Aflatoxins in contaminated corn do not degrade in corn fermentation solution (CFS) during biofuel production; rather, they are enriched in the co-product, dried distillers grain. Aflatoxin B1 (AfB1) is the most toxic form of all aflatoxins. Removing AfB1 from CFS is desirable to minimize its toxicity to animals. Smectites can adsorb AfB1 from aqueous solutions and, therefore, inactivate the toxin, but proteins in CFS inhibit the adsorption of AfB1 by smectites. The current study aimed to minimize the interference by CFS in adsorption of AfB1 on smectite by modifying a calcium-smectite (Ca-3MS) with a small nutritive organic compound, e.g. carnitine, choline, arginine, histidine, or tryptophan. The organo-smectites were characterized by X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy, and adsorption of AfB1 in CFS by these composites was examined. Various degrees of intercalation of the organic nutrients into the smectites were observed with XRD and FTIR. After immersing the smectite and organo-smectites in the CFS, the d001 values of Ca-3MS expanded to ~1.82 nm due to protein interaction, but the organo-smectites were confined to ~1.39 nm, which indicated that the protein had limited access to the organo-smectite interlayers. The IR bands at ~1652, 1544, 1538, and 1454 cm–1 from the organo-smectites revealed, however, that complete protein inhibition was not achieved. The organo-smectites were capable of adsorbing AfB1 in simple aqueous solution with maximal adsorption capacity up to 0.55 mol kg–1. Significantly greater (p ≤ 0.05) AfB1 adsorption was achieved by choline- and carnitine-modified smectites compared with the original Ca-3MS in the presence of competing protein (pepsin) in simple aqueous solution. In real CFS, both AfB1 adsorption capacities (Qmax) and affinities (K) by all organo-smectites were greater (Qmax = up to 0.45 mol kg–1 and K = up to 0.165 μM–1) than those by Ca-3MS (Qmax = 0.22 mol kg–1 and K = 0.031 μM–1). The study suggested that using smectites modified with an organic nutritive compound could be an effective, economical, and safe strategy for removing mycotoxins, including aflatoxins, during biofuel production.

With fossil-fuel consumption at an all-time high, air pollution is becoming one of the most prominent problems of the 21st century. In addition to their devastating effects on the environment, sulfur-based pollutants are problematic for infrastructure by undermining the structural stability of various oxide-based surfaces found in clays and clay minerals. Calcite (CaCO3) and alumina (α-Al2O3) are two such mineral oxides with surfaces that are potentially susceptible to damage by sulfur-based adsorbates. Their surface interactions with a wide range of sulfur-based pollutants, however, have yet to be studied adequately at the atomistic level. This problem can be addressed by utilizing density functional theory (DFT) to provide molecular-level insights into the adsorption effects of H2S, SO2, SO3, H2SO3, and H2SO4 molecules on calcite and alumina surfaces. DFT can be used to compare different types of adsorption events and their corresponding changes in the geometry and coordination of the adsorbates, as well as delineate any possible mineral-surface reconstructions. The hypothesis driving this comparative study was that the mineral-oxide surface structure will dictate the surface adsorption reactivity, i.e. the flat carbonate unit in calcite will behave differently from the Al–O octahedra in alumina under both vacuum and hydrated surface conditions. The set of sulfur-based adsorbates tested here exhibited a wide range of interactions with alumina and fewer with calcite surfaces. Events such as hydrogen bonding, sulfate formation, atom abstraction, and the formation of surface water groups were more prevalent in alumina than calcite and were found to be dependent on the surface termination. The results of this work will prove instrumental in the design of clay and mineral-based materials resilient to sulfur-based pollutants for use in construction and infrastructure such as smart building coatings and antifouling desalination membranes, as DFT methods can garner the atomistic insights into mineral-surface reactivity necessary to unlock these transformative technologies.

Polytypism is common in micas, and the frequency of polytype occurrence is believed to be related closely to the crystallization conditions and chemical compositions of the corresponding fluids and melts. Coexisting multiple standard and complex/disordered polytypes in igneous rocks generally reflect a complicated magma evolution history. The purpose of the current study was to clarify the origin of coexisting biotite polytypes and their growth mechanism. Micro-X-ray diffraction (μXRD) and transmission electron microscopy (TEM) were used to investigate Fe-rich biotite phenocrysts in rhyolite from the Long Valley Caldera, California, USA. The μXRD analyses characterized various polytypes, and TEM observations revealed that common polytypes (e.g. 1M, 2M1, and 3T) and rare polytypes (e.g. 4M2 and 4A8) coexist within biotite monocrystals. The two 4-layer polytypes of Fe-rich biotite, 4M2 and 4A8, were identified via selected-area electron diffraction (SAED) and high-resolution scanning transmission electron microscopy (HRSTEM) at the atomic resolution, with unique stacking sequences ([0222] for 4M2 and [002$\overline{2}$] for 4A8). Energy-dispersive X-ray spectroscopy (EDS) results showed differences in their chemical compositions, especially Fe and K. The 4A8 polytype is reported for the first time. The present study suggested that environmental changes, such as rapid cooling and inhomogeneous compositional distribution, led to chemical and structural oscillations and complex nucleation of the two 4-layer polytypes. Screw dislocations producing spiral growth enhance polytype stability and form ordered long-period/complex polytypes. These results are useful to understand the origin of long-period/complex polytypes and the intergrowths of diverse polytypes formed in non-equilibrium crystallization environments.

Essential oils (including carvacrol, CAR) have been used in the medicinal and health field because of their broad-spectrum antibacterial activities. However, the volatility and pungent odor are still the greatest obstacles to wider application. The purpose of the present study was to address those problems by encapsulating the antibacterial CAR in palygorskite (Plg) by integrating it into Pickering emulsions with complex coacervation. The CAR in Pickering emulsion was formed firstly by stabilization with the CAR-modified Plg; then, the emulsion droplets were embedded and fixed in the microcapsule through the subsequent complex coacervation process, which occurred between the quaternary ammonium salt of chitooligosaccharides (HACC) and sodium alginate (SA) via calcium ions. The microcapsules obtained were characterized by Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results demonstrated that the microcapsules presented a nearly sphere-like shape with a mean diameter of 3.5 mm but had a porous interior structure. The Plg plays multiple roles in the preparation process, including increasing the emulsion stability, improving the encapsulation efficiency of CAR, and the thermostability of microcapsules. The microcapsules showed remarkable antibacterial properties against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), and inhibition rates toward E. coli and S. aureus reached 100% when the microcapsules were encapsulated with 15 or 20% of CAR, respectively. The microcapsules obtained could be used as antibacterial agents in food preservatives, animal feed, and other health-related consumer products.

Biocompatible drug-delivery materials are important because they provide controlled release of biologically active agents to enhance the effectiveness of medical treatments. Montmorillonite (Mnt) has been utilized in drug-delivery systems for delayed-release application because it can safely encapsulate drug molecules via intercalation reactions. The objective of the present study was to evaluate the delivery characteristics of the drug ciprofloxacin (CIP) from a composite with Mnt (Mnt-CIP) in which the Mnt was first prepared by acid treatment and vibration ball milling. The surfaces of Mnt were modified by reacting the Mnt suspension in 1.0 M HCl acid and by dispersing the powder with a vibration ball mill, then the CIP drug was added at pH 4 and stirred. The goal was to improve the sustained-release performance of the CIP. This Mnt-CIP drug-release system was characterized by X-ray diffraction, X-ray fluorescence analysis, Fourier-transform infrared spectroscopy, surface area measurement using the Brunauer-Emmett-Teller (BET) method, and ultraviolet spectroscopy. The X-ray diffraction results confirmed the intercalation of CIP into the interlayer space of Mnt. The in vitro release properties of the intercalated CIP were investigated using a simulated phosphate-buffered saline solution (pH 7.4) at 36±0.5°C. The CIP drug exhibited a continued release for 3 h. Moreover, Mnt prepared by HCl acid treatment and dispersion in the vibration ball mill delayed the drug dissolution rate. In summary, the Mnt-CIP composite prepared in this study exhibited slow and sustained release characteristics, indicating that Mnt mined from the Gampo-40 mining area in Gyeongju can be used in various drug-delivery applications.

The state of iron in coal gangue minerals is an important factor in determining the potential for value-added utilization of this solid waste; this is especially true for the coal gangue coming from the Pingshuo open-pit mine in China. The objective of the present study was to characterize the petrological, mineralogical, and chemical states of Fe in the coal gangue from the Carboniferous Taiyuan Formation. Methods used included polarizing microscopy, X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS), X-ray fluorescence, micro-Fourier-transform infrared (micro-FTIR) spectroscopy, and Mössbauer spectroscopy. The coal gangues are mudstones, silty mudstones, and pelitic siltstones, which are composed primarily of kaolinite, quartz, feldspar, pyrite, illite, and magnesite. In coal gangue, the Fe was found to occur in ferruginous minerals, in crystal-lattice substitutions, or in a colloidal state. The ferruginous minerals in the coal gangue are pyrite and marcasite, and the pyrite morphologies are framboidal, euhedral octahedral crystals, subhedral granular crystals, and irregular crystals. The results of SEM–EDS and micro-FTIR confirmed that the lattice substitution of Fe in the coal gangue minerals occurred mainly in kaolinite, resulting in two types of kaolinite: iron-containing and iron-free kaolinite. The former may be transformed from volcanic biotite and the latter from volcanic feldspar. The Mössbauer spectra of kaolinite showed intense doublets with isomer shift and quadrupole splitting values consistent with tetrahedrally coordinated Fe3+ and ocahedrally coordinated Fe2+, suggesting the presence of two types of substitution sites: (1) Fe2+ replacing Al3+ in the octahedral sheet; and (2) Fe3+ replacing Si4+ in the tetrahedral sheet. This study has important theoretical significance for the high-value utilization of coal gangue.

The deep regolith of the southeastern United States has undergone rapid erosion in the last two centuries due to intensive agricultural practices, which has altered the landscape and its inherent fertility. Parent material, landscape position, and land use are important factors in controlling the mineral and elemental composition of soil profiles. Independent quantitative X-ray diffraction (QXRD) and whole-rock chemical analysis of eight weathering profiles agreed well and allow mineral reaction pathways to be constrained as particles are conveyed in the subsurface. QXRD analysis of saprolite, argillic, and soil A-horizons in the profiles highlights the imprint of bedrock on the regolith, which includes Neoproterozoic meta-tonalitic to meta-granodioritic and Paleozoic meta-granitic to biotite- and amphibolite-gneissic lithologies. Also, aeolian input slightly influenced A-horizon composition. The clay mineral assemblage is dominated by kaolinite, but profiles differ in the amount of interstratified clay minerals, halloysite, hematite, goethite, and gibbsite. Rare-earth element totals vary between 30 and 1048 ppm and are generally correlated positively with clay and clay mineral content. Eu and Ce anomalies reflect parent rocks and subsequent hydrolysis and redox history, with trends depending upon landscape position and clay content in the weathering profile. Weathering profiles on a high-order interfluve and those that were actively cultivated have thick argillic horizons (as defined by clay mineral abundance) and are depleted in alkali and alkaline-earth elements. Profiles proximally developed on old-field pine and never-cultivated hardwood forest land do not show large differences in mineral composition trends, whereas profiles on old-field sites with ongoing cultivation exhibit assemblages enriched in clay minerals and (oxyhydr)oxides. Old-field pine sites that were historically eroded by previous cultivation tend to have shallower and thinner argillic horizons, which may well impact critical-zone processes involving gas and water fluxes. This study highlights that mineral compositions of deep regolith, saprolite, and shallow soil horizons are dependent on local geomorphology (i.e. watershed- and hillshed-orders). Quantifying soil and regolith compositional trends across the landscape is a prerequisite for determining rates of chemical and physical erosion on human and geologic time scales.

Sepiolite-based composites have great potential for application as flame-retardant and thermal-insulation material but their application and development are limited by poor mechanical properties. The objective of the present study was to combine polyvinyl alcohol (PVA) and 3-aminopropyltriethoxysilane (KH-550) with sepiolite (Sep) to improve its aerogel strength. A universal testing machine, thermogravimetry, and microcalorimetry were used to investigate the mechanical properties, thermal-stability, and flame-retardant properties, respectively, of aerogels. The results indicated that KH-550 can enhance effectively the mechanical properties and flame retardancy of aerogels. The compressive modulus of PVA/Sep vs KH-550/PVA/Sep aerogel was 209.28 vs. 474.43 kPa, the LOI index changed from 26.4 to 30.4%. The porosity of the aerogels was > 96% and the density was < 0.05 g/cm3. The thermal conductivity remained at between 0.0340 and 0.0390 W/(m·K), and the aerogel could recover to > 85% after a 50% compressive deformation. These data indicated that Sep-based aerogel would act as a flame retardant and a thermal insulating material with excellent mechanical properties.

Kaolin waste dumps contain a huge volume of material that cannot be commercialized due to the presence of variable amounts of iron minerals, which impart a yellowish color to the kaolin. Elimination of iron from kaolin using either a chemical or a biological method was the aim of this study. The chemical leaching of iron from kaolin was carried out using response surface methodology to optimize the reaction conditions. Time was found to be the most influential variable, although oxalic acid must be present to leach 32% of the iron. Biological leaching was also assayed for 14 days using a Bacillus strain. The results of bacterial leaching of iron from kaolin showed <1% iron elimination.

Functional montmorillonite can be dispersed in polymer coatings and organic species and polymers can be intercalated into the interlayer space or grafted onto the surface of the functional montmorillonite. The addition of functional montmorillonite into polymer-based coatings can significantly improve anti-corrosion, refractory, super-hydrophobicity, antibacterial activity, and absorption of solar radiation by the resulting montmorillonite/polymer coatings. Montmorillonite can be functionalized for this purpose by ion exchange, intercalation, exfoliation, or combinations of these treatments. The rigid montmorillonite layers interspersed within the polymer matrix inhibit the penetration of corrosive substances, minimize the impact of high-temperature airflow, and thereby lead to strong resistance of the coating to corrosion and fire. The combination of polymers and dispersed montmorillonite nanolayers, which are modified by metal ions, metal oxides, and hydrophobic organic species, allows the resulting  composite coating to have quite a rough surface and a much smaller surface free energy so that the montmorillonite/polymer coating possesses superhydrophobicity. The interlayer space of functional montmorillonite can also host or encapsulate antibacterial substances, phase-change materials, and solar energy-absorbing materials. Moreover, it can act as a template to make these guest species exist in a more stable and ordered state. Literature surveys suggest that future work on the functional montmorillonite/polymer coatings should be targeted at the manufacture of functional montmorillonite nanolayers by finding more suitable modifiers and tuning the dispersion and funtionalities of montmorillonite in the coatings.

Calcined clays are used as a supplementary cementitious material (SCM) because, as hydrated aluminosilicates of the phyllosilicate group, they can be activated thermally, promoting dehydroxylation and structural disorder, i.e. making them reactive. The main effect of using calcined clay as an SCM is that CO2 emissions into the atmosphere are reduced by the reduction in the clinker/cement factor due to substitution of a proportion of clinker by calcined clay. Clays rich in kaolinite (1:1) group minerals offer most promise in terms of thermal activation. However, increased costs caused by demand for kaolinite from other industries means that type 2:1 calcined clays and mixtures of them have begun to be investigated as possible pozzolanic materials. The physical, chemical, and mineralogical characteristics that control the performance of these calcined clays as SCMs are still under discussion. Few in-depth studies of the behavior of these characteristics have been reported. The origin and geological history of raw materials, as well as their impact on the thermal activation and performance as SCM, are not well understood or, in some cases, have not been considered. The objective of the current work, therefore, was to study multicomponent clays from metamorphic rocks with low-grade kaolinite (<50%) from a tropical region of Colombia for possible use as SCMs. The clay deposit was identified by geological exploration techniques and classified in depth according to horizons of the weathering profile. The samples were extracted from the first 50 m of the deposit and characterized physically, chemically, and mineralogically; they were calcined at 650, 750, and 850°C; their degree of alteration was estimated by the Chemical Index of Alteration (CIA); and their performance as an SCM was evaluated by the Strength Activity Index (SAI) and Frattini test. As a main result, a relationship was found between the weathering profile of the deposit and the CIA of raw clays, which confirmed the high weathering and degree of alteration of the parent rock in the deposit (weathered rock and residual soil with a CIA > 80%). Furthermore, pozzolanic (physical and chemical) tests demonstrated the potential use of calcined clays from this deposit as SCMs, as well as their thermal activation at low temperature (≤750°C). In addition, the pozzolanic activity increased with the kaolinite/(muscovite+illite+vermiculite) ratio mainly, and, in turn, the thermal activation temperature increased with the mica and type 2:1 clay content.

Graphite phase carbon nitride (g-C3N4) is a non-metal semiconductor material with a suitable band gap (2.7 eV) for visible photocatalysis. However, the high cost of relevant synthesis methods and poor adsorption performance have limited its practical applications. The objective of the present study was to mitigate these problems by synthesizing the g-C3N4 in the presence of exfoliated montmorillonite (Mnt). Compared with bulk montmorillonite, the specific surface area of exfoliated two-dimensional Mnt layers was significantly increased. As a result, the light transmittance of the lamella improved noticeably due to the fact that a freshly exposed surface had a large number of active reaction sites, making Mnt an excellent carrier for the photocatalyst g-C3N4. In order to improve the photocatalytic performance of g-C3N4, a series of g-C3N4/Mnt composites was prepared by a wet chemical method using Mnt nanolayers as the matrix. X-ray diffraction, infrared spectroscopy, Brunauer-Emmett-Teller nitrogen adsorption/desorption, transmission electron microscopy, and ultraviolet-visible diffuse reflectance spectroscopy were used to analyze the phase structure, the chemical bonds, the specific surface area and pore sizes, the morphology, and the light absorption characteristics of the composites, respectively. Rhodamine B (RhB) served as the target dye to test the photocatalytic degradation performance of the composites under visible light. According to the findings, the surface of the Mnt nanolayers was densely and uniformly covered by g-C3N4, forming a multi-layered stack structure. An increase of the calcination temperature improved the crystallinity of g-C3N4, leading first to densification and then to relaxation of the layered composite structure. Conversely, the band gap of the composite gradually decreased from 2.56 to 2.4 eV. Furthermore, temperature exposure changed the photocatalytic performance of the composite drastically. While the largest photocatalytic activity was observed at 610°C, it started to decrease with further heating of the composite. The complete degradation of RhB solution occurred after 2 h of visible light irradiation. The findings of the current study provide a scientific basis for the synthesis of a new generation of photocatalysts.

Boron and lithium were analyzed in three nanometer-sized (<20, 20-50 and 50-100 nm) separates of two Santonian (85.8-83.5 Ma) bentonite samples collected closely in the Campos Basin along the southeastern Atlantic coast (Brazil). The B and Li data give various trends that suggest varied crystallization conditions for separates that consist of overwhelming smectite with less than 9% illitic layers. The δ11B of the few illitic tetrahedral sites from one of the samples remains quite constant, while its contents are strictly correlated with those of K, which suggests that illitization proceeded by interaction with pore fluids of the host sediments that supplied the K. In the second sample, the δ11B of the illite layers from the two coarser fractions is indicative of an early volcanic origin, while the smaller size fraction also interacted with sedimentary fluids. Favored by octahedral substitutions of the smectite layers, the δ7Li is more strictly regulated by a volcanic link. In turn, the information of the B and Li isotopic compositions and contents from studied mixed-layers suggests a various origin for the few illite layers of the smectite-rich I-S that contain more B than the smectite layers that host more Li. The difference appears to be sample-site and crystal-size dependent, fueled by pore fluids of the hosting turbidites.

Methoxykaolinite is a very popular organo-modified kaolinite. Even though it has a number of interesting properties, this nanohybrid material is still underused in terms of practical applications. In the present study, methoxykaolinite was synthesized and used for the first time as an electrode modifier for Pb(II) determination in various aqueous media. X-ray powder diffractometry (XRD), 13C nuclear magnetic resonance (NMR), and Fourier-transform infrared (FTIR) spectroscopy were used as characterization tools to confirm the presence of grafted methoxy groups in the interlayer space of kaolinite. The electrochemical characterization of methoxykaolinite using the cationic probe Ru(NH3)63+ showed that the modified clay presents favorable interactions with cationic compounds. A methoxykaolinite-modified electrode was applied successfully to the quantification of Pb(II) in aqueous solution. At optimized experimental conditions, the calibration curve in the concentration range 0.025–0.3 μM showed excellent linearity (R2 > 0.99), a sensitivity of 3.36 μA μM–1, and a detection limit of 5.6 nM. This detection limit was 10 times lower than the minimum concentration of Pb(II) authorized in drinking water. The sensor was used also for the determination of Pb(II) in tap, river, and well water samples with only minor loss of sensitivity and recoveries (90±5% to 110±4%). Thanks to the excellent biocompatibility of kaolinite, the sensor was applied for Pb(II) detection in human urine. Recovery in the range 98±8% to 103±6% was obtained when three freshly collected urine samples were spiked with known amounts of Pb(II). These results showed the interesting potential of methoxykaolinite as an electrode modifier for trace-level detection of cations, even in biological samples.

The supply of Corumbataí Formation rocks, which occur widely in the State of São Paulo, Brazil, and are used by Santa Gertrudes Ceramic Cluster, is dwindling and prospecting for new deposits is essential. The current study aimed to map and characterize new reserves of ceramic raw materials which would guarantee mineral and economic sustainability of the important concentration of ceramic-processing capability in that area, and thereby contribute to improving and diversifying the range of products manufactured and to promoting a greater presence in the international market. To achieve the proposed objectives, 16 profiles were sampled and the samples were submitted to granulometric analysis by laser diffraction, and the major elements by inductively coupled plasma-mass spectrometry, and the mineralogical compositions of clay samples were determined by X-ray diffraction and ceramic properties. Six lithofacies were identified and grouped into two facies associations: a lower shoreface association comprising massive siltstone (Sm) and laminated siltstone (Sl); lithofacies, and an upper shoreface association comprising heterolithic sandstone (Sh), lenticular sandstone (Sle), intercalated sandstone/siltstone (Si), and altered siltstone (Sa) lithofacies. The lithofacies of the lower shoreface association were more clayey, flux with a significant presence of illite and microcline, and a more uniform granulometry distribution, which made its classification possible, technologically, as stoneware and semi stoneware. The main application of this material is in the production of coatings through the wet milling process. The lithofacies of the upper shoreface association was sandier, had a refractory presence with kaolinite and montmorillonite, and had a less uniform granulometric distribution; technologically, it can be characterized as porous and semi-porous. The main application of this material is in the production of coatings by the dry milling process. The results obtained by facies analysis combined with the geochemical and ceramic properties of the Corumbataí Formation rocks revealed both vertical and lateral variations of the lithofacies, which influence their properties, behavior, and application as ceramic raw materials.

As 1:1 dioctahedral clay minerals, kaolinite and halloysite have similar chemical compositions. However, halloysite often possesses a nanotubular structure and special surface reactivity compared to platy kaolinite. The objective of this current work was to determine the effect of the SiO2/Al2O3 ratio on the microstructure and properties of geopolymers derived from two kinds of kaolin: platy kaolinite and nanotubular halloysite. The chemical structures and compositions of the geopolymers obtained were characterized through X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR), whereas the microstructural analysis was performed by scanning electron microscopy (SEM), the Brunauer–Emmett–Teller (BET) method, and N2 physisorption analysis. The results indicated that calcined halloysite showed greater geopolymerization reactivity than calcined kaolinite. In addition, the mechanical properties of the clay-based geopolymers depended not only on the SiO2/Al2O3 ratio but also on the morphology of the clay. Crystalline zeolite A and geopolymer were produced after alkali-activation of kaolin with a SiO2/Al2O3 ratio of 2.5; these products possessed porous and heterogeneous microstructures having poor compressive strength. As SiO2/Al2O3 ratios increased to >2.5, geopolymers with compact microstructure and high compressive strength were produced after alkali-activation of kaolin. Notably, at a given condition, halloysite-based geopolymers exhibited greater early compressive strength, more compactness, and more homogeneous microstructure than kaolinite-based geopolymers. This can be attributed to the nanotubular microstructure of halloysite, which can release more Si and Al during alkali activation than platy kaolinite. These results indicated that the various morphologies and microstructures among clays have significant impact on the microstructure and compressive strength of geopolymers.

Powder-type semiconductor photocatalysts are widely applicable but their defects (e.g. easy agglomeration during preparation and recyclability in the suspension system) limit their practical application. In the current study, perovskite oxide photocatalytic material was loaded onto a muscovite substrate to overcome the problems of low stability, easy agglomeration, and difficult recovery. A photocatalytically active LaNi0.95Fe0.05O3/muscovite composite material was synthesized by a sol-gel impregnation method. Phase composition, morphology, and interfacial interaction of the composites, denoted as LNFBY-x (x: mass ratio of LNF to muscovite), were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and other analytical methods. According to the results, the particle size of LNF nanoparticles was regulated effectively by compounding with muscovite, and the agglomeration of LNF decreased. LNF nanoparticles were distributed evenly and attached in dense fashion to the surface of muscovite, thereby increasing the contact area with the reaction medium. The nanoparticles were connected to the silicon-oxygen tetrahedral sheet of the muscovite via Si–O–La, Si–O–Ni, and Si–O–Fe bonds, which increased the bonding strength between the composite components and expedited the transfer of photogenerated charge. More highly active oxygen species were produced, and a growing number of chemically active moieties (٠O2- and ٠OH) was generated in the photocatalytic reaction. LNFBY-1.00 demonstrated the best photocatalytic activity. A degradation rate of methyl orange of 99.03% was achieved after visible-light irradiation for 120 min, which decreased to 75.75% after five repeated uses, thereby indicating high stability and recycling ability. The photocatalytic LaNi0.95Fe0.05O3/muscovite composite material exhibited potential for application in environmental remediation practices.

Diagenetic illite growth in porous sandstones leads to significant modifications of the initial pore system which result in tight reservoirs. Understanding and quantifying these changes provides insight into the porosity-permeability history of the reservoir and improves predictions on petrophysical behavior. To characterize the various stages of diagenetic alteration, a focused ion beam – scanning electron microscopy (FIB-SEM) study was undertaken on aeolian sandstones from the Bebertal outcrop of the Parchim Formation (Early Permian Upper Rotliegend group). Based on 3D microscopic reconstructions, three different textural types of illite crystals occur, common to many tight Rotliegend sandstones, namely (1) feldspar grain alterations and associated illite meshworks, (2) tangential grain coats, and (3) pore-filling laths and fibers. Reaction textures, pore structure quantifications, and numerical simulations of fluid transport have revealed that different generations of nano-porosity are connected to the diagenetic alteration of feldspars and the authigenic growth of pore-filling illites. The latter leads to the formation of microstructures that range from authigenic compact tangential grain coatings to highly porous, pore-filling structures. K-feldspar replacement and initial grain coatings of illite are composed primarily of disordered 1Md illite whereas the epitaxially grown illite lath- and fiber-shaped crystals occurring as pore-filling structures are of the trans-vacant 1Mtv polytype. Although all analyzed 3D structures offer connected pathways, the largest reduction in sandstone permeability occurred during the initial formation of the tangential illite coatings that sealed altered feldspars and the subsequent growth of pore-filling laths and fibrous illites. Analyses of both illite pore-size and crystallite-size distributions indicate that crystal growth occurred by a continuous nucleation and growth mechanism probably controlled by the multiple influx of potassium-rich fluids during late Triassic and Jurassic times. The detailed insight into the textural varieties of illite crystal growth and its calculated permeabilities provides important constraints for understanding the complexities of fluid-flow in tight reservoir sandstones.

Reducing the environmental footprint of cement is an absolute necessity to meet the commitments of COP26 and to limit global warming to + 1.5°C compared to the pre-industrial level. In this context, particular interest has developed in recent years in the use of calcined clays as supplementary cementitious materials (SCMs). Due to their high reactivity, large reserves and homogeneous distribution on the earth's surface, calcined clays represent a viable alternative to conventional SCMs. Clay minerals are highly variable and numerous, each with their own characteristics. As a result, not all of them have potential for use as SCMs. The present paper investigated the use of palygorskite (a clay that has been relatively poorly studied) as an SCM. Two commercial palygorskites of different grades were selected and their calcination was studied by X-ray diffraction and pozzolanic activity tests. Blended cements incorporating 20% of each calcined palygorskite were prepared and the mechanical performance and resistivity of the mortars measured. The results show that the optimum calcination temperature is 800°C (allowing complete amorphization of the clay fraction and the highest pozzolanic reactivity) for both clays. Mortars made with 80% ordinary Portland cement (OPC) blended with 20% of 800°C calcined palygorskite allowed a significant increase in compressive strength and electrical resistivity compared to the reference (100% OPC). The clay sample with palygorskite as the dominant mineral exhibited the greatest pozzolanic reactivity and mechanical performance in cementitious systems, confirming that palygorskite is a clay mineral with a significant potential for a use as a SCM. The second sample with smaller palygorskite content also allowed a significant increase in mechanical performance. This demonstrated that it is not necessary to use high-purity samples and enhances the value of this type of material.

Sub-surface clay samples are difficult to characterize using conventional methods so non-invasive Nuclear Magnetic Resonance (NMR) techniques were used to evaluate in a preserved state the pore structure, porosity, water mobility, and affinity of various clay systems. Within the CLAYWAT project launched by the NEA Clay Club, some of the most advanced NMR techniques were applied to samples from 11 clay-rich sedimentary formations (Boom Clay, Yper Clay (both Belgium); Callovo-Oxfordian shale, Upper Toarcian (both France); Opalinus Clay from two sites (Switzerland); Queenston Fm., Georgian Bay Fm., Blue Mountain Fm. (all Canada); Boda Clay (Hungary); and Wakkanai Fm. and Koetoi Fm. (Japan)). The degree of induration within this suite of samples varies substantially, resulting in a wide porosity range of 0.02–0.6. The key finding is the determination of pore-size distribution by NMR cryoporometry in the range of 2 nm–1 μm with the native fluid present in the pore space for most samples. The water volume in pore sizes of <2 nm could also be measured, thus providing a full description of the porosity system. A specific preparation by sample milling was applied to the preserved original cores minimizing disturbances to the samples in terms of water loss. The water content measured by NMR relaxation was comparable to values obtained by drying at 105°C. In general, the narrow T2 distributions indicate that water was diffusing throughout the pore network during the magnetization lifetime, implying that T2 distributions cannot be considered as proxies for the pore-size distributions. For the set of samples considered, the T1/T2 varied between 1.7 and 4.6, implying variable surface affinity. Finally, for most samples, a pore-shape factor of ~2.4, intermediate between a sheet (1) and a cylinder (4), was deduced.