The maximum temperature that a geotechnical bentonite barrier in a deep geological repository for radioactive waste can withstand while maintaining its integrity and meeting safety requirements is still an open question. Therefore, an international consortium set up an in situ heater test (HotBENT experiment) at the Grimsel Test Site (GTS) in Switzerland at relevant scales and gradients with temperatures ranging from 175°C to 200°C at the heater/canister surface. After dismantling (5 and 20 years, respectively), the identification of bentonite alteration processes of (clay) minerals has to be based on the comparison of data with reference values determined before the heating started. The experiment was set up using ~150 tons of two different clays (Wyoming and BCV from the Czech Republic) provided in different batches. The bentonites were used both as compacted bentonite blocks and as granular bentonite material (GBM). The determination of representative mineralogical and geochemical bentonite reference values must be based on a significant number of samples taken from all parts of the experiment, which is presented here. Most of the compositional variability was close to the accuracy of the methods used. However, chemical, mineralogical and exchangeable cation analyses showed that different raw materials were used to produce the BCV top blocks. The Wyoming bentonite used is similar to MX80 bentonite in that it is dominated by Na-rich smectite, but the HotBENT material contains slightly more feldspar and zeolite and slightly less smectite. Overall, 55 samples were analysed from different parts of the experiment, providing a statistical basis for post-excavation investigations.

Environmental problems caused by human intervention in nature are some of the most critical challenges facing human societies. It is essential to use suitable adsorbents to remove pollutants. The abundance, natural abundance and low cost of fine soil have made it a good candidate for removing environmental pollutants. In this research, removal of safranin dye by natural and acidic-organic-treated fine soil with sulfuric acid and ethanolamine was studied. The characteristics of natural and acidic-organic-treated fine soil were confirmed using X-ray diffraction, Fourier-transform infrared spectroscopy, Brunauer–Emmett–Teller and scanning electron microscopy techniques. The adsorbents were placed in contact with different concentrations of safranin dye solution separately. After that, the effects of adsorbent amount (0.4–3.2 g L−1), contact time (0–60 min), adsorbate concentration (5–20 ppm) and pH (3–11) were evaluated regarding the optimum safranin adsorption process. The greatest adsorption capacity of fine soil was calculated as 1250 mg g–1. The experimental results were evaluated using thermodynamic and kinetic models. The data showed that the process follows the Langmuir isotherm model and pseudo-second-order kinetic model. The intraparticle diffusion model estimated the possible mechanism of dye adsorption. Overall, it can be deduced that natural fine soil is an efficient remover of human pollutants.

The antibacterial, antifungal and antioxidant effects of halloysite nanoclay, Cloisite 10A (C10A) and Cloisite 15A (C15A) organonanoclays were examined in this study. The antimicrobial action was assessed using the agar-well method and the disc diffusion method. The free radical-scavenging effects of the clays were determined using the 2,2-diphenyl-1-picrylhydrazyl method. Halloysite showed antimicrobial activity against Pseudomonas aeruginosa, Enterococcus faecalis and Staphylococcus aureus. C10A was effective against both Gram-positive bacteria (S. aureus, Listeria monocytogenes, Bacillus subtilis and E. faecalis) and Gram-negative bacteria (Escherichia coli, Klebsiella pneumoniae and P. aeruginosa). Additionally, only C10A was found to have an antimicrobial effect on Candida glabrata of 18 mm amongst the tested clays. C15A showed an antimicrobial effect on S. aureus and K. pneumoniae. It was determined that the antifungal properties of organoclays were higher than those of halloysite. The most effective clay type was determined to be C10A. The positively charged inner surface of the halloysite nanoclay can provide a large area to which negatively charged free radicals can attach. The modified C15A used in this study has two long-chain alkyl groups attached, whereas the modified C10A has a single long-chain alkyl group and a benzyl group attached. It is proposed that the differences in these antimicrobial effects are due to the structures of the molecules. According to these results, organoclays as green source materials could be used as additives and coatings in food processing, biomedical devices, filters and paints due to their antimicrobial and antioxidant properties.

The interface performance between clay–sand mixtures and concrete structures is governed by the mixture's composition and its physical properties. Moisture content and particle-size distribution play important roles in deciding the mixture's arrangement of soil particles, porosity, hydraulic conductivity and behaviour under various mechanical loadings. Application of a polymer interfacial coating can improve the bond performance between soils and concrete mainly via interfacial friction/mechanical interlocking. The present work analyses the development of interfacial strength between clay–sand mixtures and a polymer coating with changes in particle gradation. The multi-scale mechanisms at the interface are investigated, giving primary attention to soil porosity. A 50:50 clay–sand mixture exhibited a greater interfacial adhesive performance compared to other soil mixtures. In addition, the moisture-controlled pores and gradation-controlled pores demonstrated differences in macroscale interfacial strength. Both mercury intrusion porosimetry (MIP) and 129Xe nuclear magnetic resonance (NMR) were utilized to detect the pore structure of the mixtures. 129Xe-NMR revealed the pore distribution of the mixtures as ranging from macropores to nanopores, and MIP complemented the pore information by determining the critical pore entry diameter in the macropore regime. Mesopores dominated with increasing fine sand content until a threshold value was reached; thereafter, merging of pores occurred and macropores dominated.

This study examines the effects of the chemical composition of the clay fraction of various soil horizons on radiation shielding parameters. X-ray fluorescence (XRF) analysis did not reveal significant differences in the concentration of the most abundant oxides (Al2O3, SiO2, Fe2O3) among the various horizons. Consequently, the mass attenuation coefficient did not vary among the horizons in terms of the photon energies studied (15 keV–10 MeV). The mean free path (MFP), half-value layer (HVL) and tenth-value layer (TVL) did not differ for energies up to 100 keV. However, at higher energies, these parameters were mainly influenced by the differences in the densities of the soil horizons. The effective atomic number did not differ across the horizons for the various photon energies, nor did the mass attenuation coefficient. It is shown that slight differences in the chemical composition of the clay fraction of soil horizons do not affect radiation shielding parameters (MFL, HVL, TVL) for low photon energies (<500 keV). Density is more important for radiation shielding than the chemical composition of the various horizons of the same soil type for higher energies (>100 keV); hence, compacting the clay fraction might be more efficient for radiation shielding purposes at higher energies.

Toxic pharmaceutical pollutants, such as nicotine, represent a significant threat to natural water sources due to their continuous discharge. To address this issue, clay minerals and their composites have demonstrated exceptional adsorptive and remedial capabilities for wastewater purification. This research focused on developing green clay-polymeric adsorbents for the efficient removal of pharmaceutical pollutants from industrial wastewater. The synthesis involves creating halloysite nanotube–polythiophene nanocomposites through a green and cost-effective method using vapour polymerization and a solvent-free, ball-milled technique for the adsorptive removal of nicotine from wastewater. The investigation evaluates the impacts of preparation, modification and environmental conditions on the adsorptive performance of these clay-based nanocomposites compared to pure polythiophene. The polymerization process was evaluated by varying the vapour polymerization holding time for a fixed amount of oxidant (FeCl3) and halloysite nanotube (HNT) to investigate the impacts of monomer vapour exposure time on the polymerization of nanocomposites. Following the characterization of the synthesized adsorbents using various methods, the study investigated the impacts of various parameters (e.g. adsorbent dosage, pH and contact time) on the adsorption capabilities of the materials on a laboratory scale. The results revealed that the incorporation of HNT improved the adsorbing performance of nanocomposites. The pH, absorbent concentration and contact time directly affect nicotine adsorption. Significantly, halloysite–polythiophene 3 with a 2 h polymerization duration demonstrated the maximum adsorption efficacy of 78.94% at pH 10 after a 24 h contact time. The environmentally friendly halloysite-based nanocomposite shows promising potential as an effective adsorbent for pharmaceutical pollutant (nicotine) removal from aquatic environments.

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.

The formation of iron-rich phyllosilicates can occur at different natural or engineered settings. In this study, the influence of pH in the hydrothermal synthesis of iron-rich phyllosilicates was investigated in the pH range 8.50–12.10 after the ageing of the precursor. The synthesized samples were characterized by powder X-ray diffraction, Raman and Mössbauer spectroscopies and transmission electron microscopy. Three domains of pH were identified, and these correlated with silica availability and its speciation in the solution. The formation of 1:1-type FeIII/FeII phyllosilicate was observed between pH 9.67 and 10.75. Above pH 10.75, two types of phyllosilicate-like mineral phases were observed. In addition to 1:1-type FeIII/FeII phyllosilicate, 2:1-type FeIII/FeII phyllosilicate was observed. Below pH 9.67, mainly amorphous silica and iron oxides were observed. The findings show that pH governed the crystallinity and nature of the obtained phyllosilicate-like phases.

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.

Lightweight expanded clay aggregates (LWAs) are porous materials with low density and high strength (EN-13055-1), and they are important in sustainable construction through their lightweight nature and ability to provide thermal or acoustic insulation. The objective of this work was therefore to evaluate the preparation of LWAs using a smectite clay (M1 formulation), whose application in common ceramic production is difficult. An alternative approach was proposed for the valorization of phosphate sludge and a palygorskite-rich sediment by mixing them with expanded clay (M2 formulation) for LWA production. This could result in economically cost-effective products with significant environmental benefits. Pellets were prepared and fired at various temperatures (1100°C, 1125°C and 1150°C), and relevant properties such as bloating index, density, water absorption and compressive strength were determined. Additionally, the microstructure, mineralogical transformations and phase compositions under various sintering temperatures were investigated. Increasing the temperature from 1000°C to 1150°C significantly improved the expansion properties of LWAs, and 1150°C seemed to be the optimal firing temperature at which the best expansion properties were achieved. In addition, the incorporation of the selected waste improved the properties of the final products, leading to lower density, greater strength and greater bloating with the development of the internal pore structure as compared to the LWAs without this addition. Because of their low density (0.6 g cm–3) and sufficient compressive strength (0.86 MPa), the manufactured LWAs can be used in construction (as insulating panels or in lightweight concrete) and in green roofs.

This work aims to characterize and study the properties of an Algerian diatomaceous earth (Sig-Mascara) as a catalyst carrier. A commercial product of diatomite was characterized by granulometric analysis, X-ray fluorescence, X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis/differential scanning calorimetry and scanning electron microscopy/energy-dispersive X-ray spectroscopy methods. To purify the diatomite and remove the impurities (iron oxides, clay minerals, quartz and organic matters), the <63 μm fraction of the diatomite was separated out. The 15Ni/Ds-700 catalyst has lower SiO2, Al2O3 and CaO contents compared with the original diatomite. The NiO content of the catalyst is 15 wt.%, indicating successful impregnation. According to the nitrogen sorption–desorption results, the specific surface area of the purified diatomite particles (<63 μm) increased from 26.47 to 46.33 m2 g–1 compared to crude diatomite. The 15Ni/Ds-700 catalyst was applied in the dry reforming of methane to obtain synthesis gas (CO and H2). The results showed that the catalyst was relatively stable during catalytic measurements for 6 h, although the conversion rate value was low (12%).

Trioctahedral phyllosilicate minerals are widely distributed on the Earth’s surface, especially in soil. The mineral–water interfacial reaction of lizardite, chlorite and talc, with various structural properties (tetrahedral sheet, octahedral sheet, 1:1-type and 2:1-type interlayer domain/two-dimensional structural units), was carried out in sulfuric acid solution (1 mol L–1). The mineral samples were characterized by powder X-ray diffraction, Fourier-transform infrared spectroscopy, scanning and transmission electron microscopy and inductively coupled plasma mass spectrometry. The dissolution concentration, dissolution rate, dissolution rules and structural changes of the components during the dissolution processes of the various two-dimensional structural units were studied. The results show that the dissolution concentrations of Si and Mg in the sulfuric acid solution decrease in the following order: chlorite > lizardite > talc and lizardite > chlorite > talc. The dissolution rates of Si in chlorite and Mg in lizardite are the greatest, while talc is the most stable compared with lizardite and chlorite. With increasing interfacial reaction time and the dissolution of the ionic components of the minerals, the structure of lizardite is gradually destroyed; the structural destruction of chlorite is more obvious during the early stages of the reaction; and the structure of talc does not significantly change over the course of the entire reaction. By analysing the microtopography of the minerals, it was found that the structural failure of lizardite occurred from the surface to the interior. Chlorite had more structural defects and showed collapse of the layered structure during structural failure. The surface layer of talc decomposed by corrosion into a small lamellae structure attached to the surface, but there was no obvious structural change similar to those of lizardite and chlorite. The relationship between the evolution of composition and structure during the mineral–water interfacial reaction process with the two-dimensional structure layer type provides the mineralogical basis for studying the coupling mechanism of the migration and transformation of materials in key regions of the Earth.

The zeolitic rocks of Akrotiri, on Santorini Island (Aegean Sea, Greece), can be grouped according to the zeolite minerals present. The first group includes zeolitic rocks that contain only clinoptilolite, the second group contains clinoptilolite and mordenite and the third group contains only mordenite. Clinoptilolite accounts for up to 56 wt.% and mordenite for up to 69 wt.% of the rocks. All samples contain feldspars (8–36 wt.%), clay minerals (6–8 wt.%), quartz (3–6 wt.%), opal-CT (2 wt.%), amphibole (2–4 wt.%) and amorphous materials (4–7 wt.%). The studied samples were classified chemically as andesites or dacites. The ammonium-exchange capacity of the studied samples was 104–158 meq 100 g–1. According to Commission Implementing Regulation (EU) No. 651/2013, zeolitic rocks that contain ≥80 wt.% clinoptilolite, ≤20 wt.% clay minerals and are free of fibrous minerals and quartz can be used as feed additives in animal husbandry. Zeolites with fibrous habit (mordenite, erionite, secondarily roggianite and mazzite) and SiO2 minerals such as quartz, cristobalite and tridymite can be dangerous to both humans and animals. The mineralogical study showed that, due to their low clinoptilolite content and the presence of both quartz and fibrous mordenite, the studied zeolitic rocks do not conform with European Regulation No. 651/2013. As a result, their use as feed additives and nutrition supplements is prohibited.

Clay minerals are effective adsorbents for the remediation of pesticides in wastewater due to their large superficial areas and excellent cation-exchange capabilities. However, this adsorption effect can be reduced by the accumulation of adsorbents on clay minerals, amongst other problems. Therefore, in this study, montmorillonite (Mnt) modified by layered double hydroxide (LDH) with different loading amounts was successfully prepared using an in situ method. The results from X-ray diffraction, Fourier-transform infrared spectrometry, Brunauer–Emmet–Teller (BET) and scanning electron microscopy analyses revealed that LDH structures were successfully combined with the Mnt layer and formed a porous structure. However, excess LDH still caused the aggregation and accumulation of layers. The adsorption performance of LDH@Mnt for atrazine (ATZ) and paraquat (PQ) was investigated, and the removal efficiency of the LDH@Mnt composite was higher than those of Mnt and LDH alone. The kinetic study revealed that the adsorption process fitted the pseudo-second-order model and internal diffusion model, and 3-LDH@Mnt had the greatest absorbability efficiency for both ATZ and PQ, indicating the adsorption process was controlled by the number of active sites of the adsorbent. The generalized Langmuir model accurately characterized the adsorption process of ATZ and PQ elimination in the adsorption isotherm investigation, indicating that the adsorption energies of the active sites on the adsorbents were different. 3-LDH@Mnt had better absorbability performance for ATZ/PQ, and the sorption capacities were 7.03 and 91.9 mg g–1, respectively. According to site energy distribution theory, the amount of sorption sites of the composite adsorbent was large and the average adsorption energy was high, both of which being beneficial for the adsorption of ATZ and PQ. The effects of pH, coexisting anions and reuse experiments were also tested, indicating that the LDH@Mnt composite possessed high adsorption stability. This excellent removal performance represents a promising strategy for the remediation and elimination of pesticide contaminations from the environment.

In the present study, a comparison of the thermal-insulation and mechanical performances of cement and heat-stabilized compressed earthen blocks (CEBs) was carried out to determine the factors which influence those properties. The raw clays used consist mainly of kaolinite, orthoclase and quartz. The mechanical strength increased with increase in both the amount of cement added and the firing temperature. However, the responses are better for cement-stabilized CEBs. The thermal insulation of fired bricks is greater than that of cement-stabilized bricks. This difference was related to the decrease in porosity and the formation of continuous-surface. The decrease in thermal insulation is mainly related to the formation of continuous-surface in cement-stabilized CEBs, whereas in the fired CEBs, it is due to the modification of pore volume. The mineralogy of the raw clays is statistically correlated to porosity and continuous-surface development that were confirmed as the main factors in the modification of both the mechanical strength and the thermal insulation. In cement-stabilization, the decrease in insulation is due to the development of continuous surface, while for heat-stabilization, mineral transformations during the sintering reduced continuous-surface formation and the insulation was controlled by both radiation and reduced surface conduction. The influence of the mineralogy of the raw material shows that clay content favours the insulation in fired bricks obtained at T ≤ 1000°C, while sand contents favour densification. In contrast, clay contents reduce the mechanical response of cement-stabilized material due to limited cement–clay interactions. In general, the mechanical response is more favourable in cement stabilization, while thermal insulation is better in fired bricks.

As a natural clay mineral, halloysite (Hal) possesses a distinctive nanotubular morphology and surface reactivity. Hal calcined at 750°C (Hal750°C; 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 wt.%) was used to replace ground granulated blast furnace slag (GGBFS; 50.0, 49.5, 49.0, 48.0, 47.0, 46.0 wt.%) and fly ash (FA; 50.0, 49.5, 49.0, 48.0, 47.0, 46.0 wt.%) for the preparation of geopolymer in this study. The effects of the replacement ratio of Hal750°C on setting time, compressive strength, flexural strength, chemical composition and microstructure of the geopolymer were investigated. The results indicated that Hal750°C did not significantly alter the setting time. The active SiO2 and Al2O3 generated from Hal750°C participated in the geopolymerization, forming additional geopolymer gel phases (calcium (aluminate) silica hydrate and sodium aluminosilicate hydrate), improving the 28 day compressive strength of the geopolymers. When the amount of Hal750°C was 2.0 wt.%, the 28 day compressive strength of the ternary (GGBFS-FA-Hal750°C-based) geopolymer was 72.9 MPa, 34.8% higher than that of the geopolymer without the addition of Hal750°C. The special nanotubular morphology of residual Hal750°C mainly acted like reinforcing fibres, supplementing the flexural strength of the geopolymer. However, excessive Hal750°C addition (>4.0 wt.%) reduced compressive and flexural strength values due to the low degrees of geopolymerization and the porous microstructure in the ternary geopolymer. These findings demonstrate that the appropriate addition of Hal750°C improved the compressive strength of geopolymers prepared using GGBFS/FA, which provides essential data for future research and supports the utilization of low-value Hal-containing clays in geopolymer preparation.

The rheological properties of three Na-activated, trioctahedral Mg-bentonites (hectorite clay from the CMS Source Clay Project repository, saponite clay from Spain and stevensite clay from Rhassoul, Morocco) and a sepiolite clay from Greece were examined after dynamic ageing at temperatures up to 230°C. The 5% w/v suspensions were prepared by dispersing the clay mineral samples in distilled water. The suspensions underwent dynamic, thermal ageing for 16 h before determination of the viscosity, filtration loss, filter cake thickness and pH and the concentration of dissolved Na+ and Mg2+. Thermal ageing contributed to the dispersion of clay particles, with a direct effect on plastic and apparent viscosity, introducing pseudoplastic behaviour. With the exception of the stevensite clay at 230°C that displayed limited dissolution at 230°C and partial conversion to kerolite, the clays were stable at high temperatures. The Na-activation of all clays except for stevensite was not adversely affected by thermal ageing. Thermal ageing of stevensite at 230°C facilitated Na exchange and yielded suspension with high viscosity and low filtrate loss. Only the suspensions of hectorite and those of stevensite aged at 230°C met with American Petroleum Institute specifications. The thermal behaviour and rheological properties of the clays might be interpreted according to the intrinsic properties of the clay minerals, such as layer charge and charge distribution.

In this study, the effects of two different ammonium-exchange methods to improve the ammonia (NH3) gas adsorption of raw clinoptilolite (CLN) from Gördes (Türkiye) was investigated. The first method involved direct modification of CLN by 0.5 or 1.0 M NH4NO3 solutions at 80°C for 4 and 8 h followed by calcination. In the second method, CLN was converted to the Na+ form prior to modification with ammonium nitrate and calcination under the same conditions. Both methods yielded H+ forms of CLN through the removal of exchangeable cations without damaging the crystal structure. Ammonia adsorption isotherms were determined at 298 K for a total of eight different H+ forms synthetized using both methods. The Na-1.0-8h CLN sample with the highest NH3 adsorption capacity obtained using the second method was selected as the parent CLN. In addition, to determine the effects of doping different cations into the structure on the NH3 adsorption properties of the selected parent CLN sample, cation-exchange processes were carried out using 0.5 and 1.0 M NaNO3, KNO3, Ca(NO3)2 and Mg(NO3)2 solutions at 80°C for 4 h. The raw and modified CLNs were characterized using X-ray diffraction, X-ray fluorescence, scanning electron microscopy and N2 adsorption analyses. Cation-exchanged samples with a wide range of NH3 adsorption capacities (3.61–4.93 mmol g–1) were compared with other zeolites from the literature.

Palygorskite (Pal) shows great potential for physical, chemical and biological uses due to its colloidal, catalytic and adsorption properties. Pal mines, however, are facing the challenge of low-grade materials (5–15%), making it difficult to use Pal in emerging fields such as new materials, environmental protection and health. Therefore, there is an urgent need to develop an efficient method for separating and purifying Pal to obtain high purity levels. Hence, we have developed a dispersant-assisted rotating liquid film reactor separation strategy based on sodium hexametaphosphate as the dispersant. This strategy utilizes the double electron layer of Pal and the density difference between impurities to achieve effective disaggregation and purification of Pal bundles through the promotion of repulsive driving effects. Under optimal conditions, the purity of Pal can be increased from less than 10% to over 80%. This research presents a novel approach to the efficient refining of low-grade Pal. The crudely purified Pal’s adsorption capacity for methylene blue increased from 84.2 to 256.4 mg g–1.