorption on different clay minerals is crucial for the development and safe implementation of geological nuclear waste disposal technologies. We apply classical molecular dynamics (MD) computer simulations to study the adsorption of uranyl on the external basal surfaces of two typical clay models. In the illite model, negative charge is primarily localized in the tetrahedral sheets, while in the lower-charge smectite model, the isomorphic substitutions are introduced in the octahedral sheet. The comparison of atomic density distributions at the clay surfaces and adsorption-free energies profiles as a function of distance from these surfaces demonstrates that overall U behavior at the basal clay surface is quite similar for illite and smectite. Uranyl is sorbed as a mixture of outer-sphere aqua complexes [UO2(H2O)5]2+ and hydrolyzed aqua complexes [UO2(H2O)4–5OH]+ on both surfaces. The structural and compositional differences between the models do not greatly affect the uranyl’s nearest coordination environment and are mainly reflected in the specific localization and orientation of the uranyl ions at both surfaces and in the magnitude of the adsorption-free energies. The observed quantitative characteristics of uranyl interactions with illite and smectite surfaces will help to better understand U behavior during the sorption process on clay minerals for the entire range of mixed-layer illite–smectite structures. A comparison of two versions of the ClayFF force field in the simulations made it possible to more accurately and quantitatively evaluate some subtle features of the uranyl–clay interactions and to obtain a more precise composition of uranyl complex with the modified ClayFF force field (ClayFF-MOH).

The Ni-laterite deposit at the San Felipe plateau, located 30 km northwest of Camagüey, in central Cuba, is the best example of a clay-type deposit in the Caribbean region. San Felipe resulted from the weathering of mantle peridotites of the Cretaceous Camagüey ophiolites. In this study, a geochemical and mineralogical characterization of two profiles (83 and 84) from the San Felipe deposit has been performed by XRF, ICP-MS, quantitative XRPD, oriented aggregate mount XRD, SEM, FE-SEM, and EMPA. Core 83, with a length of 23 m and drilled in the central part of the plateau, presents a notable concentration of cryptocrystalline quartz fragments and a rather poor content of NiO, averaging 0.87 wt.%. Core 84, which is 12 m long and drilled at the border of the plateau, lacks silica fragments and presents a higher NiO content, averaging 1.79 wt.%. The smectite structural formulae reveal that they evolve from trioctahedral to dioctahedral towards the top of the laterite profiles. Quantitative XRD analyses indicate that smectite is a dominant Ni-bearing phase, accompanied by serpentine and minor chlorite. Serpentine, as smectite, is enriched in the less soluble elements Fe3+, Al, and Ni towards the top of the profiles. Core 83 seems to have been affected by collapses and replenishments, whereas core 84 may have remained undisturbed.

In this study, raw smectite (Sm), from the Guarapuava–Parana–Brasil region, was saturated with copper ions (Cu-Sm) by ion exchange and the samples Sm and Cu-Sm were used in crystal violet (CV) adsorption and applied as an antimicrobial and antifungal hybrid pigment. Samples (Sm and Cu-Sm) were used to remove crystal violet (CV) dye from aqueous media, simulating wastewater. Samples after use as adsorbents were characterized and named smectite/adsorbed dye (Sm/Dye) and copper smectite/adsorbed dye (Cu-Sm/Dye); and they were applied as hybrid pigments with antimicrobial action. The Sm and Cu-Sm were characterized by X-ray diffractometry (XRD), energy dispersive X-ray fluorescence (EDXRF), vibrational spectroscopy (FTIR), Zeta potential (ζ), scanning electron microscopy (SEM), and colorimetry (CIE L*a*b*), enabling the identification of the presence of intercalated copper ions and on the smectite surface. The adsorption assays were carried out to evaluate the effects of initial dye concentration and contact time. Tests for application as a hybrid pigment showed good compatibility with commercial white paint being applied on plaster blocks and later photoaging and chemical stability tests were performed in acid and basic environments, both were discussed by colorimetry (CIE L*a*b*), thus being able to relate it to the color variation (∆E). The samples (Sm, Cu-Sm, Sm/Dye, and Cu-Sm/Dye) were dispersed in white paint at 10% and 20% (% w/w) to evaluate the ability to inhibit different microorganisms. The modification with copper ions promoted an increase in the adsorptive capacity relative to the raw smectite and provided antibacterial and antifungal action to the hybrid pigment against Escherichia coli, Staphylococcus aureus, Listeria monocytogenes, and Candida albicans. The Cu-Sm and Cu-Sm/Dye samples showed excellent results against all studied microorganisms and reveal successful materials that can be used in environments that require microbiological protection.

The fate of chemical pollutants in the environment is determined by various factors including the type and strength of their interactions with reactive surfaces in soils and sediments. In the present work the interactions of hexachlorobenzene (HCB) with the surface of a common clay mineral belonging to the smectite group montmorillonite (MNT) is studied by means of the density functional theory method. The MNT net surface charge, induced by isomorphic substitutions, is systematically varied and compensated by Ca2+ cations. Based on the calculated electron densities, conclusions are drawn revealing the nature of their mutual interactions, the related stability of such surface complexes as well as possible molecular arrangements. It becomes apparent that the dominant contribution to the stability of HCB-MNT complexes arises from the cation-π interactions between the HCB molecule and the nearest compensating Ca2+ cation and thus besides the MNT net surface charge the type and size of the compensating cations are expected to play a crucial role in understanding the HCB adsorption on MNT. This systematic study aims to contribute to a better mechanistic understanding of the interactions between hydrophobic organic compounds and reactive mineral surfaces.

The Mallorca coastal caves present large amounts of speleothems that have been studied for decades. However, the sedimentary deposits also present in these cases have not been given the same attention. This work is the first study entirely focused on these deposits, specifically the ones found in the Ases cave. These deposits are formed by clay minerals (illitic phases, kaolinite, smectite, and chlorite), calcite and quartz, and minor proportions of dolomite, albite, orthoclase, hematite, and goethite. The grain size and the electron microscopy studies suggested the presence of different sedimentation processes (bedrock degradation, creep or saltation, and suspension) and different origins (authigenic and detrital origins) for the different sediments. Based on these differences, two types of deposits were characterized: autochthonous and allochthonous deposits. The first ones are located on the floor of chambers and corridors in subaqueous zones, indicating the stability of the mixing zone (and therefore the sea level) over time. The second ones appear filling voids on the walls and the ceiling in the terrestrial zone, evidencing the filling of the cavity in the presence of water (during a wet period). These results are very important to complete the understanding of the caves and their evolution and support the relevance of these materials in paleoenvironmental studies.

New magnetic nanocomposite sorbents were obtained by doping natural bentonite with nanosized CoFe2O4 spinel (10 and 20 wt.%). Nanocrystals of cobalt ferrite were synthesized by a citrate burning method. The structure and physical-chemical properties of the composites were characterized by XRD, XRF, TEM, BET, FTIR and Faraday balance magnetometry. During the formation of nanocomposites, 10–30 nm particles of cobalt ferrite occupied mainly the interparticle space of Fe-aluminosilicate that significantly changed the particle morphology and composite porosity, but at the same time retained the structure of the 2:1 smectite layer. A combination of two functional properties of composites, adsorption and magnetism has been found. The adsorption capacity of magnetic nanosorbents exceeded this parameter for bentonite and spinel. Despite the decrease in the adsorption volume, pore size and specific surface area of the composite material relative to bentonite, the sorption activity of the composite increases by 12%, which indicated the influence of the magnetic component on the sorption process. FTIR data confirmed the mechanism of formaldehyde sorption by the composite sorbent. The production of a magnetic nanosorbent opens up new possibilities for controlling the sorption processes and makes it possible to selectively separate the sorbent from the adsorption medium by the action of a magnetic field.

This study reveals mineral and deformation processes associated with faulting of lacustrine unconsolidated sediments in the Guadix-Baza Basin (Betic Cordillera, S Spain) affected by the Baza Fault. Brittle carbonate and silt sediments develop deformation bands frequently sealed by dolomite crystallization, whereas ductile clay-rich sediments form clay smearing bands where late crystallization of gypsum can be observed. Granular flow and local cataclasis were the main deformation mechanisms in the brittle deformation bands. Flow alignment, grain-boundary sliding, and extrusion were predominant in the clay smearing bands. These water and clay-rich bands reduced shear strength of the faulting process due to their lubricating effect. Beidellitic smectite defines shear foliation of the smeared bands, but Mg-Fe, a K-rich smectite (Fe + Mg > 1 and K content up to 0.8 a.p.f.u), crystallizes in the micropores surrounding brittle clasts produced by deformation pressure shadows. These data suggest that the interaction of micromechanical events, which increased sediment porosity by the generation of pressure shadows, and the flow and concentration of saline fluids in these pores promoted structural diagenesis processes that favoured the beginning of local illitization.

A calcium bentonite clay from Boane region (Mozambique) was subjected to an Na2CO3 activation process. The methylene blue test together with energy-dispersive X-ray spectroscopy (EDX) analysis indicated the successful ion exchange of Ca2+ by Na+ ions since the cation exchange capacity (CEC) increased from 67.5 to 74 meq/100 g and the Na/Ca ratio from 2.91 up to 15.8, as the concentration of Na2CO3, activation temperature, and activation time were varied from 2 to 6 wt.%, from 25 to 65 °C, and from 2 to 4 h, respectively. However, the increase in the CEC did not follow the same trend as the increase in the Na/Ca ratio, and for the case of Na2CO3 concentration, the increase in the CEC was limited. The X-ray diffraction (XRD) patterns also confirmed that Ca-rich bentonite was effectively modified into Na-bentonite since after the activation, the d(001) decreased from 1.52 nm to 1.30 nm. The statistical design of the experiments showed that as well as the time and the temperature × time linear interactive effect, all the other independent factors and their interactive effects had a significant influence on the CEC. The response surface methodology (RSM) indicated that higher values of the CEC can be obtained under the optimal activation conditions of 4 wt.% Na2CO3, at a temperature of 45 °C, and with an activation time of 3 h. A statistical model was used to predict the CEC, and the R2 value was 0.99529, which denotes a satisfactory result in predicting the CEC.

Lithofacies belonging to mud-flat and palustrine deposits (lake margin) in the Miocene of the Madrid Basin (Spain) have been studied. Four lithofacies corresponding to mud flat (1 and 3) and palustrine (2 and 4) deposits have been differentiated. Units 1 and 3 consist mainly of mudstones and carbonates (calcretes and diolocretes). The clay fraction is dominated by trioctahedral smectite (up to 79%) with illite and kaolinite as minor components. The d(060) spacing value shows reflections at 1.52 and 1.50 Å indicating also the presence of dioctahedral phyllosilicates. Unit 2 consists predominantly of lutites (claystones), locally with carbonate and chert nodules. The clay fraction is dominated by sepiolite (up to 96%) with variable contents of smectite and subordinate illite. The d(060) spacing value shows reflections at 1.51 and 1.52 Å indicating trioctahedral clay minerals. Unit 4 consists mostly of carbonates (limestones) with mudstone and lutite inserts. The clay fraction shows different contents of sepiolite, palygorskite and dioctahedral smectite. The analysis of a selection of trace elements (Cr, Co, Th, La, Sc) has allowed us to determine the characteristics of the source area as dioritic, somewhat different from those of the nearby materials from the Batallones sector. Sepiolite shows FWHM values ranging between 0.68 and 1.10 (2θ), indicating “low crystallinity sepiolite”. Differences in the conditions of formation of magnesian smectite and palygorskite have been observed in the mud-flat and palustrine deposits. The formation of sepiolite mainly by neoformation in palustrine deposits with different hydrochemistry is remarkable, leading to differences in fibre size and crystallinity of the fibrous clay mineral. Authigenic transformation processes from previous Al-rich phases would be responsible for the formation of saponite and palygorskite in mud flat and palustrine environments, with different pH conditions.

Interactions of bioorganic moieties with clay minerals have attracted attention not only from the perspective of novel bioclay materials but also because they play a crucial role in our understanding of physical and chemical processes in soils. The aim of the present article is to explore the interactions responsible for the formation of a phosphatidylcholine-kaolinite bioclay by employing a series of classical molecular dynamic simulations. Detailed analysis of the structure and energies of the resulting bioclays reveals that the phosphatidylcholine molecules bind to the kaolinite surface either via their zwitterionic heads or hydrophobic aliphatic tails, depending on the kaolinite surface characteristics and the density of organic coating. The phosphatidylcholine molecules have a tendency to form irregular layers with a preferred parallel orientation of molecules with respect to the kaolinite surface. The tails exhibit varying degrees of flexibility and disorder depending on their distance from the surface and the density of surface coating. Significant differences in the binding can be spotted with respect to the two types of kaolinite basal surfaces, i.e., the hydrophobic siloxane surface, which possesses a considerable dispersion character, and the hydrophilic alumina surface, polarized by the surface hydroxyl groups.

The mineral alteration patterns in high- to low-temperature geothermal fields affect the induced polarization (electrical conductivity and chargeability) properties of volcanic rocks. Indeed, these properties are sensitive to the cation exchange capacity and the porosity of the rock, which are both dependent on the alteration path, temperature, and depth of burial. Therefore induced polarization tomography appears as a powerful non-intrusive geophysical method to investigate alteration patterns in geothermal fields. Among clay minerals, the production of smectite through prograde reactions occurs progressively in volcanic rocks up to 220 °C. The presence of smectite dominates the induced polarization response of the volcanic rocks because of its very large cation exchange capacity. It follows that induced polarization can be used as a non-intrusive temperature proxy up to 220 °C for both active and inactive geothermal fields, recording the highest temperatures reached in the past. The influence of magnetite and pyrite, two semi-conductors, also has a strong influence regarding the induced polarization properties of volcanic rocks. Various field examples are discussed to show how induced polarization can be used to image volcanic conduits and smectite-rich clay caps in volcanic areas for both stratovolcanoes and shield volcanoes.

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.

Bentonites are considered to be the most suitable materials for the multibarrier system of high-level radioactive waste repositories. Since BCV bentonite has been proved to be an ideal representative of Czech Ca-Mg bentonites in this respect, it has been included in the Czech Radioactive Waste Repository Authority (SÚRAO) buffer and backfill R&D programme. Detailed knowledge of processes in the material induced by thermal loading provides invaluable assistance regarding the evolution of the material under repository conditions. Samples of both original BCV 2017 bentonite and the same material thermally treated at 200 °C were characterised by means of chemical analysis, powder X-ray diffraction, infrared spectroscopy, thermal analysis, cation exchange capacity, specific surface area (BET) measurements, the determination of the swell index, the liquid limit, the swelling pressure and water retention curves. The smectite in BCV 2017 bentonite comprises Ca-Mg montmorillonite with a significant degree of Fe3+ substitution in the octahedral sheet. Two main transformation processes were observed following heating at 200 °C over 27 months, the first of which comprised the dehydration of the montmorillonite and the subsequent reduction of the 001 basal distance from 14.5 Å (the original BCV 2017) to 9.8 Å, thus indicating the absence of water molecules in the interlayer space. The second concerned the dehydration and partial dehydroxylation of goethite. With the exception of the dehydration of the interlayer space, the PXRD and FTIR study revealed the crystallochemical stability of the montmorillonite in BCV 2017 bentonite under the selected experimental conditions. The geotechnical tests indicated no major changes in the mechanical properties of the thermally treated BCV 2017 bentonite, as demonstrated by the similar swelling pressure values. However, the variation in the swell index and the gradual increase in the liquid limit with the wetting time indicated a lower hydration rate. The retention curves consistently showed the lower retention capacity of the thermally treated samples, thus indicating the incomplete re-hydration of the thermally treated BCV 2017 exposed to air humidity and the difference in its behaviour compared to the material exposed to liquid water.

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.

The adsorption of two pharmaceuticals, carbamazepine and paracetamol, onto the expandable clay mineral saponite has been studied through the combination of kinetic experiments, X-ray diffraction, and theoretical modeling. Kinetic experiments indicate low adsorption for carbamazepine and paracetamol on expandable smectite clay. Accordingly, X-ray diffraction experiments show that neither compound enters smectite interlayer space. Molecular dynamics simulations were carried out to understand the interactions between the two pharmaceuticals and the saponite basal surface in the presence of Na+ cations. Calculations reveal that paracetamol almost does not coordinate solution cations, whereas a rather low coordination to cation is observed for carbamazepine. As a result, the adsorption onto the clay surface results mainly from van der Waals interactions for both pharmaceuticals. Carbamazepine does adsorb the surface via two configurations, one involving cation coordination, which corresponds to a rather stable adsorption compared to paracetamol. This is confirmed by structural analyses completed with desorption free energy profile.

Mudstone samples from the Moreno (Upper Cretaceous-Paleocene) and Kreyenhagen (Eocene) formations are analysed using X-ray diffraction (XRD) and X-ray fluorescence (XRF) to determine their mineralogy. Smectite (Reichweite R0) is the predominant phyllosilicate present, 48% to 71.7% bulk rock mineralogy (excluding carbonate cemented and highly bio siliceous samples) and 70% to 98% of the

In radioactive waste disposal facilities, low-permeability engineered barrier materials are important for inhibiting radionuclide migration. However, dissolution–precipitation reactions under alkaline conditions change the permeability of engineered barriers. To understand long-term dissolution–precipitation reactions under alkaline conditions in chemically complex systems, trenches and drill holes were excavated at Narra in Palawan, where alkaline fluids (pH > 11) have been naturally produced, seeping into clastic sediments derived from serpentinized ultramafic rocks and gabbro of Palawan ophiolite. Interaction between the alkaline seepage and clastic sediments, which have been deposited since 15,000 radiocarbon years before present (14C yr BP), led to dissolution of minerals and the precipitation of Si-bearing phases which were divided into two main categories: Fe-Mg-Si infillings and Ca-Si infillings. The former category was composed of iron-magnesium-silicate-hydrate (F-M-S-H) and a nontronite-like mineral and was widely recognized in the clastic sediments. The nontronite-like mineral likely formed by interaction between silicates and alkaline seepage mixed with infiltrated seawater, whereas F-M-S-H formed by the reaction of silicates with alkaline seepage in the absence of seawater infiltration. Ca-Si infillings included 14 Å tobermorite and were precipitated from alkaline seepage combined with the Ca and Si supplied by the dissolution of calcite and silicates in the clastic sediments.

A series of clay minerals and clay-based materials have been tested to eliminate one of the most dangerous bacteria we can find in the water: Salmonella. It has been proven that the use of clays and their PCH materials can be a suitable method for removing Salmonella from water. The results of this initial study show that all the materials analyzed have great salmonella adsorption capacities ranging from the lowest value observed in the mont-PCH sample (0.29 × 1010 CFU g−1) to the highest value observed in the natural palygorskite sample (1.52 × 1010 CFU g−1). Macroporosity, accessible external surface area, and the presence of silanol groups in the external surface of the particles appears to be the controlling factors for Salmonella adsorption capacity while it seems that the structural characteristics of the clay minerals and their respective PCH does not affect the adsorption capacity.

Lithium deposits in tuffaceous sediments of the McDermitt caldera constitute possibly the world’s largest Li clay resource, yet their characteristics and origin are not established. The 40 × 25 km McDermitt caldera collapsed during the eruption of ~1000 km3 of a 16.4 Ma, zoned peralkaline to metaluminous tuff; minor caldera magmatism ceased by 16.1 Ma. About 200 m of sediments mostly composed of glass from regional pyroclastic eruptions accumulated in the caldera until about 15.7 Ma. Closed hydrologic system diagenesis (CHSD) altered the tuffaceous sediments to a consistent vertical mineral zonation of clay, analcime, K-feldspar, and albite. Entire sedimentary sections in the southern and western parts of the caldera basin have ≥1500 ppm Li. Lithium-rich intervals are dominantly claystone. The most thoroughly studied deposit is a laterally continuous, ~3000 ppm Li zone in the lower sedimentary section that also has high K, Rb, Mo, As, and Sb (and partly Mg and F). Lithium occurs as an illitic clay (tainiolite?). The overlying, upper sedimentary section averages 40Ar/39Ar age of ~14.9 Ma on authigenic K-feldspar in the illite zone is ~1.2 Ma younger than the 16.1 Ma end of magmatism in the caldera, which mitigates against a simple hydrothermal origin. Closed hydrologic system diagenesis was essential to Li mineralization, but Li budget calculations suggest a source of Li in addition to the tuffaceous sediments is required. This additional source could be Li originally in highly enriched magma that entered the diagenetic system through either (1) Li in magma exsolved into a hydrous volatile phase during eruption. The Li-rich volatile phase coated glass shards or was trapped in pumice and was quickly leached by surface or groundwater upon deposition in the caldera. (2) Residual magma immediately following ash-flow eruption and caldera collapse generated Li-rich hydrothermal fluids that mixed with meteoric water in the closed caldera basin, generating a hybrid diagenetic fluid. The hydrothermal fluid and hybrid diagenetic fluids would have existed only during initial basin sedimentation between about 16.4 and 16.1 Ma.

A review and a synthesis of the geological, mineralogical, and crystal chemical data available in the literature on active Spanish bentonitic exploitations were done, and at the same time, new data are provided from a set of representative samples from these deposits. They were located in three different areas with different geological origins: (1) Miocene sedimentary deposits from the Tajo Basin (Madrid−Toledo provinces) in the center of the Iberian Peninsula, where bentonites appear in two different units named for their colors (Green Clays and Pink Clays); (2) samples from Tamame de Sayago (Zamora province) originating from the hydrothermal alteration of granitic Variscan rocks; and 3) Miocene deposits originating from the hydrothermal alteration of volcanic or subvolcanic rocks from the Cabo de Gata volcanic area (Almería Province) in the southern part of Spain, where the three main deposits (Cortijo de Archidona, Los Trancos, and Morrón de Mateo) were studied. The bentonites from the Tajo Basin were formed mainly by trioctahedral smectites, and there were significant mineralogical differences between the Green and Pink Clays, both in terms of the contents of impurities and in terms of smectite crystallochemistry and crystallinity. The smectites from Tamame de Sayago were dioctahedral (montmorillonite−beidellite series), and they appeared with kaolinite, quartz, and mica in all possible proportions, from almost pure bentonite to kaolin. Finally, the compositions of the bentonites from the three studied deposits in Cabo de Gata were quite similar, and zeolites and plagioclases were the main impurities. The structural formulae of the smectites from Cortijo de Archidona and Los Trancos showed a continuous compositional variation in beidellite−montmorillonite, while in Morrón de Mateo, the smectites were mainly montmorillonite, although there was continuous compositional variation from Al montmorillonites to Fe−Mg-rich saponites. The variation in the smectite composition is due to the intrusion of a volcanic dome, which brings new fluids that alter the initial composition of the smectites.

In this paper, salinized soils with different degrees of salinity are sampled in Junggar Basin of Xinjiang of China. The X-ray diffraction, transmission electron microscopy, and inductively coupled plasma mass spectrometry are employed to investigate the morphology and distribution characteristics of smectite in salinized soil profiles. In the salinized soil profiles of this region, crystals of smectite are poor where lattice fringes are not parallel. In all soil layers, the content of smectite in the soil increases with the decrease in content of illite, which has demonstrated significant negative correlation (r = 0.79, n = 50, p < 0.01) between illite and smectite. This phenomenon has demonstrated that illite may be transformed into smectite in salinized soils of studied regions. In general, the transformation process of illite to smectite is affected by climate condition. The δ18O values of secondary carbonate in the 0⁻10 cm soil layers is higher than that in deep soil layers, which indicates that δ18O concentrates in surface soil and reflects temperature rise during soil layer formation. The δ13C values of secondary carbonate and soil organic matter in 0⁻10 cm soil layers are higher than that in deep soil layers. It indicates that C4 plants were the main plants, which reflects that the climate was relatively dry during the formation of the surface soil. Thus, the climate during the surface soil formation is arid, which is not conducive for leaching K+ from illite of the 0⁻10 cm soil to form smectite. As a result, the content of the smectite becomes lowest in the soil surface. In the relative humid condition of deep soil layers, the K+ of the illite of the soil would be relative easily leached and more smectite may be formed. Furthermore, the presence of salt in the salinized soil would promote the formation of smectite in Junggar Basin of Xinjiang. A lot of Ca2+, Na+ and Mg2+ in the soil solution of salinized soils would enter into the illite and occupy K+ positions. The studied result shows that the amount of smectite would increase with the increase of salt below 10 cm of the soil layer, where the amount of smectite would be significantly correlated with soil electrical conductivity (r = 0.64, n = 39, p < 0.01). In the Junggar Basin in Xinjiang, therefore, the salinized soil below 10 cm would have the necessary water conditions and chemical components for illite transformation to smectite.