Search Results (158)

Soils represent the largest reservoir of organic carbon (OC) in terrestrial ecosystems, storing approximately 1500 Gt C. Forest and grassland ecosystems contribute 39% and 34% to global terrestrial carbon stocks, with soils holding about 44% and 89% of forest and grassland carbon, respectively. Land-use changes, such as the conversions between forest and grassland ecosystems, can strongly influence soil carbon accumulation, though the direction and magnitude remain uncertain. Comparative data from paired-plot studies of forest and grassland soils are still limited. In this study, we conducted pairwise comparisons of total OC and total nitrogen (TN) stocks in mature forest and climax grassland soils along a climatic and pedogenic gradient encompassing Retisols, Luvisols, and Chernozems. Relationships between OC and TN stocks (0–10 cm) and soil physicochemical properties—OC and TN contents, bulk density, pH, clay content, and humus fractional composition, as well as biological indicators—the abundance of culturable fungi and bacteria, microbial biomass carbon, potential metabolic activity, and activities of laccase and dehydrogenase, were evaluated. Strong positive correlations were found between OC and TN stocks and OC and TN contents (r = 0.62–0.99), pH (r = 0.79–0.81), clay content (r = 0.70–0.87), and the fraction of humic acids bound with calcium (r = 0.73). OC stocks also correlated strongly with dehydrogenase activity (r = 0.85–0.95). At 0–10 cm depth, OC stocks were higher in grassland soils than in forest soils by factors of 1.6–1.7 in Retisols and 1.4–1.5 in Chernozems. Similarly, TN stocks were 1.6–2.0 times greater in grasslands across all soil types. Community-level physiological profiling revealed higher potential metabolic activity in forest soils compared with grasslands, with the strongest differences in Retisols and Luvisols, while contrasts were attenuated in Chernozems. Overall, the results highlight the fundamental role of organo-mineral interactions and calcium binding in OC stabilization, as well as the likely involvement of dehydrogenase activity in the biogenic formation of calcium carbonates that contribute to this process. Full article

With the rapid expansion in the use of nanomaterials, ensuring their reprocessability has become a critical consideration for the sustainable development of polymer-based nanocomposites. In this study, the effects of repetitive thermo-mechanical processing cycles on the properties of polycarbonate (PC)/organoclay nanocomposites, as well as the impact of reactive extrusion of reprocessed PC/organoclay nanocomposites using a chain extender, were investigated for the first time. The nanocomposites were processed three times using a twin-screw extruder, and a multi-anhydride functional chain extender was incorporated to counteract the thermo-mechanical degradation observed after the third extrusion cycle. Morphological analysis indicated that the delamination of clay nanolayers within the polymer matrix was slightly enhanced with increasing extrusion cycles, while the addition of the chain extender further promoted nanoclay exfoliation. Despite the improved clay dispersion in PC, both rheological and tensile measurements revealed the detrimental effects of repeated reprocessing on the nanocomposites. The chain extender effectively mitigated this degradation by relinking cleaved polymer chains; consequently, the complex viscosity and storage modulus at 0.1 Hz of the three-times-extruded nanocomposite increased by 248% and 426%, respectively, following chain extender incorporation. The effectiveness of the chain extender was further evidenced by a 27% enhancement in tensile strength. The glass transition temperatures of the samples were not significantly affected by either the extrusion cycles or the addition of the chain extender. The thermal stability of the nanocomposites decreased with increasing numbers of extrusion cycles; however, the incorporation of the chain extender imparted enhanced resistance to thermal degradation, as confirmed by thermogravimetric analysis. Full article

Bentonite is the most widely used raw material for producing organoclays, which have numerous industrial and environmental applications. Due to their hydrophobicity, high swelling, and strong affinity for organic compounds, organoclays are effective in removing organic solvents from contaminated water originating from pipeline leaks, oil spills, traffic accidents, and industrial discharges. Such contamination not only degrades water quality but also forms surface films that hinder oxygen transfer, threatening aquatic ecosystems. In this study, two sodium bentonites with different specific surface areas (30 and 50 m²/g) were modified with three quaternary ammonium salts of varying molar masses and alkyl chain lengths (Sun, Arq, and Arm) to evaluate their performance in organic solvent sorption (gasoline, diesel, and kerosene). The materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscopy (SEM), and swelling capacity and sorption efficiency. The swelling capacity was determined according to ASTM D5890-19 (Foster method) using gasoline, diesel, kerosene, toluene, and xylene, while the sorption efficiency was assessed following ASTM F726-17 in gasoline, diesel, and kerosene, chosen due to their high potential for water contamination and frequent occurrence in oil spill and leakage scenarios. These solvents also differ in polarity and aromatic content, providing a relevant model for hydrocarbon mixtures commonly found in the environment. Results showed that the interaction between the clay and the surfactant depended strongly on the modifier’s chemical structure. The sorption capacity increased with greater interlayer expansion, surfactant molar mass, and specific surface area of the clay. Among all samples, the Arm-modified natural bentonite (VLArm) exhibited the best performance, with adsorption capacities of up to 6 g/g for diesel, 5 g/g for gasoline, and 5 g/g for kerosene. These values exceeded most previously reported organoclays. These findings demonstrate that optimizing the combination of clay properties and surfactant chemistry can yield highly efficient, low-cost organoclays for environmental remediation of organic contaminants. Full article

Natural and modified clay minerals are widely used in environmental technologies to remove a wide range of toxic substances from aquatic and soil ecosystems. This study assessed the toxicity of synthesized organoclays compared to pure bentonite using microbiological, phytotoxic, and instrumental (biosensor) methods. Organoclay containing lauramine oxide (a non-ionic surfactant) was found to have an increased toxic effect on all test organisms analyzed. Based on the phytotesting parameters, radish was found to be the most sensitive test organism in these experiments, as it was significantly affected by toxic substances, demonstrating noticeable changes in its morphology and morphometry. Minimal toxicity was demonstrated for organoclay containing alkyl polyglucoside (a non-ionic surfactant), which was used in all tests. Furthermore, organoclay containing disodium cocoamphodiacetate (an amphoteric surfactant) also exhibited minimal toxicity in phytotesting, including germination assessment (radish) and evaluation of morphometric characteristics using a biosensor method. The study confirms that the type of organic modifier significantly impacts the biocompatibility of organoclays. Using fewer toxic surfactants can improve the environmental acceptability of these materials for use in cleaning up contaminated ecosystems. Full article

Background: Although teriparatide is efficacious, its once-daily subcutaneous injections cause local adverse events, inconvenience, and higher cost, limiting long-term adherence. Therefore, this research aims to engineer a pH-responsive oral formulation of teriparatide for osteoporosis therapy. Methods: A layered silicate nanocomplex was obtained by spontaneous self-assembly of teriparatide (Teri) with 3-aminopropyl magnesium phyllosilicate (AC). The nanocomplex (AC-Teri) was then coated with a 1:1 blend of two polymethacrylic acid derivatives (Eudragit^® L100 and Eudragit^® S 100) to provide pH-triggered drug release along the gastrointestinal tract. Results: AC-Teri and the coated nanocomplex (EE/AC-Teri) displayed high encapsulation efficiency (>90%) with narrow size distributions. In a stepwise buffer transition system, EE/AC-Teri demonstrated pH-dependent release, with less than 25% drug liberated at pH 1.2, approximately 54% at pH 6.8, and 74% at pH 7.4 over 24 h. Particle size and ζ-potential of EE/AC-Teri shifted in parallel with dissolution of the outer polymer shell. EE/AC-Teri also protected the peptide against enzymatic degradation, preserving the secondary structure of encapsulated teriparatide in simulated intestinal fluids. Compared with free drug, EE/AC-Teri enhanced transcellular drug permeation 2.7-fold in Caco-2 cells. In dexamethasone-induced osteoporotic rats, oral EE/AC-Teri significantly stimulated bone formation while suppressing resorption; micro-CT and histology confirmed recovery of trabecular architecture. Conclusions: EE/AC-Teri represents a promising oral teriparatide formulation for the effective management of osteoporosis. Full article

The microparticle-enhanced microfiltration is a technique that combines the use of microparticulate adsorbent material dispersed in aqueous solution and microfiltration membranes for the removal of ions and emerging contaminants with low energy consumption. Thus, the objective of this work was to synthesize an organoclay, BAPTES, based on bentonite and (3-aminopropyl)triethoxysilane for use as a semi-synthetic adsorbent material in the microparticle-enhanced microfiltration process for the removal of AR27 in aqueous systems. For this purpose, the obtained organoclay was structurally characterized by FTIR-ATR-FEDS, SEM-EDS, DLS, and thermal analysis. In addition, equilibrium adsorption and kinetic studies of AR27 were performed. The results showed a significant increase in the adsorption capacity of AR27 by organoclay (86.06%) compared to natural bentonite (2.10%), due to the presence of ionizable amino groups in the organoclay structure that promote electrostatic interactions with the dye. Furthermore, kinetic studies showed that the adsorption process follows a pseudo-first-order model and that the equilibrium data better fits the Temkin model, indicating a heterogeneous adsorption surface with different binding energies. The evaluation of enhanced microfiltration with BAPTES microparticles showed that the adsorption capacity obtained in continuous flow experiments (14.25–33.63 mg g⁻¹) was lower than that determined experimentally under equilibrium conditions (~39.5 mg g⁻¹), suggesting that the residence time of the analyte and the adsorbent in the filtration cell is a determining factor in the retention values obtained. In addition, desorption studies revealed that basic pH had a greater effect than the presence of salts and the use of ethanol, favoring the weakening of the AR27-BAPTES interaction. Finally, the results highlight the potential use of BAPTES microparticle-enhanced microfiltration in applications involving the treatment of contaminated industrial effluents. Full article

Water pollution by organic dyes poses serious environmental and health challenges, demanding efficient and selective remediation methods. In this study, we engineered tailored organo-clay nanocomposites by modifying montmorillonite with hexadecyltrimethylammonium bromide (HTAB) and intercalating polyethylene glycol (PEG) chains of two distinct molecular weights (PEG200 and PEG4000). Comprehensive characterization techniques (XRD, FTIR, SEM, zeta potential, and TGA) confirmed the successful modification of the composites. Notably, PEG4000 promoted significant interlayer expansion, as evidenced by the shift of the (00l) reflection corresponding to the basal spacing d, indicating an increase in basal spacing. This expansion contributed to the formation of a well-ordered porous framework with uniformly distributed pores. In contrast, PEG200 produced smaller pores with a more uniform distribution but induced less pronounced interlayer expansion. Adsorption tests demonstrated rapid kinetics, achieving equilibrium in under 15 min, and impressive capacities: 420 mg/g of methylene blue (MB) adsorbed on PEG200/MMT@HTAB, and 385 mg/g of Congo red (CR) on PEG4000/MMT@HTAB. The crucial role of PEG chain length in adsorption selectivity was assessed, showing that shorter PEG chains favored methylene blue adsorption by producing narrower pores and faster kinetics, while longer PEG chains enhanced CR uptake via a stable, interconnected pore network that facilitates diffusion of larger dye molecules. Thermodynamic and Dubinin–Radushkevich analyses confirmed that the adsorption was spontaneous, exothermic, and predominantly driven by physical adsorption mechanisms involving weak van der Waals and dipole interactions. These findings highlight the potential of PEG-modified montmorillonite nanocomposites as cost-effective, efficient, and tunable adsorbents for rapid and selective removal of organic dyes in wastewater treatment. Full article

The ice sheet and subglacial geological environment in Antarctica have become the focus of scientific exploration. The development of Antarctic drilling technology will serve as a crucial safeguard for scientific exploration. However, the extremely ultra-low temperatures and intricate geological conditions present substantial obstacles for drilling operations in Antarctica, and the existing drilling fluid technology cannot satisfy the requirements of efficient and safe drilling. To ameliorate the wettability and rheology of ultra-low-temperature drilling fluids, a new amide material (HAS) was prepared using dodecylamine polyoxyethylene ether, azelaic acid, and N-ethylethylenediamine as raw materials. Experiments using infrared spectroscopy, nuclear magnetic hydrogen spectroscopy, and contact angle indicated that the target product was successfully synthesized. Performance evaluation showed that 2% HAS could achieve a yield point of 2.5 Pa for drilling fluid at −55 °C, and it also gave the fluid superior shear-thinning characteristics and a large thixotropic loop area. This indicated that HAS significantly enhanced the rheological properties of the drilling fluid, ensuring that it can carry cuttings and ice debris. In addition, 2% HAS could also increase the colloidal rate from 8% to more than 76% at −55 °C in different base oils. Meanwhile, the colloid rate was maintained above 92.4% when the density was 0.92~0.95 g/cm³. Mechanism studies showed that HAS increased the zeta potential and decreased the particle size of organoclay. At the same time, it changed the organoclay state from a clustered state to a uniformly dispersed state, and the particle size decreased. It was found that HAS formed a weak gel grid structure through interactions between polar groups, such as amide and imino groups with organoclays particles, thus improving the rheology and wettability of drilling fluid. In addition, HAS is an environmentally friendly high-performance material. Full article

This work investigates the effect of nanoclay addition—specifically natural montmorillonite (MMT) and organo-modified montmorillonite (O-MMT)—on the elastocaloric performance of natural rubber (NR), a promising material for solid-state cooling due to its non-toxicity, low cost, and ability to exhibit large adiabatic temperature changes under moderate stress (~a few MPa). Despite these advantages, the cooling efficiency of NR remains lower than that of conventional vapor-compression systems. Therefore, improving the cooling capacity of NR is essential for the development of solid-state cooling technologies competitive with existing ones. To address this, two series of NR-based nanocomposites, containing 1, 3, and 5 phr nanofiller, were prepared by melt compounding and hot pressing and characterized in terms of morphology, thermal, mechanical, and elastocaloric properties. The results highlighted that the better dispersion of the organoclays within the rubber matrix promoted not only a better mechanical behavior (in terms of stiffness and strength), but also a significantly enhanced cooling performance compared to MMT nanofilled systems. Moreover, NR/O-MMT samples demonstrated up to a ~45% increase in heat extracted per refrigeration cycle compared to the unfilled NR, with a coefficient of performance (COP) up to 3, approaching the COP of conventional vapor-compression systems, typically ranging between 3 and 6. The heat extracted per refrigeration cycle of NR/O-MMT systems resulted in approx. 16 J/cm³, higher with respect to the values reported in the literature for NR-based systems (ranging between 5 and 12 J/cm³). These findings emphasize the potential of organoclays in enhancing the refrigeration potential of NR for novel state cooling applications. Full article

This study investigates the hydrogen permeability of injection-molded polyamide 6 (PA6) nanocomposites reinforced with organo-modified montmorillonite (OMMT) at varying concentrations (1, 2.5, 5, and 10 wt. %) for potential use as Type IV composite-overwrapped pressure vessel (COPV) liners. While previous work examined their mechanical properties, this study focuses on their crystallinity, morphology, and gas barrier performance. The precise inorganic content was determined using thermal gravimetry analysis (TGA), while differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and scanning electron microscopy (SEM) were used to characterize the structural and morphological changes induced by varying filler content. The results showed that generally higher OMMT concentrations promoted γ-phase formation but also led to increased agglomeration and reduced crystallinity. The PA6/OMMT-1 wt. % sample stood out with higher crystallinity, well-dispersed clay, and low hydrogen permeability. In contrast, the PA6/OMMT-2.5 and -5 wt. % samples showed increased permeability, which corresponded to WAXD and SEM evidence of agglomeration and DSC results indicating a lower degree of crystallinity. PA6/OMMT-10 wt. % showed the most-reduced hydrogen permeability compared to all other samples. This improvement, however, is attributed to a tortuous path effect created by the high filler loading rather than optimal crystallinity or dispersion. SEM images revealed significant OMMT agglomeration, and DSC analysis confirmed reduced crystallinity, indicating that despite the excellent barrier performance, the compromised microstructure may negatively impact mechanical reliability, showing PA6/OMMT-1 wt. % to be the most balanced candidate combining both mechanical integrity and hydrogen impermeability for Type IV COPV liners. Full article

The use of widespread and inexpensive clay minerals as adsorptive agents, as well as materials obtained by their chemical modification, can contribute to the solution of the problem of environmental pollution with antibiotics. This review considers the structural features of various natural clay minerals and the effect of these features on their sorption capacity. Based on the analysis of available papers (over the last 15 years, also including some fundamental basics over the last 20–30 years), it has been established that the main property of an antibiotic molecule affecting the ability to be adsorbed by a clay mineral is the hydrophilicity of the organic substance molecule. The leading properties that determine the ability of clays to adsorb antibiotics are the charge and area of their surfaces. The ability of antibiotic molecules to protonate and a partial change in the edge charge of mineral layers is determined by the acidity of the sorption solution. In addition, empirical evidence is provided that the most important factors affecting adsorption are the ionic strength of the sorption solution, the concentration of the adsorbent and adsorbate, and the interaction temperature. The diversity of the composition, structure, and properties of clay minerals allows them to be effective sorbents for a wide range of antibiotics. Full article

This work investigates the potential industrial applications of two sodium bentonite samples (white and yellow), obtained from raw Ca-rich bentonite from Maputo Province in Southern Mozambique. Bentonite bio-organoclays were successfully developed from two Mozambican montmorillonite clays through the intercalation of protonated dimer fatty acid-based polyamide chains using a solution casting method. X-ray diffraction (XRD) analysis confirmed polymer intercalation, with the basal spacing (d₀₀₁) increasing from approximately 1.5 nm to 1.7 nm as the polymer concentration varied between 2.5 and 7.5 wt.%. However, the extent of intercalation was limited at this stage, suggesting that polymer concentration alone had a minimal effect, likely due to the formation of agglomerates. In a subsequent optimization phase, the influence of temperature (30–90 °C), stirring speed (1000–2000 rpm), and contact time (30–90 min) was evaluated while maintaining a constant polymer concentration. These parameters significantly enhanced intercalation, achieving d001 values up to 4 nm. Statistical Design of Experiments and Response Surface Methodology revealed that temperature and stirring speed exerted a stronger influence on d001 expansion than contact time. Optimal intercalation occurred at 90 °C, 1500 rpm, and 60 min. The predictive models demonstrated high accuracy, with R² values of 0.9861 for white bentonite (WB) and 0.9823 for yellow bentonite (YB). From statistical modeling, several key observations emerged. Higher stirring speeds promoted intercalation by enhancing mass transfer and dispersion; increased agitation disrupted stagnant layers surrounding the clay particles, facilitating deeper penetration of the polymer chains into the interlayer galleries and preventing particle settling. Furthermore, the ANOVA results showed that all individual and interaction effects of the factors investigated had a significant influence on the d₀₀₁ spacing for both WB and YB clays. Each factor exhibited a positive effect on the degree of intercalation. Full article

Organo-mineral fertilizers can slow N release to plants, reducing N losses to the environment and enhancing N use efficiency (NUE). Yet, this greater NUE is not always coupled to greater crop yields, which warrants further investigation. Here, we assessed the relationship between N-NH₃ losses from volatilization and wheat (Triticum aestivum L.) biomass and N status. The following treatments were tested: conventional urea (U, 45% N), urea treated with NBPT (N-(n-butyl) thiophosphoric triamide) (U + NBPT, 45.6% N), S-coated urea (U + S; 37% N), Se-coated urea (U + Se; 45% N), organo-mineral fertilizer Azoslow 29 (OMF, 29% N + 50% Azogel^®). The above treatments and non-fertilized control were tested in two soils (LVd and LVAd, 71 and 25% clay, respectively). Semi-open static collectors were used to determine N-NH₃ volatilization 1, 2, 4, 8, 11, 15, 18, 23, 29, and 36 days after application of treatments. Wheat was cultivated for 35 days, and shoot dry mass and total leaf N were determined after harvest. Cumulative N-NH₃ losses from OMF (27 and 32% of N applied in the LVd and LVAd soils, respectively) did not differ from U and (26–32%) and U + Se (24–31%), likely due to organic matter inputs enhancing urease activity in soils. Nevertheless, OMF resulted in 2–4 times greater wheat dry matter than U, U + Se, and U + S, with similar dry mass of U + NBPT for LVAd soils. OMF application enhanced total N removal in wheat leaves relative to the unfertilized control and most N sources. N-NH₃ losses did not reduce biomass yield, but were negatively linked to N accumulation in wheat. The OMF enhanced wheat biomass and nutrition while sustaining environmental quality and promoting circularity in agroecosystems. Full article

Organoclays have been used in drug adsorption processes due being cheap and environmentally friendly materials with a good cost benefit for the water treatment industry. The present work evaluated the adsorption of chlorhexidine, an antimicrobial agent, on the organophilic clay Cloisite 30B by using a 2³ fractional factorial design. The main and interactive factors studied were the initial chlorhexidine concentration (0.4 and 0.6 mmol/L), adsorbent mass (0.3 and 0.5 g), and contact time (1 and 6 h). The organophilic clay Cloisite 30B was characterized by XRD and FTIR. To evaluate the impact of pH on the adsorption process, a range from 1 to 13 was used, in increments of one pH unit. The chlorhexidine adsorption parameters used the following adsorption conditions: an initial pH of 6, 200 rpm and a reaction temperature of 25 °C. Kinetic data followed the pseudo-second order model, while equilibrium data fit best to the Sips isotherm, suggesting high affinity and capacity. The maximum removal efficiency reached 95.77%, mainly influenced by the initial chlorhexidine concentration. These findings demonstrate the potential of organoclay for removing pharmaceutical contaminants from water pre-treatment of industrial effluents. Full article

One of the most interesting and poorly studied carriers of medicinal substances is the polymer clay composite material (PCCM). Bentonite clays are used in pharmacy for the manufacturing of various dosage forms, as well as in the adsorption of drugs to slow their release. Polymer–clay nanocomposites have demonstrated significantly improved properties compared to pure polymers. A review of recent scientific advances has shown promising results regarding the application of polymer–clay materials in medicine and bioengineering, particularly in the development of carrier sorbents with prolonged action for controlled drug release. As a result, interest in polymer–clay systems is steadily growing and gaining momentum. This paper focuses on the structure and properties of bentonite clays, including their sorption, ion exchange, binding, and rheological properties. The methods for preparing intercalated and exfoliated nanocomposites, such as radical intercalative polymerization in situ on clay surfaces, are reviewed. Furthermore, the improved efficacy and exposure times of PCCMs, combined with their enhanced bactericidal properties, are analyzed for the creation of universal and multifunctional preparations for medical use. Full article