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First-order relationships between organic matter content and mineral surface area have been widely reported and are implicated in stabilization and long-term preservation of organic matter. However, the nature and stability of organomineral interactions and their connection with mineralogical composition have remained uncertain. In this study, we find that continentally derived organic matter of pedogenic origin is stripped from smectite mineral surfaces upon discharge, dispersal, and sedimentation in distal ocean settings. In contrast, organic matter sourced from ancient rocks that is tightly associated with mica and chlorite endures in the marine realm. These results imply that the persistence of continentally derived organic matter in ocean sediments is controlled to a first order by phyllosilicate mineralogy.

Montmorillonite is a natural clay mineral linked with the smectite group of a dioctahedral 2:1 phyllosilicate formed by two tetrahedral sheets along with one octahedral sheet. In contradiction to other clay nanoparticles, the montmorillonite confers an interlayer spacing on either side of each triple-sheet layer. MMT was fashioned by dissolving rocks and minerals on Earth’s surface. The remarkable qualities responsible for the reinforcing efficiency of MMT include greater surface area and a higher aspect ratio. These qualities confer distinctive thermal, gas barrier, mechanical and rheological properties to MMT-rubber or polymer composites. It is also used as a promoter of rubber particle size reduction in polymer or rubber matrices and has attracted diverse merits for material applications globally. MMT displays potential for use as active agents and as an alternative to other expensive nanoparticles in the fabrication of multi-use and high-quality rubber nanocomposites. Rubber nanocomposites filled with MMT showed superior viscosity, toughness, and rigidity with less tensile strength and elongation at break. This paper reviews current multi-advancements in montmorillonite rubber or polymer nanocomposites (MMT-RCNs/PCNs): applications of MMT-RCNs/PCNs in aerospace, automobile, food additives, antibacterial, polymer, sorbent, catalyst, pharmaceutical, tissue engineering, biosensing, drug release and the utilization of polymer-based hydrogels investigated at both 2D and 3D nanoclay particles for various applications. Graphical Abstract

Glauconite must be assessed as mica-rich mica-smectite R3 interstratified mineral, with the pure end-member mica also having intrinsic K-deficient chemical characteristics (K ~ 0.8 apfu). This assertion is in accordance with our X‑ray diffraction (XRD) and high-resolution tranmission electron microscopy (HRTEM) studies and chemical analyses by electron probe microanalysis (EPMA) of mature glauconites in Cenozoic Antarctic sediments that indicate that: (1) It consists of a glauconite-smectite (R3 ordered) mixed-layer silicate, composed mainly of mica-type layers (>90%), but displaying slightly different proportions of Fe(III)-smectite layers (<10%). (2) More mature glaucony grains are characterized by major K and Fe (mica layers) and minor Fe (smectite layers) content in the interstratified glauconite-smectite. (3) Potassium is stabilized at the interlayer site by the octahedrally coordinated Fe . (4) Microtexture of the glauconite crystals are comparable with those of other micas and illite minerals, with straight, defect-free lattice fringes of ~10 Å spacings glauconite packets characteristic of mica with minor interstratified poorly crystalline smectite layers. In addition, our new findings give insights into the glauconitization process and at the same time investigate the potassium-deficient character of the dioctahedral mica “ .” These findings show that glauconite crystallizes by a layer-growth mechanism at the expense of a poorly crystalline smectite precursor and that smectite-to-glauconite transformations are accompanied by a gradually higher octahedral charge deficiency (Fe /Fe ) stabilized by K uptake into the interlayer sheet.

The sol–gel state of smectite clay dispersions varies with the volume fraction of clay and electrolyte concentration. In this study, it was elucidated that the drying patterns of droplets from four types of smectite clay dispersions vary according to their sol–gel states. Droplets in the sol state exhibited a ring-shaped pattern, while those in the gel state showed a bump-shaped pattern. Near the boundary between the sol and gel states, patterns featuring both ring and bump structures were observed regardless of whether the droplets were on the sol or gel side. When guest particles or molecules were introduced into the clay dispersion, they dispersed uniformly within the system, and the drying pattern depended on the sol–gel state of the droplets. These findings suggest that the presence or absence of convection within the droplets during drying governs the drying pattern.

A novel and cost-effective heterogeneous catalyst for glycerol carbonate production through transesterification was developed by impregnating smectite clay with K[sub.2]CO[sub.3]. Comprehensive structural and chemical analyses, including X-ray diffraction Analysis (XRD), Scanning Electron Microscopy (SEM)-Electron Dispersion Spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) surface area analysis measurements, were employed to characterize the catalysts. Among the various catalysts prepared, the one impregnated with 40 wt% K[sub.2]CO[sub.3] on smectite and calcined at 550 °C exhibited the highest catalytic activity, primarily due to its superior basicity. To enhance the efficiency of the transesterification process, several reaction parameters were optimized, including the molar ratio between propylene carbonate and glycerol reactor loading of the catalyst and reaction temperature. The highest glycerol carbonate conversion rate, approximately 77.13% ± 1.2%, was achieved using the best catalyst under the following optimal conditions: 2 wt% reactor loading, 110 °C reaction temperature, 2:1 propylene carbonate to glycerol molar ratio, and 6h reaction duration. Furthermore, both the raw clay and the best calcined K[sub.2]CO[sub.3]-impregnated catalysts demonstrated remarkable stability, maintaining their high activity for up to four consecutive reaction cycles. Finally, a kinetic analysis was performed using kinetic data from several runs employing raw clay and the most active K[sub.2]CO[sub.3]-modified clay at different temperatures, observing that a simple reversible second-order potential kinetic model of the quasi-homogeneous type fits perfectly to such data in diverse temperature ranges.

There are three groups of scientists dominating the search for the origin of life: the organic chemists (the Soup), the molecular biologists (RNA world), and the inorganic chemists (metabolism and transient-state metal ions), all of which have experimental adjuncts. It is time for Clays and the Origin of Life to have its experimental adjunct. The clay data coming from Mars and carbonaceous chondrites have necessitated a review of the role that clays played in the origin of life on Earth. The data from Mars have suggested that Fe-clays such as nontronite, ferrous saponites, and several other clays were formed on early Mars when it had sufficient water. This raised the question of the possible role that these clays may have played in the origin of life on Mars. This has put clays front and center in the studies on the origin of life not only on Mars but also here on Earth. One of the major questions is: What was the catalytic role of Fe-clays in the origin and development of metabolism here on Earth? First, there is the recent finding of a chiral amino acid (isovaline) that formed on the surface of a clay mineral on several carbonaceous chondrites. This points to the formation of amino acids on the surface of clay minerals on carbonaceous chondrites from simpler molecules, e.g., CO2, NH3, and HCN. Additionally, there is the catalytic role of small organic molecules, such as dicarboxylic acids and amino acids found on carbonaceous chondrites, in the formation of Fe-clays themselves. Amino acids and nucleotides adsorb on clay surfaces on Earth and subsequently polymerize. All of these observations and more must be subjected to strict experimental analysis. This review provides an overview of what has happened and is now happening in the experimental clay world related to the origin of life. The emphasis is on smectite-group clay minerals, such as montmorillonite and nontronite.

The Palaeocene-Eocene Thermal Maximum (PETM) was a global extreme climatic event, but it is relatively unknown from lower latitudes or equatorial regions in comparison to mid- and high latitudes. The present study provides the first clay mineralogical evidence of the PETM and subsequent hyperthermal events in a near-equatorial region represented by the Akli Formation in the Barmer Basin, India. The 32 m-thick succession of the Akli Formation shows abrupt changes in smectite and kaolin abundances preceding, during and succeeding the PETM event. Within the studied section, the kaolin content increases from 5-8% pre-PETM to 30-35% during the PETM, and then again decreases to 5-6% during the post-PETM period. The smectite, however, is marked by a corresponding decrease and its transformation into kaolin in acid weathering conditions. The transformation of the smectite is first marked by hydroxy interlayering and then transformation into kaolin during the PETM. The transformation of smectite into kaolin also resulted in extensive precipitation of iron oxide in sediments. The clay mineralogical changes in the Palaeocene-Eocene transition sediments of the Akli Formation were caused by 3-5°C warming and a 25-50% increase in rainfall during the hyperthermal events. Unusually high charcoal (∼20%) fragments during the Palaeocene-Eocene transition also suggest warming and widespread biomass burning during the PETM in the lower latitudes.

Clay authigenesis mostly concerns: (a) the formation of clays by direct precipitation from solution, called “neoformation” and (b) development of clays by transformation of precursor minerals. Precipitation from solution implies that a new mineral structure crystallizes, so that a prior mineral structure is not inherited. Transformation of precursor detrital minerals, a process also termed “neoformation by addition”, can be conducted whether throughout precipitation on pre-existing natural surfaces or transformation and reaction on pre-existing surfaces. Both processes have been recognized as effective mechanisms in the formation of Mg-clays, which mostly include 2:1 clay minerals, such as talc-kerolite and Mg-smectites, as well as fibrous clays (sepiolite, palygorskite). Authigenic Mg-clay minerals occur in both modern and ancient marine and non-marine depositional environments, although formation of these clays in hydrothermal continental and seafloor settings must be also outlined. Most favourable conditions for the formation of Mg-clays on earth surface are found in evaporitic depositional environments, especially where parent rocks are enriched in ferromagnesian minerals. In these settings, Mg-clays are important constituent of weathering profiles and soils and can form thick deposits of significant economic interest. Based on this review of authigenic clay deposits, we propose three geochemical pathways, mainly related to continental environments, for the origin of authigenic Mg-clays: formation of Al-bearing Mg-clays (pathway 1), formation of Al-free Mg clays (pathway 2) and formation of sepiolite from other Mg-clay minerals (pathway 3).

Lithium deposits in tuffaceous sediments of the McDermitt caldera constitute possibly the world’s largest Li clay resource, yet their characteristics and origin are not established. The 40 × 25 km McDermitt caldera collapsed during the eruption of ~1000 km3 of a 16.4 Ma, zoned peralkaline to metaluminous tuff; minor caldera magmatism ceased by 16.1 Ma. About 200 m of sediments mostly composed of glass from regional pyroclastic eruptions accumulated in the caldera until about 15.7 Ma. Closed hydrologic system diagenesis (CHSD) altered the tuffaceous sediments to a consistent vertical mineral zonation of clay, analcime, K-feldspar, and albite. Entire sedimentary sections in the southern and western parts of the caldera basin have ≥1500 ppm Li. Lithium-rich intervals are dominantly claystone. The most thoroughly studied deposit is a laterally continuous, ~3000 ppm Li zone in the lower sedimentary section that also has high K, Rb, Mo, As, and Sb (and partly Mg and F). Lithium occurs as an illitic clay (tainiolite?). The overlying, upper sedimentary section averages <2000 ppm Li which resides in smectite (hectorite). A transitional zone has variably mixed smectite–illite clay and averages ~2000 ppm Li. An 40Ar/39Ar age of ~14.9 Ma on authigenic K-feldspar in the illite zone is ~1.2 Ma younger than the 16.1 Ma end of magmatism in the caldera, which mitigates against a simple hydrothermal origin. Closed hydrologic system diagenesis was essential to Li mineralization, but Li budget calculations suggest a source of Li in addition to the tuffaceous sediments is required. This additional source could be Li originally in highly enriched magma that entered the diagenetic system through either (1) Li in magma exsolved into a hydrous volatile phase during eruption. The Li-rich volatile phase coated glass shards or was trapped in pumice and was quickly leached by surface or groundwater upon deposition in the caldera. (2) Residual magma immediately following ash-flow eruption and caldera collapse generated Li-rich hydrothermal fluids that mixed with meteoric water in the closed caldera basin, generating a hybrid diagenetic fluid. The hydrothermal fluid and hybrid diagenetic fluids would have existed only during initial basin sedimentation between about 16.4 and 16.1 Ma.

Soil absorbs about 20% of anthropogenic carbon emissions annually, and clay is one of the key carbon-capture materials. Although sorption to clay is widely assumed to strongly retard the microbial decomposition of soil organic matter, enhanced degradation of clay-associated organic carbon has been observed under certain conditions. The conditions in which clay influences microbial decomposition remain uncertain because the mechanisms of clay-organic carbon interactions are not fully understood. Here we reveal the spatiotemporal dynamics of carbon sorption and release within model clay aggregates and the role of enzymatic decomposition by directly imaging a transparent smectite clay on a microfluidic chip. We demonstrate that clay-carbon protection is due to the quasi-irreversible sorption of high molecular-weight sugars within clay aggregates and the exclusion of bacteria from these aggregates. We show that this physically-protected carbon can be enzymatically broken down into fragments that are released into solution. Further, we suggest improvements relevant to soil carbon models. Clays in soil impact atmospheric CO 2 by stabilizing soil organic matter, yet the dynamics of this process under future climate conditions are unknown. Here the authors present a way to observe clay-carbon dynamics within micro-aggregates using 4D imaging and a customized microfluidic chip.