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Carbon capture and storage (CCS) in subsurface reservoirs represents a highly promising and viable strategy for mitigating global carbon emissions. In the context of CCS implementation, it is particularly crucial to understand the complex molecular diffusive and adsorptive behaviors of anthropogenic carbon dioxide (CO 2 ) in the subsurface at the nanoscale. Yet, conventional molecular models typically represent only single-slit pores and overlook the complexity of interconnected nanopores. In this work, finite kaolinite lamellar assemblages with abundant nanopores ( r < 2 nm) were used. Molecular dynamics simulations were performed to quantify the spatial distribution correlations, adsorption preference, diffusivity, and residence time of the CO 2 molecules in kaolinite nanopores. The movement of the CO 2 molecules primarily occurs in the central and proximity regions of the siloxane surfaces, progressing from larger to smaller nanopores. CO 2 prefers smaller nanopores over larger ones. The diffusion coefficients increase, while residence times decrease, with the pore size increasing, differing from typical slit-pore models due to the pore shape and interconnectivity. The perspectives in this study, which would be challenging in conventional slit-pore models, will facilitate our comprehension of the CO 2 molecular behaviors in the complex subsurface clay sediments for developing quantitative estimation techniques throughout the CCS project durations.

Metoclopramide is an antiemetic agent prescribed for motion sickness, cancer chemotherapy, and pregnancy. The present work aimed to design a metoclopramide-loaded halloysite nanotubes (HNTs) drug-in-adhesive transdermal drug delivery system. Four formulations F1, F2, and F3 with different ratios of HNTs to metoclopramide and a F4 without HNTs were developed using acrylic adhesive DURO-TAK 387-2510 by the solvent casting method. These formulated patches were thoroughly evaluated and in-vitro release and permeation studies were performed. The optimized formulation was analyzed using skin irritation, SEM, DSC, and FTIR studies. The GASTROPLUS TCAT model was used to predict the in-vivo performance. HNT-based formulations exhibited controlled drug release, achieving approximately 60% in 4 h, compared to over 80% release in the same period from the formulation without HNT. The optimized formulation (F3) demonstrated a lag time of 1.802 h with a flux of 0.103 mg/cm 2 /hr. The shelf life was 19.279 months at 5 ± 3 °C. The C max , T max , AUC t, and AUC inf were predicted as 40.84 ng/mL, 6.32 h, 561.51 ng/mL×h and 599.61 ng/mL×h for a 30 mg patch. The study demonstrated that metoclopramide can be effectively loaded into HNTs and proved safe and effective in drug-in-adhesive type transdermal systems using HNTs as a drug carrier., Competing Interests: Declarations Competing interests The authors declare no competing interests., (© 2024. The Author(s).)

Biocompatible and biodegradable nerve growth conduits (NGCs) provide a promising alternative to conventional nerve grafting for peripheral nerve regeneration. Incorporating nanoclay (NC) has been shown to increase the hydrophilicity and flexibility of polymeric scaffolds. In the present study, poly caprolactone-alginate (PCL-ALG) conduits with varying percentages of NC (0.1%, 0.2%, and 0.5%) were fabricated using the electrospinning technique. The conduit containing 0.5% NC showed a greater increase in elongation (33%) and porosity, reaching 95% with the lowest contact angle (10°). For in vitro, human olfactory ectomesenchymal stem cells (OE-MSCs) were used as a favorable choice for neuronal differentiation owing to the origin from the neural crest. The viability and proliferation of OE-MSCs were maintained after 5 days on scaffolds with 0.5% NC, as confirmed by the MTT assay, cell adhesion analysis, and live/dead staining. Furthermore, the impact of 0.5% PCL-ALG-NC on the paracrine activity of OE-MSCs was studied for a period of 7 days. Our results indicated that human OE-MSCs, when cocultured with PC12 cells on NGC, have the capability to release nerve growth factor levels of up to 1392.83 pg/mL. In summary, the electrospun PCL-ALG conduit containing an optimal NC dosage (0.5%) and seeded with human OE-MSCs shows promising outcomes as NGC scaffold for peripheral nerve regeneration.

Catalytic Wet Air Oxidation (CWAO) has recently been recognized as a promising technique for degrading persistent organic pollutants, such as phenol, in wastewater. Among various catalysts, Pillared Interlayer Clays (PILCs) stand out due to their high specific surface area and porous nature. This review delves into the latest progress in CWAO processes utilizing PILCs for the degradation of organic contaminants such as phenol in wastewater. It meticulously assesses the synthesis of PILCs, and their structural properties, including monolithic forms, to understand their effect on catalyst efficiency. Key insights into how these attributes affect the phenol degradation rate and the CWAO process's stability are discussed, providing crucial direction for enhancing catalyst performance. The review highlights the significance of choosing catalysts that offer a balance between cost-efficiency and operational efficacy under mild conditions. The recent results are reported, summarized, and compared, thus proving the feasibility of using PILCs as promising materials for phenol removal. The reaction parameters, phenol conversion, and degradation mechanisms are highlighted. The catalytic efficiency of PILCs was significantly affected by the synthesis methods and reaction parameters, and outperformed most costly catalysts. PILCs are highlighted as especially advantageous catalysts, offering strong performance at lower costs, which boosts the up-scaling opportunities of CWAO methods. This analysis also points out research gaps and proposes directions for future studies, such as exploring innovative PILC synthesis methods to improve their catalytic effectiveness and durability further. It stresses the need to incorporate environmental and sustainability considerations into catalyst design and selection, aligning with the principles of green chemistry in wastewater treatment. Finally, we conclude that proposing new directions for PILCs in CWAO in further naturally-based surface modifications, is also a promising approach for PILCs to perform more efficiently., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Autotrophic microorganisms, the pivotal carbon fixers, exhibit a broad distribution across diverse environments, playing critical roles in the process of carbon sequestration. However, insights into their distribution characteristics in aquifers, particularly in those petroleum-hydrocarbon-contaminated (PHC) aquifers that were known for rich in heterotrophs, have been limited. In the study, groundwater samples were collected from red clay aquifers in the storage tank leakage area of a PHC site, a prevalent aquifer type in southern China and other regions. Metagenomics combined with hydrochemical and inorganic carbon isotope analyses were employed to elucidate the presence of microbial carbon fixation and its driving forces. Results showed that there were hundreds of autotrophic microorganisms participating in distinct carbon fixation processes in the red clay PHC aquifers. Reductive tricarboxylic acid (rTCA) and dicarboxylate/4-hydroxybutyrate (DC/4HB), as well as 3-hydroxypropionate (3HP or/and 3-hydroxypropionate/4-hydroxybutyrate (3HP/4HB)) were the predominant carbon fixation pathways. The abundances of carbon fixation genes and autotrophic microorganisms were significantly and positively correlated with hydrocarbon concentrations and δ 13 C of dissolved inorganic carbon (δ 13 C-DIC) values. This finding indicated that the petroleum hydrocarbon significantly promoted the proliferation of carbon fixation microorganisms, leading to a substantial uptake of inorganic carbon. Therefore, we deduce that this process holds considerable potential for carbon sequestration in PHC-contaminated aquifers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The accurate determination of polar cationic pesticides in food poses a challenge due to their high polarity and trace levels in complex matrices. This study hypothesized that the use of halloysite nanotubes (HNTs) can significantly enhance the extraction efficiency and sensitivity of these analytes because of their rich hydroxyl groups and cation exchange sites. Therefore, we chemically incorporated HNTs with organic polymer monoliths for in-tube solid-phase microextraction (SPME). This novel hybrid monolith extended service life, improved adsorption capacity, and exhibited excellent extraction performance for polar cationic pesticides. Based on these advancements, a robust and sensitive in-tube SPME-HILIC-MS/MS method was constructed to determine trace levels of polar cationic pesticides in complex food matrices. The method achieved limits of detection of 1.9, 2.1, and 0.1 μg/kg for maleic hydrazide, amitrole, and cyromazine, respectively. The spiked recoveries in five food samples ranged from 80.2 to 100.8%, with relative standard deviations below 10.7%., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Nanocomposites composed of the cationic polypeptide ε-poly-l-lysine (ε-PL) and natural sodium montmorillonite (MMT) were prepared and evaluated. These MMT/ε-PL composites formed highly ordered nanostructures resembling natural nacreous layers by a simple process. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses confirmed that a small amount of ε-PL remarkably enhanced the MMT orientation in the composites. This MMT orientation-enhancing effect of ε-PL was more pronounced than that of poly(vinyl alcohol) (PVA), which is one of the most popular ingredients of MMT-based composites. The orientation enhancement provided by ε-PL was primarily driven by ionic interactions and responsible for high mechanical properties at low polymer content. This remarkable reinforcing effect of ε-PL on MMT at a low polymer content will help to develop high-performance and sustainable nacreous composites. In addition, it improves our understanding of the reinforcing mechanism of natural nacre, which exhibits excellent mechanical properties even with relatively small amounts of organic component.

Polymeric hydrogels are among the most studied materials due to their exceptional properties for many applications. In addition to organic and inorganic-based hydrogels, "hybrid hydrogels" have been gaining significant relevance in recent years due to their enhanced mechanical properties and a broader range of functionalities while maintaining good biocompatibility. In this sense, the addition of micro- and nanoscale clay particles seems promising for improving the physical, chemical, and biological properties of hydrogels. Nanoclays can contribute to the physical cross-linking of polymers, enhancing their mechanical strength and their swelling and biocompatibility properties. Nowadays, they are being investigated for their potential use in a wide range of applications, including medicine, industry, and environmental decontamination. The use of microorganisms for the decontamination of environments impacted by toxic compounds, known as bioremediation, represents one of the most promising approaches to address global pollution. The immobilization of microorganisms in polymeric hydrogel matrices is an attractive procedure that can offer several advantages, such as improving the preservation of cellular integrity, and facilitating cell separation, recovery, and transport. Cell immobilization also facilitates the biorecovery of critical materials from wastes within the framework of the circular economy. The present work aims to present an up-to-date overview on the different "hybrid hydrogels" used to date for bioremediation of toxic metals and recovery of critical materials, among other applications, highlighting possible drawbacks and gaps in research. This will provide the latest trends and advancements in the field and contribute to search for effective bioremediation strategies and critical materials recovery technologies.

Iron-bearing smectite clay minerals can act as electron sources and sinks in the environment. Previous studies using mediated electrochemical analyses to determine the reduction potential ( E H ) values of smectites observed that the relationship between the structural Fe 2+ (s) /Fe Total ratio in the smectite and E H varied based on the redox history of the smectite. We hypothesize that this behavior, referred to as redox hysteresis, results from the smectite particles not equilibrating with the applied E H over the course of the experiment (∼30 min). To test this hypothesis, we developed a model incorporating interfacial electron transfer kinetics and charge redistribution within the particle to simulate the mediated electrochemical experiments from previous studies. The simulated redox curves accurately matched the previously reported experimental redox curves of the smectite SWa-1, demonstrating that longer equilibration periods led to a decrease in redox hysteresis. We validated this experimentally by measuring the redox curve of SWa-1 after an equilibration period of at least 12 h. Furthermore, we extended the simulations to three other smectites (NAu-1, NAu-2, and SWy-2) and extracted their respective thermodynamic and kinetic parameters. This work offers a framework for interpreting and modeling redox reactions on clay surfaces, along with key parameters for four commonly studied smectites.

Photocatalysis stands out as a promising technique for treating organic contaminants, yet the quest for visible light active composite materials, crafted through cost-effective, eco-friendly, and uncomplicated processes, poses formidable challenges. Here, we introduce a successful endeavor, the synthesis of a CuO/SnO 2 (CS) composite via a microwave method, employing Carissa edulis fruit extract as a reducing as well as capping agent. Various loadings of CS-HNT composites were prepared by ultrasonically incorporating CS onto nanotubular halloysite (HNT) clay. Employing a suite of types of characterization, including XRD, XPS, FT-IR, FE-SEM, HR-TEM, ζ potential, UV-vis-DRS, TGA, BET, and EIS, we meticulously explored the morphology, structure, stability, surface area, electrochemical, and optical properties of the developed CS-HNT composites. HR-TEM observations unveiled the formation of a heterojunction between cubic CuO and spherical SnO 2 on the HNT clay surface. Optical and EIS analysis highlighted that the 20CS-HNT composite displayed significant absorption in the visible region, efficient electron-hole pair separation, and enhanced interfacial charge transport relative to other loadings. Photocatalytic evaluations and optimization studies revealed that the 20CS-HNT photocatalyst achieved notable removal efficiencies, eliminating 85% of Congo red (CR) and 80% of tetracycline (TC) within 90 min and 74% of ATZ in 3 h under visible light conditions. Scavenging investigations, the fluorescence probe method, and a NBT transformation study underscored the pivotal roles of hydroxyl and superoxide radicals in pollutant removal. The reusability trials highlighted the exceptional stability and recyclability of the photocatalyst, even after five cycles. In addition, zebrafish embryo toxicity tests revealed improved survival and hatching rates in photocatalyst-treated samples compared to those of controls. Moderate toxicity was observed in treated TC, while the treated CR sample showed non-lethal toxicity. In essence, this study unveils a straightforward and efficacious approach for developing photocatalysts for large-scale wastewater treatment. Furthermore, it proposes the adoption of safe clay-based bimetal oxide photocatalysts in diverse environmental applications.

Neonicotinoids, highly toxic to insects, are among the world's most used insecticides. However, their harmful effects on pollinators like honeybees and potential to contaminate water bodies have drawn significant criticism. Herein, a nanopesticide, NTP@LDH, was developed by intercalating the model neonicotinoid insecticide nitenpyram (NTP) within layered double hydroxide (LDH) materials using a simple one-pot method. The NTP@LDH showed a nano-sized sheet structure, with an average particle size of 206.2 nm and a loading capacity of 14.6 %. The release rate of NTP@LDH under acidic conditions was higher than that under alkaline or neutral conditions. The photodegradation capacity and insecticidal activity of NTP were unaffected by intercalation in LDH. Importantly, NTP@LDH could significantly enhance the foliar adhesive properties of NTP, retard its leaching through the soil, and improve its safety for honeybees. Moreover, LDH was safe for crops and can improve their growth. This work provides a promising strategy with a simple procedure that could reduce leaching risks of neonicotinoids while concurrently enhancing their safety to pollinating creatures., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Given the research situation of toxic metals (TMs) pollution in farmland soil, it is very critical to study the clay influence on TMs environmental behavior to meet the aim of lowering TMs pollution. This research explores the association among clay minerals and TMs and the health risks in TMs combined polluted farmland of northern China. In this study, agricultural soil, wheat grain, and atmospheric sediments from nonferrous metal smelting (NMS) areas were collected and investigated to determine the effect of clay minerals on TMs. The results show that the content ranges of Cd (0.199 mg/kg ∼1.98 × 10 2  mg/kg), Pb (0.228 × 10 2  mg/kg ∼ 4.87 × 10 3  mg/kg), Cu (0.187 × 10 2  mg/kg ∼ 4.57 × 10 3  mg/kg), and Zn (0.559 × 10 2  mg/kg ∼ 3.04 × 10 3  mg/kg) in the agricultural soil. In particular, Cd has reached heavy pollution by the high pollution index (6.74). The findings indicate that Cd and Pb in wheat grain were influenced by their exchangeable fractions in soil, according to a significant relationship between Cd and Pb in soil and wheat grain. XRD-SEM suggests that TMs come from atmospheric sediments associated with NMS emissions by microsphere signatures with surface burn marks. Meanwhile, Geographical detector indicated that clay was the primary contributor to spatial distribution of Cd and Pb. In addition, XRD results showed that I/S (a mixed layer of illite and smectite), illite, chlorite, and kaolinite co-existed. Whereas the clay minerals with this ratio did not demonstrate better adsorption capacities for Cd and Pb due to the Cd percentage of the residual fraction being less than 9%. The result of negative correlation between exchangeable Cd and clay minerals implies that illite, chlorite, and kaolinite may preferentially adsorb Cd and Pb. It is similar to the relationship between Cd and Pb in wheat grain and illite, chlorite, and kaolinite. In addition, the health assessment result show that the negative correlation between clay minerals and the noncarcinogenic hazard quotient (HQ) and indicate that clay minerals could reduce the noncarcinogenic risk of Pb and Cd for children. Our findings provide a potential mechanism and application of clay minerals for the remediation of soil contaminated with TMs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The purpose of this study is to formulate and characterize the cryogels containing halloysite nanotube (HNT)/lipase nanohybrid (NH-cryogel) in comparison to pure cryogels as well as cryogels containing lipase (lipase-cryogel). The cryogels were synthesized using polyvinyl alcohol (PVA) and sodium alginate (SA). The products are tested to explore the influence of the HNT/lipase nanohybride (NH) as nanofillers on the cryogel properties using methods such as swelling degree, water uptake measurement, TGA, XRD, FESEM and FTIR. Additionally, the effects of cryogels on the stability and biocatalytic activities of lipase and NH, were studied and compared to the free lipase to evaluate their potential applications as enzyme carriers. The addition of nanofillers into the cryogel improved is thermal stability. The results implied that NH-cryogel had better enzyme activity than lipase-cryogel and free lipase at different temperatures and pH values. The NH-cryogel residual activity was 85.5 % after ten cycles of reuse while lipase-cryogel showed lower residual activity (60.3 %). Furthermore, the NH-cryogel retained 81.1 % of its residual activity while this was 51.0 % for lipase-cryogel after thirty days of storage. Therefore, the presented results in this study provide a pathway to show that produced nano-composite cryogels could be useful substances for food and pharmaceutical industries applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The rapid industrial progress in today's world has led to an alarming increase in water pollution caused by various contaminants such as synthetic dyes. To address this issue, a new hydrogel sorbent, BC-r-Na-Alg-g-p(NIPAm-co-AAc), was developed by combining bentonite clay, sodium alginate, and poly(N-isopropyl acrylamide-co-acrylic acid) through one-pot free radical polymerization at 60 °C. The developed sorbent was characterized using several analytical techniques including SEM, FTIR, TGA, UTM, and swelling studies. The swelling capacity of the sorbent was observed to increase remarkably with an increase in pH, reaching a maximum of 9664 % at pH 11. In batch mode sorption experiments, the sorbent's performance toward methylene green (MG) was investigated by analysing the effects of contact time, pH, temperature, and concentration. The experimental data were fitted to pseudo-second-order kinetic and Langmuir isotherm models, indicating chemisorption as the dominant interaction mode between the anionic sorbent and cationic MG. However, physisorption may also occur to a lesser extent, indicated by the significant R 2 of the pseudo-first-order kinetic and Freundlich isotherm models. Additionally, the sorbent exhibited very little decrease (approximately 5 %) in sorptive performance for six sorption-desorption cycles. Overall, the facile fabrication, excellent swelling (9664 %), promising sorption performance (2573 mg.g -1 ), and good recyclability (6 cycles) make the developed sorbent a potential candidate for various industrial applications., Competing Interests: Declaration of competing interest I on the behalf of all the co-authors confirm that we have no conflict of interest in submission of this paper to the Journal of “International Journal of Biological Macromolecules” for possible publication., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A special nano-filter made of cellulose acetate (CA) was developed, including a 3D hierarchically porous structure. The nano-filter utilized nano-clay (hydrophilic bentonite (NC B )), comprising 0.5-1.5 % of its weight. The objective of this study was to evaluate the adsorption properties of four carcinogenic polyaromatic hydrocarbons (benz[α] anthracene (BαA), chrysene (CHR), benzo[β]fluoranthene (BβF), and benzo[α] pyrene (BαP)) during the rice smoking process. The evaluation of the nano-filter encompassed an analysis of its mechanical attributes, surface qualities, morphology, and adsorption efficacy. The experimental results demonstrated that adding NC B to the nano-filter composition of CA led to substantial improvements in tensile strength, elongation at break, and maximum load stress values compared to the control group. The nano-filter displayed a uniform and homogeneously distributed arrangement of nanoparticles. The GC-MS analysis demonstrated that the enhanced nano-filter, comprising nano-clay particles, successfully absorbed the polycyclic aromatic hydrocarbons (PAHs) over a 21-day rice smoking period. The performance, removal efficiency and porosity during repetitive filtering and cleaning cycles in the rice samples at different smoking times were approved reusability of CA-NC B filter. It is recommended to explore the application of hybrid CA nano-filter s, namely those containing NC B , as a cutting-edge filtration technique for smoked food products., Competing Interests: Declaration of competing interest The Authors declare that there is no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Novel thiomer/nanoclay nanocomposites based on a thiomer and montmorillonite (MMT) were prepared in order to obtain a mucoadhesive material with controlled release properties for its potential use as drug carrier. The thiomer was synthesized by immobilization of L-cysteine in alginate mediated by carbodiimide reaction and further characterized by FT-IR and Ellman's reaction. Nanocomposites with growing concentrations of thiomer and MMT were prepared and analyzed by XRD, TGA and TEM. Rheological behavior of nanocomposite in contact with mucin and intestinal mucus were studied as in vitro and in situ mucoadhesion approach, showing until ∼10-fold increasing in the complex viscosity and ∼27-fold in elastic modulus when the amount of thiomer is increased. Higuchi and Korsmeyer-Peppas kinetic models were evaluated in order to study the release of deltamethrin from nanocomposite films. Release profiles showed a retard in the migration of the drug influenced by the amount of MMT (P < 0.05). Diffusion coefficient (D) showed a significant decrease (P < 0.0001) when concentration of MMT is increased reaching D = 4.18 × 10 -7 m 2 h -1 , which resulted ∼7-fold lower in comparison with formulation without MMT. This hybrid nanocomposite can be projected as a potential mucoadhesive drug carrier with controlled release properties., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 American Pharmacists Association. Published by Elsevier Inc. All rights reserved.)

Amine functionalized bentonites were used as adsorbents for the bioremoval of Fe(III) ions, which led to the inclusion of functional groups such as -OH, -NH2, -OCH3, etc. FTIR, XRD, SEM, AFM, TG, BET, XRF, and CHNS analyzer were used to analyze the surface and textural characteristics. The influence of adsorption factors, such as pH, contact time, temperature, and initial concentration, have been investigated and tailored in batch adsorption experiments of Fe (III) metal ions. The maximum adsorption efficiency and capacity of modified BNT-APTMS is 100.90 % and 103.91 mg/g respectively. The adsorption process is best fit with Freundlich model (R 2 =0.998) than Langmuir model (R 2 =0.788) and the Temkin model D-R isotherm parameters indicating a physisorption process. A mechanism of spontaneous complexation was accomplished, because of the heterogeneity of the surface, electrostatic forces, pore filling, and π-π stacking. Follows PSO kinetics and favours Freundlich isotherm. The adsorbent substance showed a remarkable capacity for regeneration, assuring the substance's stability and reusability., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

High-performance poly(lactic acid) (PLA) blend-based composites were fabricated with a poly(ether-block-amide) (PEBA) elastomer acting as the blend counterpart. It was confirmed that a compatibilizer (ADR) enhanced the interaction between PLA and PEBA. Carbon nanotubes (CNTs) and organoclay (30B) were added individually and simultaneously into the blend to produce bionanocomposites. Morphological results showed that CNTs were mainly dispersed in PEBA domains, whereas 30B was mainly localized at the interfacial region of PLA and PEBA phases. The selective localization of added CNTs and 30B led to significant modification of the properties of the compatibilized PLA/PEBA blend. The brittleness and flammability of PLA were evidently improved after forming the bionanocomposites. Differential scanning calorimetry results revealed that CNTs and 30B assisted the crystallization of both PLA and PEBA in the composites, with CNTs providing superior nucleation efficiency to 30B. Thermogravimetric analysis revealed the thermal stability enhancement of the blend after adding CNTs and/or 30B, with up to 16 °C increase at 20 wt% loss with inclusion of 2 phr 30B. Addition of CNTs and/or 30B improved the blend's anti-dripping performance during burning tests, and CNT exhibited better anti-dripping efficiency. Ductility of PLA was drastically improved after forming the compatibilized blend, and further improved with incorporation of CNTs and/or 30B (increased from 9 % for neat PLA to 252 % for the hybrid composite containing CNT/30B). The impact strength of 1 phr CNTs-added composite was about 3 times that of PLA. Rheological properties indicated the (pseudo)network formation of added filler(s), leading to a significant reduction in electrical resistivity, up to six orders of magnitude with addition of 3 phr CNTs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Soil stabilisation by waste materials has been recently employed to enhance soil engineering properties. The purpose of this study is to compare the impact of utilising sawdust in its raw form versus sawdust ash as a soil stabiliser. This is to determine if sawdust (SD) can be considered as a substitute for sawdust ash (SDA) in order to reduce incineration and air pollution. To fulfil this aim, the Atterberg limits, modified Proctor test, and Direct Shear test were performed on both stabilised and non-stabilised mixtures of clayey soil. The soil was treated with 2%, 5%, 8%, 12%, 15%, and 20% by soil dry weight of both SD and SDA. The findings show that the use of SD and SDA leads to a reduction in the plasticity index and the maximum dry unit weight of the soil while increasing its optimum moisture content. The bearing capacity of the soil was greatest at 5% for both SD and SDA, with SD exhibiting a greater enhancement (31.89%) than SDA. Therefore, it is recommended to utilise SD instead of SDA for soil stabilisation due to its superior effectiveness and less harmful environmental impact.

Microbial fuel cells (MFC) have emerged as a sustainable wastewater treatment technique that offers simultaneous energy generation; however, the high cost of electrodes and their reduced catalytic activity have hindered their widespread adoption. To overcome this, an activated carbon synthesised from Areca nut husk was coated on different anodes viz. Carbon cloth and Stainless Steel (SS) mesh. Activated carbon was found to be highly porous with a carbon content of 85.39%, and a surface area of 767.98 m 2 /g, and was found to be amorphous with a high degree of graphitic structure. The electrical conductivities of the catalyst-coated SS mesh and carbon cloth were comparable, and the performance of the MFC was studied using both electrodes as anodes. A batch MFC with modified SS mesh as anode exhibited the highest power density of 155.35 mW/m 3 in synthetic wastewater and 101.68 mW/m 3 in kitchen wastewater, with COD removal efficiencies of 95.32% and 95.24%, respectively. In a continuous mode, the MFC delivered a maximum current density and power of 52.38 mA/m 2 and 21.60 mW, respectively, with a maximum COD removal efficiency of 80.70% for an HRT of 20 hrs. These findings underscore the viability of using biomass-derived activated carbon as an anode catalyst in both batch and continuous modes of MFC.

The presence of organic phosphorus may influence the characteristics of Cr(VI) reduction and immobilization on Fe(II)-bearing clay minerals under anoxic conditions, as the organic phosphorus tends to bind strongly to clay minerals in soil. Herein, reduced nontronite (rNAu-2) was used to reduction of Cr(VI) in the presence of phytic acid (IHP) at neutral pH. With IHP concentration from 0 to 500 μM, Cr(VI) reduction decreased obviously (17.8%) within first 5 min, and then preferred to stagnate during 4-12 h (≥50 μM). After that, Cr(VI) was reduced continuously at a slightly faster rate. Density functional theory (DFT) calculations revealed that IHP primarily absorbed at the edge sites of rNAu-2 to form Fe-IHP complexes. X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), and Fourier transform infrared spectroscopy (FTIR) results demonstrated that IHP hindered the ingress of CrO 4 2- into the interlayer space of rNAu-2 and impeded their reduction by trioctahedral Fe(II) and Al-Fe(II) at basal plane sites in the initial stage. Additionally, Fe(II) extraction results showed that IHP promoted the electron from interior transfer to near-edge, but hindered it further transfer to surface, resulting in the inhibition on Cr(VI) reduction at edge sites during the later stage. Consequently, IHP inhibits the reduction and immobilization of Cr(VI) by rNAu-2. Our study offers novel insights into electron transfer pathways during the Cr(VI) reduction by rNAu-2 with coexisting IHP, thereby improve the understanding of the geochemical processes of chromium within the iron cycle in soil., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Phosphorus is a critical nutrient that significantly enhances tomato production, so maintaining an adequate level of phosphorus plays an essential role in enhancing the growth of tomato by being present in the soil. This study assessed the impact of soil texture and phosphorus content on tomato plant properties using a factorial, complete, randomized design with four replications. Treatments included clayey and sandy soils with varying phosphorus sources: non-phosphorus (P0), calcium phosphate (CaP1 and CaP2), and nano-hydroxyapatite (PN1 and PN2), where 1 indicates a concentration of 0.12 g and 2 indicates a concentration of 0.23 g per 5-kilogram pot of fertilizer. Results indicated that treatments significantly influenced yield parameters such as average fruit weight, juice content, antioxidant activity, and fruit volume. In the clayey soil, CaP2 treatment had a superior effect on yield, average fruit weight, and shoot fresh weight. In comparison with sandy conditions, CaP2 produced a 50% increase in fruit number, 29% increase in average fruit weight, and 91% increase in fruit yield. The treatments then impacted the shoot fresh weight and root length, while the phosphorus concentration appeared to be more dependent on soil type than on phosphorus sources. Similar to the CaP1 and CaP2 treatments, the PN1 treatment in clay soil also resulted in the highest fresh and dry weights of tomato shoots when compared with the control group. Generally, the findings from this study suggest that the use of CaP2 can serve as a reliable method to improve the growth, yield, and fruit quality of tomatoes, especially in clayey soil environments. However, nano-based phosphorous sources need to be tested more to see if they can improve tomato performance in a range of soil conditions. Also, further research should look into the long-term effects of phosphorous interventions on soil health and sustainability., (© 2024. The Author(s).)

This study investigated the distribution of Cd in soil water-stable aggregate particles of varying sizes, revealing that smaller particles have higher total Cd content as well as different forms of Cd content, with the clay particle showing a greater tendency to accumulate Cd. However, the proportion of high activity Cd is lower in clay particles, posing a lower environmental risk of Cd transformation compared to silt particles. Adsorption experiments indicated that the clay particle exhibits the strongest adsorption capacity and highest adsorption rate. Additionally, correlation and principal component analyses identified Fe-Mn oxides and organic matter as the primary influencing factors on Cd distribution characteristics, with pH playing a secondary role. These findings provide valuable insights for the remediation of heavy metal-contaminated soil., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Biochar exhibits numerous advantages in enhancing the soil environment despite a few limitations due to its lower surface energy. Nanomodified biochar combines the advantages of biochar and nanoscale materials. However, its effects on water infiltration and N leaching in a clayey soil remain unclear. Therefore, this study prepared rice straw nano-biochar by a ball milling method, and investigated its physicochemical properties and effects of bulk biochar and nano-biochar at various addition rates (0 %, 0.5 %, 1 %, 2 %, 3 %, and 5 %) on wetting peak migration, cumulative infiltration, water absorption and retention, and N leaching. The results showed that, compared with bulk biochar, nano-biochar presented a more abundant pore structure with an increase in specific surface area of approximately 1.5 times, accompanied by a 20 % increase in acid functional groups. Compared with those for clayey soil without biochar addition, the wetting front migration time was increased by 10.2 %-123.9 % and 17.0 %-257.9 %, and the cumulative infiltration volume at 60 min was decreased by 26.0 %-48.4 % and 14.1 %-62.4 % for bulk biochar and nano-biochar, respectively. The parameter S of Philip model and the parameter a of Kostiakov model for nano-biochar were lower than those for bulk biochar, whereas the parameter b of Kostiakov model was greater, indicating that nano-biochar decreased initial soil infiltration rate and increased attenuation degree of the infiltration rate. Nano-biochar increased water absorption by 8.03 % and subsequently enhanced water retention capacity relative to bulk biochar. In addition, bulk biochar and nano-biochar reduced NH 4 + -N leaching by 3.0 %-13.1 % and 5.7 %-39.2 %, respectively, and NO 3 - -N leaching by 2.7 %-3.6 % and 9.0 %-43.3 %, respectively, by decreasing N concentration and leachate volume relative to those with no biochar addition. This study provides new knowledge for nano-biochar application in a clayey soil., Competing Interests: Declaration of competing interest The authors declared that they have no conflicts of interest related to this work, and they have no commercial or associative interests that represent a conflict of interest related to the submitted work., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The environmental transport and fate of nanoscale zero-valent iron particles (nZVI) in soil and groundwater can be altered by their hetero-aggregation with clay mineral particles (CMP). This study examines the interactions between bare or carboxymethyl cellulose (CMC)-coated nZVI with typical CMP, specifically kaolinite and montmorillonite. Methods include co-settling experiments, aggregation kinetic studies, electron microscopy, Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DLVO (EDLVO) energy analysis, and density functional theory calculations, focusing on the pH dependency of these interactions. The EDLVO theory effectively described the interactions between nZVI and CMP in aquatic environments. Under acidic conditions (pH 3.5), the interfacial interaction between bare nZVI and kaolinite is regulated by van der Waals forces, while complexation, van der Waals forces, and electrostatic attraction govern the interaction of bare nZVI with montmorillonite, primarily depositing on the SiO face. In contrast, the positively charged AlO face and edge of CMP are the main deposition sites for CMC-coated nZVI through hydrogen bonding, van der Waals forces, and electrostatic attraction. At neutral (pH 6.5) and alkaline (pH 9.5) conditions, both bare and CMC-coated nZVI predominantly attach to the AlO face and edge, facilitated by complexation or hydrogen bonding, alongside van der Waals forces. The attachment of CMC-coated nZVI to CMP surfaces shows reversible aggregation or deposition due to the steric repulsion from the CMC coating. These findings hold significant implications for the environmental applications and risk of nZVI., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Textile industries contribute to water pollution through synthetic dye discharge. This study explores the use of natural bio-coagulants to remove acid dyes from wastewater, investigating factors like pH, coagulant dose, dye concentration, contact time, and temperature for optimal results. The optimum pH and coagulants capabilities of (CAAPP, CAAPH, CBAGL, CBAPP and CBAPH) were 3 (49.6 mg/g), 3 (42.5 mg/g), 3 (38.9 mg/g), 4 (35.7 mg/g), 4 (34.1 mg/g), and 4 (29.4 mg/g) respectively, while treating of selected BRF-221 dyes from water solution. The acidic range (3-4) was found to have the best pH for the maximal coagulation, and the optimal dose were found to be 0.05 g/50 mL. The equilibrium was attained within 45-60 min for all coagulants. After 60 min of shaking, the maximum coagulation capacities (21.9, 21.02, 16.5, 27.9, 25.3, and 23.4 mg/g) of several coagulant composites (CAAGL, CAAPP, CAAPH, CBAGL, CBAPP, CBAPH) were determined. The initial BRF-221 dye concentration in the range of 10-200 mg/L was considered as optimum for gaiting maximum elimination of dye using different coagulants. At a dye value of 100 mg/L of BRF-221, maximal coagulation capacities CAAGL (179.19 mg/g), CAAPP (166.06 mg/g), CAAPH (141.60 mg/g), and CBAGL (126.49 mg/g), CBAPP (113.9 mg/g), CBAPH (93.08 mg/g) were attained. The study found 35 °C to be the optimal temperature for maximum acid dye removal using bio-coagulants. Increasing temperature reduced coagulation capacity, indicating an exothermic process. Freundlich and Langmuir isotherms showed suitability for pseudo-first-order and pseudo-second-order kinetics in biosorption. Thermodynamic parameters were assessed for process feasibility. Effective coagulants demonstrated sensitivity to electrolyte variations. In column studies, adjusting parameters achieved maximum coagulation efficiency for removing BRF-221 dyes. The study successfully applied optimal parameters to remove real textile effluents at a practical scale. SEM, FT-IR, BET and XRD characterized coagulants, providing insights into stability and morphology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Wastewater textile dye treatment is a challenge that requires the development of eco-friendly technology to avoid the alarming problems associated with water scarcity and health-environment. This study investigated the potential of phengite clay as naturally low-cost abundant clay from Tamgroute, Morocco (TMG) that was activated with a 0.1 M NaOH base (TMGB) after calcination at 850 °C for 3 h (TMGC) before its application in the Congo red (CR) anionic dye from the aqueous solution. The effect of various key operational parameters: adsorbent dose, contact time, dye concentration, pH, temperature, and the effect of salts, was studied by a series of adsorption experiments in a batch system, which affected the adsorption performance of TMG, TMGC, and TMGB for CR dye removal. In addition, the properties of adsorption kinetics, isotherms, and thermodynamics were also studied. Experimental results showed that optimal adsorption occurred at an acidic pH. At a CR concentration of 100 mg L -1 , equilibrium elimination rates were 68%, 38%, and 92% for TMG, TMGC, and TMGB, respectively. The adsorption process is rapid, follows pseudo-second-order kinetics, and is best described by a Temkin and Langmuir isotherm. The thermodynamic parameters indicated that the adsorption of CR onto TMGB is endothermic and spontaneous. The experimental values of CR adsorption on TMGB are consistent with the predictions of the response surface methodology. These led to a maximum removal rate of 99.97% under the following conditions: pH = 2, TMGB dose of 7 g L -1 , and CR concentration of 50 mg L -1 . The adsorbent TMGB's relatively low preparation cost of around $2.629 g -1 and its ability to regenerate in more than 6 thermal calcination cycles with a CR removal rate of around 56.98%, stimulate its use for textile effluent treatment on a pilot industrial scale., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

This paper delves into the engineering applications of lime-stabilized red clay, a highly water-sensitive material, particularly in the context of the climatic conditions prevalent in the Dalian region. We systematically investigate the impact of water content, dry density, and freeze-thaw cycles (with a freezing temperature set at -10°C) on the thermal conductivity of stabilized soil, a crucial parameter for analyzing soil temperature fields that is influenced by numerous factors. By developing and validating both empirical and machine learning prediction models, we unravel the evolution of thermal conductivity in response to these factors: within the range of influencing variables, thermal conductivity exhibits an exponential or linear increase with rising water content and dry density, while it decreases exponentially with increasing freeze-thaw cycles. Furthermore, we quantitatively analyze the specific influence of water content and other factors on the thermal conductivity of stabilized soil and construct a comprehensive prediction model encompassing BP neural network, gradient boosting decision tree, and linear regression models. Comparative analysis highlights the significant enhancement in prediction accuracy achieved by the proposed ensemble model over single machine learning models, with root mean square error (RMSE) values below 0.05 and mean absolute percentage error (MAPE) values remaining under 2.5% in both frozen and unfrozen states. Additionally, a secondary validation using experimental data from other researchers confirms the model's good agreement with previous results, demonstrating its robust generalization ability. Our findings provide valuable insights for engineering studies in the Dalian region and red clay areas subjected to extreme climatic conditions., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Wang et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Recent advances in subsurface microbiology have demonstrated the habitability of multi-million-year-old igneous rocks, despite the scarce energy supply from rock-water interactions. Given the minimal evolution coupled with exceedingly slow metabolic rates in subsurface ecosystems, spatiotemporally stable igneous rocks can sustain microbes over geological time scales. This study investigated a 2-billion-year-old mafic rock in the Bushveld Igneous Complex, South Africa, where ultradeep drilling is being executed by the International Continental Scientific Drilling Program (ICDP). New procedures were successfully developed to simultaneously detect indigenous and contaminant microbial cells in a drill core sample. Precision rock sectioning coupled with infrared, fluorescence, and electron microscopy imaging of the rock section with submicron resolution revealed microbial colonization in veins filled with clay minerals. The entry and exit of microbial cells in the veins are severely limited by tight packing with clay minerals, the formation of which supplies energy sources for long-term habitability. Further microbiological characterization of drilled rock cores from the Bushveld Igneous Complex will expand the understanding of microbial evolution in deep igneous rocks over 2 billion years., (© 2024. The Author(s).)

Developing an effective and user-friendly hemostatic agent is highly desired in the treatment of hemorrhage. Inspired by the natural nanostructure and abundant hydroxyl groups of cellulose and clay minerals, we designed an aerogel (HNTs/TOCNs) composed of halloysite nanotubes (HNTs) and TEMPO-oxidized cellulose nanofibers (TOCNs) with a hierarchical porous structure for the treatment of bleeding, using a simple and environmentally friendly self-assembly method. TOCNs formed a three-dimensional porous scaffold with excellent water-holding capacity. The incorporation of HNTs enhanced the hemostatic efficiency and mechanical properties of the 3D framework. The large interlayer spaces and wide channels within the HNTs/TOCNs aerogel provided rapid passage for blood, facilitating blood concentration and offering ample room for interactions between the HNTs/TOCNs aerogel and platelets, erythrocytes, and coagulation factors, thereby promoting hemostasis. Benefiting from the natural hemostatic properties and well-designed structure, the HNTs/TOCNs aerogel displayed excellent hemostatic performance both in vitro and in vivo. Notably, the hemostatic time of HNTs/TOCNs-2 was only 74 ± 8 s, which is approximately 50 % shorter than the blank control (151 ± 20 s) in liver femoral artery injury model. This design of an HNTs/TOCNs aerogel presents a unique opportunity to enhance hemostatic efficacy by synergizing the advantages of natural materials., Competing Interests: Declaration of competing interest The authors declare no competing financial interests., (Copyright © 2024. Published by Elsevier B.V.)

The development of smart systems for pesticidal delivery presents a significant advancement in enhancing the utilization efficiency of pesticides and mitigating environmental risks. Here an acid-responsive pesticidal delivery system using microspheres formed by the self-assembly of halloysite clay nanotubes (HNTs) is proposed. Insecticide avermectin (AVM) and herbicide prometryn (PMT) are used as two models of hydrophobic pesticide and encapsulated within the porous microspheres, followed by a coating of tannic acid/iron (TA/Fe III ) complex films to generate two controlled-release pesticides, named as HCEAT and HCEPT, resulting in the loading capacity of AVM and PMT being 113.3 and 120.3 mg g -1 , respectively. Both HCEAT and HCEPT exhibit responsiveness to weak acid, achieving 24 h-release ratios of 85.8% and 80.5% at a pH of 5.5. The experiment and simulation results indicate that the coordination interaction between EDTA 2- and Ca 2+ facilitates the spherical aggregation of HNTs. Furthermore, these novel pesticide formulations demonstrate better resistance against ultraviolet (UV) irradiation, higher foliar affinity, and less leaching effect, with negligible impact of the carrier material on plants and terrestrial organisms. This work presents a promising approach toward the development of efficient and eco-friendly pesticide formulations, greatly contributing to the sustainable advancement of agriculture., (© 2024 Wiley‐VCH GmbH.)

New hybrid hydrogel composites based on a mixture of natural polysaccharides (sodium alginate, κ-carrageenan, and chitosan) filled with the clay mineral of natural origin, montmorillonite (MMT), were studied. The structure of intercalated/flocculated MMT distribution in the interpenetrating network of polysaccharide matrix was characterized using FTIR, X-ray diffraction, and SEM techniques. Swelling kinetics was investigated using the weight analysis, whereas the phase transition of water in the composition of hybrid hydrogels, by DSC method. Their biosafety was estimated using the Nelyubov method, germination test on cress (L. sativum) seeds, and metabolic fingerprinting of microbial communities and dehydrogenase assay. The obtained results indicated promising water-retaining properties of the synthesized materials. The hydrogels had a good sorption affinity for cadmium (Cd) ions confining bioavailability of the selected toxic heavy metal. They were safe for soil microorganisms and did not generate metabolic stress for them. Moreover, they did not reduce the viability of pea seeds. Thus, the development of biosafe hybrid hydrogel composites with a comprehensive, good effect on the environment could be considered as successful., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

This study developed a multifunctional paper-based freshness antibacterial indicator card by dual-sided coating on conventional filter paper. The indicator coating was composed of anthocyanins from purple cabbage, and polyvinyl alcohol and sodium carboxymethyl cellulose as substrates while the antibacterial coating contained halloysite nanotubes for loaded thyme essential oil and chitosan. FT-IR, XRD, and SEM analyses revealed that the components were well-mixed, and the paper was tightly bound to the coatings through hydrogen bonds. Additionally, the coating effectively filled the porous fiber gaps in the paper, significantly enhancing the mechanical properties of the paper. The tensile strength of the coated paper was enhanced from 14.28 MPa to a range of 42.25-47.71 MPa, and the bending resistance was increased from 0.35 N·mm to a range of 1.72-1.99 N·mm compared to the uncoated paper. The addition of anthocyanins provided excellent sensitivity to pH and ammonia for the indicator card. Furthermore, the coating including halloysite nanotubes for loaded thyme essential oil exhibited antimicrobial resistance against Escherichia coli and Staphylococcus aureus. When used on fresh carp, the antibacterial indicator card not only indicated the freshness of the carp but also extended the best before date of the fish meat by 1-2 days. The indicator exhibited the most pronounced color transformation and optimal freshness indication performance when the mass fraction of anthocyanins was 2 %., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. This work is original research and the data presented in the manuscript has not been published elsewhere., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The use of modified clays can play an effective role as an effective adsorbent in removing fluoride (Flu) ions from water and aqueous solutions. In the present research, montmorillonite clay (MMt) was modified using CoFe 2 O 4 magnetic particles and Al-Fe fumarate metal-organic framework (Al-Fe Fum) and was utilized as an efficient adsorbent for removing Flu from aqueous solution. The properties of MMt and MMt/CoFe 2 O 4 /Al-Fe Fum samples were investigated using different techniques. The results showed that with the modification of MMt using CoFe 2 O 4 magnetic particles and the metal-organic framework of Al-Fe Fum, the BET surface has increased notably from 13.217 to 365.80 m 2 /g. To investigate the effect of independent variables and their interaction on the efficiency of the Flu adsorption, response surface method-central compound design (RSM-CCD) was served. Based on the results of ANOVA, the F-value and p-value parameters for the desired model were determined to be 783.09 and < 0.0001, respectively, which confirms the success and high ability of the model. The number of R 2 , adjusted R 2 , and Predicted R 2 for adsorption of Flu ion was determined to be 0.998, 0.997, and 0.995, respectively, which shows that the proposed regression model can describe the process of adsorption and interaction between variables well. Compared to other kinetic models, the pseudo 2nd order kinetic model has a greater ability to describe the Flu adsorption behavior. The R 2 parameter value determined that the Freundlich isotherm model has a suitable ability to investigate the isotherm behavior and confirms the effect of heterogeneous surfaces in the process. Generally, the outcomes signified that the MMt and MMt/CoFe 2 O 4 /Al-Fe Fum samples can be reused several times in the process of Flu adsorption, while the efficiency is more than 90%., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Protein therapeutics hold immense promise for treating a wide array of diseases. However, their efficacy is often compromised by rapid degradation and clearance. The synthetic smectite clay Laponite emerges as a promising candidate for their sustained delivery. Despite its unique properties allow to load and release proteins mitigating burst release and extending their effects, precise control over Laponite-protein interactions remains challenging since it depends on a complex interplay of factors whose implication is not fully understood yet. The aim of this review article is to shed light on this issue, providing a comprehensive discussion of the factors influencing protein loading and release, including the physicochemical properties of the nanoclay and proteins, pH, dispersion buffer, clay/protein concentration and Laponite degradation. Furthermore, we thoroughly revise the array of bioactive proteins that have been delivered from formulations containing the nanoclay, highlighting Laponite-polymer nanocomposite hydrogels, a promising avenue currently under extensive investigation., Competing Interests: Declaration of competing interest None., (Copyright © 2024. Published by Elsevier B.V.)

The aim of this work was to evaluate the influence of halloysite clay nanoparticles - unmodified (Hal) and organically modified (mHal) - and oregano essential oil (OEO), used as an antimicrobial agent in active packaging, on the biodegradation behavior of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) films. Five samples were prepared by melt mixing using 3 wt% clay, and 8 wt% and 10.4 wt% OEO. PHBV compositions containing OEO presented the highest rate of biodegradation, achieving 46% of mass loss after aging for 12 weeks in simulated soil. The addition of clay nanoparticles reduced the polymer's biodegradation to 32%. The compositions containing OEO showed a rough and layered surface with visible cracks, indicating degradation occurring through layer-by-layer erosion from the surface. This degradation was confirmed by the chemical changes on the surface of all samples, with a slight decrease in molar masses. The composition containing 8 wt% OEO presented an increase in the crystallization degree as a result of the preferential consumption of amorphous phase, whereas for the compositions containing clay nanoparticles, both crystalline and amorphous regions were degraded at similar rates. Therefore, the combination of additives allows the biodegradation process of PHBV to be controlled for use in the production of active packaging., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A fluorescent hybrid film composed of nitrogen-doped graphene quantum dots (N-GQDs) loaded on halloysite nanotubes (HNTs) (N-GQDs/HNTs nanocomposite) as a sensitive element and polyvinyl alcohol (PVA) as a film-forming matrix was designed for freshness detection. The PVA-N-GQDs/HNTs hybrid film exhibited significantly enhanced fluorescence attributed to the loading of N-GQDs onto the surface of HNTs through electrostatic interactions and hydrogen bonding, effectively reducing their aggregation. The fluorescence of the hybrid film could be quenched by ammonia via photoinduced electron transfer (PET), with good linearity in the range of 20 ppm to 500 ppm ammonia and a limit of detection (LOD) of 0.63 ppm. In addition, the hybrid film was applied to monitor the freshness of seawater fish and freshwater fish stored at refrigeration and room temperature to evaluate the practicality of this approach. The developed hybrid film showed promise for nondestructive and on-site monitoring of fish spoilage., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The development of functional bionanocomposites for active food packaging is of current interest to replace non-biodegradable plastic coatings. In the present work, we report the synthesis of an alginate-based nanocomposite filled with modified halloysite nanotubes (HNTs) to develop coatings with improved barrier properties for food packaging. Firstly, HNTs were chemically modified by the introduction of carbon dots units (CDs) onto their external surface (HNTs-CDs) obtaining a nanomaterial where CDs are uniformly present onto the tubes as verified by morphological investigations, with good UV absorption and antioxidant properties. Afterwards, these were dispersed in the alginate matrix to obtain the alginate/HNTs-CDs nanocomposite (Alg/HNTs-CDs) whose morphology was imaged by AFM measurements. The UV and water barrier properties (in terms of moisture content and water vapor permeability) were investigated, and the antioxidant properties were evaluated as well. To confer some antimicrobial properties to the final nanocomposite, the synthetized filler was loaded with a natural extract (E) from M. cisplatensis. Finally, the extract kinetic release both from the filler and from the nanocomposite was studied in a medium mimicking a food simulant and preliminary studies on the effect of Alg/HNTs-CDs/E on coated and uncoated fruits, specifically apples and bananas were also carried out., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Developing durable protective cotton fabrics (CF) against potential environmental dangers such as fire hazards and bacterial growth remains an imperative but tough challenge. In this study, flame retardant, antibacterial and hydrophobic CF were successfully prepared via two-step coating. The inner coating entailed polyelectrolyte complexes consisting of polyethyleneimine and ammonium polyphosphate with the goal of enhancing the flame retardancy of CF. Halloysite nanotubes (HNTs), a kind of tubular silicate mineral, were creatively modified and introduced to multifunctional coatings to improve flame retardant and antibacterial properties of CF. N-halamine modified HNTs (HNTs-EA-Cl) and polydimethylsiloxane were applied as the outer coating to endow CF with antibacterial and hydrophobic properties and further improve the flame retardancy of CF. After halloysite-based inorganic-organic hybrid coatings, the limiting oxygen index of the treated samples (PAHP-CF) was over 28 %, and the release of heat and smoke was significantly inhibited. PAHP-CF could inactivate 100 % E. coli and S. aureus within 2 h. More importantly, PAHP-CF showed excellent hydrophobicity with a water contact angle of 148° and exhibited great prevention of bacterial adhesion. PAHP-CF exhibited excellent washing durability undergoing 5 washing cycles. This study promotes the development of multifunctional coatings and offers a new way to manufacture multifunctional cotton fabrics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This work combines experimental and computational modeling studies for the preparation of a composite of metformin and an organoclay, examining the advantages of a Tunisian clay used for drug delivery applications. The clay mineral studied is a montmorillonite-like smectite (Sm-Na), and the organoclay derivative (HDTMA-Sm) was used as a drug carrier for metformin hydrochloride (MET). In order to assess the MET loading into the clays, these materials were characterized by means of cation exchange capacity assessment, specific surface area measurement, and with the techniques of X-ray diffraction (XRD), differential scanning calorimetry, X-ray fluorescence spectroscopy, and Fourier-transformed infrared spectroscopy. Computational molecular modeling studies showed the surface adsorption process, identifying the clay-drug interactions through hydrogen bonds, and assessing electrostatic interactions for the hybrid MET/Sm-Na and hydrophobic interactions and cation exchange for the hybrid MET/HDTMA-Sm. The results show that the clays (Sm-Na and HDTMA-Sm) are capable of adsorbing MET, reaching a maximum load of 12.42 and 21.97 %, respectively. The adsorption isotherms were fitted by the Freundlich model, indicating heterogeneous adsorption of the studied adsorbate-adsorbent system, and they followed pseudo-second-order kinetics. The calculations of ΔGº indicate the spontaneous and reversible nature of the adsorption. The calculation of ΔH° indicates physical adsorption for the purified clay (Sm-Na) and chemical adsorption for the modified clay (HDTMA-Sm). The release of intercalated MET was studied in media simulating gastric and intestinal fluids, revealing that the purified clay (Sm-Na) and the modified organoclay (HDTMA-Sm) can be used as carriers in controlled drug delivery in future clinical applications. The molecular modeling studies confirmed the experimental phenomena, showing that the main adsorption mechanism is the cation exchange process between proton and MET cations into the interlayer space.

Polymers of natural origin, such as representatives of various polysaccharides (e.g., cellulose, dextran, hyaluronic acid, gellan gum, etc.), and their derivatives, have a long tradition in biomedical applications. Among them, the use of chitosan as a safe, biocompatible, and environmentally friendly heteropolysaccharide has been particularly intensively researched over the last two decades. The potential of using chitosan for medical purposes is reflected in its unique cationic nature, viscosity-increasing and gel-forming ability, non-toxicity in living cells, antimicrobial activity, mucoadhesiveness, biodegradability, as well as the possibility of chemical modification. The intuitive use of clay minerals in the treatment of superficial wounds has been known in traditional medicine for thousands of years. To improve efficacy and overcome the ubiquitous bacterial resistance, the beneficial properties of chitosan have been utilized for the preparation of chitosan-clay mineral bionanocomposites. The focus of this review is on composites containing chitosan with montmorillonite and halloysite as representatives of clay minerals. This review highlights the antibacterial efficacy of chitosan-clay mineral bionanocomposites in drug delivery and in the treatment of topical skin infections and wound healing. Finally, an overview of the preparation, characterization, and possible future perspectives related to the use of these advancing composites for biomedical applications is presented.

Soil salinization poses a significant ecological challenge, emerging as a critical constraint to agricultural development in the arid and semi-arid regions of China, especially in southern Xinjiang. In particular, Yuepuhu County, situated in Kashgar, faces a distinctive issue. Impermeable thin clay layers within the vadose zone impede year-round leaching of salts, significantly impacting the growth of cotton. Through a combination of indoor testing, experiments, and statistical analyses, this study elucidated the varying permeability of soil layers at different depths and explored the forms and accumulation characteristics of soil salts in Yuepuhu County. It unveiled patterns of water and salt movement in soils with variable permeability layers, identifying key influencing factors. The research also proposed an irrigation regime suitable for cultivating vadose zone soils in the local context. The findings revealed a progression of increasing soil complexity and decreasing burial depth of clay layers from northwest to southeast, aligned with the direction of groundwater flow. With increasing depth, a noticeable reduction in soil saturated hydraulic conductivity was observed, indicating significant variability in permeability. Predominantly chloride-sulfate type saline soils in Yuepuhu County contained potassium (K + ) and sodium (Na + ) as the main cations in surface soils. Salinity strongly correlated with calcium (Ca 2+ ) and magnesium (Mg 2+ ). Chloride (Cl - ), sulfate (SO 4 2- ), K + , Na + , and bicarbonate (HCO 3 - ) reflected the degree of soil salinization in Yuepuhu County. The clay interlayers in variable permeability zones significantly impeded water and salt movement in the vadose zone. Moving from west to east, thicker and shallower clay interlayers hindered downward water movement, increasing the difficulty of salt leaching. Additionally, the irrigation regime influenced water and salt movement in the vadose zone. Under the same soil structure, flood irrigation with a higher water flux resulted in more significant salt leaching, and lower total dissolved solids (TDS) in irrigation water were more favorable for effective salt leaching. Collectively, our findings provided a theoretical foundation for improving and managing local saline soils, as well as guiding the implementation of rational agricultural irrigation practices., (© 2024. The Author(s).)

Depending on the texture of soil, different physicochemical and microbiological parameters are characterized, and these characteristics are influenced by crop cultivation. Stevia , a popular zero-calorie sweetener crop, is widely cultivated around the world on various soil textures. Sandy loam and clay soil show great differences in physicochemical and biological parameters and are often used for Stevia cultivation. To understand the effects of Stevia cultivation on soil physicochemical and biological features, we investigated the changes of physicochemical and microbiological parameters in sandy loam and clay soil following Stevia cultivation. This study was carried out through different physiological and biochemical assays and microbiomic analysis. The results indicated that the sandy loam soil had significantly lower pH and higher nutrient content in the rhizosphere and bulk soils after the Stevia cultivation. The sandy loam soil maintained higher bacterial diversity and richness than the clay soil after Stevia harvest. Beneficial bacteria such as Dongia, SWB02 , Chryseolinea , Bryobacter and Devosia were enriched in the sandy loam soil; however, bacteria such as RB41 , Haliangium and Ramlibacter , which are unfavorable for nutrient accumulation, predominated in clay soil. Redundancy analysis indicated that the variation in the composition of bacterial community was mainly driven by soil pH, organic matter, total nitrogen, available phosphorus, and microbial biomass phosphorus. This study provides a deeper understanding of physicochemical and microbiological changes in different soil textures after Stevia cultivation and guidance on fertilizer management for Stevia rotational cultivation., Competing Interests: The authors declare there are no competing interests., (©2024 Xu et al.)

The persistent water treatment and separation challenge necessitates innovative and sustainable advances to tackle conventional and emerging contaminants in the aquatic environment effectively. Therefore, a unique three-dimensional (3D) network composite film (B N C-KC) comprised of bacterial nanocellulose (B N C) incorporated nano-kaolinite clay particles (KC) was successfully synthesized via an in-situ approach. The microscopic characterization of B N C-KC revealed an effective integration of KC within the 3D matrix of B N C. The investigated mechanical properties of B N C-KC demonstrated a better performance compared to B N C. Thereafter, the sorption performance of B N C-KC films towards basic blue 9 dye (Bb9) and norfloxacin (NFX) antibiotic from water was investigated. The maximum sorption capacities of B N C-KC for Bb9 and NFX were 127.64 and 101.68 mg/g, respectively. Mechanistic studies showed that electrostatic interactions, multi-layered sorption, and 3D structure are pivotal in the NFX/Bb9 sorption process. The intricate architecture of B N C-KC effectively traps molecules within the interlayer spaces, significantly increasing sorption efficiency. The distinctive structural configuration of B N C-KC films effectively addressed the challenges of post-water treatment separation while concurrently mitigating waste generation. The environmental evaluation, engineering, and economic feasibility of B N C-KC are also discussed. The cost estimation assessment of B N C-KC revealed the potential to remove NFX and Bb9 from water at an economically viable cost., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Natural attenuation (NA) is of great significance for the remediation of contaminated groundwater, and how to identify NA patterns of toluene in aquifers more quickly and effectively poses an urgent challenge. In this study, the NA of toluene in two typical soils was conducted by means of soil column experiment. Based on column experiments, dissolved organic matter (DOM) was rapidly identified using fluorescence spectroscopy, and the relationship between DOM and the NA of toluene was established through structural equation modeling analysis. The adsorption rates of toluene in clay and sandy soil were 39 % and 26 %, respectively. The adsorption capacity and total NA capacity of silty clay were large. The occurrence of fluorescence peaks of protein-like components and specific products indicated the occurrence of biodegradation. Arenimonas, Acidovorax and Brevundimonas were the main degrading bacteria identified in Column A, while Pseudomonas, Azotobacter and Mycobacterium were the main ones identified in Column B. The pH, ORP, and Fe(II) were the most important factors affecting the composition of microbial communities, which in turn affected the NA of toluene. These results provide a new way to quickly identify NA of toluene., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Benggangs are a special type of soil erosion in the hilly granite regions of the tropical and subtropical areas of Southern China. They cause severe soil and water loss, which can severely deteriorate soil quality and threat to the local ecological environment. Soils (red soil, sandy soil and detritus soil) were collected from collapsing wall of a typical Benggang in Changting County of Fujian Province, and their physicochemical and mineralogical properties were analyzed. Five different monovalent cations were used to saturate the soil samples to examine the specific ion effects on the shear strength and clay surface properties. Red soil had a higher clay content, plastic limit, liquid limit and shear strength than sandy soil and detritus soil. The studied soils mainly consisted of kaolinite, hydroxy-interlayer vermiculite, illite and gibbsite clay minerals. The soils saturated with K + , NH 4 + and Cs + had greater cohesion than the Li + - and Na + -saturated soils, e.g. , the cohesion of the red soil saturated with Li + , K + , NH 4 + and Cs + cations were 1.05, 1.23, 1.45 and 1.20 times larger than that of the Na + -saturated soil, respectively. While the internal friction angle was slightly different, which indicated that different monovalent cations affected the shear strength differently. K + -, NH 4 + - and Cs + -saturated clay particles had higher zeta potentials and thinner shear plane thicknesses than Li + - and Na + -saturated clay particles and showed strong specific ion effects on the clay surface properties. The changes in clay surface properties strongly affected the soil mechanical properties. Soils saturated with K + , NH 4 + and Cs + could increase the shear strength, and then increase the stability of the collapsing wall, thus might decrease the erosion intensity of Benggang. The results provide a scientific basis for the interpretation of and practical treatment of Benggang., Competing Interests: The authors declare there are no competing interests., (©2024 Huang et al.)

Using halloysite clay and vitamin B1 hydrochloride, a novel acidic halloysite-dendrimer catalytic composite has been developed for conversion of fructose to 5-hydroxymthylfurfural. To grow the dendritic moiety on halloysite, it was first functionalized and then reacted with melamine, epichlorohydrin and vitamin B1 hydrochloride respectively. Then, the resulting composite was treated with ZnCl 2 to furnish Lewis acid sites. Use of vitamin B1 as the cationic moiety of ionic liquid obviated use of toxic chemicals and resulted in more environmentally friendly composite. Similarly, dendritic moiety of generation 2 was also grafted on halloysite and the activity of both catalysts for conversion of fructose to 5-hydroxymthylfurfural was investigated to disclose the role of dendrimer generation. For the best catalytic composite, the reaction variables were optimized via RSM and it was revealed that use of 0.035 g catalyst per 0.1 g fructose at 95 °C furnished HMF in 96% yield in 105 min. Turnover numbers (TONs) and frequencies (TOFs) were estimated to be 10,130 and 5788 h -1 , respectively. Kinetic studies also underlined that Ea was 22.85 kJ/mol. The thermodynamic parameters of Δ H ≠ , Δ S ≠ and Δ G ≠ , were calculated to be 23 kJ/mol, - 129.2 J/mol and 72.14 kJ/mol, respectively. Notably, the catalyst exhibited good recyclability and hot filtration approved heterogeneous nature of catalysis., (© 2024. The Author(s).)

In recent years, red tides have increased worldwide in frequency, intensity, involving a higher number of causative species during the events. As the most commonly used method for control of red tides, modified clay (MC) was found to have differential ability to remove various red tide species. However, the underlying mechanisms have not yet been completely elucidated. In this study, the use of MC to remove three typical disaster-causing species, Aureococcus anophagefferens, Prorocentrum donghaiense and Heterosigma akashiwo, was investigated, and differential removal of these species was probed with insights into their biocellular properties and mechanical interactions. The results showed that removal efficiencies of the three species by MC decreased in the order P. donghaiense > A. anophagefferens > H. akashiwo, while the sedimentation rates decreased in the order H. akashiwo > P. donghaiense > A. anophagefferens. Analyses of the cell surface properties and redundancy analysis (RDA) revealed that the highest surface zeta potential of -5.32±0.39 mV made P. donghaiense the most easily removed species; the smallest cell size of 3.30±0.03 μm facilitated the removal of A. anophagefferens; and the highest hydrophobicity with a H 2 O surface contact angle of 98.50±4.31° made the removal of H. akashiwo difficult. X-ray photoelectron spectroscopy (XPS) data indicated that the electronegativity of P. donghaiense was caused by carboxyl groups and phosphodiester groups, and the hydrophobicity of H. akashiwo was associated with a high C-(C, H) content on the cell surface. According to the extended Derjaguin, Landau, Verwey, and Overbeek (ex-DLVO) theory calculation, differences in the interaction energies between MC and the three red tide species effectively explained their different sedimentation rates. In addition, the degree of oxidative damage caused by MC to the three red tide species differed, which also affected the removal of red tide organisms., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Our laboratory recently developed a new class of high surface area, honeycomb Nanoclay Microsphere Framework absorbents (NMFs) that prompt rapid hemostasis. In the present work, we propose a novel approach to develop antibacterial Topical Hemostatic Agents (THAs) by anchoring silver nanoparticles (AgNPs) onto NMFs. This combination was obtained by a chemical co-reduction approach, followed by freeze-processing, and was shown to ensure stability and on-site delivery of AgNPs, without altering the hemostatic properties of NMFs. Silver-loaded NMFs showed no change in their unique architecture and led to a 55% increase in clot strength, compared to standard control plasma or commercially available THA, and a significant decrease in mean fibrin fiber diameter. Silver nanoparticles were successfully released when solubilized and prevented the growth of both Pseudomonas aeruginosa and Staphylococcus aureus at concentrations of 22 and 30 ppm of silver released, respectively. Overall, cell mortality was between 9.1 ± 5.1% and 6.3 ± 3.2%, depending on AgNP concentration, confirming a low cytotoxicity. Silver-loaded nanoclay microsphere frameworks appear to constitute promising candidates as topical hemostatic agents for secondary management of hemostasis when infection control is needed., (© 2024 The Author(s). Journal of Biomedical Materials Research Part B: Applied Biomaterials published by Wiley Periodicals LLC.)

Spent bleaching clay (SBC) is a hazardous waste produced by vegetable oil refining industries. SBC contains a residual oil (RO) with a lot of organic and inorganic impurities and its disposal leads to severe environmental consequences. In this study, SBC regeneration by extraction, acid modification and pyrolysis under various conditions and biodiesel production were studied. The GC-MS of the extracted RO shows that the fatty acid content is in conformity with crude oil and is appropriate for biodiesel production. FTIR was recorded in order to evaluate the main functional groups of fresh-, spent-, regenerated bleaching clay. The specific surface area (SSA) of fresh bleaching clay (FBC) (166.1 ± 1.7 m 2 /g) was lower than regenerated bleaching clay (RBC) one. The highest SSA (252.1 ± 1.7 m 2 /g) was revealed by pyrolysis at 550°C and activation with 10% sulfuric acid. Subsequent increase in the acid concentration and temperature of pyrolysis caused a decrease in the SSA. The heavy metals concentration in RBC was lower than the limits for activated bleaching clay in the National Food Safety Standard. Hence, RBC effectively copes with heavy metal removal. The peroxide, anisidine, acid values and oxidation stability of oil bleached with RBC are comparable to the FBC. Implications : The disposal of spent bleaching clay from vegetable oil refining industries has been recognized as a significant environmental issue. After adsorbing the impurities, spent bleaching clay becomes contaminated with a high concentration of organic and inorganic substances, including residual oils, fatty acids, phospholipids, and potentially toxic heavy metals. This makes spent bleaching clay a hazardous waste and improper disposal can lead to severe environmental consequences. Due to the potential environmental harm caused by spent bleaching clay disposal, it is crucial for vegetable oil refining industries to adopt proper waste management practices. Overall, the proper management and disposal of spent bleaching clay is essential to prevent environmental contamination and safeguard human health.