Search Results (168)

The reliable quantification of urea in agricultural systems requires methods that combine metrological rigor with low environmental impact. This work develops and validates a micro-Raman method (λ = 532 nm) for the direct determination of urea in aqueous solutions and soils. The method is formally compared with the reference procedure ISO 19746:2017 (HPLC). Calibration, based on the 1000–1200 and 1460–1670 cm⁻¹ windows, showed near-ideal linearity in the 0.25–25% w/w range (r² = 0.9999). LOD and LOQ values were 0.178 and 0.735% w/w, respectively. Intra- and inter-day accuracy proved adequate for routine use (RSD ≤ 5%). A one-way ANOVA (p = 0.983) confirmed no statistically significant differences between concentrations obtained by micro-Raman and ISO 19746:2017. In the soil matrix, recoveries ranged between 94 and 101, and the contained biases demonstrate good tolerance to matrix effects. Application to maize plots allowed for monitoring urea disappearance at three depths (0–2 cm, 5–7 cm and 10–15 cm) over 90 days. These differentiated areas of rapid surface hydrolysis from more persistent fractions at depth. The Eco-Scale (96), GAPI (pictogram dominated by green areas), and AGREE (0.88) metrics confirm a significantly lower environmental footprint than that of the chromatographic method. The proposed micro-Raman methodology is emerging as a green, fast, and traceable alternative for monitoring urea in fertilizers and agricultural soils. Full article

To improve the efficiency of CO₂ hydrogenation, it is essential to develop new catalysts as well as new methods of producing them. In our work, we propose a new Fe-, Co-, Cu-containing catalyst preparation technique based on depositing the active component through urea hydrolysis using microwave heating. We also compare catalysts produced with microwave synthesis to samples obtained through traditional synthesis methods, including impregnation and thermal deposition. The obtained catalysts were characterized by XRD, low-temperature N₂ adsorption, SEM., and UV-VIS methods. The catalytic properties of the catalysts depend not only on the nature of the active component, but also on the preparation method. The best results for CO₂ hydrogenation were achieved with Ni-containing catalysts produced by the impregnation method and microwave synthesis. Full article

Fine and ultra-fine sugarcane bagasse (SCB) fractions (≤200 μm) that are naturally generated during industrial grinding have been systematically overlooked in lignocellulosic pretreatment research. Previous studies have largely relied on commercially processed pulps or coarse particles (>200 μm), typically without systematic size fractionation. Here, we demonstrate that these fine fractions—including ultra-fines (≤45 μm), which are often excluded from analytical workflows due to concern about excessive degradation—are viable feedstocks for producing lignin-containing cellulose nanofibers (LCNF) via a sequential thermal hydrolysis treatment (THT)–deep eutectic solvent (DES) pretreatment specifically designed to retain lignin. Size-fractionated SCB (≤45, 45–100, and 100–200 μm) was subjected to THT (190 °C, 15 min), followed by DES treatment using choline chloride/urea (1:2 molar ratio, 130 °C, 2 h). Multi-technique characterization using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and X-ray diffraction (XRD) indicated substantial hemicellulose removal (>70%), effective lignin retention (7.6–9.1%), cellulose enrichment (74.0–77.5%), and preservation of cellulose I structure allomorph. The crystallinity index increased from 46.5–52.7% after THT to 56.7–57.2% after DES treatment, and notably, uniform compositional and structural features were obtained across all particle size classes after DES treatment. Subsequent high-pressure microfluidization (700 bar, five passes) yielded LCNF with consistent morphology across all fractions: uniform fibril diameters (24.6–26.2 nm), a discernible lignin coating, and excellent colloidal stability (zeta potential: −86.3 to −95.0 mV). Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) confirmed well-dispersed nanofibrous networks. Collectively, these findings show that the full range of fine SCB fractions can be effectively valorized into high-performance LCNF through sequential THT–DES pretreatment, enabling comprehensive utilization of industrial grinding outputs and advancing circular bioeconomy objectives. Full article

Urease, a metalloenzyme widely present in various organisms, catalyzes the hydrolysis of urea to ammonia and CO₂ and has been extensively utilized in studies and applications of microbially induced calcium carbonate precipitation (MICP). While microbially induced calcium carbonate precipitation (MICP) and silicate mineral bio-weathering are both important biogeochemical processes mediated by microorganisms, and their coupling has been verified in some geological environments, the potential role of urease (a key enzyme in MICP) in mineral weathering remains unreported. In this study, Bacillus velezensis LB002 served as the urease gene donor for the construction of a Bacillus subtilis strain with heterologous overexpression of urease genes. The effects of this engineered strain and the wild-type strain on serpentine weathering and secondary mineral formation were compared. The results showed that the urease activity of the overexpression strain was approximately 3.8 times higher than that of the wild-type strain, and the release of Mg²⁺ during serpentine weathering increased by 17 mg/L. XRD and SEM-EDS analyses revealed that the wild-type strain promoted the formation of vaterite as a secondary mineral, whereas the overexpression strain induced the precipitation of both vaterite and magnesium-containing calcite. These findings demonstrate that urease plays a synergistic role in mineral weathering and that urease overexpression significantly enhances the release of Mg²⁺ from serpentine and the formation of magnesium-containing calcite. Full article

Agro-industrial chestnut waste derived from chestnut processing is usually discharged without further use. However, these residues are attractive due to their high-value composition, rich in sugars and lignin. Among these residues, chestnut burrs (CB) represent a promising feedstock for biorefinery applications aimed at maximizing the valorization of their main constituents. In this study, we propose an environmentally friendly approach based on deep eutectic solvents (DES) formed by choline chloride and urea (ChCl/U) (1:2, mol/mol) for the selective deconstruction of lignocellulosic architecture, followed by enzymatic hydrolysis to release second-generation (2G) fermentable sugars. Pretreatments were applied to raw CB, washed CB (W-CB), and the obtained solid fraction after prehydrolysis (PreH). Structural and morphological modifications, as well as crystallinity induced by DES pretreatment, were characterized using attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), field emission scanning electron microscopy (FE-SEM), and X-ray diffraction (XRD). Remarkable results in terms of effectiveness and environmental friendliness on saccharification yields were achieved for PreH subjected to DES treatment for 8 h, reaching approximately 60% glucan and 74% xylan conversion under the lower enzyme loading (23 FPU/g) and liquid-to-solid ratio (LSR) of 20:1 studied. This performance significantly reduces DES pretreatment time from 16 h to 8 h at mild conditions (100 °C), lowers the LSR for enzymatic hydrolysis from 30:1 to 20:1, and decreases enzyme loading from 63.5 FPU/g to 23 FPU/g, therefore improving process efficiency and sustainability. Full article

The massive accumulation of agricultural waste, such as wheat straw, and its disposal by burning pose significant environmental challenges. This study explores a sustainable solution by converting wheat straw into composite superabsorbent polymers (SAPs)—superabsorbents contain both synthetic and biodegradable fragments—for improved agricultural water and nutrient management. Wheat straw (WS) was sequentially processed via acid and alkaline hydrolysis to yield fractions with different lignin contents, which were then carboxymethylated (CMWS-Ac and CMWS-Al) to enhance hydrophilicity. These derivatives were incorporated at 20 and 33 wt. %. into SAPs synthesized by copolymerization with acrylamide and acrylic acid. The CMWS-Al-based SAPs exhibited superior properties, including higher equilibrium swelling ratios (up to 566 g/g in water), excellent mechanical strength, and robust gel structure, as confirmed by rheological studies. Furthermore, SAPs demonstrated a significant capacity to retain urea in sand columns, with SAP-CMWS-Al-33 achieving 56% urea retention, highlighting their potential for mitigating fertilizer leaching. The results establish a correlation between the extent of straw processing, the physicochemical properties and lignin content of the derivatives, and the performance of the final SAPs. These wheat straw-based SAPs present a promising, sustainable technology for enhancing soil moisture retention, improving fertilizer use efficiency, and valorizing agricultural waste. Full article

Microbially induced calcium carbonate precipitation (MICP) is recognized as a promising, environmentally sustainable technology with diverse applications in environmental engineering. A bibliometric analysis of 5373 publications indexed in Web of Science from 2005 to 2024 was conducted using CiteSpace and VOSviewer to identify research trends and hotspots in biomineralization and calcium carbonate (CaCO₃) studies. The results showed exponential growth in publications, increasing from 96 in 2004 to 397 in 2024 and spanning 91 interdisciplinary research areas. China, United States of America, and Germany were identified as the leading contributors. Research evolution was categorized into five distinct phases, progressing from initial crystal formation investigations to the current emphasis on underlying microbial mechanisms. Trend analysis revealed four emerging research hotspots: interfaces (0.22), crystal morphology (0.18), amorphous calcium carbonate (0.05), and bacteria (0.02). Mechanisms of MICP across bacteria, fungi, and algae were examined, revealing diverse metabolic pathways, including urea hydrolysis, denitrification, and photosynthesis. These findings suggest a paradigm shift in research toward microbial diversity and the role of extracellular polymeric substances. This shift provides valuable insights for developing sustainable biotechnological applications in environmental remediation. Full article

Compost amendments are widely recognized as an effective strategy for improving soil quality, modulating enzyme activities, and enhancing nitrogen cycling. Urease, a key enzyme in nitrogen transformation, is characterized by kinetic parameters such as the maximum reaction rate (V_max) and Michaelis constant (K_m), as well as thermodynamic attributes including temperature sensitivity (Q₁₀), activation energy (E_a), enthalpy change (ΔH), Gibbs free energy change (ΔG), and entropy change (ΔS). However, how different compost sources regulate urease kinetics, thermodynamics, and nitrogen availability remains poorly understood. In this study, we evaluated the effects of three compost amendments—mushroom residue (MR), mushroom residue–straw mixture (MSM), and leaf litter (LL)—on urease kinetics and thermodynamics in a temperate agroecosystem. The MSM treatment significantly enhanced urea hydrolysis capacity and catalytic efficiency. In contrast, LL treatment resulted in the highest Km value, indicating a substantially lower enzyme-substrate affinity. Furthermore, MSM reduced the E_a and increased the thermal stability of urease, thereby supporting enzymatic performance under fluctuating temperatures. Collectively, our findings highlight that compost composition is a critical determinant of urease function and nitrogen turnover. By elucidating the coupled kinetic and thermodynamic responses of urease to compost inputs, this study provides mechanistic insights to guide optimized soil management and sustainable nitrogen utilization in temperate agricultural systems. Full article

Phosphorylated cellulose nanocrystals (P-CNCs) are a superior alternative to conventional sulfuric acid-derived CNCs because of their enhanced thermal and colloidal stability. However, further research is needed to understand the factors influencing their synthesis and properties for advanced material applications. In this study, P-CNCs were synthesized from bleached hardwood kraft pulp (BEKP) using a controlled hydrolysis method involving pretreatment with H₃PO₄ followed by reaction with metaphosphoric acid (HPO₃) and urea. To optimize the process, a full factorial design was employed to evaluate the effects of reaction time (60–90 min) and HPO₃ concentration (3–4 M). The P-CNCs were characterized using physicochemical, morphological, and thermal analyses. Surface charge densities ranged from 757 to 1993 mmol/kg, with exceptional colloidal stability, as evidenced by zeta potentials ranging from −30.17 to −67.40 mV. Statistical analysis showed that reaction time had a significant main effect on surface charge (p-value = 0.0022) and zeta potential (p-value = 0.0448), while a significant interaction between reaction time and HPO₃ concentration was observed when analyzing the surface charge (p-value = 0.0097), suggesting a combined effect of these factors on the surface modification of CNC. Crystallinity indices ranged from 63.6% to 71.3%, and the thermal stability exceeded that of the raw material. These findings contribute to a better understanding of the surface modification and stability of P-CNCs and support efforts to sustainably produce functional CNCs for advanced composite applications. Full article

Optimizing resources to produce higher quality food is key to promoting more resilient agroecosystems. Although the use of biostimulants in agriculture has been gaining importance in recent years, their success depends on edaphoclimatic conditions and on the specific plant species. For this reason, the main aim of this study was to evaluate the effect of biostimulants (amino acids obtained from the enzymatic hydrolysis of plant extracts) on durum wheat yield variables and grain quality (protein content). Five treatments (control treatment—T1, biostimulants—T2, slow-release urea—T3, biostimulants plus slow-release urea—T4, Mg and micronutrients—T5) were tested in a field experiment conducted over 3 seasons in the south of Spain; all were dosed at 120 kg N ha⁻¹. The number of spikes increased significantly with biostimulant treatments in the first season (up to 33%, T2 and T4), while the highest significant grain yields were obtained with biostimulants applied individually in the first season (29.5%-T2) and biostimulants in combination with slow-release urea the second season (27.3%-T4), related to T1. Grain protein concentration was influenced by the treatment only in the second season, the driest during the study, when it was increased with biostimulants up to 4.2% with T2 in comparison with T1. Total protein production increased (28.1%T2) in the first season, (8.1–21.9% for T2–T4) in the second season and (6.5% T4) in the third season, when biostimulants were applied alone or in combination with slow-release urea, respectively. In general, plants treated with Mg and micronutrients produced a lower number of spikes, less yield, and reduced total protein compared to those doses with biostimulants. The application of amino acids as biostimulants was demonstrated to enhance durum wheat yield and total protein production and could be a potential tool for promoting nitrogen use efficiency in semi-arid areas. Full article

This study examines the effects and mechanisms of different Enzyme-Induced Carbonate Precipitation (EICP) treatments on loess structure improvement. The study focuses on ordinary EICP and three modified methods using MgCl₂, NH₄Cl, and CaCl₂. A series of unconfined compressive strength (UCS) tests, scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and elemental mapping were used to assess both macroscopic performance and microscopic characteristics. The results indicate that ordinary EICP significantly enhances loess particle bonding by promoting calcite precipitation. MgCl₂-modified EICP achieves the highest UCS (820 kPa) due to delayed urea hydrolysis and the formation of aragonite alongside calcite, which results in stronger and more continuous cementation. In contrast, NH₄Cl reduces urease activity and reverses the reaction, which limits carbonate precipitation and weakens structural cohesion. Excessive CaCl₂ leads to a “hijacking mechanism” where hydroxide ions form Ca(OH)₂, restricting carbonate formation and diminishing the overall enhancement. This study highlights the mechanisms behind enhancement, degradation, and diversion in the EICP process. It also provides theoretical support for optimizing loess subgrade reinforcement. However, challenges such as uneven permeability, environmental variability, and long-term durability must be addressed before field-scale applications can be realized, necessitating further research. Full article

Efficient use of nitrogen and phosphorus is crucial for achieving sustainable wheat production. Slow-release nano-fertilizers offer a targeted strategy to minimize nutrient losses, reduce excessive fertilizer application, and improve crop yield. This study introduces urea–hydroxyapatite (n-UHA) nanohybrid as a slow-release fertilizer synthesized to enhance nitrogen (N) and phosphorus (P) delivery efficiency in wheat (Triticum aestivum L.). Physical characterization techniques, including Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Spectroscopy (EDS), Zetasizer, and Fourier Transform Infrared Spectroscopy (FTIR), confirmed the formation of spherical n-UHA with a particle size of 106 nm. FTIR results indicated the formation of physically bound urea as a coating layer on the particle surface. Foliar application of n-UHA at 2500 and 5000 ppm N significantly increased tiller intensity and grain yield compared to conventional urea. The highest biological yield, approximately 16 t ha⁻¹, was achieved with 5000 ppm n-UHA plus supplemental soil phosphorus (P), representing a 4-fold increase over the control. Conventional urea treatments, in comparison, only doubled yield. Notably, increasing conventional urea concentration from 2500 to 5000 ppm N did not significantly increase the yield even with additional P-soil supplement, while applying 5000 ppm N from n-UHA with supplemental P provided an approximate 25% yield increase compared to 2500 ppm n-UHA without P. The n-UHA’s slow-release mechanism supported prolonged tiller intensity, enhanced protein content, and higher biomass yield and chlorophyll content. This study showed that the slow-release mechanism of urea in the monohybrid due to hydrolysis resulted in localized acidity from carbonic acid production on the leaf surface area and contributed to dissociating phosphate ions from hydroxyapatite, making phosphorous more accessible. The enhanced performance of n-UHA is due to its controlled nutrient release, enabled by the physical binding of urea with hydroxyapatite nanoparticles. This binding ensures a synchronized supply of nitrogen and phosphorus aligned with plant demand. The nano-hydroxyapatite composite (N/Ca 6:1) supplies balanced nutrients via efficient stomatal absorption and gradual release. As an eco-friendly alternative to conventional fertilizers, n-UHA improves nitrogen delivery efficiency and reduces N-evaporation, supporting sustainable agriculture. Full article

Microbially induced carbonate precipitation (MICP) refers to the formation of calcium carbonate driven by microbial metabolic processes, such as ureolysis. As an emerging biocementation technique, MICP has garnered attention for various applications in environmental and civil engineering. This study evaluated the feasibility of MICP implementation in a limestone mine. Ureolytic bacteria were isolated from an active limestone quarry at Mt. Buko, Saitama, Japan. Located at an elevation above 1000 m, the site represents a low-temperature environment with an average annual temperature of ~10 °C. The representative isolates, Rhodococcus sp. strains L6 and L8, exhibited tolerance to key environmental factors relevant to MICP applications in the limestone-rich settings, including alkaline pH, high calcium levels, and elevated urea concentrations. Additionally, both strains were psychrotolerant, maintaining growth and urease activity at temperatures as low as 5 °C. Notably, both strains induced calcite crystal formation at 10 °C and 5 °C, although the reaction was slower at 5 °C. Furthermore, strain L6 demonstrated the ability to induce MICP on limestone surfaces, effectively sealing rock fissures. These findings suggest that indigenous microbes retain metabolic activity in the limestone mine and are well suited for MICP applications. Full article

Biothiols, including cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), are crucial for physiological regulation and their imbalance poses severe health risks. Herein, we developed a pH-responsive liquid crystal (LC)-based sensing platform for detection of biothiols by doping 4-n-pentylbiphenyl-4-carboxylic acid (PBA) into 4-n-pentyl-4-cyanobiphenyl (5CB). Urease catalyzed urea hydrolysis to produce OH⁻, triggering the deprotonation of PBA, thereby inducing a vertical alignment of LC molecules at the interface corresponding to dark optical appearances. Heavy metal ions (e.g., Hg²⁺) could inhibit urease activity, under which condition LC presents bright optical images and LC molecules maintain a state of tilted arrangement. However, biothiols competitively bind to Hg²⁺, the activity of urease is maintained which enables the occurrence of urea hydrolysis. This case triggers LC molecules to align in a vertical orientation, resulting in bright optical images. This pH-driven reorientation of LCs provides a visual readout (bright-to-dark transition) correlated with biothiol concentration. The detection limits of Cys/Hcy and GSH for the PBA-doped LC platform are 0.1 μM and 0.5 μM, respectively. Overall, this study provides a simple, label-free and low-cost strategy that has a broad application prospect for the detection of biothiols. Full article

Nowadays, nanosized mesoporous oxides are of increasing interest to scientists. They can be used as components of heterogeneous catalysts, for photo- and electrocatalysis, as gas sensors, etc. For instance, the desired properties in catalysts include a nano size and homogeneity of the particles that form the catalyst. The particle sizes of oxides are set at the initial stage of their formation, as precursors of precipitation in the context of wet chemistry. The creation of optimal conditions is possible through the use of homogeneous precipitation, where the precipitant is formed within the solution itself as a result of a hydrolysis reaction. The resolution of this issue involved the utilization of urea in our experimental setup, obtaining the hydrolysis products of ammonia and carbon dioxide. Consequently, precipitation reactions can be utilized to obtain hydroxides, carbonates, or hydroxy carbonates of metals. The precursors were calcined, obtaining nanosized mesoporous oxides, which can have a wide range of applications. Nanosized 0.1–50 nm metal oxides were obtained, including those aluminum, iron, indium, zinc, nickel, and cobalt. Full article