Hydrocalumite (HC) is a type of synthetic layered double hydroxide (LDH) that has many important industrial uses and is commonly synthesized by a co-precipitation method in a water:ethanol (2:3) mixture; however, atmospheric carbon dioxide interferes with the synthesis by decreasing the solubility of other gases in the reaction medium. The aim of the present study was to vary the temperature and aging time used in the coprecipitation method in order to mitigate the adverse effects of carbon dioxide. The water/ethanol mixture (2:3) was able to prevent atmospheric carbon dioxide contamination of the sample, as it decreased the solubility of the gas in the reaction mixture. Aging time (9–36 h) and temperature (35–95°C) were varied to modify the hydrocalumite structure, textural properties, thermal stability, and basicity. The characterization of the samples was performed using X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier-transform infrared spectroscopy (FTIR), nitrogen physisorption, thermogravimetric analysis (TGA), and CO2 temperature-programmed desorption (TPD-CO2) techniques. The aging time of 9 h and temperature of 95°C provided the most crystalline sample with the largest mean crystallite size (49 nm). The variation of the synthesis conditions also provided changes in the surface area (6.5–20.2 m2 g–1), pore diameter (116–148 Å), and pore volume (0.0147–0.0499 cm3 g–1). The temperature ranges for thermal decomposition of structural water and carbonate varied among the samples, indicating different thermal stabilities. The basicity (basic sites quantified by TPD-CO2) was also affected by the change in aging conditions; the sample aged for 9 h at 65°C presented the greatest basicity (1557 μmol g–1), whereas that aged for 36 h at 35°C had the least basicity (337 μmol g–1).

Enzymes adsorbed on clay minerals and soil colloids may exhibit lower activities compared to those of free enzymes. A particular toxic metal may affect the activity of the adsorbed enzyme less critically than that of the free form, however. This information is necessary for predicting catalytic performances of clay-immobilized enzymes in natural soils as well as in food, pharmaceutical, and chemical systems. The objective of the present study was to find out how adsorption on palygorskite and sepiolite minerals modifies the catalytic activity and the Michaelis–Menten kinetics of alkaline phosphatase (ALP). Inhibition kinetics of adsorbed ALP by Cd was also compared to that of the free enzyme. The results revealed that the affinity to the substrate and the maximum reaction velocity of ALP decreased upon adsorption on the fibrous clay minerals. The ALP adsorbed maintained a reasonably high activity recovery (AR) compared to the free enzyme. The AR of the adsorbed ALP ranged from 76.9 to 92.5% for palygorskite and from 71.2 to 90.2% for sepiolite, depending on the substrate concentration applied. The presence of Cd decreased the affinity to the substrate of both the free and the adsorbed ALP, while the maximum reaction velocity remained nearly unchanged, indicating that the inhibitory effects of Cd on both the free and adsorbed ALP activities were competitive in nature. The adsorbed enzyme, however, was inhibited less severely by Cd compared to the free enzyme. The adsorption of ALP on the fibrous clay minerals, therefore, maintains the ALP activity to a great extent and provides more resistance for the enzyme against the inhibitory effects of Cd.

Because long-term leachate migration through a hydraulic barrier is inevitable, compacted clay and cementitious liners are commonly used as ‘active-passive’ liners to attenuate percolated leachate. The scarcity of suitable clay and because of the CO2 emitted during the production of Portland cement as well as drying shrinkage, flow rate due to consolidation, limited attenuation capacity, and chemical instability may mean that these are not the best choices of materials to use for this purpose. An environmentally friendly method to improve the properties of local clay and provision for a long-term physical and chemical containment are essential. Geopolymers can be environmentally friendly substitutes for Portland cement to improve soil properties, not just because of the reduced carbon dioxide emission, but also because of its superior physical and chemical properties, as well as significant early strength, reduced shrinkage, freeze-thaw resistance, long-term durability, and attenuation capacity. According to previous studies, class-F fly ash-based geopolymers activated with NaOH exhibit superior attenuation capacity and long-term durability. The presence of silica, alumina, and iron oxides and the lack of calcium oxide play pivotal roles in the acceptable attenuation capacity and chemical stability of class-F fly ash. Accordingly, a clay-fly ash geopolymer may also work as a sustainable liner with appropriate physical and chemical performance. Clay can also participate in the geopolymerization process as an alumino-silicate precursor. All components of clay-fly ash geopolymers possess acceptable adsorption capacity. The type and percentage of the constituent raw materials control the attenuation capacity and physical properties of final products, however. The porosity and conductivity of typical geopolymers are related to the activator type and concentration, water content, and curing condition. Furthermore, the properties of liner materials can be adjusted with respect to the target contaminants. The present study aimed to present a comprehensive review of the relevant studies to highlight the properties required.

The negative effects of dye-contaminated wastewater on humans and the environment are well known, so the wastewater must be treated carefully before discharge into the environment. To overcome those impacts, the search for environmentally friendly and low-cost materials is essential, especially in developing countries The objective of the present study was to determine the feasibility of using bauxite from Malaysia as a new and efficient ceramic, hollow-fiber membrane for the degradation of reactive dyes in wastewater. A porous, hollow-fiber membrane was fabricated from bauxite (BHFM) using a phase-inversion technique, followed by sintering at various temperatures. The BHFM consisted of two types of voids, having either a finger-like or a sponge-like structure. As the sintering temperature was increased, the porosity of the BHFM decreased from 46.5 to 9.5%. The greatest mechanical strength of 308.1 MPa was achieved when the BHFM was loaded with 55 wt.% of bauxite and sintered at 1450°C. The remaining 45 wt.% consisted of solvent, polymer binder, and dispersant. The BHFM functioned well as a membrane for microfiltration and a support membrane for ultrafiltration. BHFM with loading of 45 wt.%, 50 wt.%, and 55 wt.% successfully eliminated 90%, 94%, and 98% of 10 ppm reactive dye (RB5) when sintered at the highest temperature.

Kaolins and clays are important raw materials for production of supplementary cementitious materials and geopolymer precursors through thermal activation by calcination beyond dehydroxylation (DHX). Both types of clay contain different polytypes and disordered structures of kaolinite but little is known about the impact of the layer stacking of dioctahedral 1:1 layer silicates on optimum thermal activation conditions and following reactivity with alkaline solutions. The objective of the present study was to improve understanding of the impact of layer stacking in dioctahedral 1:1 layer silicates on the thermal activation by investigating the atomic structure after dehydroxylation. Heating experiments by simultaneous thermal analysis (STA) followed by characterization of the dehydroxylated materials by nuclear magnetic resonance spectroscopy (NMR) and scanning electron microscopy (SEM) together with first-principles calculations were performed. Density functional theory (DFT) was utilized for correlation of geometry-optimized structures to thermodynamic stability. The resulting volumes of unit cells were compared with data from dilatometry studies. The local structure changes were correlated with experimental results of increasing DHX temperature in the following order: disordered kaolinite, kaolinite, and dickite, whereupon dickite showed two dehydroxylation steps. Intermediate structures were found that were thermodynamically stable and partially dehydroxylated to a degree of DHX of 75% for kaolinite, 25% for disordered kaolinite, and 50% for dickite. These thermodynamically stable, partially dehydroxylated intermediates contained AlV while metakaolinite and metadickite contained only AlIV with a strongly distorted coordination shell. These results indicate strongly the necessity for characterization of the structure of dioctahedral 1:1 layer silicates in kaolins and clays as a key parameter to predict optimized calcination conditions and resulting reactivity.

Dioctahedral micas are composed of two tetrahedral sheets and one octahedral sheet to form TOT or 2:1 layers. These minerals are widespread and occur with structures differing by (1) the layer stacking mode (polytypes), (2) the location of vacancies among non-equivalent octahedral sites (polymorphs), and (3) the charge-compensating interlayer cation and isomorphic substitutions. The purpose of the present study was to assess the potential of parallel-illumination electron diffraction (ED) to determine the polytype/polymorph of individual crystals of finely divided dioctahedral micas and to image their morphology. ED patterns were calculated along several zone axes close to the c*- and c-axes using the kinematical approximation for trans- and cis-vacant varieties of the four common mica polytypes (1M, 2M1, 2M2, and 3T). When properly oriented, all ED patterns have similar geometry, but differ by their intensity distribution over hk reflections of the zero-order Laue zone. Differences are enhanced for ED patterns calculated along the [001] zone axis. Identification criteria were proposed for polytype/polymorph identification, based on the qualitative distribution of bright and weak reflections. A database of ED patterns calculated along other zone axes was provided in case the optimum [001] orientation could not be found. Various polytype/polymorphs may exhibit similar ED patterns depending on the zone axis considered.

Çayırbağı magnesite is one of numerous magnesite deposits occurring throughout Turkey. In this deposit, sepiolite and newly found stevensite occur locally as two daughter minerals formed from magnesite. The sepiolite and stevensite show distinctive compositions and modes of formation compared to those described in the literature. The objective of the current study was to characterize these minerals by means of mineralogic, thermal, structural, geochemical, and textural analyses and to describe their mechanisms of formation. The geology, mineralogy, and geochemistry were examined by field work followed by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential thermal (DTA), and thermogravimetric (TG) analyses. Chemical analyses were performed by means of electron microprobe (EMPA), inductively coupled plasma-optical emission spectrometry (ICP-OES), and laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS). The XRD analyses showed that the d110 of the sepiolite was at 12.64 Å and at 13 Å after air-drying and ethylene-glycol solvation, respectively. Identification of the sepiolite as sepiolite-13 Å was supported by FTIR and TG-DTA data. Chemical analyses showed an ideal composition with a structural formula of (Ca0.05K0.02)(Mg7.79Al0.10□0.11)Si12O30(OH)4. Stevensite displayed distinctive results for XRD, FTIR, and thermal characteristics. The structural formula of stevensite was: (Ca0.01Na0.20K0.04)(Mg1.90Al0.30Fe3+0.37Ti0.01□0.43)(Si3.93Al0.07)O10(OH)2, indicating a layer charge arising mainly from octahedral sheets. Field and SEM observations demonstrated that sepiolite was formed from magnesite by transformation via a dissolution–precipitation mechanism. Descending surface waters were responsible for this transformation. Thick magnesite veins were partly replaced whereas in thin veins sepiolite replaced the overall mass. Both surface waters with high Si, low Al and Fe activities, and pH values of 8–9.5 were responsible for sepiolite formation. Stevensite was formed similarly to sepiolite with respect to the mechanism and parent mineral under permanent groundwater; where both Si, Fe, Al activities and pH (>9.5) were high.

Bisphenol A (BPA), an endocrine disrupting compound, is of concern because of its wide presence throughout the environment and its harmful effects. The present study aimed to prepare an eco-friendly, low-cost, and efficient adsorbent for removal of BPA from wastewater. A natural Tunisian clay was used as a raw material. First, the clay was purified and then modified with hexadecyltrimethylammonium bromide (HDTMA) using microwave heating. The optimal conditions for clay modification were as follows: activation ratio = 0.3:(g/g), solid/liquid ratio = 5%, and microwave heating condition (2:min, 100:W). The purified and modified clays, abbreviated as HP and HMH, respectively, were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and nitrogen adsorption/desorption analysis (BET). Adsorption tests were conducted in a batch reactor process under various conditions. The tests showed that the BET specific surface area of HMH is considerably smaller than that of HP, whereas the basal spacing increased from 14.99 to 22.07 Å after modification, indicating the success of HP organophilization. The adsorption of BPA onto HMH was not affected by the pH of solution between 2 and 10 and only slightly by temperature variation from 23 to 50°C, but was affected significantly by the initial concentration of BPA, contact time, and organo-clay dose. At equilibrium, the data obtained were fitted to Langmuir and Freundlich models. The best fit was obtained by the Langmuir model with a maximum monolayer adsorption capacity of 217.39 mg/g at 23°C. The thermodynamic study suggested that the removal of BPA by HMH was spontaneous (ΔG < 0), exothermic (ΔH < 0), and favorable. The present study demonstrated that HMH synthesized from an abundant and cheap natural clay could be used successfully as a low-cost adsorbent for the removal of BPA from wastewater.

Soil–alkali interaction leads to abnormal soil behavior due to significant changes in mineralogy and morphology. The effect of alkali on the swelling behavior of natural clays has been explored in recent years, but the swelling behavior of alkali-transformed clay minerals is still unclear. The objective of the current study was to investigate the effect of alkali concentration on swelling characteristics of natural and alkali-transformed kaolinitic clays. The study was complemented further with micro-level investigations. Red earth and kaolin, which are regarded as non-swelling kaolinitic clays, were utilized. The results showed that alkalis induced greater swelling in natural clays than in alkali-transformed clays. The results revealed further that alkali-transformed clays exhibited decreases in swelling when exposed to increased alkali concentrations. Moreover, the degree of transformation played an important role in the swelling behavior of alkali-transformed kaolinitic clays when inundated with water and with various alkali concentrations. These variations may be attributed to the different extents of mineralogical and microstructural changes caused by alkali treatment.

The formation conditions and stability fields of Fe-serpentines are still poorly understood in both terrestrial (natural or anthropic) and extraterrestrial environments. Knowledge of the effects of physical-chemical parameters on compositional and structural features of Fe-serpentines is lacking, and only a few thermodynamic parameters of these minerals are available in the literature. To fill these gaps, the synthesis of these minerals, while controlling all the physicochemical experimental parameters, was undertaken. Two hydrothermal syntheses were carried out at 90°C to investigate the effect of two different starting mineralogical mixtures on the nature of Fe-serpentines. The run products were identified by several analytical techniques (powder X-ray diffraction, transmission, and scanning electron microscopy). Berthierine crystals were synthesized from a starting mixture of kaolinite and metal iron. The berthierines synthesized show different morphologies and iron contents (~3–38 at.%). From a starting mineralogical mixture composed of quartz and metal iron, cronstedtite crystallizes. Most of the crystals are 1M polytypes. Magnetite is always associated with both berthierine and cronstedtite. Lepidocrocite was observed only in the experiment with kaolinite. These experimental results demonstrated that Fe enrichment in serpentines depends on the silicate precursor (kaolinite or quartz) of the starting mixture. The results are also in agreement with the geochemical equilibrium predicted by thermodynamic modeling, i.e. the formation of berthierine and cronstedtite in association with magnetite at the expense of metal iron and silicates.