This study investigates the hydrogenetic ferromanganese crust (HFMC) from the Magellan Seamounts in the northwest Pacific Ocean, focusing on its mineralogy, crystal chemistry, and paleoclimatic records. Given that ferromanganese is composed of poorly crystalline MnOx phases, such as vernadite, structural determination using conventional X-ray diffraction (XRD) methods is challenging and has very limited effectiveness. Therefore, synchrotron-based pair-distribution function (PDF) analysis of total X-ray scattering and high-resolution electron microscopy techniques were employed to characterize the structures and compositions of HFMC. The results from the synchrotron XRD and transmission electron microscopy (TEM) reveal that the studied HFMC consists primarily of poorly crystalline Fe-bearing vernadite. The chemical analysis of the HFMC layers indicates that the rare-earth elements (REE) and P were preferentially adsorbed on the Fe-rich vernadite, whereas platinum-group elements (PGE), Co, and Ni were enriched in the Mn-rich vernadite. The top layers of the HFMC display fine-scale compositional variations (cycle of ~1600 y) that signify millennial-scale paleoclimate oscillations during the Middle-Late Pleistocene and Holocene periods linked to the glacial termination event that occurred ~126,000 y ago. This millennial-scale oscillation correlates with sea-level variations influenced by the expansion and contraction of ice sheets, offering a crucial signal for understanding the paleoclimatic interpretation throughout the glacial periods. To fully decipher the fine-scale paleoclimate signals and assist in forecasting future climatic conditions, a more extensive examination of ferromanganese crusts from diverse depths, sources, and locations is necessitated.

The increasing contamination of water by organic dyes causes water pollution in the enviroment. Factories discharge untreated effluents into nearby water courses adding to the existing water pollution; this poses a significant environmental challenge. Hence there is a pressing demand to develop efficient technology for wastewater treatment, and photocatalysis has emerged as an advanced oxidation process with a green chemical approach for such treatment. This study aims to synthesize montmorillonite/TiO2 (Mnt/TiO2) photocatalysts and clarify the effect of montmorillonite content on the photodegradation of the organic dye rhodamine B (RhB). Mnt/TiO2 was prepared by a chemical method with various mass ratios of mMnt:mTiO2 based on the cation exchange capacity (CEC) of Mnt. The physicochemical properties of the samples prepared were determined by the following methods: energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The photocatalytic degradation efficiency of the RhB solution of Mnt/TiO2 was investigated by UV-Vis spectroscopy under UVC irradiation. Liquid chromatography-mass spectrometry (LCMS) was used to identify the photocatalytic by-products. The results showed that the structure of the nanocomposites has a ‘house-of-cards’ form with TiO2 nanoparticles randomly distributed on the surface and sheets of clay minerals. The best mass ratio of mMnt:mTiO2 is 10:1, corresponding to a 10 ppm RhB solution decolorization efficiency of 91.5% in 210 min. In this study, Mnt/TiO2 successfully cleaved the dye chromophore structure and broke the RhB rings into small and broken-ring compounds.

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

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

With the over-use of tetracycline (TC) and its ultimate accumulation in aquatic systems, the demand for TC removal from contaminated water is increasing due to its severe threat to public health. Clay minerals have attracted great attention as low-cost adsorbents for controlling water pollution. The objective of the present study was to measure the adsorption behavior and mechanisms of TC on allophane, a nanosized clay mineral with a hollow spherical structure; to highlight the advantage of the allophane nanostructure, a further objective was to compare allophane with halloysite and montmorillonite, which have nanostructures that differ from allophane. Structural features and surface physicochemical properties were characterized by transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), zeta potential, N2-physisorption, and acid–base titration. The adsorption data showed that TC adsorption followed the pseudo-second order and Langmuir models. The adsorption was pH dependent, as all three clay minerals performed better under neutral to weakly alkaline conditions and maintained high adsorption performance in the presence of co-existing Na+/K+/Ca2+/Mg2+ cations. Regeneration of the adsorbent was excellent, with efficiencies exceeding 75% after five recycles. By comparison, allophane always exhibited the greatest adsorption capacity, up to 796 mg g–1 at ~pH 9. The TC adsorption on allophane and halloysite was dominated by inner-sphere complexation, together with a small amount of electrostatic adsorption, while that on montmorillonite involved mainly interlayer cation exchange. The findings provide insights into the effects of nanostructures of clay minerals on their TC adsorption performance and highlight the huge potential of allophane as an efficient and inexpensive adsorbent for TC removal.

Transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) represents an effective tool for determining the stoichiometric composition of clay minerals, but the methodology is often hampered by analytical difficulties. Studies of beam-sensitive minerals, such as smectites, are associated with low count intensities and dynamic loss of cations (e.g. K+, Na+, and Al3+), which can lead to erroneous quantifications of composition. After exploring how to minimize cation migration by reducing the beam current density to <5 pA cm–2, the most reliable and consistent compositions were determined using 1 μm2 area measurements of particles acquired in normal TEM mode where the electron beam was parallel, the degree of specimen damage was at its minimum and good acquisition intensities (>10,000 cps) were acquired. Based on 528 TEM-EDX area analyses, the composition of Wyoming montmorillonites (SWy-1, SWy-2, and SWy-3) was studied in their natural and Ca-saturated states from thin (<50 nm thick) particle aggregates lying on lacey carbon films. Overall, the TEM-EDX results confirmed the heterogeneous charge distributions of montmorillonite at the particle and sample levels. The average composition per formula unit of SWy-1 to -3 was determined as: (Na0.12Ca0.04Mg0.03K0.02)(Si3.91Al0.09)(Al1.57Mg0.27Fe0.19)2.03 O10(OH)2 · nH2O, where the tetrahedral and octahedral layer charges are –0.09 and –0.19 per O10(OH)2, respectively, and the total layer charge ranges from –0.25 to –0.30 per O10(OH)2 (mean of –0.28). This study demonstrates how TEM-EDX can provide new insight into the natural heterogeneities of smectite chemistry as long as adequate calibration and specimen damage control procedures are implemented.

Fe2+-catalyzed transformation of poorly crystalline ferrihydrite into highly crystalline forms is critical in the biogeochemical cycles of Fe, nutrients, and trace elements. The co-existence of ferrihydrite and kaolinite is widespread in soils of tropical and subtropical regions. In this investigation, three associations of ferrihydrite–kaolinite with ratios of 10, 30, and 50% (10% Fhy–Kln, 30% Fhy–Kln, and 50% Fhy–Kln) were examined to study the impact of the initial Fe2+ concentration and pH on Fe2+-catalyzed transformation under anoxic conditions. The findings reveal that the ferrihydrite in the 10% Fhy–Kln associations has the smallest particle size and the largest number of surface hydroxyl groups. At 0.5 mM Fe2+ and pH 7.5, ferrihydrite underwent transformation into lepidocrocite, with the presence of kaolinite promoting the formation of goethite. Moreover, the presence of kaolinite influenced the morphology of the resulting transformation products. A decrease in pH hindered the transformation of ferrihydrite, while an increase in Fe2+ concentration resulted in the formation of magnetite. The impact of kaolinite in the association system on the transformations of ferrihydrite occurs primarily through alteration of the properties of ferrihydrite during its formation process.

Recent years have seen significant interest in the mechanical properties of clay–polymer hybrids due to their suitability for possible application as sustainable materials in green chemistry. The objective of the present study was to investigate the mechanical properties of clay–polymer hybrids and their corresponding pristine smectite clay minerals. The density functional theory (DFT) method, employing the D3 scheme for corrections of dispersion interactions, was used to calculate elastic constants (Cij) of models of pristine smectites, particularly montmorillonite, beidellite, saponite, and hectorite, and their hybrids built on the polymer poly(2-methyl-2-oxazoline), PMeOx. Following that, the elastic moduli, encompassing the bulk modulus (KVRH), shear modulus (GVRH), Young’s modulus (EVRH), and Poisson’s ratio (ν), were calculated. The results revealed a reduction in elastic constants and elastic moduli following the intercalation of smectite clay minerals with the PMeOx polymer. The findings highlighted a distinctive ranking of mechanical properties among pristine smectite clay minerals and clay–polymer hybrids, with hectorite and its hybrid (Htr-PMeOx) demonstrating better performance compared with saponite, montmorillonite, and beidellite and their respective hybrids.

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

Acid activation of clay minerals is one of the most effective methods for production of materials with increased acidity and porosity. In this review, the benefits of infrared (IR) spectroscopy in studies of acid-treated clay minerals are demonstrated. Protons penetrating into the clay mineral layers evoke structural modifications that can be followed readily by changes in the characteristic absorption bands attributed to the vibrations of the OH and Si–O groups. In the first part of the review the effect of the clay mineral type, composition, layer charge, non-swelling layers, and organo-modification on the dissolution rate is reported. The identification of the acid sites via pyridine adsorption also included. The purpose was to gather the IR results published in previous studies in a single summary paper. In the second part select recent studies reporting the utilization of IR spectroscopy for the characterization of acid-activated clay minerals, mainly applied as catalysts or adsorbents, are discussed. IR spectroscopy as a simple and non-destructive technique deserves attention also today.

Determining the chemical composition of sub-micrometer rock-forming minerals is still a challenging task. The electron probe micro-analyzer (EPMA) is considered the most accurate analytical way to obtain chemical data on amorphous and crystalline materials. However, performing EPMA analyses on sub-micrometer-sized grains is uncertain not recommended as the risk of obtaining analyses contaminated from the surrounding phases. A transmission electron microscope (TEM) equipped with an energy dispersive X-ray spectrometer (EDS) provides a greater spatial resolution, making it possible to obtain trustworthy chemical information on sub-micrometer-sized material. In this work, we present a fast and cheap data-reduction protocol for TEM-EDS chemical analysis, where k-factors derived experimentally for each element of interest and absorption correction are implemented. The results are compared with those determined using standardless and non-corrected TEM-EDS protocols. The k-factor for oxygen plays a fundamental role and its value should be calculated from compounds similar to the phase of interest. For absorption correction, the contribution of hydrogen during structural formula recalculation is taken into account, like a lower net valence of oxygen. The robustness of this protocol was tested by performing TEM-EDS analyses on white mica grains from metapelites, belonging to the Internal Ligurian Units exposed in the Northern Apennines, the chemical composition of which is well constrained. Such a protocol has proven to provide high-quality results from both statistical and crystallo-chemical perspectives. Remarkably, the tested data-reduction protocol for TEM-EDS analysis provided chemical compositions consistent with the EPMA results previously obtained from the same samples.

Serpentine is widely distributed in the regolith and occurs in different types (chrysotile, lizardite, antigorite). The physical and chemical processes such as composition dissolution and structure evolution of serpentine occur constantly under the action of aqueous solutions. Based on the similarities and differences of polysomic structures and properties of chrysotile (tubular shapes) and lizardite (flat structural layers), the mineral–water interfacial reaction of these two minerals was carried out in a sulfuric acid solution with a concentration of 1 mol L–1. The mineral samples were characterized by powder X-ray diffraction, Fourier-transform infrared spectroscopy, scanning and transmission electron microscopy, Brunauer–Emmett–Teller surface area analysis, magic angle spinning nuclear magnetic resonance, and inductively coupled plasma mass spectrometry. The Si, Mg, and Fe dissolution concentrations, dissolution rates, and dissolution rules and structural changes of chrysotile and lizardite were studied and compared. The results show that H+ is more aggressive toward lizardite in sulfuric acid solution. The dissolution rate of Si, Mg, and Fe was faster, the dissolution concentration was greater, and structural changes occurred preferentially in lizardite. Specifically, Mg dissolved first in the octahedral sheets, and Si and Fe dissolved later in the tetrahedral sheets. After the water interfacial reaction with the sulfuric acid solution, the ion dissolution rates of both chrysotile and lizardite were Mg > Fe > Si. In summary, this work investigates the mineral–water interfacial reaction of chrysotile and lizardite in sulfuric acid media from different crystal structures and demonstrates that the crystal structure has a significant effect on the acid reactivity of lizardite minerals. Furthermore, the crystal chemistry patterns for the structural dissociation of different two-dimensional structural units were studied. This work provides a mineralogical basis for the study of the mechanisms of ion migration and crystal-structure evolution of serpentine under acidic media.

Halloysite nanotubes (often abbreviated as HNTs) are technologically important owing to their unique structural and morphological features. Some of these features pre-exist in the naturally hydrated halloysite-(10 Å) parent clay mineral; others may develop during its dehydration towards halloysite-(7 Å). This is the first infrared spectroscopic study of the transition to halloysite-(7 Å), which, in combination with X-ray diffraction (XRD), aimed at advancing the structural description of the process. Three cylindrical and two polygonal halloysite-(10 Å) samples, in both their H- and D-forms, were measured by attenuated total reflectance (ATR), non-invasively and in situ, following step-wise equilibration from 70% relative humidity (RH) to <10% RH and back to 70% RH at ambient temperature. This approach allowed for recording the spectrum of the dehydrating (but not rehydrating) interlayer in the νO–D range, without interference from the inner νOH groups, or from the inner-surface νOH of anhydrous interlayers already present in the parent material. Besides the well-known ‘hole’ H2O species, a new type of H2O-decorated defect was detected at frequencies normally dominated by the inner νOH. This defect is linked to the microenvironment created by the detachment between layer packets and forming ‘crevices’ or ‘slits’ upon dehydration. In addition, the study of the νSi–O spectrum demonstrated that the dehydration of halloysite-(10 Å) leads to the parallel formation of localized, ordered, kaolinite-like domains co-existing with regions of accumulated disorder. The as-produced halloysite-(7 Å) had a non-ideal, open structure that resisted rehydration because the kaolinite-like domains do not rehydrate and act as permanent cross-links.

In recent years, water pollution caused by industrial waste has been a major problem throughout the world. To remove harmful impurities from water, using methylene blue (MB) as a model compound, modified clays were used, as they are capable of adsorbing various substances on their surfaces. The modified clays were obtained by grafting dimethyl sulfoxide (DMSO) and triethanolamine (TEOA) in the space between the layers of Shymkent clay. DMSO was first added to the natural clay; TEOA was also added at a temperature of 180°C and then held at that temperature for 2 h. The resulting modified clays were dried at 60°C for 24 h and characterized by X-ray diffraction (XRD), surface area analysis (SAA), Fourier-transform infrared spectroscopy (FT-IR), elemental analysis, and thermogravimetric analysis (DTA and TGA). Natural and modified clays (0.25–2.5 g L–1, pH=1–12, and 50°C) were used to adsorb MB from an aqueous solution at a concentration of 50 mg L–1. Contact with the adsorbent was maintained for 8 h. As much as 95.9% of the MB was removed from the aqueous solution in as little time as 15 min. Adsorption conditions were optimized, and the clay modified with TEAO showed better results than the natural clay (85% for modified clay vs 40% for original clay, at a clay concentration of 0.5 g L–1); significant adsorption was obtained over a wide pH range (>85% from pH 1 to 12).