The increasing pollution of water bodies by tetracycline (TC) has emerged as a looming threat to both environmental sustainability and human health, and the development of novel and effective remediation techniques is essential. The purpose of the present research was to explore the potential of montmorillonite (Mnt) and ZnO/Mnt composites as cost-effective and eco-friendly adsorbents for the removal of TC from polluted water sources. Batch adsorption experiments were carried out under controlled laboratory conditions, where adsorption isotherms, kinetic studies, and zero-charge point (pHzcp) determinations were performed systematically to evaluate the performance of ZnO, Mnt, and ZnO/Mnt composites. The results highlighted the underlying importance of surface charge to adsorption by establishing pHzcp for ZnO, Mnt, and the ZnO/Mnt composite. The effects of pH on the surface charge of adsorbents (ZnO, Mnt, and the ZnO/Mnt) and the equilibrium structure of TC were measured systematically and trends that are imperative for understanding the dynamics of adsorption were identified. The removal efficiencies of TC at the optimal pH of 5 were 100% for Mnt, 70% for ZnO/Mnt, and 4% for ZnO. Mnt exhibited the greatest adsorption capacity (125 mg g–1), particularly effective within the pH range of 3–7, demonstrating its strong potential for pollutant removal. However, the ZnO/Mnt composite, although showing a lower adsorption capacity (72 mg g–1), offers additional advantages due to the photocatalytic properties of ZnO. Under light irradiation, ZnO promotes the mineralization of adsorbed TC into harmless products such as CO₂ and H₂O, thereby reducing the risk of secondary pollution. While Mnt alone efficiently captures TC, the lack of degradation may pose environmental challenges. By integrating adsorption with photocatalysis, the ZnO/Mnt composite provides a more sustainable, dual-functional approach, highlighting the significance of coupling pollutant capture with degradation for effective and eco-friendly water treatment.

The present study addressed the influence of lithological variability on hydrothermal alteration processes in the Çubuk region of Ankara, recognized globally for its agate occurrences. The objective was to clarify how differing host rocks, tuff and ignimbrite in Karadana, and perlitic units in Yukarıemirler, affect secondary mineral formation and alteration pathways. A combination of mineralogical (X-ray diffraction, Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy) and geochemical (energy-dispersive X-ray spectroscopy, whole-rock geochemistry, δ18O–δD) methods was utilized to characterize alteration assemblages and fluid conditions. The alteration sequence progressed through five stages, beginning with unaltered volcanic rocks. In the second stage, smectite-group clays, particularly montmorillonite, were formed under mildly alkaline and low-temperature conditions (pH 7.5–9.0; T 43–50°C). This initial clay formation was followed by zeolitization along two distinct pathways: clinoptilolite crystallized (K-rich, Si/Al ~4.2) in the Karadana tuff–ignimbrite units, while heulandite formed (Ca-rich, Si/Al ~2.7) in the perlitic host rocks of Yukarıemirler. These variations are attributed to differences in host-rock composition, permeability, and hydrothermal fluid chemistry. In more advanced stages, mordenite and chabazite precipitated under progressively higher pH and temperature conditions (pH 9.5–10.0; T 70–80°C). In the final stage, opal–quartz formed due to silica supersaturation triggered by a drop in pH, despite rising temperatures (pH ~8.5–9.0; T ~250°C). The paragenetic sequence confirms that clay mineral formation preceded zeolitization in both zones. Variations in zeolite types reflect strong lithological and hydrochemical controls, as well as the origin of the hydrothermal fluids; clinoptilolite formation in Karadana is associated with Na- and K-rich supergene fluids, while Ca-rich hypogene fluids promoted heulandite precipitation in Yukarıemirler. This study presents the first detailed paragenetic model for zeolite–clay alteration in the Çubuk volcanic system and offers new insights into post-caldera hydrothermal evolution in Central Anatolia.

This study investigates the influence of interlayer cations on the thermodynamics and sorption mechanisms of water in a reference Wyoming montmorillonite. The behaviour of the montmorillonite exchanged with monovalent cations (Li+, Na+, K+, Rb+, Cs+) or divalent cations (Mg2+, Ca2+, Ba2+) is compared. The analysis combines X-ray diffraction (XRD), water sorption isotherms at various temperatures and mid-infrared spectroscopy. Li+, Mg2+ and Ca2+ promote greater water uptake and swelling, whereas K+, Rb+ and Cs+ significantly limit these processes. The behaviour of Na+ and Ba2+ stands out, demonstrating intermediate water uptake and high swelling. Mid-infrared spectral analysis supports these observations. It is shown that a cation’s effect on water uptake and swelling correlates best with the product of its elementary charge and ionic radius rather than with other properties such as the electrostatic potential, solvation enthalpy or chemical hardness. However, differences in isotherm shapes, hysteresis between adsorption and desorption and the variation of isosteric heat with water content suggest the presence of two distinct sorption mechanisms: one involving Li+, Cs+, Mg2+, Ca2+ and Ba2+, and another involving Na+, K+ and Rb+. These findings indicate that isotherm shape and swelling alone do not directly reflect water uptake capacity. These findings thus outline that the chaotropic (structure-breaking) or kosmotropic (structure-making) nature of the cations, along with the complex interplay between cation hydration and TOT layer attraction, may explain the complex observed differences.

Laterite could play a crucial role in soil stabilization and environmental remediation, but its internal particle interaction mechanism remains unclear. This study, based on molecular dynamics simulations, used umbrella sampling methods to measure the interaction strength between amorphous alumina and montmorillonite particles in laterite. The mechanisms were explored using differential charge density analysis and bond energy analysis. The results show that the interaction process between alumina and montmorillonite exhibited initial repulsion, then attraction, followed again by repulsion. Calcium ion-induced polarization, the negative charge on the alumina surface and the bonding strength during adsorption played key roles in this interaction. Notably, the bond energy measurement results in this study are consistent with data from other related research, validating the data’s accuracy. These findings improve our understanding of the microscopic mechanisms of laterite particle interactions, providing a scientific basis for its application in soil stabilization and environmental remediation.

Carbon black is commonly used as a filler in the rubber industry. However, it can cause serious damage to human health and to ecosystems. Today, reducing the use of this substance via alternative materials is receiving increased attention. Clay minerals such as montmorillonite can be substituted for carbon black as environmentally friendly fillers for rubber compounds. The uniform dispersion of montmorillonite and its compatibility with the rubber matrix are the main principles for using this material in the rubber industry. To this end, montmorillonite was surface treated with various dosages (1.0, 1.5 and 2.0 wt.%) of polypropylene glycol. The surface-treated montmorillonites were investigated using attenuated total reflection Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and X-ray diffraction analysis. The results indicated that the treatment expanded the interlayer spaces of the montmorillonite and improved surface hydrophobicity. The untreated and treated montmorillonites were used with carbon black as dual fillers in natural rubber/styrene butadiene-based compounds. The cure characteristics, thermal stability, some mechanical properties and dispersion states were evaluated. The curing study indicated a faster optimum cure time, scorch time and increased torque difference for the rubber compounds filled with surface-treated montmorillonites. Thermal analysis of the rubber compounds illustrated that the interval between the initial and final temperature of decomposition could be increased via the treatment. Surface-treated montmorillonite samples, especially the sample containing 1 wt.% polypropylene glycol, showed improved abrasion resistance, resilience and compression set values.

Paraquat, one of the most widely utilized herbicides globally, causes a significant environmental challenge due to its poor degradation rate and tendency to adsorb into clay interlayers. Several remediation methods have been proposed but their effectiveness remains suboptimal. The primary reason for this is the lack of microscopic understanding of paraquat–montmorillonite interactions. In this work molecular dynamics simulations were applied to study the interlayer structures and mobility of paraquat intercalated montmorillonite. Two stable hydration states were identified from the calculated immersion energy curve, which corresponded to a water content of 185 mgwater/gclay and 278 mgwater/gclay (the most stable). Paraquats remained in direct contact with the clay surface in both the anhydrous and hydrated states. At the water content of 185 mgwater/gclay, paraquats formed π-π stacking while at 278 mgwater/gclay, they were separated by a layer of water. Paraquat showed very small self-diffusion coefficients in the interlayer space of montmorillonite, indicating rather limited motions. The results in this work provide a basis for a better understanding of the interaction of paraquat with clay minerals.

Conceptual models of smectite hydration include planar (flat) clay layers that undergo stepwise expansion as successive monolayers of water molecules fill the interlayer regions. However, X-ray diffraction (XRD) studies indicate the presence of interstratified hydration states, suggesting non-uniform interlayer hydration in smectites. Additionally, recent theoretical studies have shown that clay layers can adopt bent configurations over nanometer-scale lateral dimensions with minimal effect on mechanical properties. Therefore, in this study we used molecular simulations to evaluate structural properties and water adsorption isotherms for montmorillonite models composed of bent clay layers in mixed hydration states. Results are compared with models consisting of planar clay layers with interstratified hydration states (e.g. 1W–2W). The small degree of bending in these models (up to 1.5 Å of vertical displacement over a 1.3 nm lateral dimension) had little or no effect on bond lengths and angle distributions within the clay layers. Except for models that included dry states, porosities and simulated water adsorption isotherms were nearly identical for bent or flat clay layers with the same averaged layer spacing. Similar agreement was seen with Na- and Ca-exchanged clays. While the small bent models did not retain their configurations during unconstrained molecular dynamics simulation with flexible clay layers, we show that bent structures are stable at much larger length scales by simulating a 41.6×7.1 nm2 system that included dehydrated and hydrated regions in the same interlayer.

Compacted bentonite, used as an engineering barrier for permanent containment of high-level radioactive waste, is susceptible to mineral evolution resulting in compromise of the expected barrier performance due to alkaline–thermal chemical interaction in the near-field. To elucidate the mineral-evolution mechanisms within bentonite and the transformation of the nuclide adsorption properties during that period, experimental evolution of bentonite was conducted in a NaOH solution with a pH of 14 at temperatures ranging from 60 to 120°C. The results showed that temperature significantly affects the stability of minerals in bentonite under alkali conditions. The dissolution rate of fine-grained cristobalite in bentonite exceeds that of smectite, with the phase-transition products of smectite being temperature-dependent. As the temperature rises, smectite experiences a three-stage transformation: initially, at 60°C, the lattice structure thins due to the collapse of the octahedral sheets; at 80°C, the lattice disintegrates and reorganizes into a loose framework akin to albite; and by 100°C, it further reorganizes into a denser framework resembling analcime. The adsorption properties of bentonite exhibit a peak inflection point at 80°C, where the dissolution of the smectite lattice eliminates interlayer pores and exposes numerous polar or negatively charged sites which results in a decrease in specific surface area and an increase in cation exchange capacity and adsorption capacity of Eu3+. This research provides insights into the intricate evolution of bentonite minerals and the associated changes in radionuclide adsorption capacity, contributing to a better understanding of the stability of bentonite barriers and the effective long-term containment of nuclear waste.

Nano-silicon has been regarded as the most promising anode material for next-generation lithium-ion batteries (LIBs). However, the preparation of nano-silicon suffers from high cost, complex procedures, and low yield, which hinders its commercial application. In this study, porous nano-silicon with particle sizes in the range of 50–100 nm was prepared through molten salt-assisted magnesiothermic reduction using porous nano-silica derived from clay minerals as the precursor. Through combining ball milling and acid activation, the synthesised nano-silica derived from montmorillonite exhibited smaller particle sizes (below 50 nm), higher specific surface area (647 m2 g–1), and total pore volume (0.71 cm3 g–1). This unique structure greatly facilitated the conversion efficiency of silica into nano-silicon by maximising the contact area between silica and magnesium powder and optimising the diffusion kinetics of magnesium atoms. When used as anodes in LIBs, the synthesised nano-silicon materials demonstrated a high specific capacity of up to 1222 mAh g–1 and an excellent capacity retention rate of 79% after 150 cycles at a current density of 0.5 A g–1. This method provides a novel approach for the cost-effective and large-scale production of nano-silicon materials for high-performance anodes.

Amino acids have been detected in some meteorites and are readily synthesized in prebiotic experiments. These molecules may have been precursors of oligomers and polymers in the early Earth. These reactions were likely to happen in the protected confined spaces on the porous surface of olivine and in the interlayer nanospace of montmorillonite. This study describes experimental and theoretical research on the sorption of l-alanine onto surfaces of silicate minerals, olivine and montmorillonite. Kinetics of the sorption of this amino acid at different pH media was performed. This sorption has been also studied at atomic scale by means of quantum mechanical calculations finding that this sorption is energetically favourable. These results strongly support the premise that minerals could have actively participated in prebiotic reactions.

The adsorption of acetamide and partly hydrolyzed Polyacrylamides onto montmorillonite has been investigated with emphasis on the valency of the exchangeable cation of the clay and the ionic strength of the medium. A difference in the adsorption of acetamide from 3 mg/g to 0.6 mg/g was observed when a Na+-clay was changed to a Al3+-clay. For Polyacrylamide, an opposite effect was observed, and the fixation increased from 3 mg/g (Na+-clay) to 18 mg/g (Al3+-clay). This difference in behavior may be accounted for by the decrease in adsorption sites due to partial flocculation in the presence of polyvalent cations (tactoid formation). Adsorption in a saline medium is two- to fivefold greater for diverse polymers and substantially less for acetamide (from 3.0 mg/g to 0.77 mg/g). An increase in the degree of hydrolysis of the polymer results in a significant increase in adsorption. In contrast, a change of molecular weight has practically no influence upon the adsorption ratio. The results obtained in saline medium may be explained by a size decrease of the macromolecules, allowing a closer approach to the surface of the mineral substrate, and by a chain lengthening as the degree of hydrolysis increases, induced by the electrostatic repulsions between the COO− groups.

Cation-exchange capacities determined by methylene blue adsorption (CEC MB) and by the amount of K displaced from a K-saturated clay by NH4 (CEC K//NH4) correlate closely in five soil clays from Pennsylvania, but differ greatly in two soil clays with a large content of amorphous material. CEC MB was found to provide a more precise distinction between montmorillonite and vermiculite than CEC K//NH4. Synthetic aluminosilicate gels showed CEC K//NH4 > CEC Ca/Mg > CEC MB, but no relation to the behavior of the two soil clays with a large content of amorphous material was found.

Organic matter present in clayey sediments may act as a cement between the clay particles as well as a blocking agent for the swelling of clay minerals like montmorillonite.

Removal of the organic matter is important when a clay sample is to be characterized by X-ray powder diffraction, or when it is to be separated into the composing minerals on the basis of differences in density.

Eight different methods for the removal of organic matter from a North Sea clay sample have been studied. Of all methods tried bromine oxidation was found to be the most effective.

Hydroxy-Al- and hydroxy-Mg-montmorillonite were prepared by treating dispersed Na-montmorillonite with aluminum and magnesium nitrate solutions and titrating with NaOH solutions so that the OH/Al ratio varied from zero to 3.0 and the OH/Mg ratio from zero to 2.0. External precipitation of Al and Mg hydroxides was observed when the OH/M ratios (M = metal) approached 3 and 2, respectively. From chemical analyses of the initial Na-montmorillonite and the hydroxy-metal montmorillonites, structural formulae were derived by assuming that the silicate layer compositions remained unchanged. Prior to the addition of NaOH, the average interlayer material approximated in composition to [Al(OH)2]+ and [Mg(OH)]+. With additions of NaOH the interlayer compositions moved progressively towards Al(OH)3 and Mg(OH)2. When the hydroxy interlayers approached completion, external precipitation was observed. X-ray powder diffraction data showed that the hydroxy-Mg products have less tendency to swell in ethylene glycol and water, and greater thermal stability than the hydroxy-Al products. Initially, when the average interlayer compositions were near Al(OH)2 and Mg(OH), swelling followed more nearly the normal behavior.

Adsorption of Co2+ and Cd2+ on Wyoming montmorillonite was studied by the batch equilibration technique, as a function of salt concentration (0.01–4 M NaCl and NaNO3), pH (5.0–6.5), adsorbate concentration (trace-10−2 moles/liter), and presence of complexing ions. Comparison was made with the adsorbability of Sr2+, known to follow simple ion-exchange equations. The distribution coefficients for Co and Cd in noncomplexing media varied with salt concentration (from ∼500 liters/kg in 0.01 M Na+ to ∼10 liters/kg in 1 M Na+; pH = 5), but to a lesser extent than that of Sr. Adsorbability varied also with pH (∼1 order of magnitude/pH unit), especially at high ionic strength, compared to a negligible pH effect on Sr. The distribution coefficients of Cd and Co decreased with increasing loading on the clay at a very low percentage (0.2%) of the ion-exchange capacity compared to Sr (20%). These data suggest two classes of sites participating in the adsorption of Cd and Co.

The adsorbability of Cd in highly concentrated chloride solution (>1 M) was less than 1 liter/kg, presumably because of the chloride complex formation. This effect increased with increasing pH. The low adsorbability of Cd on montmorillonite from concentrated NaCl solution is promising with respect to its use as a tracer for monitoring flow through formations containing montmorillonite.

The charge density distribution among different classes of a series of reduced charge mont-morillonites is heterogeneous as in the parent Camp Berteau clay. In addition, charge reduction proceeds inhomogeneously. Up to 20% differences in charge density can be accounted for by aikyl chains extending at the edges of the clay particle. A realistic charge density-cation-exchange capacity relationship for hec-torite, Otay montmorillonite, and a series of reduced charge montmorillonites of Camp Berteau is obtained by accounting for the influence of particle radius and for the extent of alkyl chains lying outside the clay layers in the charge density calculations.

Acidified suspensions of Al-saturated kaolinite, montmorillonite, mica, illite, and biotite in 10−3 M NaNO3 were potentiometrically titrated with 0.1 N NaOH and 0.1 N HNO3 in succession in a CO2-free nitrogen atmosphere. The resulting curves were compared with those for Al(NO3)3 solutions of similar Al concentration in the supernatant solution and corrected for Al in the entrained solution in the clay.

Base titrations of Al ions adsorbed on all the minerals, except montmorillonite, showed two pH inflections separated by a buffering range. With montmorillonite, there were three pH inflections similar to those for Al in solution. The first inflections in the titration of suspensions occurred at lower pHs and were less pronounced than for Al in solution. These represent the titration of H3O+ sorbed during the pretreatment. The buffering by adsorbed Al ions is also less than that by Al in solution.

The OH− used up by adsorbed Al ions between the first and last inflections was equal to, or slightly greater than, the CEC of the minerals, except for mica where it was more than twice the CEC, because new interlayer surfaces were formed during the acid pretreatment. Acid titration curves of Al ions in the adsorbed and solution states showed hysteresis when related to the base titration curves. The use of two titration speeds (3 and 0.3 pH units/hr) only slightly affected the titration curves of the minerals suggesting that the observed effects were not caused by lack of equilibrium with added base or acid.

A stable porous system consisting of montmorillonite cross-linked by Al-hydroxide oligomers was synthesized by reacting at room temperature an aqueous solution of such oligomers with a unit-layer dispersion of montmorillonite. The resulting cross-linked montmorillonite (Al-CLM) is a nonswelling material, showing basal spacings of 14.4 to 18.8 Å after air drying and between 14.2 to 18.0 Å after treatment at 110°C. The basal spacing is found to depend on the age and OH/Al ratio of the Al-hydroxide solution, as well as on the relative amounts of the two reactants. A specific surface area of 160 m2/g and a diffraction pattern with a dominant basal spacing of 17.5 Å is obtained by using Al-hydroxide with OH/Al = 1.85, aged for at least 5 days, and by applying an Al/montmorillonite ratio greater than 1.5 in the cross-linking process. The basal spacing of Al-CLM remains essentially unchanged after heating at 220°C, while the specific surface area is not affected by heat treatment up to 480°C.

Two possible configurations of Al-hydroxide oligomers, homogeneously distributed between parallel montmorillonite unit-layers, were considered in order to account for the basal spacing of 17.5–18.8 Å, viz. (a) stacking of two oligomeric ring units in parallel orientation relative to the clay lamellae and (b) perpendicular orientation of individual oligomeric units.

Mössbauer spectroscopy of dioctahedral phyllosilicates showed that on dehydroxylation iron which originally occupied M(2) and M(l) sites became, respectively, 5- and 6-coordinated. The 6-coordinated sites are very distorted. No migration of cations occurs in the course of heating the specimens for 1–3 hr at 600°–700°C.

By using a combination of several physicochemical methods, different successive stages of the dehydroxylation process could be distinguished: (1) migration of protons; (2) localized dehydroxylation of individual associations without significant change in the overall configuration of the octahedral sheets; and (3) loss of most of the hydroxyl groups with concomitant changes in the cell dimensions. Penetration of Li into the octahedral sheets does not affect the course of the reaction, but reduces the dehydroxylation temperature and the stability of the products.

Dehydroxylation was preceded by or associated with the oxidation of any divalent iron present. Fe3+ derived from Fe2+ was indistinguishable by Mössbauer spectroscopy from iron initially present in the trivalent form. High concentrations of Fe lower the dehydroxylation temperature and reduce the stability of the dehydroxylate to the extent that partial disintegration may precede complete dehydroxylation.