The characterization of magnetic minerals and the relationship of these minerals to the magnetic susceptibility of soils that have developed on various parent materials can provide valuable information to various disciplines, such as soil evolution and environmental science. The aim of the study reported here was to investigate variations in the magnetic susceptibility (χ) of soils in western Iran due to differences in lithology and to examine the relationship of χ to ferrimagnetic minerals. Eighty samples were collected from eight parent materials taken from both intact rocks and associated soils. The soil parent materials included a range of igneous and sedimentary rocks, such as ultrabasic rocks (Eocene), basalt (Eocene), andesite (Eocene), limestone (Permian), shale (Cretaceous), marl (Cretaceous), and the Qom formation (partially consolidated fine evaporative materials, early Miocene). The 80 samples were analyzed for χ using a dual-frequency magnetic sensor and for mineralogy using X-ray diffraction (XRD). The highest χ values were found in the ultrabasic rocks and associated soils, while the lowest χ values were observed in the limestone rocks and associated soils. The pedogenic processes significantly enhanced the χ values of soils developed on the sedimentary rocks due to the formation of ferrimagnetic minerals. In contrast, χ values decreased as a result of pedogenic processes in soils developed on igneous rocks due to the dilution effects of diamagnetic materials, such as halite, calcite, phyllosilicates, and organic matter. The significant positive correlation between the XRD peak intensity of the maghemite/magnetite particles and χ values confirmed that χ values in soils are largely controlled by the distribution and content of ferrimagnetic minerals. These results show that χ measurements can be used to quantify low concentrations of ferrimagnetic minerals in the soils of semiarid regions.

A siliceous sinter collected from Octopus Spring in Yellowstone National Park, USA contains an occluded volcanic rock fragment that has undergone alteration. The sinter piece beyond the fragment is mostly dominated by opal-A with trace amounts of bacterial cells, calcite and detrital quartz. Within the altered rock region, the mineral assemblage is dominated by dioctahedral smectite and quartz with trace amounts of pseudobrookite, ilmenite, rutile and hematite. Onset of opal-CT formation was only found in the outer spicular region of the sinter, which is unexpected given that this outer part represents newest growth. A reaction mechanism is proposed whereby the alteration of feldspar to smectitic clay locally produces excess silica, and alkali metal, and raises pH. As the clay mineral forms, it sequesters ions from pore fluids thereby inhibiting the opal-A phase change to more ordered opal-CT. Ions such as Mg are known to promote the opal-A to opal-CT reaction. Smectite formation therefore may assist microbial-texture preservation processes as excess silica produced increases the rate at which primary opal-A is formed. The altered zone also retains the greatest amount of fixed C and fixed N (operationally defined as C and N retained upon combustion at 450°C). The fixed N probably represents ammonium trapped in the exchangeable interlayer site of the smectite. This fixed N may serve as a potential biological signature of microbial activity in ancient rocks formed in similar environments.

Kaolin-group clay minerals can be modified to form nanotubular and mesoporous structures with interesting catalytic properties, but knowledge of the best methods for preparing these structures is still incomplete. The objective of this study was to investigate intercalation/deintercalation as a method for the delamination and rolling of kaolinite layers in relation to structural order. To prepare nanotubular material, kaolinites of different crystallinities and halloysite (all from Polish deposits) were chosen. The experimental procedure consisted of four stages: (1) preparation of a dimethyl sulfoxide precursor intercalate; (2) interlayer grafting with 1,3-butanediol; (3) hexylamine intercalation; and (4) deintercalation of amine-intercalated minerals using toluene as the solvent. Structural perturbations and changes in the morphology of the minerals were examined by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM). The number of rolled kaolinite layers depended heavily on the efficiency of the intercalation steps. An increase in the structural disorder and extensive delamination of the minerals subjected to chemical treatment were recorded. Kaolinite particles which exhibited tubular morphology or showed rolling effects were observed using TEM. The nanotubes formed were ∼30 nm in diameter, with their length depending on the particle sizes of the minerals.

The aqueous chemistry of water films confined between clay mineral surfaces remains an important unknown in predictions of radioelement migration from radioactive waste repositories. This issue is particularly important in the case of long-lived anionic radioisotopes (129I-, 99TcO4-, 36Cl-) which interact with clay minerals primarily by anion exclusion. For example, models of ion migration in clayey media do not agree as to whether anions are completely or partially excluded from clay interlayer nanopores. In the present study, this key issue was addressed for Cl- using MD simulations for a range of nanopore widths (6 to 15 Å) overlapping the range of average pore widths that exists in engineered clay barriers. The MD simulation results were compared with the predictions of a thermodynamic model (Donnan Equilibrium model) and two pore-scale models based on the Poisson-Boltzmann equation under the assumption that interlayer water behaves as bulk liquid water. The simulations confirmed that anion exclusion from clay interlayers is greater than predicted by the pore-scale models, particularly at the smallest pore size examined. This greater anion exclusion stems from Cl- being more weakly solvated in nano-confined water than it is in bulk liquid water. Anion exclusion predictions based on the Poisson-Boltzmann equation were consistent with the MD simulation results, however, if the predictions included an ion closest approach distance to the clay mineral surface on the order of 2.0 ± 0.8 Å. These findings suggest that clay interlayers approach a state of complete anion exclusion (hence, ideal semi-permeable membrane properties) at a pore width of 4.2 ± 1.5 Å.

Catanionic surfactant systems are used as drug-delivery vehicles and as nanocompartments in the formation of biomaterials and nanosized particles. Clay minerals are compatible with organic tissues and also have biomedical applications. The aim of the present study was to combine the properties of catanionic surfactants and clay minerals to obtain new materials with potential uses in medicine, waste-water treatment, and antibacterial applications. The surfactants chosen to make the catanionic surfactant were cetylpyridinium (CP) and lauroyl sarcosinate (SR), which interact strongly in aqueous media and cause specific aggregations such as ion-pair amphiphiles and needle- and leaf-like structures. Aside from the aqueous solution, new ternary systems are formed with different structures and properties through the addition of montmorillonite (Mnt). The surface and interlayer structures of the different Mnt-CP-SR samples prepared by using CP and SR in amounts equal to various ratios of cationic exchange capacity of the clay mineral were studied. They were also compared with the structured surfactant aggregates formed in aqueous media. The Mnt-CP-SR samples were subjected to X-ray diffraction (XRD), thermogravimetric analyses, and zeta-potential measurements to elucidate the interlayer- and external-surface structures. The XRD analyses showed the formation of a compact structure in the interlayer region resulting from the interaction between randomly oriented pyridinium and negatively charged SR head groups. The triple interactions among the Mnt surface, CP, and SR were more complex than the double interactions between the Mnt and cationic surfactant, and the CP played a dominant role in the formation of external and interlayer surface structures regardless of the amount and order of the addition of SR. The new findings support new applications for organoclays in the fields of biomedicine, remediation of polluted water, and nanocomposite materials.

Bentonite-bonded molding sand is one of the most common mold materials used in metal casting. The high casting temperatures cause dehydration and alteration of the molding sand, thereby degrading its reusability. Neutron radiography and neutron diffraction were applied to study these processes by using pure bentonite-quartz-water mixtures in simulation casting experiments. The aim of the experiments was to compare the dehydration behavior of raw and recycled mold material in order to assess possible causes of the limited reusability of molding sands in industrial application. Neutron radiography provided quantitative data for the local water concentrations within the mold material as a function of time and temperature. Dehydration zones, condensation zones, and areas of pristine hydrated molding sand could be established clearly. The kinematics of the zones was quantified. Within four cycles of de- and rehydration, no significant differences in water kinematics were detected. The data, therefore, suggest that the industrial handling (molding-sand additives and the presence of metal melt) may have greater effects on molding-sand reusability than the intrinsic properties of the pure bentonite–quartz–water system.

Highly weathered soils of the humid tropics generally provide a poor mineral reserve of potassium (K), but evidence has been found which indicates that even in such soils non-exchangeable forms of K can be made plant available and this warrants further investigation. The objective of this study was, therefore, to determine the extent to which K can be released from poorly available reserves over a long period of time. The focus was on an Oxisol in southern Brazil cultivated for 32 years with a rotation of soybeans (Glycine max L.), maize (Zea mays L.), wheat (Triticum aestivum L.), and oats (Avena strigosa L.) with and without K fertilization. Mineral sources of K were identified by X-ray diffraction and by sequential chemical extraction from the clay fraction. The amounts of K-bearing mineral species and the amounts of total and plant-available K were quantified, then the effects of the long-term K-fertilization regime on these values were evaluated. The clay fraction was dominated by hematite, gibbsite, and phyllosilicates such as kaolinite. These minerals were unaffected by the K deprivation in the cropping systems, but in the clay fraction the absence of K fertilization for 32 years reduced the structural order of the 2:1 phyllosilicates associated with K reserves. This effect was most prominent in the root zone of the soil. Deprivation of K for more than three decades decreased the crystallinity of 2:1 phyllosilicates, which could be better evaluated from XRD patterns after the removal of kaolinite and Fe (oxyhydr)oxides. The K-free cultivation reduced the amounts of total soil K by increasing the depletion of K from pools that typically are poorly accessible to plants.

Scholars generally agree that Moses and Elijah appear at the Transfiguration because they are connected to each other in some way, and that this connection informs the significance of the story as a whole. However, there is no consensus regarding how Moses and Elijah are related, and consequently there is significant disagreement about how their presence contributes to the Transfiguration. The present study, which focuses on Mark's account (Mark 9.2–8), argues that Moses and Elijah appear together because they received similar theophanies at Mount Sinai and, as a result, the Transfiguration should be read as a mountaintop theophany in which Jesus constitutes the personal presence of Israel's God.

The first item of business at the February group of sessions was to revive the General Synod (Remote Meetings) (Temporary Standings Orders) Measure 2020, which enabled Synod to conduct hybrid meetings. Previously in operation during the COVID-19 pandemic, the standing order had lapsed and was brought back into operation until 5 February 2026.

Thirty six bentonite samples from 16 different locations were examined in order to demonstrate the applicability of a new Rietveld description approach for quantitative phase analysis. X-ray diffraction patterns of the bulk material were obtained and analyzed by the Rietveld method. The samples contain up to ten different minerals, with dioctahedral smectite as the major component. A model for turbostratic disorder of smectites was formulated inside a structure-description file of the Rietveld program BGMN. The quality of the refinements was checked using an internal standard mineral (10.0 or 20.0 wt.% corundum) and by cross-checking results with X-ray fluorescence (XRF) data. The corundum content was reproduced with only small deviations from the nominal values. A comparison of the chemical composition obtained by XRF and the composition as re-calculated from quantitative Rietveld results shows a satisfactory agreement, although X-ray amorphous components such as volcanic glasses were not considered. As a result of this study, the Rietveld method combined with the new structure model for turbostratic disorder has proven to be a suitable method for routine quantitative analysis of bentonites with smectites as the dominant clay minerals.

Large transition-metal contents add desirable physical properties, such as redox reactivity, magnetism, and electric or ionic conductivity to micas and make them interesting for a variety of materials-science applications. A Mn- and F-rich tainiolite mica, , was synthesized by a high-temperature melt-synthesis technique. Subsequent annealing for 10 days led to a single-phase and coarsegrained material. Single-crystal X-ray diffraction studies were performed and characteristic geometric parameters were compared to the analogous ferrous compound, synthetic Fe-rich tainiolite, . Both tainiolite structures are outside the compositional stability limits for the 2:1 layer structure, and incorporating the relatively large cation Mn2+ requires significant structural adjustments in both the octahedral and tetrahedral sheets. As expected, increasing the ionic radius of the octahedral cation from 0.78 Å (VIFe2+) to 0.83 Å (VIMn2+) reduces the octahedral flattening angle from <Ψ> = 57.05° to <Ψ> = 56.4°, the smallest value ever observed for a tetrasilicic mica. However, even this small <Ψ> value is insufficient to match the lateral sizes of the tetrahedral and octahedral sheets and, in addition, unusual structural adjustments in the tetrahedral sheet are required. The average tetrahedral bond length <T-O> is much greater (1.643 Å) than the average value observed for tetrasilicic micas (1.607 Å,) and a significant difference between the <T-O>apical (1.605 Å) and the <T-O>basal bond lengths (1.656 Å) and an enlarged basal flattening angle (τbas = 106.29°) are noted. These parameters indicate: (1) that the 2:1 layer might be more flexible than previously thought, to allow matching of the lateral dimensions of the tetrahedral and octahedral sheets; and (2) that many other compositions that appear interesting from a materials-science point of view might be accessible.

Acid-base titrations and attenuated total reflectance-infrared (ATR-IR) spectroscopy of solutions containing Zn(NO3)2 and the herbicide 3-amino-1,2,4-triazole suggested that soluble complexes ZnL2+ and Zn(OH)L+ form, where L represents aminotriazole. Sorption experiments and modeling in systems containing K-saturated Wyoming (SWy-K) montmorillonite suggest that at low concentrations the aminotriazole sorbs primarily in cationic form via an ion-exchange mechanism. Sorption isotherms for aminotriazole are ‘s’-shaped, indicating a co-operative sorption mechanism as the concentration of the molecule increases. At higher concentrations, ATR-IR spectroscopy indicated the presence of cationic and neutral triazole molecules on the surface, while X-ray diffraction data suggest interaction with interlayer regions of the clay. When the concentration of the herbicide was high, initial sorption of aminotriazole cations modified the clay to make the partitioning of neutral molecules to the surface more favorable. Experiments conducted in the presence of Zn(II) indicated that below pH 7, Zn(II) and aminotriazole compete for sorption sites, while above pH 7 the presence of Zn(II) enhances the uptake of aminotriazole. The enhancement was attributed to the formation of an inner-sphere ternary surface complex at hydroxyl sites (SOH) on crystal edges, having the form [(SOZn(OH)L)]0.

Geological disposal is the preferred option for the final storage of high-level nuclear waste and spent nuclear fuel in most countries. The selected host rock may be different in individual national programs for radioactive-waste management and the engineered barrier systems that protect and isolate the waste may also differ, but almost all programs are considering an engineered barrier. Clay is used as a buffer that surrounds and protects the individual waste packages and/or as tunnel seal that seals off the disposal galleries from the shafts leading to the surface.

Bentonite and bentonite/sand mixtures are selected primarily because of their low hydraulic permeability in a saturated state. This ensures that diffusion will be the dominant transport mechanism in the barrier. Another key advantage is the swelling pressure, which ensures a self-sealing ability and closes gaps in the installed barrier and the excavation-damaged zone around the emplacement tunnels. Bentonite is a natural geological material that has been stable over timescales of millions of years and this is important as the barriers need to retain their properties for up to 106 y.

In order to be able to license a final repository for high-level radioactive waste, a solid understanding of how the barriers evolve with time is needed. This understanding is based on scientific knowledge about the processes and boundary conditions acting on the barriers in the repository. These are often divided into thermal, hydraulic, mechanical, and (bio)chemical processes. Examples of areas that need to be evaluated are the evolution of temperature in the repository during the early stage due to the decay heat in the waste, re-saturation of the bentonite blocks installed, build-up of swelling pressure on the containers and the surrounding rock, and degradation of the montmorillonite component in the bentonite. Another important area of development is the engineering aspects: how can the barriers be manufactured, subjected to quality control, and installed?

Geological disposal programs for radioactive waste have generated a large body of information on the safety-relevant properties of clays used as engineered barriers. The major relevant findings of the past 35 y are reviewed here.

Antibacterial clays in nature include a variety of clay mineral assemblages that are capable of killing certain human pathogens. Although clays have been used for medicinal applications historically, only in the last decade have analytical methods and instrumentation been developed that allow researchers to evaluate the antibacterial mechanisms of various clays applied medicinally. Comparisons of the mineralogical and chemical compositions of natural clays that kill bacteria have promoted a better understanding of the mineral properties that are toxic to a broad-spectrum of human pathogens, including bacteria that have developed resistance to antibiotics. Popular literature is filled with reports of ‘healing’ clays, that, when tested against pathogens in vitro and compared to controls, do not appear to have bactericidal properties. It is important, however, to differentiate what properties make a clay ‘healing,’ versus what makes a clay ‘antibacterial.’ Most antibacterial clays identified to date buffer pH conditions of a hydrated clay outside the range of conditions in which human pathogens thrive (circum-neutral pH) and require oxidation reactions to occur. It is the change in oxidation state and pH imposed by the hydrated clay, applied topically, that leads to a chemical attack of the bacteria. Healing clays, on the other hand, may not kill bacteria but have soothing effects that are palliative. This article reviews some of the historical uses of clays in medicine but focuses primarily on the common characteristics of natural antibacterial clays and early studies of their antibacterial mechanisms. In this era of bacterial resistance to antibiotics, mimicking the antibacterial mechanisms exhibited by natural clays could be advantageous in the development of new antimicrobial agents.

Interactions between smectite clay minerals and various organic dyes have been studied extensively, but little information has accumulated from dye interactions with mixed-layer illite-smectite (I-S) minerals, especially regarding relationships with clay layer expandability, layer charge, particle size/shape, and molecular aggregation of organic dye molecules. The purpose of this study was to investigate the surface interactions of a set of mixed-layer illite-smectites from different geological environments with Rhodamine 6G dye. The samples used have different amounts of expandable smectite interlayers, different particle size and/or shape, and different layer-charge density at the surface. Five smectites with differences in layer charge and some non-expandable layer silicates were also tested. The interactions detected by UV-vis spectroscopy show no reaction between R6G and non-expandable minerals (kaolinite, mica), and intense reactions forming H-aggregates and monomers with smectites and illite-smectites. The intensity of H-aggregate formation increases with increase in the layer charge of smectites. Mixed-layer illite-smectites interact with R6G more intensely than do smectites. H-aggregate and monomer formation increases with the illitization process for randomly ordered illite-smectites (R = 0) and decreases in the course of illitization for the ordered illite-smectites (R > 0).