Ion adsorption-type rare earth deposits (IADs) are developed via prolonged weathering of REE-rich volcanic and metamorphic rocks. Intense magmatic activity which occurred during the Yanshanian (199.6–65.5 Ma) and Caledonian periods (542–359.2 Ma) provided an abundant material basis for the formation of IADs in South China. High concentrations of REE and the high proportion of ion-exchangeable REE were found in the Maofeng Mountain regolith, Guangzhou city. However, the geochemical patterns and mechanisms of REE enrichment in the regolith were still poorly understood. The present study investigated the regolith profile (0–8 m) developed in Maofeng Mountain based on metallogenic and geochemical characteristics, sequential extraction, and physical and chemical parameters of the regolith profile. The bedrock contained abundant REE resources (245–287 mg kg–1) and the chondrite-normalized REE patterns showed the enrichment of light REE (LREE) and negative cerium (Ce) and europium (Eu) anomalies. The distribution patterns of REE in the bedrock were inherited by the regolith. REE enrichment of the regolith occurred mainly in the completely weathered layer (B1, B2, and B3 horizons), particularly in the depth range 2.5–4.5 m (849–2391 mg kg–1). The position of REE enrichment was controlled by the soil pH (5.52–6.02), by the amount of kaolinite and halloysite, and by the permeability of the metamorphic rock. In the REE-enriched horizon (2–8 m), the REE were hosted mainly in ion-exchangeable fractions (75–2158 mg kg–1), representing 79% of the total REE. Given the pH of 4.73–6.02, REE fractionation driven by the adsorption of kaolinite was limited. Fe–Mn (oxyhydr)oxides played an important role in REE enrichment and the reducible fraction holds up to 21% (139 mg kg–1) of the total REE. The enrichment of LREE was observed in the reducible fraction potentially because of the preferential release of LREE from the LREE-bearing minerals (monazite) and then scavenged by Fe–Mn (oxyhydr)oxides. Positive Ce anomalies (Ce/Ce*: 10) were found in the reducible fraction because trivalent Ce was oxidized by Fe–Mn (oxyhydr)oxides to cerianite (CeO2). The present study helps to understand the enrichment and fractionation of REE in the IADs of South China.

The identification of raw materials and an effective maturation process for the development of peloids is essential to ensure consistent comparisons between commonly used peloids in ‘thermal centers’ (places that offer a variety of health and wellness treatments, also known as spas) and their therapeutic and well-being effects. The present study supports the need for scientific research which examines the variations in physicochemical, technological, and biological properties of peloids resulting from varying maturation conditions. These studies are necessary for establishing quality and safety standards and expanding our understanding of the therapeutic significance of peloids. The objective of the present study was to characterize an experimental maturation procedure using a specific Portuguese clay (bentonite) sourced from Benavila—Avis, which has particular physico-chemical characteristics, in conjunction with two distinct Portuguese mineral-medicinal waters (Hotel Cró and Thermal Spa, and Caldas da Rainha Thermal Hospital) as raw materials. The main aim of the study was to assess and characterize the resulting peloids by evaluating their physicochemical, technological, and biological properties. The experiment was conducted over a period of 90 days under carefully controlled lighting and agitation conditions. The rheological, mineralogical, and chemical properties relevant to a peloid intended for topical application and its potential transdermal delivery of elements were characterized. Additionally, the study investigated the biological activity within the maturation habitat, including chlorophyll, microalgae, and microorganisms. Eight samples, representing the four maturation conditions (stirring with light; stirring without light; no stirring with light, and no stirring and no light), were examined for 30, 60, and 90 days. The study showcased the influence of different mineral-medicinal waters on maturation conditions and on the final bentonite characteristics. Furthermore, it reinforced the importance of establishing quality-control procedures throughout the maturation cycle for bentonitic peloids, as well as the importance of monitoring their usage, reutilization, and disposal.

Direct application of heavy metals as antibacterial agents can cause skin irritations and discoloration of the tissue and it can result in short-term applicability. One of the ways to solve these problems is to immobilize these agents on bentonite. Treatment of textile materials with such activated bentonite for use in various branches of industry has attracted the attention of many researchers in recent years. The objective of the present study was to develop a potential use of Cu- and Zn-modified bentonites as antibacterial finishing agents for two textile materials, non-woven textile (NT) and knitted fabric (PL). The bentonite samples were characterized using ED-XRF (energy dispersive X-ray fluorescence spectrometry), XRPD (X-ray powder diffraction), SEM (scanning electron microscopy), FTIR (Fourier-transform infrared spectroscopy), and BET (N2 adsorption-desorption) analyses. SiO2 and Al2O3 oxides were the main components of all bentonite samples indicated by ED-XRF analysis, while the XRPD analysis confirmed that the natural bentonite (NB) consisted of montmorillonite (Mnt) as the dominant mineral (peaks at 6.94, 19.94, 35.09, and 54.09°2θ) and small amounts of quartz and calcite. A reduction in the basal plane spacing, d001, of Mnt occurred in Cu/Zn-B1, Cu/Zn-B3, and CuB, while in Cu/Zn-B2 and ZnB the basal spacing increased. Also, the size and form of particles and porosity changed, which was confirmed by the BET analysis. Modified bentonite samples experienced a reduction in the specific surface area and total pore volume, as well as movement of the middle mesopore diameter toward the larger diameters. The Zn-modified bentonite demonstrated a greater antibacterial effect on Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus cereus than Cu- and Na-modified bentonite samples with a MIC (minimum inhibitory concentration) of 0.94 mg/mL, while among Cu/Zn bentonite samples, Cu/Zn-B2 had the strongest antibacterial effect (MIC 0.47 mg/mL). Cu/Zn-B2 was integrated on NT and PL using a screen printing method and showed good antibacterial activity. The printed NT showed better activity than printed PL, and increasing the concentration of applied Cu/Zn-B2 also increased the antibacterial properties.

The most potent and significant polyphenolic molecule from tea catechins is epigallocatechin gallate (EGCG); it has potential anti-cancer and anti-inflammatory properties. Methods are needed to mitigate its presence in the environment and protect humans from exposure. The objective of the present study was to investigate a functionalized, low-cost clay mineral as an adsorbent for the tea polyphenol EGCG. Hydrophilic bentonite (Bn) was functionalized using Aliquat 336 (A336) and isobutyl(trimethoxy)silane (IBTS). The degree of clay functionalization depended on the extent of introduction of alkyl linkages between the superimposed clay layers. Results revealed that Aliquat 336 functionalized clay (A336-Bn) exhibited maximum thermal stability at 500°C and it is a promising adsorbent for ECGC with a maximum adsorption capacity of 196.26 mg/g at equilibrium. Experimental data were analyzed using pseudo-first order and pseudo-second order models. Adsorption isotherms were interpreted from the Freundlich adsorption isotherm.

Modified kaolinites possess excellent adsorption properties and, therefore, are regarded widely as potential catalytic components. The use of modified kaolinites as a catalytic component for Fischer–Tropsch synthesis (FTS) has remained unexplored, however. In the current study, delaminated and pit-rich nano-kaolinite was prepared via acid treatment of N-methylformamide (NMF)-intercalated kaolinite (intercalation-etching strategy), and was used as a support to prepare a cobalt-based FTS catalyst (denoted as 15%-Co-HNKln). Compared with other FTS catalysts, the supports for which were raw kaolinite or directly acid-treated kaolinite, the 15%-Co-HNKln showed several advantages such as large specific surface area, dispersed Co particles with small particle size, more new active sites, and significant surface acidity. Given the aforementioned advantages, the 15%-Co-HNKln catalyst demonstrated very good FTS performance. Compared with that of the raw kaolinite-supported FTS catalyst, the CO conversion rate and C5–C12 hydrocarbon selectivity of 15%-Co-HNKln increased by 20% and 15%, respectively.

Clays are extremely variable materials with different mineral compositions, and they are the main ingredients in ceramics applications. Their properties play specific roles in influencing the technological properties and performance of ceramics products. Evaluating the various properties can help to determine the best way to utilize clay materials, such as the locally available Bombawuha (BC) and Denkaka (DC) clays mined from Ethiopia's Bombawuha and Denkaka areas, respectively. The objective of this study was to examine these materials for the purpose of using them to produce quality electrical porcelain insulators. The clay samples were characterized for their chemical composition, mineralogy, thermal properties, plasticity, and particle-size distribution, using atomic absorption spectrometry (AAS), X-ray diffractometry (XRD), differential thermal analysis coupled with thermogravimetric analysis (DTA-TGA), the Atterberg plasticity test, and sieve hydrometer analysis. Based on the characteristics, suitable clay materials were selected and mixed with feldspar and quartz to formulate various porcelain body compositions which were fired at three different temperatures (1200, 1250, and 1300°C) and dwell times (1.5, 2.0, and 2.5 h). The mineralogy, water adsorption, apparent porosity, bulk density, dielectric strength, flexural strength, and microstructure of the fired bodies were measured. The results revealed that, compared to DC, BC contains kaolinite as the major mineral with appreciable amounts of silica (46.72 wt.%), alumina (35.32 wt.%), and fluxing oxides but smaller amounts of CaO. BC contains greater clay fractions (20.58 wt.%); and has a middle-range plasticity index (PI = 11.2 wt.%), thus making BC suitable for producing porcelain insulators. A test-body composition of 40 wt.% BC, 40 wt.% feldspar, and 20 wt.% quartz, fired at 1250°C for 2 h, exhibited water adsorption of 0.17 wt.%, apparent porosity of 0.42 wt.%, bulk density of 2.45 g/cm3, a dielectric strength of 8.22 kV/mm, and flexural strength of 43.63 MPa and, thus, satisfied the required properties for quality porcelain insulators.

Alumina is produced from bauxite, which contains a mixture of various oxides, such as aluminum (Al), iron (Fe), silicon (Si), and titanium (Ti). Bauxite can also be considered a source of several other valuable metals, such as scandium (Sc), vanadium (V), and gallium (Ga). The composition and mineralogy of alumina determine their economic value, but their characteristics vary by locality. The physicochemical characteristics of bauxites can also be influenced largely by weathering processes, even within the same locality. For this reason, the present study was undertaken with the objective of comparing the characterization data of three bauxite samples collected, which will be referred to as D, E, and F, from the Cruz Alta do Pará plateau in northern Brazil. The samples were solubilized by multi-acid digestion and fusion with lithium metaborate to quantify their metal compositions by inductively coupled plasma optical emission spectrometry (ICP-OES). The mineralogical characterization was conducted by X-ray diffraction (XRD), and the phase changes of minerals in bauxite were detected by thermogravimetric analysis (TGA/DTG). The total organic carbon (TOC) technique was used to quantify the C in the samples, and the moisture content was also measured. Alumina was 30 wt.% on average for all samples, good for producing high-purity alumina by hydrometallurgical processes. The results, however, showed high (~20 at.%) silica concentrations in two samples and ~3 wt.% Fe in one sample, which can pose a challenge in the Bayer process. The X-ray diffraction (XRD) analysis showed that gibbsite (Gbs), kaolinite (Kln), anatase (Ant), and hematite (Hem) were the major mineral phases in these samples. The study showed that the samples from the same mine vary in their metal content, especially with regard to Si, and they, thus, need to be processed selectively to maximize their economic value.

Geologic repositories for spent nuclear fuel use bentonite as a buffer to protect the metallic containers confining the radioactive material. Sulfate-reducing bacteria, which may be present in groundwater, at the bentonite–host rock interface or eventually within the bentonite may produce sulfide, representing a potential threat for the metallic canisters, particularly copper. Bentonites can act as potential sulfide scavengers. Little is yet known, however, regarding the underlying mechanisms, the maximum extent of sulfide consumption, and the potential impacts on bentonite structure under repository conditions. In the current study, concentrated (4–150 mM) sulfide solutions were reacted in batch experiments with six natural Fe-bearing bentonites, with various purified Fe-bearing components of bentonite (a series of purified montmorillonites and three iron (oxyhydr)oxides), and with one synthetic mixture, for up to 1.5 months at pH values ranging from 7 to 13. The solutions were analyzed by colorimetry to determine sulfide and polysulfide concentrations and the solids were analyzed by 57Fe Mössbauer spectrometry to determine iron speciation. Important sulfide consumption coupled with a reduction of structural Fe in the clay samples was observed. Not all clay structural Fe was reactive toward sulfide; the proportion of active structural Fe depended on the clay structure and pH. In the presence of excess sulfide in solution regarding Fe in the solid sample, the clay structural Fe was found to be the main reactant while the reaction with iron (oxyhydr)oxides was largely inhibited. Three bentonite groups were distinguished, based on the sulfide oxidation capacity of their main clayey component.

The reduction of azo dyes to less toxic and more easily biodegradable amine derivatives is an effective strategy for the treatment of industrial wastewater. The present work aimed to study the reduction reaction of azo dye Congo red (CR) catalyzed by nanoparticles (NPs) of chromium oxides (Cr2O3NPs) immobilized on bentonite in the presence of NaBH4. Cr(III) ions were intercalated using ion exchange reactions to obtain Cr-bentonite, and then the immobilized chromium cations were treated using NaBH4 leading to the formation of Cr2O3NPs-bentonite. The physicochemical properties of the samples were investigated using X-ray diffraction (XRD), scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS), atomic absorption spectrometry (AAS), UV–Visible diffuse reflectance (UV–Vis DR), and Fourier-transform infrared (FTIR) spectroscopy techniques. The results showed the formation of various chromium species, in which the most dominant were chromium oxide nanoparticles, on the bentonite surface with an average particle size between 20 and 35 nm. Line-scan analysis showed a reactive catalytic surface due to the excellent distribution of Cr on the bentonite surfaces. The best-performing catalyst, Cr2O3NPs-bentonite, displayed significant catalytic activity compared to the bentonite and Cr-bentonite materials, with a full reduction time of 630 s and a rate constant, kapp, equal to 0.034 s–1. The resulting products (benzidine and sodium 3, 4-diaminonaphthalene-1-sulfonate) from the catalytic reduction exhibited low toxicity compared to the CR dye; these products are easy to use in chemical synthesis. All results collected from this work indicated that this low-cost catalyst can be exploited to eliminate other dyes from the environment.

The wide application of rare earth elements (REEs) in the development of a carbon–neutral society has urged resource exploration worldwide in recent years. Regolith-hosted REE deposits are a major source of global REE supply and are hosted mostly in clay minerals. Nonetheless, the ways in which changes in the physicochemical properties of clay minerals during weathering affect the concentrations of REEs in the regolith are not well known. In the current study, a world-class regolith-hosted REE deposit (Bankeng, South China) has been studied to illustrate further the effect of clay minerals on sorption and fractionation of REEs during weathering to form economic deposits. In the weathering profile, halloysite and illite are abundant in the saprolite due to weathering of feldspars and biotite from the bedrock. During weathering, halloysite and illite transform gradually to kaolinite and vermiculite. The large specific surface area, pore volume, and cation exchange capacity of the clay mineral assemblages are favorable to the sorption of REEs, probably because of the formation of vermiculite. The abundance of vermiculite could explain the enrichment of REEs in the upper part of the lower pedolith. For the saprolite-pedolith interface, halloysite is probably the main sorbent for the REEs, as indicated by the distinctive appearance of pore sizes of 2.4–2.8 nm characteristic of halloysite. The progressive transformation of halloysite to kaolinite reduces the pores and desorbs the REEs, causing REE depletion in the shallower soils. As a result, REEs were mobilized downward and re-sorbed in the lower pedolith-upper saprolite causing gradual enrichment and formation of these regolith-hosted deposits.

A hybrid of montmorillonite (Mnt) and rifampicin (RIF) was synthesized and the structure and stability of the drug carrier system clarified. Density functional theory calculations involving dispersion corrections (DFT-D3) were performed to characterize interactions acting in the interlayer space of montmorillonite intercalated with rifampicin. The structure and stability of the RIF-Mnt intercalated complex were determined. Calculations revealed the deformation of the molecular structure of rifampicin after intercalation into the Mnt interlayer space due to the clay environment. The ansa chain of RIF was bent in the interlayer space compared with the structure of the RIF molecule in the monocrystal. RIF was keyed into the Mnt surface by means of numerous hydrogen bonds of weak to moderate strength. The calculated vibrational spectrum from ab initio molecular dynamics (AIMD) was in good agreement with the FTIR measured spectra and helped to analyze the overlapped vibrational bands. Based on analysis of structural stability, theoretical calculations revealed that Mnt is a suitable drug carrier for delayed release of the RIF drug. Batch adsorption experiments showed the large adsorption capacity of montmorillonite for RIF.

Phyllosilicates are hypothesized to be primarily of pedogenic origin in shallowly buried paleosols (≤3 km depth), regardless of the age of the paleosol. To test this hypothesis, this work evaluates the possible presence of detrital and diagenetic phyllosilicates in middle and upper Pennsylvanian paleosols, collected from three drill cores along a north–south transect in the Illinois Basin. The abundances of 2M1 muscovite, quartz, and K-feldspar are greater in a morphologically immature Protosol from the southernmost core; 1Md illite and interstratified illite-smectite with R1 and R0 stacking orders are more abundant in the more mature Vertisols of the central and northern cores. K-Ar age values of multiple clay-size fractions from each paleosol averaged ~260 Ma in the northern core, 270 Ma in the central core, and 295 Ma in the southern core. While considering the complex tectonic and thermal history of the Illinois Basin, detrital minerals are more abundant in immature paleosols that experienced relatively greater maximum burial depths and thus greater sediment supply whereas illitization in more mature paleosols was probably initiated primarily during protracted burial diagenesis. As the present study found evidence for diagenetic and detrital minerals in clay-size fractions of shallowly buried, deep-time paleosols, caution is advised when using paleosol minerals for ancient climate and environment reconstructions.

The passive film of reinforcing steel in marine concrete is damaged by the infiltration of chloride and sulfate ions. Layered double hydroxide (LDH) can adsorb anions and release interlayer ions to form passive films due to its ion exchange property. A Mg-Al-NO3 layered double hydroxide/montmorillonite (LDH/Mnt) composite inhibitor was prepared by layer-by-layer self-assembly (LBL) of LDH and Mnt. The structure and morphology of the LDH/Mnt composites were characterized by X-ray diffraction (XRD), laser Raman spectroscopy, N2-adsorption/desorption measurements, and transmission electron microscopy (TEM). The LDH/Mnt composites, as inhibitors of chloride ions and sulfate ions, exhibited high slow-release efficiency. The mass ratio of LDH and Mnt affected the curing capacity of the synthesized composites, and the optimum mass ratio was LDH/Mnt = 1:1 for which slow-release efficiency reached 94.16%.

Clay minerals are suitable matrices to anchor organic molecules such as antimicrobial peptides (AMPs) so that their bioactivity is maintained, enabling the formation of new materials with potential for new applications in biotechnology. The objective of the present study was to develop a nanostructured film where the properties of palygorskite (Plg) were combined at the molecular level with Dermaseptin 01 (DRS 01), in which the clay mineral also served as a substrate for the immobilization of this peptide. The films were prepared using the Layer-by-Layer (LbL) self-assembly technique. Crude palygorskite without purification (Plg IN) was subjected to physical and chemical procedures to increase its adsorptive properties. The structure, chemical composition, and morphology of Plg were investigated by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray fluorescence spectrometry (XRF), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). LbL films were adsorbed onto ITO (Indium Tin Oxide) and characterized electrochemically by cyclic voltammetry (CV), UV-Visible spectroscopy, and atomic force microscopy (AFM). For the ITO/DRS 01 and ITO/Plg/DRS 01 films, an oxidation process at +0.77 V was observed, confirming that the DRS 01 maintained its electroactive behavior and intrinsic properties. The results also showed that Plg served as excellent support for the immobilization of DRS 01, increasing its concentration and availability in the film form. This work reported immobilizing the DRS 01 peptide with Plg for the first time in an ultrathin film with bioactive properties. Thus, the film developed can be explored for applications such as biosensor devices and antimicrobial coating materials as well as other biotechnological applications.

Humic acid (HA) can cause environmental pollution, due to which, its removal from aqueous solutions has become an increasingly important issue. Although bentonite has an affinity for HA, the adsorption capacity of raw bentonite is still poor. As a commonly used organic modifier, 3-aminopropyltriethoxyorganosilane (APTES) exhibits excellent flocculation capability for HA. Therefore, the objective of the present study was to investigate the effectiveness of the addition of 3-aminopropyltriethoxyorganosilane (APTES) to raw bentonite to increase the adsorption of HA from aqueous solution. The experimental results showed that, when the solid-to-liquid ratio was 1:1, the amino-modified bentonite exhibited the highest adsorption capacity (qmax = 272.23 mg g-1). The adsorption affinity of amino-modified bentonite was mainly determined by the number of amino groups loaded onto its surface. The adsorption of HA on amino-modified bentonite occurred through electrostatic interactions and hydrogen bonding. These findings demonstrate the excellent potential of amino-modified bentonite in effectively remediating HA pollution.

The colluvium and saprolite deposits in the Fran Ali area (Oued Laou, northern Morocco) constitute the main source of raw materials used in traditional pottery. These materials are becoming scarce, however, so alternative materials with the same characteristics are needed; this would ensure the sustainability of pottery activities in the area. The objective of the present study was to examine ten representative samples of clayey materials extracted from the Fran Ali area, i.e. the Ikhadimene, Dar Haddoune, Ihadounene, Aqqbat Ajjoua, and Isalahene sites. The geological materials consist mainly of grayish to brownish phyllites, thin layers of yellowish clay, thicker intervals of reddish-yellow soils ranging in depth from 1 to 4 m, and reddish colluvium soils. The physical properties of these materials were determined using semi-wet sieving and Atterberg limit tests, while chemical, mineralogical, and thermal properties were obtained from the methylene blue test (MBT), the calcimetry test, X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), and thermogravimetric and differential thermal (TGA/DTGA) analysis. The results suggest that the soils contain 21–35% clay, 28–34% silt, and 37–52% sand. They are moderately plastic, with methylene blue adsorption capacities ranging from 3 to 7% and minimal CaCO3 carbonate contents (1–4%). Samples are dominated by SiO2 (51–57%), Al2O3 (17–21%), and Fe2O3 (8–10%). Mineralogically, they are composed of illite (19–27%), chlorite (0–22%), kaolinite (5–9%), and quartz (29–32%). Thermal analysis showed a relatively large mass loss of ~10%. The samples are deemed to be moderately plastic. The results indicate that this raw material is acceptable for pottery fabrication, given the small proportion of irregular interlayer content and its average geotechnical properties. In addition, extraction of the colluvium material is not sustainable because of the relative scarcity of the material. Given the mineralogical similarity between the weathered layers (colluvium) and their parent rock (shales), the present results suggest that the latter is a suitable alternative to the former.

The purposes of this study were: (1) to review the preparation and characterization of the intergrowth between goethite and hematite crystals; and (2) to propose a schematic diagram of the epitaxial relationships among three sets of (100) goethite twin crystals associated with the (001) orientation of the hexagonal prism of hematite. The Fe(ClO4)3 solution was prepared and aged at 70°C, which precipitated goethite initially and produced hematite later with prolonged aging. Goethite and hematite aged for 20 days were observed as star-shaped and hexagonal prisms, respectively. The results suggest that hematite could form later using goethite as a template surface. A selected area electron diffraction (SAED) pattern showed the epitaxial relationship among three sets of (100) goethite intergrowth crystals and hexagonal prisms with the (001) orientation of hematite. Goethite can be produced as lath-, X-, K-, or star-shaped crystals on the (100) orientation, depending on the Fe(ClO4)3 concentrations and the addition of HClO4 to Fe solution samples which were aged for a prolonged period at room temperature. The initial solubility products [(Fe3+)(OH–)3] of the sample solution, rather than the nature of the nuclei, are the key factors governing the formation of goethite or hematite. The addition of acids and high concentrations of iron solutions extend the secondary hydrolysis and induction period (IP) and favor the formation of hematite. The index of the SAED pattern of the star-shaped goethite intergrowth twin crystal has a (100) plane parallel to this basal plane and rotates at a 60° angle between two or three sets of lath-shaped goethite crystals, which share the (011) plane and form goethite twins with ‘interpenetrated’ crystal growth. Stereoscopic viewing using Oak Ridge Thermal Ellipsoid Plot (ORTEP) and CrystalMaker software was deployed to explore the relationship and configuration of oxygen atoms between pseudo-hexagonal (100) goethite associated with hexagonal (001) hematite lattice planes. A schematic diagram of the epitaxial relationship between star-shaped (100) goethite, which is acting as a template facilitating later precipitation of (001) hexagonal prisms of hematite on it, is presented.

Natural clays are often employed as substrates for heterogeneous catalysts. However, the direct use of raw clays as catalysts has received less research attention. The objective of the present study was to help fill this gap by investigating catalytic properties of raw pelagic clays (PC) collected from the Indian Ocean. The raw PC were discovered to be efficient catalysts in the reduction of 4-nitrophenol (4-NP) in the presence of NaBH4. The effects of parameters including pH values, dosages of PC, and initial concentration of 4-NP and NaBH4 on the conversion or degradation rate of 4-NP have been investigated. The 4-NP was observed to be completely degraded within 480 s under conditions of 0.10 mM 4-NP, 25.0 mM NaBH4, and 0.20 g/L PC at an initial pH value of 7.0. The apparent rate constant was evaluated to be 27.53 × 10–3 s–1. Unlike previous pseudo-first order kinetics experiments, the induction period and degradation stages were observed to occur simultaneously during the PC catalysis. The S-shaped kinetics for 4-NP conversion was found to be perfectly matched by Fermi's function, and the enzyme-like catalysis by PC was appointed to describe the kinetics. Species of Fe(III), Mn(IV), and Mn(III) in PC were found to be essential, and were partly reduced to Fe(0) and Mn(II) by NaBH4 in our reaction, contributing to rapid conversion of 4-NP to 4-aminophenol (4-AP). The raw PC was converted to magnetic PC (m-PC) particles, which made PC particles separate easily for cycling use. This discovery would also have applications in continuous flow-fluid catalysis.

The formation of manganese (Mn) oxides is influenced by environmental conditions and, in some red soils, Mn oxides occur as coatings on the surface of kaolinite particles in the form of colloidal films or fine particles. The present study aimed to explore the types of formation mechanisms of Mn oxide minerals on the surface of kaolinite. Mn oxide minerals synthesized by reducing the Mn in KMnO4 with a divalent Mn salt (MnSO4) were examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of various initial molar ratios of Mn2+/Mn7+ (R = 1:0.67, 1:1, 1:2, and 1:4), cationic species (Na+ or Mg2+), synthesis temperatures (30, 60, and 110°C), and amount of added kaolinite (0.25, 0.5, 1.0, 2.0, and 5.0 g) on the formation of Mn oxides were studied. The results showed that Mn oxide mineral types were affected by the initial R value and the background cation. With decreases in the initial R value, the synthesized minerals transformed from cryptomelane to birnessite. The relative mass ratios of kaolinite to Mn oxide were calculated as 1:0.92, 1:0.63, 1:1.15, and 1:1.63. The sodium cation (Na+) had a greater role than Mg2+ in promoting the dissolution–recrystallization of birnessite to cryptomelane. The synthesis temperature had no effect on mineral types, but Mn content increased as temperature increased. When the amount of added kaolinite was increased from 0.25 to 5.0 g, Mn oxide minerals formed gradually and transformed from birnessite to cryptomelane. This work revealed a possible formation process and reaction mechanism on the surface of kaolinite particles in some red soils.

A geological, mineralogical, and geochemical characterization of the Tamame de Sayago (Zamora, Spain) deposit was carried out with the aim of knowing the conditions that facilitated the genesis in the same deposit of kaolinite and smectites. The alteration processes affecting a Variscan granite were deduced throughout the study of a very wide group of representative samples by X-ray diffraction (XRD), scanning electron microscopy (SEM), chemical analyses of major, minor, and trace elements, as well as δ18O, δ34S stable isotope and K/Ar dating analyses. In addition, 2D and 2.5D graphs of the kaolinite and smectite isoconcentrations were obtained from core data. According to the color and texture, two different clayey rock types were identified and named as homogeneous alteration zones (ZAHO) and heterogeneous alteration zones (ZAHE). The ZAHO are regoliths in which the granite texture is preserved, and the feldspars are almost completely kaolinized. In the ZAHE, the original texture of the granitic rock is lost, and the main clay mineral is smectite. The mineralogical composition is similar, with kaolinite, smectite, mica, quartz, scarce feldspar, and occasionally natroalunite and APS (aluminum-phosphate-sulphate); however, the mineral concentration varies considerably because ZAHO are rich in kaolin areas whereas ZAHE are bentonitic areas. Both rock types contain numerous veins and nodules. The weathering of the Paleozoic granite alongside the absence of sedimentation during the Mesozoic led to the formation of kaolinite that is preserved in ZAHO materials. Nonetheless, during the Cretaceous–Tertiary transit, the conditions of tectonic stability varied. Late Variscan faults reactivated which allowed the percolation of Mg- and Ca-rich hydrothermal fluids through the already kaolinized granite, increasing the alteration of the primary silicates and leading to the formation of smectites in ZAHE materials. The amount of smectites is greater closer to the faults. The stable isotopes indicate the meteoric nature of the low-temperature hydrothermal fluids. The K/Ar data obtained from the natroalunite of veins indicate that those hydrothermal fluids circulated in different pulses from 66.4 ± 1.7 to 58.8 ± 1.5 Ma, as a minimum. Those ages are coincident with the first formation stages of the Duero Basin.