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Organic compounds pose significant environmental concerns, including groundwater contamination. Clays are commonly used as liners to prevent contaminant permeation into the groundwater tables, necessitating an understanding of clay's behavior in the presence of organic compounds. The presence of organic contaminants results in changes in the dielectric constant of pore fluid, which influences the interparticle energies and double layer thickness in the soil-pore fluid system. This study aims to elucidate the mechanisms of these changes by examining the response of smectite and kaolinite to variations in the dielectric constant. Experimental tests, including Atterberg limits, unconfined compression strength, water adsorption, sedimentation, pH, and XRD, were performed on clay samples at different concentrations of water-isopropyl alcohol mixtures. Results indicate that smectite exhibits higher Atterberg limits and water adsorption capacity compared to kaolinite. Smectite also shows more pronounced changes in response to decreasing dielectric constant. Conversely, changes in kaolinite's behavior were attributed to variations in pore fluid viscosity and dipole moment. These findings emphasize the importance of considering viscosity and dipole moment alongside dielectric constant in predicting kaolinite behavior. Overall, this study enhances the understanding of how variations in pore fluid dielectric constant affect the geotechnical and geo-environmental behavior of smectite and kaolinite. [ABSTRACT FROM AUTHOR]

Microbial activity has been documented in various lacustrine environments, suggesting its fundamental role in mineral precipitation and, therefore, in the formation of organo-deposits such as microbialites. Many studies are currently focused on documenting how the association of microbes and extracellular polymeric substances (EPSs) may influence the authigenesis of Mg-rich clay minerals and the subsequent carbonate precipitation in growing microbialites in lacustrine environments. In this study, we investigate the present-day microbialites of the alkaline Bagno dell'Acqua lake (Pantelleria Island, Italy) using X-ray diffraction (XRD) scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). Our results reveal the intimate association of Mg-smectite/carbonate minerals with the EPS and microbes, and, for the first time, we selected microbes belonging to phylum Firmicutes (Bacillus sp.), from natural microbialites, to carry out laboratory experiments that testify their direct role in the precipitation of clay and carbonate minerals. [ABSTRACT FROM AUTHOR]

Potassium behavior in calcareous soils are very complex and are affected by several factors, such as the content of carbonates and soil heating. In the present research, the comparison of four calcareous soils with varying amounts of carbonates, different mineralogy, and texture (collected from Fars province, southern Iran) was compared to analyze the content of K species, K release by solutions of 0.01 M CaCl2 and 1% wood vinegar, and K re-fixation. The study also investigated the impact of heating K-depleted soils to 100°C on the secondary release and re-fixation of K. The results showed that the studied soils contained 3–60% carbonates, 14–53% clay, and a relatively similar mineral composition: smectite, illite, chlorite, palygorskite (in dry areas), and vermiculite (in humid areas). Wood vinegar extracted more K from soils with less carbonates than CaCl2, while this difference was not significant for Fluvisols, which contains about 60% carbonates. Mollic Vertisols with low carbonate content (about 3%) and high levels of clay and smectite released less K in the initial phase. However, K release by this soil decreased less in the second phase, indicating the higher buffering capacity of Mollic Vertisols in providing soluble K. Heating the soil increased the secondary release of K, but decreased the amount of K re-fixation in soils treated with CaCl2. Generally, Mollic Vertisols fixed more K than other soils. In addition, the type of extractant had no effect on the content of K fixation in the studied soils except Mollic Vertisols. However, wood vinegar reduced the K fixation content in Mollic Vertisols compared to CaCl2. In general, it can be concluded that wood vinegar can provide more K to the plants without dissolving K-bearing minerals compared to CaCl2. In addition, soil heating can influence the process of K release and fixation in K-depleted soils. [ABSTRACT FROM AUTHOR]

This work combines experimental and computational modeling studies for the preparation of a composite of metformin and an organoclay, examining the advantages of a Tunisian clay used for drug delivery applications. The clay mineral studied is a montmorillonite-like smectite (Sm-Na), and the organoclay derivative (HDTMA-Sm) was used as a drug carrier for metformin hydrochloride (MET). In order to assess the MET loading into the clays, these materials were characterized by means of cation exchange capacity assessment, specific surface area measurement, and with the techniques of X-ray diffraction (XRD), differential scanning calorimetry, X-ray fluorescence spectroscopy, and Fourier-transformed infrared spectroscopy. Computational molecular modeling studies showed the surface adsorption process, identifying the clay–drug interactions through hydrogen bonds, and assessing electrostatic interactions for the hybrid MET/Sm-Na and hydrophobic interactions and cation exchange for the hybrid MET/HDTMA-Sm. The results show that the clays (Sm-Na and HDTMA-Sm) are capable of adsorbing MET, reaching a maximum load of 12.42 and 21.97 %, respectively. The adsorption isotherms were fitted by the Freundlich model, indicating heterogeneous adsorption of the studied adsorbate–adsorbent system, and they followed pseudo-second-order kinetics. The calculations of ΔGº indicate the spontaneous and reversible nature of the adsorption. The calculation of ΔH° indicates physical adsorption for the purified clay (Sm-Na) and chemical adsorption for the modified clay (HDTMA-Sm). The release of intercalated MET was studied in media simulating gastric and intestinal fluids, revealing that the purified clay (Sm-Na) and the modified organoclay (HDTMA-Sm) can be used as carriers in controlled drug delivery in future clinical applications. The molecular modeling studies confirmed the experimental phenomena, showing that the main adsorption mechanism is the cation exchange process between proton and MET cations into the interlayer space. [ABSTRACT FROM AUTHOR]

Illitization of smectite in sedimentary systems, a process akin to "reverse weathering," is a diagenetic process that has significant implications for sediment paragenesis and hydrocarbon exploration. However, the potential influence of chemical weathering on the illitization of smectite and its possible control of the neogenesis of titanium (Ti)-oxides remain unclear. Altered volcanic tephra layers (i.e., K-bentonites) characterized by an interstratified illite-smectite (I-S) clay mineralogy serve as an excellent medium to investigate the illitization of smectite. In this study, we first investigated the fine structure of clay minerals and in situ nano-mineralogy of Ti-bearing minerals from altered volcanic ashes and then undertook a meta-analysis of geochemical compositional data for bentonites spanning a wide range of ages and depositional environments globally. We found that Ti mainly occurs as discrete micrometer-scale magmatic srilankite and nanoscale authigenic anatase crystals. During the weathering process, the magmatic srilankite partly dissolved under acidic conditions, resulting in a local buildup of Ti in porewaters. The I-S displays a platy habit and curved edges and is found closely associated with anatase crystals under TEM. Our compilation results combined with microscopic evidence suggest that chemical weathering may potentially promote the illitization reaction by changing the chemical composition of the fluids through increased terrestrial inputs and by creating larger pore spaces through the decomposition of weatherable components. Positive correlations between K and Ti are especially common in (K-)bentonites that are dominated by I-S, suggesting that I-S can adsorb Ti during the weathering process and provide a suitable site for the nucleation of anatase. Our study highlights the role of chemical weathering in the illitization of smectite and their combined effect on the formation of Ti-oxides. [ABSTRACT FROM AUTHOR]

Using a complex of analytical methods, clay minerals were studied in Pleistocene sediments from Hole ODP 1038B (120.50 m deep), drilled on the northwestern edge of the Central Hill (Escanaba Trough, Gorda Ridge) near the hydrothermal source with a temperature of 108°C, as well as in Pleistocene background terrigenous sediments from reference Hole ODP 1037B, drilled in the Escanaba Trough 5 km south of the Central Hill. The terrigenous clay mineral assemblage in sediments from Hole 1037B consists of the mixed-layer smectite-illites, smectite, chlorite, illite, and kaolinite. Sediments from Hole 1038B in the interval from the bottom surface to a depth of 5–7 m are composed of terrigenous clay minerals. In the rest of the sedimentary section, clay minerals are represented by the newly formed biotite, chlorite, and dioctahedral smectite. They were formed during the basaltic melt intrusion into the Escanaba Trough with the formation of a laccolith and the subsequent rapid cooling of its flank. The intrusion was accompanied by the ascent of high-temperature hydrothermal fluid in the central discharge channel, interacting with the adjacent sediments. As a result, the fine-dispersed biotite was formed in sediments at the high-temperature stage of this interaction due to the primary terrigenous clay minerals, K-feldspar, and amphiboles. The rapid cooling of the hydrothermal fluid to a temperature of presumably 270–330°C promoted the partial replacement of biotite by chlorite. The further rapid cooling of the hydrothermal fluid to 200°C and lower and its mixing with seawater seeping into sediments of the Central Hill fostered the formation of smectite. [ABSTRACT FROM AUTHOR]

Expansive soils are characterized by significant swelling and shrinkage due to changes in water content, which could threaten the safety of buildings. In this study, an electrochemical treatment method was used to modify bentonite, with subsequent analysis focused on evaluating the alterations in its physical and chemical properties. The electrical resistance between the soil and the electrodes was significantly reduced by injecting a CaCl2 solution, leading to a substantial decrease in voltage loss at the anode. The thickness of the electrical double layer decreased as the Na+ cations adsorbed by smectite particles were exchanged by Ca2+ ions, which significantly decreased the water adsorption and free swelling ratio. The electrochemical treatment method removed more pore water from soil samples than the electroosmotic consolidation method. Furthermore, the results indicated that the injection of a CaCl2 solution could be effective in restraining the swelling potential of bentonite. The most suitable concentration for CaCl2 solution to modify bentonite by electrochemical treatment method might be 1 mol/L, and the injection volume could be 125 mL/L of soil. The results indicated that the electrochemical treatment method could be a promising in situ technique for modifying expansive soil. [ABSTRACT FROM AUTHOR]

To better understand the transport behavior of nitroaromatic compounds (NACs) in soils, it is significant to systematically evaluate the factors influencing NACs adsorption to smectite clays and thoroughly elucidate major interactive mechanisms. The binding affinity of smectite clays for NACs was clearly influenced by both interlayer cations and surface charge density of smectite. When saturated with K+, Cs+ or NH4+, smectite clays exhibited higher binding abilities for 2,4-dinitrobenzene (2,4-DNT), as compared to those saturated with Na+, Ca2+ or Al3+. A negative correlation existed between the charge density of K+-smectite and its binding ability for 2,4-DNT (not including the smectite with the lowest charge density). As pH decreased, the main interaction between dissociable NACs and smectite clays shifted from the electrostatic repulsion to the specific adsorption, resulting in higher adsorption at lower pH. With higher solution ionic strength, the quasi-crystal structure of smectite formed mainly due to the better-ordered lamellae, which led to the stronger sorption potential of the smectites for NACs. The adsorption of dimethylnitrobenzenes differed to some extent among the isomers, attributed to the steric hindrance related to the position of nitro and methyl groups. The adsorption of NACs was promoted slightly due to substitution of -CH3 for -H and considerably substitution of -NO2 for -CH3. The presence of cation binders (crown ether 18c6e and 15c5e) evidently weakened the adsorption of 2,4-DNT by K+- and NH4+-smectite. Macroscopic adsorption results, along with electronic property of NAC molecules (atomic charge and electrostatic potential), demonstrated that the electrostatic interaction between smectite cations and nitro of NACs was the predominant force in mediating their adsorption. [ABSTRACT FROM AUTHOR]

The early Martian atmosphere had 0.25 to 4 bar of CO2 but thinned rapidly around 3.5 billion years ago. The fate of that carbon remains poorly constrained. The hydrothermal alteration of ultramafic rocks, rich in Fe(II) and Mg, forms both abiotic methane, serpentine, and high-surface-area smectite clays. Given the abundance of ultramafic rocks and smectite in the Martian upper crust and the growing evidence of organic carbon in Martian sedimentary rocks, we quantify the effects of ultramafic alteration on the carbon cycle of early Mars. We calculate the capacity of Noachian-age clays to store organic carbon. Up to 1.7 bar of CO2 can plausibly be adsorbed on clay surfaces. Coupling abiotic methanogenesis with best estimates of Mars' d13C history predicts a reservoir of 0.6 to 1.3 bar of CO2 equivalent. Such a reservoir could be used as an energy source for long-term missions. Our results further illustrate the control of water-rock reactions on the atmospheric evolution of planets. [ABSTRACT FROM AUTHOR]

Addressing climate change requires transitioning to cleaner energy sources and adopting advanced CO2 capture techniques. Clay minerals are effective in CO2 adsorption due to their regenerative properties. Recent advancements in nanotechnology further improve their efficiency and potential for use in carbon capture and storage. This study examines the CO2 adsorption properties of montmorillonite and saponite, which are subjected to a novel microwave-assisted acid treatment to enhance their adsorption capacity. While montmorillonite shows minimal changes, saponite undergoes significant alterations. Furthermore, the addition of silica pillars to smectites results in a new nanomaterial with a higher surface area (653 m2 g−1), denoted as reversed smectite, with enhanced CO2 adsorption capabilities, potentially useful for electrochemical devices for converting captured CO2 into value-added products. [ABSTRACT FROM AUTHOR]

The widespread use of clay minerals and clays in environmental engineering, industry, medicine, and cosmetics largely stems from their adsorption properties and surface charge, as well as their ability to react with water. The dissolution and growth of minerals as a function of pH are closely related to acid–base reactions at their surface sites and their surface charge. The vivid tapestry of different types of surface sites across different types of clay minerals generates difficulties in experimental studies of structure–property relationships. The aim of this paper is to demonstrate how a mesoscale stochastic kinetic Monte Carlo (kMC) approach altogether with atomistic acid-base models and empirical data can be used for understanding the mechanisms of dissolution and surface charge behavior of clay minerals. The surface charge is modeled based on equilibrium equations for de/protonated site populations, which are defined by the pH and site-specific acidity constants (pKas). Lowered activation energy barriers for these sites in de/protonated states introduce pH-dependent effects into the dissolution kinetics. The V-shaped curve observed in laboratory experiments is reproduced with the new kMC model. A generic rate law for clay mineral dissolution as a function of pH is derived from this study. Thus, the kMC approach can be used as a hypothesis-testing tool for the verification of acid–base models for clay and other minerals and their influence on the kinetics of mineral dissolution and growth. [ABSTRACT FROM AUTHOR]

The low frictional strength of smectite minerals, such as montmorillonite, is thought to play a critical role in controlling the rheology and the stability of clay‐rich faults. In this study, we perform molecular dynamics simulations on a model clay system. Clay platelets are simplified as oblate ellipsoids interacting via the Gay‐Berne potential. We study the rheology and structural development during shear in this model system, which is sheared at constant strain rates for 10 strains after compression and equilibrium. We find that the system exhibits velocity‐strengthening behavior over a range of normal stresses from 1.68 to 56.18 MPa and a range of strain rates from 6.93 × 105 to 6.93 × 108/s. The relationship between shear stress and strain rate follows the Herschel‐Bulkley model. Shear localization is observed at lower strain rates despite the velocity‐strengthening friction, while homogeneous shear is realized at higher strain rates. The structure change due to shear is analyzed from various aspects: the porosity, particle orientation, velocity profile, and the parallel radial distribution function. We find that particle rearrangement and compaction dominate at the early stage of shear when the shear stress increases. The shear band starts to form in the later stage as the shear stress decreases and relaxes to a steady‐state value. The structural development at low strain rates is similar to previous experimental observations. The stacking structure is reduced during shear and restores logarithmically with time in the rest period. Plain Language Summary: Smectite clay minerals have relatively low frictional strength compared to other geomaterials. The strength and stability of clay‐rich faults depend on the shear behavior of clay minerals. In this study, we perform a series of simulations to investigate the shear behavior and structure of a simple clay model. The complex shape and interactions of natural clay are simplified as disc‐shaped ellipsoid and a generalized potential. The system is sheared at constant strain rates for 10 strains after compression and relaxation. The simulations focus on the effect of normal stress and strain rate on shear stress and clay structure. We find that the shear stress increases with strain rate for all conditions tested. Two shear scenarios are observed with shear localization in a narrow region at low strain rate while shear is homogeneous at high strain rate. The structural development at low strain rates is similar to previous experimental observations. We observe that the stacking structure of clay platelets weakens during shear. In the rest period after shear, the stacking structure restores logarithmically with resting time and can be associated with the healing of clay‐rich fault. Key Points: A model clay system shows velocity‐strengthening behavior following the Herschel‐Bulkley modelDespite the velocity‐strengthening friction, shear band is formed at low strain ratesThe stacking structure of clay platelets is reduced during shear and undergoes logarithmic healing with time in the system at rest [ABSTRACT FROM AUTHOR]

The release of Neogene volcanism in the southeastern part of the Iberian Peninsula produced a series of volcanic structures in the form of stratovolcanoes and calderas; however, other materials also accumulated such as large amounts of pyroclastic materials such as cinerites, ashes, and lapilli, which were later altered to form deposits of zeolites and bentonites. This work has focused on an area located on the northern flank of the San José-Los Escullos zeolite deposit, the only one of its kind with industrial capacity in Spain. The main objective of this research is to characterize the zeolite (SZ) of this new area from the mineral, chemical, and technical points of view and establish its possible use as a natural pozzolan. In the first stage, a study of the mineralogical and chemical composition of the selected samples was carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray fluorescence (XRF), and thermogravimetric analysis (TGA); in the second stage, chemical-qualitative and pozzolanicity technical tests were carried out at 8 and 15 days. In addition, a chemical analysis was performed using XRF on the specimens of mortars made with a standardized mixture of Portland cement (PC: 75%) and natural zeolite (SZ: 25%) at the ages of 7, 28, and 90 days. The results of the mineralogical analyses indicated that the samples are made up mainly of mordenite and subordinately by smectite, plagioclase, quartz, halloysite, illite, and muscovite. Qualitative chemical assays indicated a high percentage of reactive silica and reactive CaO and also negligible contents of insoluble residues. The results of the pozzolanicity test indicate that all the samples analyzed behave like natural pozzolans of good quality, increasing their pozzolanic reactivity from 8 to 15 days of testing. Chemical analyses of PC/SZ composite mortar specimens showed how a significant part of SiO2 and Al2O3 are released by zeolite while it absorbs a large part of the SO3 contained in the cement. The results presented in this research could be of great practical and scientific importance as they indicate the continuation of zeolitic mineralization beyond the limits of the San José-Los Escullos deposit, which would result in an increase in geological reserves and the extension of the useful life of the deposit, which is of vital importance to the local mining industry. [ABSTRACT FROM AUTHOR]

The source of sulfuric acid and associated aqueous alteration of ancient martian sedimentary rocks remain under debate in the context of divergent models of jarosite formation. Here, we report the formation of sulfates, including jarosite in K-bentonites within shallow-water facies of the Permian-Triassic (P-T) transition at Xiakou in South China. In these strata, jarosite is dispersed in the clay matrix or forms aggregates in pore spaces, has a euhedral morphology, and coexists with variably 34S-depleted paragenetic gypsum and bassanite (δ34S = –37.23‰ to +3.20‰ VCDT). Subaqueous alteration of volcanic tuffs concurrently with oxidation of upwelled, biogenically sourced H2S is the process of jarosite formation in the Xiakou K-bentonites. This mechanism of jarosite precipitation and stability over geological time challenges the long-held view of acidic, water-limited conditions leading to iron(III) sulfate precipitation and would be consistent with possible microbial or nanobial life on early Mars. [ABSTRACT FROM AUTHOR]

This article examines the clay mineralogy of twelve representative soils developed from gypsum-rich parent materials on several geomorphic positions. These soils were classified as Haploxerept, plus one profile as Humixerept and another as Xerorthent. The clay mineralogy, determined by X-ray diffraction, showed quite a similar clay composition in all profiles, with mica, chlorite, and smectite, from most to less abundant. Mica and chlorite are deemed inherited, while smectite—appearing in minor proportions—could result from both transformation and/or neoformation, because the leaching of bases by free drainage does not favor the transformation of mica to smectite. Therefore, the differences in clay mineralogy appeared to be lithogenic rather than pedogenic. These compositional data are an advance in the basic knowledge of the studied soils. [ABSTRACT FROM AUTHOR]

Ceres is a partially differentiated dwarf planet located in the main asteroid belt. Consus crater (diameter ∼64 km) is one of the oldest impact features (∼450 Ma) on the Cerean surface that surprisingly still shows a large variety of color lithologies, including exposures of bright material, which are thought to be brine residues. Here, we present new results that help in understanding the structure and composition of the Cerean crust. These results were deduced by using newly processed Dawn Framing Camera (FC) color imagery and FC clear filter images combined with infrared spectral data of Dawn's Visible and Infrared Spectrometer (VIR). Consus exhibits a variety of color lithologies, which we describe in detail. Interestingly, we found three spectrally different types of bright material exposed by a large old crater on Consus' floor. One of these, the yellowish bright material (Nathues et al., 2023, https://www.hou.usra.edu/meetings/lpsc2023/pdf/1073.pdf) and its modification, shows spectral signatures consistent with ammonium‐enriched smectites. We hypothesize that the ammonium in these smectites stems from contact with ascending brines, originating from a low‐lying former brine ocean that has been enriched in ammonium during the differentiation and freezing process of the Cerean crust. This enrichment is mainly due to ammonium uptake by sheet silicates. If such an ammonium enrichment occurred over long‐time scales on a global scale, this process may explain the vast presence of ammonium on the Cerean surface. Therefore, an outer solar system origin of Ceres is possibly not needed to explain the global presence of ammonium. Plain Language Summary: Ceres is the largest object in the asteroid belt and surprisingly exhibits surface features formed by recent cryo‐volcanism, although evolution models predicted an inactive, completely frozen body. Cryo‐volcanism possibly stems from a brine layer at the crust‐mantle transition. The global presence of ammonium on the Cerean surface led to the conclusion of a potential outer solar system origin of Ceres. Here, we investigate the structure of its crust, by studying one of the older, but still mineralogical diverse, impact craters that excavated originally low‐lying materials. For our study, we are using data of the Dawn Framing Camera, spectral data of the Visible and Infrared Spectrometer as well as several geoscientific remote sensing methods. We describe "yellowish bright material" for the first time (Nathues et al., 2023, https://www.hou.usra.edu/meetings/lpsc2023/pdf/1073.pdf), that is spectrally unique in our color data and exhibits a strong absorption feature in the near‐infrared caused by ammonium. We hypothesize that the ammonium enrichment of this surface material is mainly a consequence of an ammonium exchange between rising brines and near‐surface phyllosilicates. If true, this would strengthen the case for the existence of a low‐lying ammonium‐rich brine layer, which in turn could weaken the hypothesis of an outer solar system origin for Ceres. Key Points: The old impact crater Consus still shows a large variety of color lithologiesThe yellow bright material lithology is ammonium‐enrichedWe hypothesize that this ammonium stems from ascending originally low‐lying brines [ABSTRACT FROM AUTHOR]

With the increasing usage of nuclear energy, how to properly dispose nuclear waste becomes a critical issue. In this study, a multiscale modeling approach combining the experimental findings is presented to address the illitization process, its impact on transport properties, and system behavior of bentonite buffer in engineered barrier systems (EBS). Through the pore-scale modeling, reactive transport properties such as illite generation rate and effective diffusion coefficient of potassium ion as a function of porosity and temperature are quantified by employing the findings of hydrothermal reaction experiments of Bentonil-WRK. The capability of pore-scale modeling has been developed based on the Darcy-Brinkmann-Stokes equation, involving the processes of smectite illitization and clay swelling. Obtained reactive transport properties are utilized as input parameters for the macroscale modeling to predict the long-term behavior of bentonite buffer in EBS. As such, this study involves the whole workflow of quantifying the reaction parameters of smectite illitization through the hydrothermal reaction experiments, and numerically modeling the reactive transport process of smectite illitization in bentonite buffer of EBS from pore-scale to macroscale. The presented multiscale modeling findings are expected to provide reliable solution for safe nuclear waste disposal with EBS.

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. [ABSTRACT FROM AUTHOR]

Ryugu asteroid grains brought back to the Earth by the Hayabusa2 space mission are pristine samples containing hydrated minerals and organic compounds. Here, we investigate the mineralogy of their phyllosilicate‐rich matrix with four‐dimensional scanning transmission electron microscopy (4D‐STEM). We have identified and mapped the mineral phases at the nanometer scale (serpentine, smectite, pyrrhotite), observed the presence of Ni‐bearing pyrrhotite, and identified the serpentine polymorph as lizardite, in agreement with the reported aqueous alteration history of Ryugu. Furthermore, we have mapped the d‐spacings of smectite and observed a broad distribution of values, ranging from 1 to 2 nm, with an average d‐spacing of 1.24 nm, indicating significant heterogeneity within the sample. Such d‐spacing variability could be the result of either the presence of organic matter trapped in the interlayers or the influence of various geochemical conditions at the submicrometer scale, suggestive of a range of organic compounds and/or changes in smectite crystal chemistry. [ABSTRACT FROM AUTHOR]

The deposition of fine‐grained material of low permeability on the borehole wall during drilling (wellbore skin) is a common problem affecting the operation and efficiency of water wells. Here, we present new data and novel insights from four excavated dewatering wells from a lignite surface mine. All wells have the same age, are of similar construction, and were sampled at two different depths each. The thickness of the skin layer increases with depth. Its composition and permeability is strongly influenced by the surrounding aquifer material. Nonuniform sediments of low permeability result in less permeable wellbore skin deposits. The presence of discontinuities in the skin layer may be a determining feature for the resulting flow to wells, especially with skin layers of low permeability. The presence of naturally occurring swelling clay (smectite) provides the skin layer with a significant self‐sealing capacity. Article impact statement: In‐depth analysis of samples of wellbore skin, insights into formation, dependency on aquifer properties, and role of discontinuities. [ABSTRACT FROM AUTHOR]

Knowing the influence of isomorphic substitutions on the acid-base properties of smectite edge surfaces is an important aspect of the detailed understanding of clay minerals' interfacial properties with implications in the modeling of adsorption processes. We investigated the intrinsic acidity constants of Fe(II)/Fe(III) and Al(III) substituted edge surface sites of montmorillonite with a cis-vacant structure, which includes four crystallographic orientations perpendicular to [010], [0 1 0], [110], and [ 1 1 0], using the first-principles molecular dynamics (FPMD) based vertical energy gap method. Fe(II) and Fe(III) substitutions resulted, respectively, in a significant increase and decrease in pKa values of amphoteric groups directly associated with Fe octahedra. In addition, Fe(II) substitution increased the pKa values of the neighboring silanol sites, while Fe(III) substitution had a weak influence on these sites. The Al-substituted tetrahedra had amphoteric sites with higher pKa values than the non-substituted Si tetrahedra, and they increased significantly the pKa values of the sites bridging the tetrahedral and octahedral sheets on surfaces perpendicular to [010] and [110]. The acid-base properties of substituted and non-substituted surface sites of cis-vacant montmorillonite were used to build a state-of-the-art surface complexation model, which successfully reproduced the best available experimental acid-base titration data. This model was further used to predict acid-base properties of dioctahedral smectites (montmorillonite, beidellite, and nontronite) according to their cis- or trans-vacant structures and their layer chemistry. According to these predictions, these smectites exhibit very similar overall pH buffering properties despite significant differences in structure and chemistry. A detailed analysis of the acid-base properties as a function of crystallographic directions demonstrated, however, that these differences should have a large influence on the adsorption of ionic species. [ABSTRACT FROM AUTHOR]

The sol–gel state of smectite clay dispersions varies with the volume fraction of clay and electrolyte concentration. In this study, it was elucidated that the drying patterns of droplets from four types of smectite clay dispersions vary according to their sol–gel states. Droplets in the sol state exhibited a ring-shaped pattern, while those in the gel state showed a bump-shaped pattern. Near the boundary between the sol and gel states, patterns featuring both ring and bump structures were observed regardless of whether the droplets were on the sol or gel side. When guest particles or molecules were introduced into the clay dispersion, they dispersed uniformly within the system, and the drying pattern depended on the sol–gel state of the droplets. These findings suggest that the presence or absence of convection within the droplets during drying governs the drying pattern. [ABSTRACT FROM AUTHOR]

In contrast to the prevalence of dolomite [CaMg(CO3)2] in the geological record, there are few instances of recent formation. This discrepancy occurs despite supersaturation with respect to dolomite in many modern marine and lacustrine environments. Additionally, laboratory experiments have struggled to precipitate dolomite at ambient temperatures (<40°C) even under highly saturated conditions. However, recent work has found dissolved silica to be an effective catalyst for the direct precipitation of dolomite. To test this hypothesis, the hydrology and mineralogy of Deep Springs Lake, a playa setting with primary dolomite precipitation has been explored. In this study, the central playa sites with the highest sedimentation rates were found to have dissolved silica concentrations close to saturation. Rietveld refinement showed that bulk mineral assemblages of core samples contain 20 to 40% fine‐grained, partially ordered dolomite along with a 10 to 20% poorly crystalline clay fraction, while transmission electron microscopy imaging found a co‐precipitation relationship between the fine‐grained dolomite and Mg‐rich smectite clays, where the Mg‐rich smectite clays act as a sink for the excess dissolved silica during evaporation. Transmission electron microscopy results indicate that the nanodolomite crystals formed through surface‐induced nucleation and growth processes in the presence of dissolved silica as a catalyst. The broad coincidence of conditions for the direct precipitation of dolomite and Mg‐rich smectite clays provides evidence that silica may be a key to the dolomite problem, as well as constraining palaeoenvironments such as the Pre‐salt Barra Velha Formation. [ABSTRACT FROM AUTHOR]

Fracture filling minerals and the smectite-group clay minerals in particular play a significant role in the geotechnical stability of the fractured rock mass. Smectites have multiple uses as geomaterials in waste management solutions, of which the most technically demanding is the geological disposal of radioactive waste. Here, the stability and occurrence of smectites as fracture filling minerals were studied with two main objectives: 1) to test the capability of short-wave infrared spectroscopy as a tool to streamline the site assessment where clay mineralogy needs to be characterised in detail, and 2) to provide a first assessment of naturally occurring smectites in various sample types collected from two Finnish sites (Olkiluoto and Hyrkkölä) and their potential as natural analogues of smectite stability for bentonite used in the engineered barrier systems of geological disposal repositories. The short-wave infrared (SWIR) method has been validated to be a useful tool in fracture mineral characterisation, specifically due to its fast acquisition and interpretation time compared to the conventional methods. The study confirms the in situ occurrence of smectites at both sites studied showing that, especially in Hyrkkölä, the smectite-group member is close to montmorillonite, the main constituent of bentonite. At Olkiluoto, the smectites studied show more interstratified features. The differences in the mode of occurrence are related to the history of their formation, especially hydrothermal alteration, and parent rock composition. Highlights: Fracture filling mineral analysis using short-wave infrared spectroscopy for site characterisation is non-destructive providing an efficient method for investigating large sample sets Fast data collection and interpretation from field for rock engineering can indicate presence of swelling minerals that may cause rock collapse Fracture filling smectites, specifically montmorillonites, provide natural analogues for bentonites used in geological disposal facilities for radioactive waste Short-wave infrared spectroscopy methods can partially exceed X-ray diffraction-based smectite identification especially for bentonites (e.g., beidellite vs. montmorillonite) which is important in quality assurance of bentonites used in geological disposal. [ABSTRACT FROM AUTHOR]

Three types of smectite with various crystallochemical compositions and interlayer cations as well as kaolinite and illite were fired at 800°C and 650°C and tested for their rehydroxylation's (RHX) potential and kinetics in the presence of water vapor at 200°C–350°C. A dehydroxylated structure of 2:1 Al‐rich mineral with the interlayer pillared by a large cation (like K+ or Cs+) is wide enough to allow H2O diffusion which results in advanced RHX, that is, restoring up to several tens of percent of the original OH content. Such 2:1 layer structures (beidellite, illite) do not follow the time‐to‐the‐quarter (TTTQ) kinetics during RHX and show a non‐Arrhenius behavior for isothermal RHX. Because TTTQ kinetics is assumed in an RHX dating of ceramic artifacts in archaeometry, fired‐clay ceramics prepared from material dominated by Al‐rich 2:1 minerals was found unfeasible for RHX dating. Kaolinite and Mg2+‐ or Ca2+‐exchanged smectites show the Arrhenius behavior and follow the TTTQ kinetics of RHX, resulting in apparent Ea increase with the progress of reaction (up to α ∼0.2) of ∼20–50 kJ/mol in beidellite and 15–35 kJ/mol in montmorillonite. We suggest using 'hydroxylation' rather than 'rehydroxylation' for structurally‐disordered fired clays gaining OH groups in an unknown position. [ABSTRACT FROM AUTHOR]

The smectite group of clay minerals (smectites) consists of negatively charged clay layers and interlayer exchangeable cations. They are spontaneously delaminated in water to form single clay layers when the interlayer cations are small alkaline cations such as Na+ or Li+. This phenomenon known as osmotic swelling has fundamental importance in constructing novel clay-based nanomaterials. However, osmotic swelling of smectites has not been systematically investigated in organic solvents although this phenomenon should be useful for developing novel clay-organic nanocomposites. We report herein that montmorillonite, a typical smectite, with monovalent and divalent inorganic interlayer cations shows osmotic swelling accompanied by delamination of clay layers in water-acetonitrile and water-2-propanol mixed solvents, although inorganic interlayer cations have been believed to be inappropriate for delamination of smectites in organic solvents. The delamination is confirmed by a combination of macroscopic sample appearances, XRD patterns, and SEM images. Montmorillonite with interlayer Na+ or Li+ ions shows osmotic swelling in pure water and the mixed solvents but not in pure organic solvents. Montmorillonite with alkaline earth dications in the interlayer spaces is swollen in water-organic mixed solvents but not in either pure water or organic solvents alone. Partial delamination in several systems can be clarified from SEM images even though the sample appearances and XRD patterns do not give firm evidence. Such non-uniform swelling behavior of montmorillonite is related to the disordered stacking of the aluminosilicate layers with different morphologies in the clay powders as observed by SEM. [ABSTRACT FROM AUTHOR]

Concentrating simple organic molecules, such as amino acids, in the adsorbed phase could have been an early step in prebiotic evolution towards more complex bio-macromolecules on the early Earth. Smectite clay minerals represent potential selective sorbents for prebiotic molecules because of their negative structural charge and high surface area. This study evaluated the adsorption behavior of amino acids to montmorillonite, a well-characterized smectite, at varying pH and fluid compositions. At both pH 5 and 7 in a sodium chloride fluid, amino acids with basic sidechains (L-arginine and L-lysine), which are primarily cationic under these conditions, were selectively adsorbed to montmorillonite with Langmuir constants much greater than amino acids that were predominantly zwitterionic or anionic in solution. On average, the Langmuir constants for the cationic amino acids were 30 (pH 5) and 50 (pH 7) times greater than the constants for zwitterionic amino acids and 120 (pH 5) and 80 (pH 7) times greater than the constants for L-glutamic acid. Under the same pH conditions in a magnesium chloride solution, the adsorption of L-arginine and L-lysine was substantially inhibited with Langmuir constants ∼ 10 times smaller. These observations suggest that cation exchange is the dominant adsorption mechanism for amino acids on montmorillonite. X-ray diffraction and infrared spectroscopy indicate that L-arginine and L-lysine enter the smectite interlayer where the protonated amino sidechain has the strongest interactions with the mineral surface, further supporting adsorption driven primarily through electrostatic interactions. Therefore, smectites on the early Earth may have selectively concentrated cationic amino acids, providing a potential template for the polymerization of α-amine linked peptides. [ABSTRACT FROM AUTHOR]

The present study investigates the chemical weathering characteristics of an amphibolite enclave within granite from Bundelkhand region, central India. The mineral composition varies from core to rind with depletion of hornblende and plagioclase and enrichment of clay minerals and oxyhydroxides. The chemical index of weathering (CIA) indicates an incipient stage of weathering, within the enclave (CIA = 52.22 – 54.74). A-CN-K (Al2O3-CaO + Na2O-K2O) plot reveal samples plot along the A-CN line, indicating the removal of Ca and Na, due to plagioclase destruction. The weathering trend progresses towards the formation of smectite, a significant component within the clay composition of the enclave. The results of mass balance calculation reveal a substantial mass decrease of approximately 50% to 82% in the amphibolite. Furthermore, major oxides in the amphibolite enclave, experience significant losses. Trace elements display general losses in the enclave. This study provides valuable insights into the complex dynamics of elemental behavior during weathering by shedding light on the processes shaping the geochemical evolution of these rock types and their response to weathering conditions. [ABSTRACT FROM AUTHOR]

Smectites are reactive minerals that are present in surface environments. Most of the smectite dissolution kinetics reported in the literature are related to Al-rich smectites, whereas Fe(III)-rich smectites, which are commonly found in soils, have not been well studied. In this study, the impact of structural Fe(III) in smectites on the dissolution kinetics is determined under acidic conditions. The dissolution kinetics of three pure Fe(III)-rich smectites with different crystal chemistries (Si 7.16 Fe3+ 0.84)(Fe3+ 3.46 Mg 0.54)O 20 (OH) 4 Na 1.38 , (Si 6.86 Fe3+ 1.14)(Fe3+ 4)O 20 (OH) 4 Na 1.14 , and (Si 7.34 Fe3+ 0.66)(Fe3+ 4)O 20 (OH) 4 Na 0.66 are investigated at 25 °C using flow-through experiments at pH values between 1.8 and 5.5. The measured dissolution rates are compared with published rates for Al-rich smectites. The concentrations of dissolved Si, Fe and Mg are measured as a function of time, and the retrieved residual solids are analyzed via infrared spectroscopy and transmission electron microscopy. The steady-state dissolution rates of the synthetic smectites, calculated from the amount of Si release (R Si), decrease with increasing pH. A comparison of the dissolution rates as a function of pH does not allow us to observe major effects of the crystal chemistry among the synthetic smectites, demonstrating the need to develop another approach. However, the dissolution rates calculated for synthetic Fe(III)-rich smectites are systematically greater than those of Al-rich smectites. The measured dissolution rates decrease as the aqueous system approaches equilibrium. Different behaviors are observed for Fe(III)-rich (i.e., > 4 Fe(III)/O 20 (OH) 4) and Al-rich smectites as the R Si = f(ΔG) functions differ, with Fe(III)-rich smectites exhibiting greater instability than Al-rich smectites. Under the most acidic conditions investigated (pH 1.8 and 2), the crystal chemistry and mineralogy of the smectite changed during dissolution, with a relatively greater loss of tetrahedral Fe than of octahedral Fe and the formation of amorphous silica phases. These results show that the amount and location of structural Fe(III) in smectites impact the stability of the minerals. This suggests that the dissolution rate of smectites as a function of the ionic activity product classically used to describe reactive transport should consider the effects of the crystal chemistry, in particular, the amount of structural Fe(III), which is rather high, especially in soil smectites. [ABSTRACT FROM AUTHOR]

The dependence of the ζ-surface potential of synthetic aluminosilicates with a montmorillonite structure of systematically varying Na2x(Al2(1 –x),Mg2x)Si4O10(OH)2·nH2O composition, where 0.1 ≤ x ≤ 0.9, on the chemical composition of the samples and the pH of the environment is studied. The influence of the degree of isomorphic substitution of magnesium atoms by aluminum on the nature of the change of the ζ‑potential is shown. An increase in the degree of isomorphic substitution and an increase in the pH of the medium is accompanied by an increase in the negative charge of the sample surface. The results obtained make it possible to select the optimal compositions of aluminosilicate sorbents for the extraction of differently charged ions from aqueous solutions with different pH values and for use as carriers of drugs. [ABSTRACT FROM AUTHOR]

Using through diffusion method at room temperature, migration of simulants of RW elements (P, Se, Br, Mo, Cs, U) in compacted samples of clay materials of various mineral compositions was studied during porous diffusion from model solutions: underground water and leachates of phosphate waste forms having a total salt content of up to 500 mg/L. Based on the results of experiments, effective diffusion coefficients and sorption distribution coefficients of elements in barrier materials were determined. Numerical models are proposed to describe diffusion transfer of selenium, cesium, and uranium depending on porosity, mineral composition of materials, and concentration of elements in pore solution. Patterns of diffusion of elements from solutions of different salt composition were revealed. [ABSTRACT FROM AUTHOR]

Bottom current activity has been responsible for the formation of a multitude of erosional and depositional features recorded in chalk. Advanced knowledge on the mobility and transport of unlithified calcareous nannofossil ooze by bottom currents is increasingly important not only for understanding the deposition of ancient chalk, but also for modelling the behaviour of modern pelagic carbonate sediments. Whereas the erosional behaviour of very pure calcareous nannofossil ooze has recently been investigated, the effect of organic matter and clay minerals on the erosional behaviour of calcareous nannofossil ooze is as yet unquantified. The results of the present study are based on laboratory flume studies utilizing chalk ooze with varying concentrations of smectite clay (1 to 30 wt.%), two types of organic matter and bed porosity. Phytoplankton (Pavlova lutheri) was used as a proxy for particulate marine organic matter, and xanthan gum as a proxy for extracellular polymeric substances. The results show a significant decrease in nannofossil ooze mobility with increasing content of clay or marine organic matter. Organic matter is found to reduce erodibility at much lower concentrations than clay minerals at porosities equivalent to those of the seafloor. At lower porosities, corresponding to some depth below the seafloor, organic matter and clay minerals are less effective in bed stabilization. This suggests that clay minerals and especially organic matter will affect the likelihood of initiation of severe erosion on the seafloor, whereas their inhibiting effect will decrease as erosion scours progressively deeper into the sediment column. The effect of extracellular polymeric substances is more complex than marine organic matter, probably due to detachment of large aggregates from the bed and resulting increase in bed roughness. The choice of organic matter in sedimentological experiments may lead to significant differences in sediment behaviour and should therefore involve careful consideration. [ABSTRACT FROM AUTHOR]

Clays are layered materials with several unique features, which lead to many useful applications for natural products. In particular, raw clay has been increasingly utilized in skin care products and major advances have been achieved in the research and innovation related to these materials. This scientific manuscript addresses topical applications that include the development of O/W emulsions containing two types of raw clay such as kaolinite and sodium smectite associated with ascorbyl glucoside. The topical formulations were submitted to in vitro assays such as release, permeability using human cadaver skin as well as a skin retention study. The results of the release study showed that ascorbyl glucoside was delivered by the five formulations of this study. However, the skin permeation study of ascorbil glucoside showed that the formulation with smectite clay had a higher permeation and retention of AA2G in the skin layers suggesting that the smectitic clay (W4) acts as a promising permeation enhancer for this cosmetic active. Additionally, no cytotoxicity was detected in HaCaT and HDF cell lines, highlighting the safe character of the formulations, at least at short-term. [ABSTRACT FROM AUTHOR]

In contrast to the western part of the Lower Silesia, information about the basalt-derived weathering crusts occurring in the Opole region is rather limited. However, in 2018, significant volumes of such regolith (about 20,000 m3) were discovered during development works in the NW part of the Rutki Quarry near Niemodlin. This weathering crust is rich in clay minerals and represents a smectite-kaolinite mixture with some halloysite, the latter being a poorly ordered member of the kaolinite group. The minerals of the smectite group contain in their interlayer spaces bivalent cations (calcium and magnesium), which is the most often case in the nature. The mineral composition of the regolith mass is supplemented by iron-containing phases, i.e. goethite and magnetite, and traces of phosphate mineral - crandallite. A significant amount of clay minerals, particularly those belonging to the smectite group and halloysite, results in high value of the specific surface area (up to 100 m2/g) of the studied crust. Such favorable property of the crust makes it a promising sorptive raw material that can be applied, even in an unprocessed form, for waterproofing. It must be emphasized that the sorption properties of basalt weathering crusts were noticed some centuries ago in the western part of Lower Silesia, where medicine called terra sigillata was produced from them. Moreover, the crust from Rutki was also used in the XIXth century, in a ceramic manufacture located in nearby Tułowice, where the so-called "Silesian black porcelain" was produced. [ABSTRACT FROM AUTHOR]

Clay minerals have a great influence on the resulting properties of ceramic bodies. Fly ash as a waste material from burning black coal in power plants is a potentially valuable source of oxides (Al2O3, SiO2 or Fe2O3) for this production. Considering the process of ceramic firing, it is important to understand the thermal behavior of individual ingredients. The thermal behavior of natural smectite minerals (montmorillonite, beidellite, hectorite and nontronite) and their mixtures with added fly ash at different ratios (10%, 30% and 50%) was investigated. The phase analysis was obtained using X-ray diffraction and FT-IR spectroscopy. Under heating to 1200 °C, the structural changes of smectites were divided into four steps including dehydration, dehydroxylation, decomposition and crystallization of new phases. The addition of fly ash caused a shift in the reaction temperatures for all the mentioned phases. These changes were most noticeable for mixtures with hectorite; on the contrary, they were least noticeable for beidellite mixtures. Total mixture mass loss continually decreased with increasing fly ash amount. The obtained experimental thermal data can be applicable not only in the production of ceramic bodies or energy waste processing but also in construction and ensuring the safety of municipal waste landfills. [ABSTRACT FROM AUTHOR]

In this paper, the mechanisms of long‐term CO2 sequestration and the effects of injection modes (including injection temperature, injection rate and injection cycle) in Zhujiang Formation characterized by high porosity and permeability were investigated using the numerical simulation method. Simulation results showed that more than 88% of the injected CO2 would exist in a supercritical state during the injection period and more than 79% of CO2 would be sequestrated in the reservoir by mineral trapping after 5,000 years. Eventually, the distribution shape of SC‐CO2 was a quarter funnel near the injection well, while the distribution shapes of dissolved and mineralized CO2 were both one quarter rotunda. During the long‐term CO2 sequestration in Zhujiang Formation, the dissolved minerals were anorthite, chlorite and smectite in turn, while the top three main precipitated minerals were calcite, dawsonite and albite. Moreover, higher injection temperature leads to a higher mineral tapping and more dissolved/precipitated minerals. While higher injection rate reduces the mineral tapping and total amount of dissolved/precipitated mineral. Compared to injection temperature and injection rate, the injection cycle has little effect on the CO2 phase evolution and mineral dissolution/precipitation process. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Sedimentary rock–hosted stratiform copper deposits are the world's second largest source of copper and the largest source of cobalt, with about 73% of the copper occurring in two basins: the Katangan Basin (Central African Copperbelt) and the Permian Basin (Kupferschiefer). Why these two sedimentary basins are so highly endowed in copper is puzzling because sedimentary rock–hosted stratiform copper deposits have formed since the Paleoproterozoic and they all share remarkably similar ore mineralogy, host-rock characteristics and basin settings. We suggest that this discrepancy is due to the development of these two basins close to the bases of ~ 8000-km-long supermountain belts. The supermountain belts were instrumental in raising oxygen levels in Earth's atmosphere, as well as providing a voluminous source of groundwater and a powerful and long-lived driver for the fluid-flow system. The elevated oxygen levels facilitated the diagenetic processes that converted copper-bearing labile minerals to amorphous iron-oxides and smectite and then in turn to hematite and illite. When oxidized brines flushed through the basin successions, the liberated copper was transported to units containing carbon-rich mudstone and the metals were deposited. For the Katangan Basin, development of the Transgondwanan supermountain belt along its margins between about 525 and 510 Ma explains the delay of several hundreds of millions of years between basin formation and mineralization in the Central African Copperbelt. In contrast, development of the Mid-Pangean supermountain belt formed penecontemporaneous with the Permian Basin explains the similarity in timing between basin formation and mineralization in the Kupferschiefer. [ABSTRACT FROM AUTHOR]

The emergent secondary phases and surface altered layer (SAL) during the aqueous corrosion of borosilicate glass have a great impact on its chemical durability. However, the formation and evolution of these structures are still unclear. Here, by studying the borosilicate glass altered at 90 °C in pore water, the water in pore space between glass powders, the formation of secondary phases could follow two ways: 1. the consumption of aqueous ions forms analcime, zeolite, calcium silicate and barite at the surface of glass; 2. the reorganization of silica aggregates leads to smectite within the SAL. Small-angle X-ray scattering and cross-sectional scanning electron microscopy results show that the release of soluble elements and the formation of smectite within the SAL significantly increase the porosity of SAL. Furthermore, the layer containing smectite reorganizes inwardly and the crystallinity of smectite is gradually increased over time. The observations of transmission electron microscopy reveal that the dissolution of glass potentially goes through an interface-coupled dissolution-reprecipitation process. [ABSTRACT FROM AUTHOR]

Due to various historical events, in the Russian Federation, in addition to the radioactive waste storage facilities used in world practice, there are various nuclear and radiation hazardous facilities that require special procedures for monitoring and decommissioning. One of these facilities is the disposal site for LRW on the territory of the JSC Siberian Chemical Plant, where specially prepared waste is injected into sand reservoirs lying at depths of 300–350 m between clayey strata. This study examines in detail the features of the lithological and mineral composition of reservoir sands and aquitards. The processes of environmental transformation in reservoir sands, which lead to changes in the composition and structure of rocks, were characterized. These processes manifest themselves in the form of the development of leaching zones and their "healing" with newly formed smectite, the destruction of terrigenous grains, including the development of cracks, and the growth of newly formed smectite in the pore space of reservoirs. The forms of occurrence and localization of authigenic smectite formed as a result of technogenic impact are described. It has been shown that, despite the obvious impact of highly reactive solutions accompanying liquid radioactive waste, the insulating properties of the geological environment are maintained and even improved to some extent. [ABSTRACT FROM AUTHOR]

Montmorillonite (Mnt), belonging to the smectite group and representing a 2:1-type clay mineral with good cation-exchange and swelling capacities, is a common clay component of soils. It was observed that some Mnt preparations exhibit peroxidase-like (P-L) activity using N,N-diethyl-p-phenylenediamine sulfate salt as a substrate. Both native (non-swelling) and swelling Mnt exhibited similar P-L activity. Modification of Mnt with copper and iron influenced both P-L activity and phenol polymerization. Both free and textile-bound Cu-Mnt (Sigma-Aldrich) enabled phenol removal. Soil Mnt P-L activity is probably involved in lignin breakdown and decontamination of soils polluted with phenol-containing molecules. [ABSTRACT FROM AUTHOR]

The purpose of this study was to determine the mineral-associated organic carbon (MOC) and its relationship to clay minerals under different temperatures and precipitation. We selected three typical grassland transects in China: Titanium Plate (TP), Mongolian Plate (MP), and Loess Plate (LP) with natural temperature gradients. Along the transect, there is a gradient in the precipitation between the various types of grasslands. The surface soil (0–10 cm) was sampled to determine the MOC. Clay minerals were charactered by X-ray diffraction (XRD). According to the findings, the MOC content increased with decreasing temperature (5.41–14.89 g/kg). MOC had a positive correlation (r = 0.67) with the amount of clay mineral content. In the large-scale study of transects, precipitation masks the effect of temperature change on the MOC to a certain extent. It indirectly affected the MOC content by affecting the mixed-layer illite/smectite (I/Sme) content, and this effect was strongest at the lowest temperature TP (r = −0.73). Except for precipitation, CaO in the soil can affect soil organic carbon (SOC) stability by influencing the pH and I/Sme. The amount of bacteria increased as a result of I/Sme, and the influence of bacteria on the MOC was surpassed only by the soil pH. Climate and clay mineral composition characteristics affected the MOC to a certain extent. Among them, the effect of precipitation change on the MOC is higher than temperature, but it has little effect on soil with a higher weathering degree and CaO content. [ABSTRACT FROM AUTHOR]

This work combines experimental and computational modeling studies for the preparation of a composite of metformin and an organoclay, examining the advantages of a Tunisian clay used for drug delivery applications. The clay mineral studied is a montmorillonite-like smectite (Sm-Na), and the organoclay derivative (HDTMA-Sm) was used as a drug carrier for metformin hydrochloride (MET). In order to assess the MET loading into the clays, these materials were characterized by means of cation exchange capacity assessment, specific surface area measurement, and with the techniques of X-ray diffraction (XRD), differential scanning calorimetry, X-ray fluorescence spectroscopy, and Fourier-transformed infrared spectroscopy. Computational molecular modeling studies showed the surface adsorption process, identifying the clay–drug interactions through hydrogen bonds, and assessing electrostatic interactions for the hybrid MET/Sm-Na and hydrophobic interactions and cation exchange for the hybrid MET/HDTMA-Sm. The results show that the clays (Sm-Na and HDTMA-Sm) are capable of adsorbing MET, reaching a maximum load of 12.42 and 21.97 %, respectively. The adsorption isotherms were fitted by the Freundlich model, indicating heterogeneous adsorption of the studied adsorbate–adsorbent system, and they followed pseudo-second-order kinetics. The calculations of ΔGº indicate the spontaneous and reversible nature of the adsorption. The calculation of ΔH° indicates physical adsorption for the purified clay (Sm-Na) and chemical adsorption for the modified clay (HDTMA-Sm). The release of intercalated MET was studied in media simulating gastric and intestinal fluids, revealing that the purified clay (Sm-Na) and the modified organoclay (HDTMA-Sm) can be used as carriers in controlled drug delivery in future clinical applications. The molecular modeling studies confirmed the experimental phenomena, showing that the main adsorption mechanism is the cation exchange process between proton and MET cations into the interlayer space.

This article examines the clay mineralogy of twelve representative soils developed from gypsum-rich parent materials on several geomorphic positions. These soils were classified as Haploxerept, plus one profile as Humixerept and another as Xerorthent. The clay mineralogy, determined by X-ray diffraction, showed quite a similar clay composition in all profiles, with mica, chlorite, and smectite, from most to less abundant. Mica and chlorite are deemed inherited, while smectite—appearing in minor proportions—could result from both transformation and/or neoformation, because the leaching of bases by free drainage does not favor the transformation of mica to smectite. Therefore, the differences in clay mineralogy appeared to be lithogenic rather than pedogenic. These compositional data are an advance in the basic knowledge of the studied soils.

The release of Neogene volcanism in the southeastern part of the Iberian Peninsula produced a series of volcanic structures in the form of stratovolcanoes and calderas; however, other materials also accumulated such as large amounts of pyroclastic materials such as cinerites, ashes, and lapilli, which were later altered to form deposits of zeolites and bentonites. This work has focused on an area located on the northern flank of the San José-Los Escullos zeolite deposit, the only one of its kind with industrial capacity in Spain. The main objective of this research is to characterize the zeolite (SZ) of this new area from the mineral, chemical, and technical points of view and establish its possible use as a natural pozzolan. In the first stage, a study of the mineralogical and chemical composition of the selected samples was carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray fluorescence (XRF), and thermogravimetric analysis (TGA); in the second stage, chemical-qualitative and pozzolanicity technical tests were carried out at 8 and 15 days. In addition, a chemical analysis was performed using XRF on the specimens of mortars made with a standardized mixture of Portland cement (PC: 75%) and natural zeolite (SZ: 25%) at the ages of 7, 28, and 90 days. The results of the mineralogical analyses indicated that the samples are made up mainly of mordenite and subordinately by smectite, plagioclase, quartz, halloysite, illite, and muscovite. Qualitative chemical assays indicated a high percentage of reactive silica and reactive CaO and also negligible contents of insoluble residues. The results of the pozzolanicity test indicate that all the samples analyzed behave like natural pozzolans of good quality, increasing their pozzolanic reactivity from 8 to 15 days of testing. Chemical analyses of PC/SZ composite mortar specimens showed how a significant part of SiO2 and Al2O3 are released by zeolite while it absorbs a large part of the SO3 contained in the cement. The results presented in this research could be of great practical and scientific importance as they indicate the continuation of zeolitic mineralization beyond the limits of the San José-Los Escullos deposit, which would result in an increase in geological reserves and the extension of the useful life of the deposit, which is of vital importance to the local mining industry.

Introduction: There is growing evidence from animal and clinical studies suggesting probiotics can positively affect type 2 diabetes (T2D). In a previous randomized clinical study, we found that administering a live multistrain probiotic and absorbent smectite once a day for eight weeks to patients with T2D could reduce chronic systemic inflammatory state, insulin resistance, waist circumference and improve the glycemic profile. However, there is a lack of evidence supporting the efficacy of probiotic co-supplementation with absorbent smectite on pancreatic b-cell function in T2D. Aim: This secondary analysis aimed to assess the effectiveness of an alive multistrain probiotic co-supplementation with absorbent smectite vs placebo on b-cell function in T2D patients. Material and Methods: We performed a secondary analysis on a previously published randomized controlled trial (NCT04293731, NCT03614039) involving 46 patients with T2D. The main inclusion criteria were the presence of b-cell dysfunction (%B<60%) and insulin therapy alone or combined with oral antidiabetic drugs. The primary outcome was assessing b-cell function as change Cpeptide and %B. Results: We observed only a tendency for improving b-cell function (44.22 ± 12.80 vs 55.69 ± 25.75; p=0.094). The effectiveness of the therapy probioticsmectite group was confirmed by fasting glycemia decreased by 14% (p=0.019), HbA1c - 5% (p=0.007), HOMA-2 - 17% (p=0.003) and increase of insulin sensitivity by 23% (p=0.005). Analysis of the cytokine profile showed that statistical differences after treatment were in the concentration of both proinflammatory cytokines: IL-1b (22.83 ± 9.04 vs 19.03 ± 5.57; p=0.045) and TNF-a (31.25 ± 11.32 vs 26.23 ± 10.13; p=0.041). Conclusion: Adding a live multistrain probiotic and absorbent smectite supplement slightly improved b-cell function and reduced glycemic-related parameters in patients with T2D. This suggests that adjusting the gut microbiota could be a promising treatment for diabetes and warrants further investigation through more extensive studies. [ABSTRACT FROM AUTHOR]

A novel and cost-effective heterogeneous catalyst for glycerol carbonate production through transesterification was developed by impregnating smectite clay with K2CO3. Comprehensive structural and chemical analyses, including X-ray diffraction Analysis (XRD), Scanning Electron Microscopy (SEM)-Electron Dispersion Spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) surface area analysis measurements, were employed to characterize the catalysts. Among the various catalysts prepared, the one impregnated with 40 wt% K2CO3 on smectite and calcined at 550 °C exhibited the highest catalytic activity, primarily due to its superior basicity. To enhance the efficiency of the transesterification process, several reaction parameters were optimized, including the molar ratio between propylene carbonate and glycerol reactor loading of the catalyst and reaction temperature. The highest glycerol carbonate conversion rate, approximately 77.13% ± 1.2%, was achieved using the best catalyst under the following optimal conditions: 2 wt% reactor loading, 110 °C reaction temperature, 2:1 propylene carbonate to glycerol molar ratio, and 6h reaction duration. Furthermore, both the raw clay and the best calcined K2CO3-impregnated catalysts demonstrated remarkable stability, maintaining their high activity for up to four consecutive reaction cycles. Finally, a kinetic analysis was performed using kinetic data from several runs employing raw clay and the most active K2CO3-modified clay at different temperatures, observing that a simple reversible second-order potential kinetic model of the quasi-homogeneous type fits perfectly to such data in diverse temperature ranges. [ABSTRACT FROM AUTHOR]

Clay-hosted rare earth element (REE) deposits, generally considered products of extended subtropical weathering of REE-rich igneous protoliths, are a critical source of REEs globally. The Koppamurra deposit of southeast South Australia, in contrast, is developed in Pleistocene lacustrine clays overlying a REE-poor marine limestone. Here we examine the REE + Y (REY) sources and enrichment mechanisms of this unusual setting. We find that the greatest REY enrichment (up to 5000 ppm) occurs in lacustrine clays at the base of a ∼1–2 m thick contact zone with the underlying limestone. This zone features an increased proportion of leachable REYs (>50 %), increased smectite abundance and a sharp increase in pH from ∼5.0 to ∼8.3. Co-variation of HREEs with a suite of clay-specific elements demonstrates that HREEs are hosted mainly by Fe-rich smectite, with separate sorbed vs structurally bound HREE pools that are of similar magnitude. LREEs are mainly hosted in secondary LREE carbonates, these are preferentially intergrown with smectite but are only rarely present in kaolinite domains. Cerium occurs mainly as cerianite. The narrow range and overlapping εNd of samples within and above the REY enriched zone suggests that enrichment is related to internal redistribution within the clay unit. The clays are isotopically incompatible with local igneous or metasedimentary rocks, but 87Sr/86Sr and εNd isotopic fingerprinting shows that they were deposited by the Murray River, Australia's largest river system. Murray sediments are enriched in REY due to the presence of material eroded from the Lachlan Orogen granites of southeast Australia. Deposition of these sediments occurred in a coastal lacustrine setting analogous to the modern-day Coorong, with tectonic uplift and shoreline progradation allowing the onset of subaerial weathering ∼1–2 Mya. We propose that vertical and lateral solute transport allowed for the concentration of REEs in local depressions in the karst-weathering surface which separates the limestone and overlying clay, facilitated by water table oscillation and pore water redox cycling driven by seasonally contrasted rainfall. Poor soil drainage, evaporative concentration of soil waters and alkaline pH adjacent to the limestone immobilized REEs in secondary carbonates and Fe-rich smectite. Our findings illustrate that REE mobilization and enrichment in clay deposits can occur more rapidly, over a larger area and in a broader range of host phases and geologic settings than is currently appreciated, with important implications not only for REE exploration but also for the use of REEs as tracers in the Earth Sciences. [ABSTRACT FROM AUTHOR]