Sustained wet-dry cycling on early Mars.

The presence of perennially wet surface environments on early Mars is well documented1,2, but little is known about short-term episodicity in the early hydroclimate3. Post-depositional processes driven by such short-term fluctuations may produce distinct structures, yet these are rarely preserved in the sedimentary record4. Incomplete geological constraints have led global models of the early Mars water cycle and climate to produce diverging results5,6. Here we report observations by the Curiosity rover at Gale Crater indicating that high-frequency wet-dry cycling occurred in early Martian surface environments. We observe exhumed centimetric polygonal ridges with sulfate enrichments, joined at Y-junctions, that record cracks formed in fresh mud owing to repeated wet-dry cycles of regular intensity. Instead of sporadic hydrological activity induced by impacts or volcanoes5, our findings point to a sustained, cyclic, possibly seasonal, climate on early Mars. Furthermore, as wet-dry cycling can promote prebiotic polymerization7,8, the Gale evaporitic basin may have been particularly conducive to these processes. The observed polygonal patterns are physically and temporally associated with the transition from smectite clays to sulfate-bearing strata, a globally distributed mineral transition1. This indicates that the Noachian-Hesperian transition (3.8-3.6 billion years ago) may have sustained an Earth-like climate regime and surface environments favourable to prebiotic evolution.

Characterization and application of the nanocompiste packaging films containing clay and TiO2 on preservation of tomato fruit under cold storage.

BACKGROUND: Tomato (Lycopersicon esculentum), a valuable economic crop worldwide, often goes to waste due to improper packaging and handling. In the present study, three types of low-density polyethylene nanocomposite films containing 3% clay (Closite 20A), 3% TiO2 nanoparticles, and their combination were synthesized using melt blending method, and evaluated on the quality parameters of tomato fruit during 42 days of storage at 4 °C. RESULTS: Transmission electron microscopy confirmed the degree of dispersion and exfoliation of the nanoparticles. The TiO2/clay-nanocomposite films exhibited notable enhancements in Young's modulus and tensile strength compared to conventional films. The addition of clay and TiO2 nanoparticles resulted in reduced permeability to CO2, O2, and water vapor. Fruits packed with clay/TiO2 nanocomposite films showed decreased ethylene production, mitigated weight loss, and maintained pH, titratable acidity, total soluble solids, and firmness. Furthermore, clay/TiO2 nanocomposite films enhanced membrane stability, decreased membrane lipid peroxidation, and enhanced catalase and ascorbate peroxidase enzyme activity in fruits. CONCLUSIONS: The relatively good exfoliation of clay nanoparticles and the proper dispersion of TiO2 nanoparticles, which were confirmed by TEM, led to an increase in mechanical and physical properties in the Clay/TiO2 nanocomposite. This film displayed more potential in maintaining the quality properties of tomato fruit during cold storage. Therefore, this film can be considered a practical solution for minimizing pathogen risks and contamination, and enhancing the overall quality of tomato fruit.

Recent Advances of Halloysite Nanotubes in Biomedical Applications.

Halloysite nanotubes (HNTs) have emerged as a highly regarded choice in biomedical research due to their exceptional attributes, including superior loading capacity, customizable surface characteristics, and excellent biocompatibility. HNTs feature tubular structures comprising alumina and silica layers, endowing them with a large surface area and versatile surface chemistries that facilitate selective modifications. Moreover, their substantial pore volume and wide range of pore sizes enable efficient entrapment of diverse functional molecules. This comprehensive review highlights the broad biomedical application spectrum of HNTs, shedding light on their potential as innovative and effective therapeutic agents across various diseases. It emphasizes the necessity of optimizing drug delivery techniques, developing targeted delivery systems, rigorously evaluating biocompatibility and safety through preclinical and clinical investigations, exploring combination therapies, and advancing scientific understanding. With further advancements, HNTs hold the promise to revolutionize the pharmaceutical industry, opening new avenues for the development of transformative treatments.

Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.

Critical Role of Mineral Fe(IV) Formation in Low Hydroxyl Radical Yields during Fe(II)-Bearing Clay Mineral Oxygenation.

In subsurface environments, Fe(II)-bearing clay minerals can serve as crucial electron sources for O2 activation, leading to the sequential production of O2•-, H2O2, and •OH. However, the observed •OH yields are notably low, and the underlying mechanism remains unclear. In this study, we investigated the production of oxidants from oxygenation of reduced Fe-rich nontronite NAu-2 and Fe-poor montmorillonite SWy-3. Our results indicated that the •OH yields are dependent on mineral Fe(II) species, with edge-surface Fe(II) exhibiting significantly lower •OH yields compared to those of interior Fe(II). Evidence from in situ Raman and Mössbauer spectra and chemical probe experiments substantiated the formation of structural Fe(IV). Modeling results elucidate that the pathways of Fe(IV) and •OH formation respectively consume 85.9-97.0 and 14.1-3.0% of electrons for H2O2 decomposition during oxygenation, with the Fe(II)edge/Fe(II)total ratio varying from 10 to 90%. Consequently, these findings provide novel insights into the low •OH yields of different Fe(II)-bearing clay minerals. Since Fe(IV) can selectively degrade contaminants (e.g., phenol), the generation of mineral Fe(IV) and •OH should be taken into consideration carefully when assessing the natural attenuation of contaminants in redox-fluctuating environments.

Abiotic synthesis of amino acids in the recesses of the oceanic lithosphere.

Abiotic hydrocarbons and carboxylic acids are known to be formed on Earth, notably during the hydrothermal alteration of mantle rocks. Although the abiotic formation of amino acids has been predicted both from experimental studies and thermodynamic calculations, its occurrence has not been demonstrated in terrestrial settings. Here, using a multimodal approach that combines high-resolution imaging techniques, we obtain evidence for the occurrence of aromatic amino acids formed abiotically and subsequently preserved at depth beneath the Atlantis Massif (Mid-Atlantic Ridge). These aromatic amino acids may have been formed through Friedel-Crafts reactions catalysed by an iron-rich saponite clay during a late alteration stage of the massif serpentinites. Demonstrating the potential of fluid-rock interactions in the oceanic lithosphere to generate amino acids abiotically gives credence to the hydrothermal theory for the origin of life, and may shed light on ancient metabolisms and the functioning of the present-day deep biosphere.

Eco-friendly synthesis of clay-chitosan composite for efficient removal of alizarin red S dye from wastewater: A comprehensive experimental and theoretical investigation.

Alizarin Red S (ARS) is commonly utilized for dyeing in textile industry. The dye represents a refractory pollutant in the aquatic environment unless properly treated. To tackle this pollutant, the applicability of chitosan-clay composite (3C) for the ARS removal from textile wastewater was studied. Characterization studies were conducted on the synthesized adsorbent using Fourier transformation infrared (FT-IR), X-ray diffraction (XRD), and energy dispersive X-ray (EDX) techniques. Optimized parameters such as adsorbent's dosage, pH, reaction time, and initial concentrations were tested in a batch system. Additionally, density functional theory (DFT) was calculated to understand the adsorption mechanism and the role of benzene rings and oxygen atoms in the ARS as electron donors. At the same initial concentration of 30 mg/L and optimized conditions of 50 mg of dose, pH 2, and 10 min of reaction time, about 86% of ARS removal was achieved using the composite. The pseudo-second-order kinetic was applicable to model a reasonable fitness of the adsorption reaction, while the Temkin model was representative to simulate the reaction with a maximum adsorption capacity of 44.39 mg/g. This result was higher than magnetic chitosan (40.12 mg/g), or pure chitosan (42.48 mg/g). With ΔH = 27.22 kJ/mol and ΔG<0, the data implied the endothermic and spontaneous nature of the adsorption process. Overall, this implies that the clay-chitosan composite is promising to remove target dye from contaminated wastewater.

Augmentin loaded functionalized halloysite nanotubes: A sustainable emerging nanocarriers for biomedical applications.

Clay minerals such as Halloysite nanotubes (HNTs), abundantly available green nanomaterial, exhibit a significant advantage in biomedical applications such as drug delivery, antibacterial and antimicrobials, tissue engineering or regeneration, etc. Because of the mesoporous structure and high absorbability, HNTs exhibit great potential as a nanocarrier in drug delivery applications. The sulfuric acid treatment enhances the surface area of the HNTs and thereby improves their drug-loading capacity by enlarging their lumen space/inner diameter. In the present investigation, based on the literature that supports the efficacy of drug loading after acid treatment, a dual treatment was performed to functionalize the HNTs surface. First, the HNTs were etched and functionalized using sulfuric acid. The acid-functionalized HNTs underwent another treatment using (3-aminopropyl) triethoxysilane (APTES) to better interact the drug molecules with the HNTs surfaces for efficient drug loading. Augmentin, a potential drug molecule of the penicillin group, was used for HNTs loading, and their antibacterial properties, cytotoxicity, and cumulative drug release (%) were evaluated. Different characterization techniques, such as X-ray diffractometer (XRD) and Fourier Transform Infra-Red (FT-IR), confirm the loading of Augmentin to the APTES@Acid HNTs. TEM images confirm the effective loading of the drug molecule with the HNTs. The drug encapsulation efficiency shows 40.89%, as confirmed by the Thermogravimetric Analysis (TGA). Also, the Augmentin-loaded APTES@Acid HNTs exhibited good antibacterial properties against E. coli and S. aureus and low cytotoxicity, as confirmed by the MTT assay. The drug release studies confirmed the sustainable release of Augmentin from the APTES@Acid HNTs. Hence, the treated HNTs can be considered as a potential nanocarrier for effectively delivering Augmentin and promoting enhanced therapeutic benefits.

Enhancing clayey soil performance with lime and waste rubber tyre powder: Mechanical, microstructural, and statistical analysis.

Nowadays, for soil stabilisation and cleaner production of geo-composites, the possibility of utilizing waste rubber is in vogue. The present paper deals with experimentally investigating the mechanical and micro-structural characteristics of weak Indian clayey soil partially substituted with lime (0-3.5%) and waste rubber tyre powder (0-15%). It was observed that, with increasing lime and rubber powder content, the plasticity index of the soil decreases. The shear strength and compaction testing results reveal that adding lime and rubber tyre powder (RTP) enhances the geotechnical performance of clayey soil up to an optimum dosage value. Also, the tri-axial shear testing was performed to obtain stress-strain curves for all considered soil mixes. For modified clayey soil containing 3% lime and 12.5% rubber powder, the cohesion values and bearing capacities improved phenomenally by 36.1% and 88.6% respectively, when compared to clayey soil. Further for this mix, SEM analysis reveals a compacted microstructure which improves dry-density and California's bearing ratio among all modified mixes. The novel co-relations upon regression analysis are found able to predict plasticity index, dry density, bearing capacity and shear strength with higher confidence levels. Overall, the cost-benefit analysis worked out to obtain the optimum cost of construction of footings and flexible pavement shows cost deductions up to 19% and 39% respectively while utilizing modified clay soil mixes containing 3% lime and 12.5% rubber powder in subgrade, ultimately making production stronger, cheaper and environment friendly.

Cefixime loaded bare and functionalized halloysite nanocarriers and their biomedical applications.

Effective drug delivery for is the foremost requirement for the complete recovery of the disease. Nanomedicine and nanoengineering has provided so many spaces and ideas for the drug delivery design, whether controlled, targeted, or sustained. Different types of nanocarriers or nanoparticles are aggressively designed for the drug delivery applications. Clay minerals are identified as a one of the potential nanocarrier for the drug delivery. Owing to their biocompatibility and very low cytotoxicity, clay minerals showing effective therapeutic applications. In the present investigation, clay mineral, i.e., Halloysite nano tubes are utilized as a nanocarrier for the delivery of antibiotic cefixime (CFX), a third-generation cephalosporin. The HNT was first functionalized with the sulfuric acid and then further treated with the 3-(aminopropyl)triethoxysilane (APTES). The drug is loaded on three different classifications of HNTs, i.e., Bare-CFX-HNT, Acid-CFX-HNT, and APTES-CFX-HNT and their comparative analysis is established. Different characterization techniques such as X-ray diffractometry (XRD), Fourier transform infra-red (FT-IR), Transmission electron microscopy TEM), Brunauer-Emmett-Teller (BET), adsorption studies, and Thermogravimetric analysis (TGA) were performed to evaluate their chemical, structural, morphological, and thermal properties. TGA confirmed the encapsulation efficiency of Bare-CFX-HNT, Acid-CFX-HNT, and APTES-CFX-HNT as 42.65, 52.19, and 53.43%, respectively. Disk diffusion and MTT assay confirmed that the drug loaded HNTs have potential antibacterial activities and less cytotoxicity. The adsorption capacity of CFX with different HNTs are evaluated and Different adsorption and kinetic models have been discussed. Drug release studies shows that APTES-CFX-HNT showing sustained release of cefixime as compared to Bare-CFX-HNT and Acid-CFX-HNT.

Analysing the role of Fe (II) on flocculation of sand-clay mixtures under estuarine mixing.

Estuaries are fragile environment that are most affected by climate change. One of the major consequences of climate change on estuarine processes is the enhancement in salt intrusion leading to higher salinity values. This has several implications on the estuarine sediment dynamics. Of the various factors that affect the flocculation of cohesive sediments, salinity and turbulence have been recognized as to have great significance. Many of the estuaries are contaminated with heavy metals, of which, the concentration of Iron (Fe (II)) are generally on the higher range. However, the influence of Fe (II) on the flocculation of cohesive sediments at various estuarine mixing conditions is not well known. The present study investigated the influence of Fe (II) on the flocculation of kaolin at various concentration of Fe (II), salinity and turbulence shear. The results indicated that Fe (II) and salinity have a positive influence on kaolin flocculation. The increase in turbulence shear caused an initial increase and then a decrease in floc size. In case of sand-clay mixtures, that are observed in mixed sediment estuarine environments, a reduction in the floc size was observed, which is attributed to the breakage of flocs induced by the shear of sand. Breakage coefficient, which is a measure of break-up of flocs, is generally adopted as 0.5 assuming binary breakage. The present study revealed that the breakage coefficient can take values from 0 to 1 and is a direct function of Fe (II) and salinity and an inverse function of turbulence and sand concentration. Thus, a new model for breakage coefficient with the influencing parameters has been proposed, which is an improvement of existing model that is expressed in terms of turbulence alone. Sensitivity analysis showed that the proposed model can very well predict the breakage coefficient of Fe (II) - kaolin flocs. Thus, the model can quantify the breakage coefficient of flocs in estuaries contaminated with Fe (II) that is a vital parameter for population balance models.

Bio-based composite from chitosan waste and clay for effective removal of Congo red dye from contaminated water: Experimental studies and theoretical insights.

Water pollution due to dyes in the textile industry is a serious environmental problem. During the finishing stage, Congo red (CR) dye, water-soluble, is released into wastewater, polluting the water body. This study explores the effectiveness of utilizing a composite composed of Safi raw clay and chitosan to remove an anionic dye from synthetic wastewater. The chitosan was extracted from crab shells. Its removal performance was compared to that of natural clay. Both the composite and raw clay were used to remove target pollutant. The effects of the chitosan load in the composite, size particles, initial dye concentration, contact time, pH, and temperature on the dye's elimination were tested in batch modes. The composite with 30% (w/w) of chitosan exhibited the highest dye removal. At pH 2, an adsorption capacity of 84.74 mg/g was achieved, indicating that the grafting of the polymer onto clay surface enhances its efficacity and stability in acidic environments. This finding was supported by characterization data obtained from X-ray diffraction (XRD), scanning electron microscopy (SEM), dispersive X-ray spectroscopy (EDX), and Fourier transform infrared (FT-IR) analyses. Under optimized conditions of 20 mg dose, pH 2, 30 min of reaction time, and 20 mg/L of dye concentration, about 92% of dye removal was achieved. The Langmuir isotherm model represents dye adsorption by the composite, while dye removal was controlled by pseudo-second-order model. Thermodynamic data of the adsorption (ΔH = +8.82 kJ/mol; ΔG <0) suggested that the dye adsorption was spontaneous and endothermic. The findings provide insights into the dye elimination by the adsorbent, indicating that the removal occurred via attractive colombic forces, as confirmed by density functional theory (DFT) analysis. Overall, the composite of natural clays and chitosan waste is a promising and innovative adsorbent for treating wastewater containing recalcitrant dyes.

Biocompatibility of nano/micro-sized pyrophyllite particles by pulmo, liver, kidney and gastric mucosis cells.

Pyrophyllite is the least studied natural clay in terms of its potential in biomedical applications, although there are many deposits of this aluminosilicate around the world. Genotoxicity study was performed in vitro for this mineral. Subsequently, Wister rats were exposed to the pyrophyllite micronized to below 100 µm. After the exposure period, histology of the lung, liver, kidney and gastric tissues were performed, followed by the stereological and hematological analysis. The physicochemical analyses revealed typical XRD characteristics of pyrophyllite clay with particle-size distribution ranging 50 nm-100 µm with stable mineral composition and unique buffering property to pH around 8. The results showed that there were no cytotoxic effects on to THP-1 cells, or genotoxicity of pyrophyllite measured by the Comet assay. In vivo studies are accompanied by the thorough physicochemical characterization of the micronized pyrophyllite. Histology of the lung tissue proved presence of an inflammatory reaction. On the other hand, gastric tissue has shown the selective accumulation of nanoparticles in enterocytes of the stomach only, as supported by ultrastructural analysis. Liver and kidney tissues have shown tolerability for pyrophyllite particles. The results give directions for further comprehensive studies of potential biomedical applications of the pyrophyllite.

Heteroaggregation and deposition behaviors of carboxylated nanoplastics with different types of clay minerals in aquatic environments: Important role of calcium(II) ion-assisted bridging.

The widespread utilization of plastic products ineluctably leads to the ubiquity of nanoplastics (NPs), causing potential risks for aquatic environments. Interactions of NPs with mineral surfaces may affect NPs transport, fate and ecotoxicity. This study aims to investigate systematically the deposition and aggregation behaviors of carboxylated polystyrene nanoplastics (COOH-PSNPs) by four types of clay minerals (illite, kaolinite, Na-montmorillonite, and Ca-montmorillonite) under various solution chemistry conditions (pH, temperature, ionic strength and type). Results demonstrate that the deposition process was dominated by electrostatic interactions. Divalent cations (i.e., Ca2+, Mg2+, Cd2+, or Pb2+) were more efficient for screening surface negative charges and compressing the electrical double layer (EDL). Hence, there were significant increases in deposition rates of COOH-PSNPs with clay minerals in suspension containing divalent cations, whereas only slight increases in deposition rates of COOH-PSNPs were observed in monovalent cations (Na+, K+). Negligible deposition occurred in the presence of anions (F-, Cl-, NO3-, CO32-, SO42-, or PO43-). Divalent Ca2+ could incrementally facilitate the deposition of COOH-PSNPs through Ca2+-assisted bridging with increasing CaCl2 concentrations (0-100 mM). The weakened deposition of COOH-PSNPs with increasing pH (2.0-10.0) was primarily attributed to the reduce in positive charge density at the edges of clay minerals. In suspensions containing 2 mM CaCl2, increased Na+ ionic strength (0-100 mM) and temperature (15-55 ◦C) also favored the deposition of COOH-PSNPs. The ability of COOH-PSNPs deposited by four types of clay minerals followed the sequence of kaolinite > Na-montmorillonite > Ca-montmorillonite > illite, which was related to their structural and surface charge properties. This study revealed the deposition behaviors and mechanisms between NPs and clay minerals under environmentally representative conditions, which provided novel insights into the transport and fate of NPs in natural aquatic environments.

Kinetic modeling and optimization of the mono- and diglycerides synthesis mediated by the lipase Lipozyme® TL 100 L immobilized on clayey support.

Mono- and diglycerides play a crucial role in the food industry as multifunctional food additives and emulsifiers. Their importance stems from their unique properties, which allow them to improve the quality, texture, and stability of various food products. Here, results of the kinetic modeling of the mono- and diglycerides synthesis mediated by the lipase Lipozyme® TL 100 L immobilized on the clayey support Spectrogel® type C are reported. The support was characterized by TEM, SEM, and FTIR. Firstly, the influence of pH and lipase load on the immobilization process was analyzed, resulting in an enzymatic activity of 93.2 ± 0.7 U g-1 under optimized conditions (170.9 U g-1 of lipase and pH of 7.1). Afterward, the effects of reaction temperature and concentration of immobilized biocatalyst in the feedstock conversion were evaluated. At optimized parameters, a triglycerides conversion of 97% was obtained at 36.5 °C, 7.9 vol.% of enzyme, a glycerol to feedstock molar ratio of 2:1, and 2 h. The optimized conditions were used to determine the kinetic constants of the elementary reactions involved in the glycerolysis, where a fit superior to 0.99 was achieved between experimental values and predicted data.

Development of toothpaste formulations containing mineral clays as abrasive agents and their effects on the physical properties of dental enamel.

To assess the physical properties and topographical aspect of dental enamel's surface microhardness (KHN), surface roughness (Ra), and color parameters CIELAB (∆Eab*), CIEDE 2000 (∆E00), and whiteness index for dentistry (∆WID) after toothbrushing with experimental toothpaste formulations with the following mineral clay types: kaolin, Sparclay SGY, and Tersil CGY used as abrasive component. Scanning electron microscopy (SEM) was performed for topographical analyses purposes. A total of 96 bovine incisors were used in the experiment. They were divided into eight experimental groups (n = 12), namely: NC-negative control (no treatment), CT12-Colgate Total 12®, CMP-Colgate® Máxima Proteção Anticáries, K-kaolin experimental toothpaste, SGY-Sparclay SGY experimental toothpaste; CGY-Tersil CGY experimental toothpaste, SD-SiO2 experimental toothpaste, and CC-CaCO3 experimental toothpaste. All samples were subjected to mechanical brushing protocol with 5000 cycles and kept in artificial saliva with daily exchanges. KHN was analyzed through the mixed linear model for repeated measures over time. Ra was analyzed through nonparametric Kruskal Wallis and Dunn tests to compare the groups. Paired Wilcoxon test was run to compare experimental times. ∆WID, ∆Eab*, and ∆E00 were analyzed through Kruskal Wallis and Dunn tests. All analyses were performed in R* software, at 5% significance level. EXP_SGY recorded higher KHN than EXP_SiO2 and EXP_CaCO3, whereas EXP_K showed increased Ra in comparison to CMP (p = 0.0229). ∆Eab and ∆E00 were significantly higher in the CT12, EXP_SiO2, and EXP_CaCO3 groups than in the NC and EXP_K (p < 0.0001). There were no significant changes in ∆WID (p = 0.0852). According to SEM results, toothbrushing with experimental toothpastes added with mineral clay types did not have significant impact on enamel's polishing and smoothness. CLINICAL RELEVANCE: Mineral clays have a broad application in the cosmetic industry, and recently, they have been used in the formulation of vegan toothpaste.

Comparison of Synthetic Pathways for Obtaining Fluorescent Nanomaterials Based on Halloysite and Carbon Dots for Potential Biological Sensing.

Recently, fluorescent sensors have gained considerable attention due to their high sensitivity, low cost and noninvasiveness. Among the different materials that can be used for this purpose, carbon dots (CDs) represent valuable candidates for applications in sensing. These, indeed, are easily synthesized, show high quantum yield and are highly biocompatible. However, it was pointed out that the photoluminescence properties of these nanomaterials are strictly dependent on the synthetic and purification methods adopted. The presence of halloysite nanotubes (HNTs), a natural, low cost and biocompatible clay mineral, has been found to be efficient in obtaining small and highly monodispersed CDs without long and tedious purification techniques. Herein, we report the comparison of synthetic pathways for obtaining halloysite-N-doped CDs (HNTs-NCDs) that could be used in biological sensing. One was based on the synthesis of N-doped CDs by a bottom-up approach on HNTs' surface by a MW pyrolysis process; the other one was based on the post-modification of pristine N-doped CDs with halloysite derivatives. The evaluation of the best synthetic route was performed by different physico-chemical techniques. It was found that the bottom-up approach led to the formation of N-doped CDs with different functional groups onto the HNTs' surface. This evidence was also translated in the different fluorescence quantum yields and the existence of several functional groups in the obtained materials was investigated by potentiometric titrations. Furthermore, the ability of the synthesized nanomaterials as sensors for Fe3+ ions detection was assessed by spectroscopic measurements, and the cellular uptake was verified by confocal/fluorescence microscopies as well.

Mechanism of clay mineral modified biochar simultaneously immobilizes heavy metals and reduces soil carbon emissions.

Heavy metal pollution in farmland soil has become increasingly severe, and multi-element composite pollution has brought enormous harm to human production and life. Environmental changes in cold regions (such as freeze-thaw cycles and dry-wet alternations) may increase the potential physiological toxicity of heavy metals and exacerbate pollution risks. In order to reveal the effectiveness of sepiolite modified biochar in the remediation of the soil contaminated with lead (Pb), cadmium (Cd), and chromium (Cr), the rice husk biochar pyrolyzed at 500 and 800 °C were selected for remediation treatment (denoted as BC500 and BC800). Meanwhile, different proportions of sepiolite were used for modification (biochar: sepiolite = 1: 0.5 and 1: 1), denoted as MBC500/MBC800 and HBC500/HBC800, respectively. The results showed that modified biochar with sepiolite can effectively improve the immobilization of heavy metals. Under natural conservation condition, the amount of diethylenetriaminepentaacetic acid (DTPA) extractable Pb in BC500, MBC500, and HBC500 decreased by 5.95, 12.39, and 13.55%, respectively, compared to CK. Freeze-thaw cycles and dry-wet alternations activated soil heavy metals, while modified biochar increased adsorption sites and oxygen-containing functional groups under aging conditions, inhibiting the fractions transformation of heavy metals. Furthermore, freeze-thaw cycles promoted the decomposition and mineralization of soil organic carbon (SOC), while sepiolite hindered the release of active carbon through ion exchange and adsorption complexation. Among them, and the soil dissolved organic carbon (DOC) content in HBC800 decreased by 49.39% compared to BC800. Additionally, the high-temperature pyrolyzed biochar (BC800) enhanced the porosity richness and alkalinity of material, which effectively inhibited the migration and transformation of heavy metals compared to BC500, and reduced the decomposition of soil DOC.

Novel fibrous Ag(NP) decorated clay-polymer composite: Implications in water purification contaminated with predominant micro-pollutants and bacteria.

Due to the potential harm caused by emerging micro-pollutants to living organisms, contaminating water supplies by micro-pollutants like EDCs, pharmaceuticals, and microorganisms has become a concern in many countries. Considering both microbiological and micro-pollutant exposure risks associated with water use for agricultural/or household purposes, it is imperative to create a strategy for improving pollutant removal from treated wastewater that is both effective and affordable. Natural clay minerals efficiently remove contaminants from wastewater, though the pristine clay has less affinity to several organic pollutants. Hydrophilic polymers, viz., poly(ethylene glycol) (PEG), improve the dispersion of particles, flocculation processes, and surface properties. In this study, PEG grafted with attapulgite, thereby providing a high-specific surface-area, mesoporous materials for the adsorption of micro-pollutants like ciprofloxacin (CIP) and 17α-ethinylestradiol (EE2) at high rates. A gentle washing process regenerates the clay-polymer material several times with no performance loss, and the natural water implications show fair applicability of solid in decontaminating the CIP and EE2 in an aqueous medium. Further, greenly synthesized silver nanoparticles in situ disperse with the clay polymer efficiently remove the gram-positive and gram-negative bacterium viz., Bacillus subtilis, and Pseudomonas aeruginosa, which are commonly persistent in aquatic environments. The clay polymer outperformed a modified clay composite to eliminate microorganisms and organic micro-pollutants in significant quantities quickly. These results clearly show the importance of fibrous clay-polymer composite for water purification technologies.

Natural peloids originating from subsea depths of 200 m in the hupo basin, South Korea: physicochemical properties for potential pelotherapy applications.

The present study firstly reports surface sediment from the subsea depth of 200 m as a potential natural peloid. The fine-silt sediment exhibited a consistent clay mineral composition dominated by illite, chlorite, kaolinite, and diatomite. The most abundant clay mineral was illite/mica, with other minerals loosely packed in a face-to-face orientation. The thermal conductivity, specific heat capacity, and cation-exchange capacity of the sediment were in the range 0.855-0.885 W/m K, 2.718-2.821 J/g °C, and 23.06-32.96 cmol/kg, respectively. The concentrations of most toxic elements in the sediment were considerably lower than the limits set by domestic cosmetic regulations and other international standards. The analyzed samples exhibited similar properties to those of previously reported peloids, thus making them suitable for use in the field of pelotherapy; furthermore, the consistency in data across a wide peloid-distribution area is expected to enable economically viable mining. Future investigations should aim to to evaluate the long-term effects on the skin, the bioavailability of potentially hazardous substances, and the therapeutic efficacy for various skin conditions.