Search Results (411)

This work focuses on the effectiveness of removing ammonium from real municipal wastewater using synthetic faujasite (FAU-type) and β (BEA-type) zeolites and a commercial β (BEA-type) sample. The results demonstrated that synthetic samples presented enhanced performance on ammonium removal in comparison with commercial zeolite due to higher Al content and larger specific surface area, promoting better accessibility to active adsorption sites of the adsorbents. Synthetic FAU-type and BEA-type zeolites achieved a maximum adsorption capacity of 28.87 and 12.62 mg·g⁻¹, respectively, outperforming commercial BEA-type zeolite (6.50 mg·g⁻¹). Adsorption assays, associated with kinetic studies and adsorption isotherms, were better fitted using the pseudo-second order model and the Langmuir model, respectively, suggesting that chemisorption, involving ion exchange, and monolayer formation at the zeolite surface, was the main mechanism involved in the NH₄⁺ adsorption process. After ammonium adsorption, the NH₄⁺-loaded zeolite samples were used to stimulate the growth of tomato seedlings; the results revealed a change in the biomass production for seedlings grown in vitro, especially when the BEA_C_NH₄ sample was employed, leading to a 15% increase in the fresh mass in comparison with the control sample. In contrast, the excess of ammonium adsorbed over the BEA_S_NH₄ and FAU_NH₄ samples probably caused a toxic effect on seedling growth. The elemental analysis results supported the hypothesis that the presence of NH₄⁺-loaded zeolite into the culture medium was important for the release of nitrogen. The obtained results show then that the investigated zeolites are promising both as efficient adsorbents to mitigate the environmental impact of ammonium-contaminated water bodies and as nitrogen-rich fertilizers. Full article

Magnetite (Fe₃O₄) provides a protective corrosion layer in the steam generators of nuclear power plants. The presence of monoethanolamine (MEA) in coolant water has a beneficial effect on corrosion processes. In that context, the adsorption of MEA and ethanol–ammonium cation on the {111} surface of magnetite was studied using the molecular dynamics (MD) method. A modified version of the mechanical force field (ClayFF) was used. The systems were simulated at different temperatures (423 K; 453 K; 503 K). Surface coverage data were obtained from adsorption simulations; the root-mean-square deviation (RMSD) of the target molecules were calculated, and their minimum distance to the magnetite surface was traced. The potential and adsorption energies of MEA were calculated as a function of temperature. It has been established that the interaction between MEA and magnetite is due to electrostatic phenomena and the adsorption rate increases with temperature. A comparison was made with existing experimental results and similar MD simulations. Full article

Phosphorylated cellulose is proposed as a bio-resin for the removal of heavy metals, as a substitute for synthetic polymer-based materials. Phosphorylation is carried out using kraft pulp fibers as the cellulose source, with phosphate esters and urea as reactants to prevent significant fiber degradation. Herein, phosphorylated fibers, with three types of counterions (sodium, ammonium, or hydrogen), are used in adsorption trials involving four individual metals: nickel, copper, cadmium, and lead. The Langmuir isotherm model is applied to determine the maximum adsorption capacities at four different temperatures (10, 20, 30, and 50 °C), enabling the calculation of the Gibbs free energy (ΔG), entropy (ΔS), and enthalpy (ΔH) of adsorption. The results show that the adsorption capacity of phosphorylated fibers is equal or even higher than that of commercially available resins (1.7–2.9 vs. 2.4–2.6 mmol/g). However, the nature of the phosphate counterion plays an important role in the adsorption capacity, with the alkaline form showing a superior ion exchange capacity than the hybrid form and acid form (2.7–2.9 vs. 2.3–2.7 vs. 1.7–2.5 mmol/g). The thermodynamic analysis indicates the spontaneous (ΔG = (-)16–(-)30 kJ/mol) and endothermic nature of the adsorption process with positive changes in enthalpy (0.45–15.47 kJ/mol) and entropy (0.07–0.14 kJ/mol·K). These results confirm the high potential of phosphorylated lignocellulosic fibers for ion exchange applications, such as the removal of heavy metals from process or wastewaters. Full article

This study examined a strategy for effective reject water treatment involving hydrodynamic cavitation (HC) combined with subsequent adsorption using natural zeolites. Two experiments were conducted: The first involved the selection of optimal pre-treatment conditions of HC for biodegradability and to reduce the ammonium nitrogen and phosphate content. Three inlet pressures of 3, 5, and 7 bar and two types of cavitation inducers, i.e., multiple- and single-hole orifice plates, were evaluated. Adsorption experiments were conducted in batch mode using natural zeolite, and three doses of zeolite (50, 100, and 200 g/L) and six contact times (4–24 h) were examined. In the HC experiments, the application of 3 bar pressure, a single-hole cavitation inducer, and a cavitation time of 30 min resulted in the removal of ammonia nitrogen and phosphates amounting to 26.5 and 23%, respectively. In this case, 3.6-fold enhancement in the biodegradability index was also found. In the second experiment, the use of zeolite led to a decrease in the remaining content of both ammonia nitrogen and phosphates, improving the chemical oxygen demand-to-total nitrogen ratio. The highest removal efficacy was found for the highest zeolite dose of 200 g/L and the longest cavitation time of 24 h. Under these conditions, the ammonia nitrogen and phosphate removal rates were 70 and 94%, respectively. Full article

Soil salinization severely limits global agricultural sustainability, particularly across the saline–alkaline landscapes of the Qinghai–Tibet Plateau. We examined how potassium fulvate (PF) modulates oat (Avena sativa L.) performance, soil chemistry, and rhizospheric microbiota in the saline–alkaline soils of the Qaidam Basin. PF markedly boosted shoot and root biomass, with the greatest response observed at 150 kg hm⁻². At the same time, it enhanced soil fertility by increasing organic matter, nitrate-N, ammonium-N, and available potassium, and improved ionic balance by lowering Na⁺ concentrations and the sodium adsorption ratio (SAR), while increasing Ca²⁺ levels and soil moisture content. Under the high-dose treatment (F2), endogenous fungal contributions declined sharply, exogenous replacements increased, and fungal α-diversity fell; multivariate ordinations confirmed that PF reshaped both bacterial and fungal communities, with fungi exhibiting the stronger response. We integrated three machine learning algorithms—least absolute shrinkage and selection operator (LASSO), Random Forest (RF), and eXtreme Gradient Boosting (XGBoost)—to minimize the bias inherent in any single method. We identified microbial β-diversity, organic matter, and Na⁺ and Ca²⁺ concentrations as the most robust predictors of the Soil Salinization and Alkalization Index (SSAI). Structural equation modeling further showed that PF mitigates salinity chiefly by improving soil physicochemical properties (path coefficient = −0.77; p < 0.001), with microbial assemblages acting as key intermediaries. These findings provide compelling theoretical and empirical support for deploying PF to rehabilitate saline–alkaline soils in alpine environments and offer practical guidance for sustainable land management in the Qaidam Basin. Full article

A sensitive method was developed for detecting diazepam residues in aquatic products using magnetic dispersive solid-phase extraction (MDSPE) coupled with ultra-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS). Samples extracted with 1% ammonia–acetonitrile were purified using synthesized Fe₃O₄@SiO₂-PSA nanoparticles via MDSPE before UPLC-MS/MS analysis. Separation was performed on a C₁₈ column with gradient elution using 0.1% formic acid–2 mM ammonium acetate/methanol. Detection employed positive electrospray ionization (ESI⁺) in multiple reaction monitoring (MRM) mode. Characterization confirmed Fe₃O₄@SiO₂-PSA’s mesoporous structure with excellent adsorption capacity and magnetic properties. The method showed good linearity (0.1–10 μg/L, r > 0.99) with an LOD and LOQ of 0.20 μg/kg and 0.50 μg/kg, respectively. Recoveries at 0.5–15.0 µg/kg spiking levels were 74.9–109% (RSDs 1.24–11.6%). This approach provides rapid, accurate, and high-precision analysis of diazepam in aquatic products, meeting regulatory requirements. Full article

Implementing efficient strategies for the circular recovery and reuse of nutrients from wastewaters is mandatory to meet the Green Deal objectives and Sustainable Development Goals. In this context we investigated the use of zeolitic tuff (containing chabazite and phillipsite) in the selective recovery and reuse of N from various anaerobic liquid digestates in view of their implementation in farm-scale treatment plants. We tested the method on three livestock digestates and two municipal organic solid waste digestates. Adsorption isotherms and kinetics were assessed on each digestate, and a large set of parameters, including (i) contact time, (ii) initial NH₄⁺ concentration, (iii) presence of competing ions, (iv) total solids content, and (vi) separation methods (microfiltration and clarification), were considered in the experimental design. Our results showed that the adsorption mechanism can be explained by the Freundlich model (R² up to 0.97), indicating a multilayer and heterogeneous adsorption, while the kinetic of adsorption can be explained by the pseudo-second-order model, indicating chemical adsorption and ion exchange. The efficiency in the removal of NH₄⁺ was indirectly related to the K⁺ and total solids content of the digestate. Maximum NH₄⁺ removal exceeded 90% in MSW-derived digestates and 80% within 60 min in livestock-derived digestates at a 5% solid/liquid ratio. Thermodynamic parameters confirmed favorable and spontaneous adsorption (ΔG up to −7 kJ⋅mol⁻¹). Farm-scale projections estimate a nitrogen recovery potential of 1.2 to 16 kg N⋅day⁻¹, depending on digestate type and process conditions. These findings support the application of natural zeolitic tuffs as a low-cost, chemical-free solution for ammonium recovery, contributing to sustainable agriculture and circular economy objectives. Full article

Multifunctional water-treatment materials urgently need to be developed to avoid normal organic matter, inorganic anions, resistant bacteria, and hazardous disinfection by-products in conventional drinking water treatment strategies. While quaternary ammonium pyridine resins (QAPRs) possess porous adsorption structures and incorporate antibacterial groups, enabling simultaneous water disinfection and purification, their limited bactericidal efficacy hinders broader utilization. Therefore, a deeper understanding of the structure-dependent antimicrobial mechanism in QAPRs is crucial for improving their antibacterial performance. Hexyl (C₆) was proved to be the optimal antibacterial alkyl in the QAPRs. A new antibacterial quaternary ammonium pyridine resin Py-61 was prepared by more surficial bactericidal N⁺ groups and higher efficient antibacterial hexyl, performing with the excellent antibacterial efficiency of 99.995%, far higher than the traditional resin Py-6C (89.53%). The antibacterial resin Py-61 completed the disinfection of sand-filtered water independently to produce safe drinking water, removing the viable bacteria from 3600 to 17 CFU/mL, which meets the drinking water standard of China in GB5749-2022 (<100 CFU/mL). Meanwhile, the contaminants in sand-filtered water were obviously removed by the resin Py-61, including anions and dissolved organic matter (DOM). The resin Py-61 can be regenerated by 15% NaCl solution, and keeps the reused antibacterial efficiency of >99.97%. As an integrated disinfection–purification solution, the novel antibacterial resin presents a promising alternative for enhancing safety in drinking water treatment. Full article

Magnesium whitlockite (Mg-WH) has emerged as a promising biomaterial for bone regeneration due to its compositional similarity to natural bone minerals. This study aimed to systematically modify a dissolution–precipitation synthesis method to produce Mg-WH granules with tailored morphologies and controlled phase compositions for possible use in bone regeneration applications. Three distinct precursor granules were prepared by mixing varying amounts of ammonium dihydrogen phosphate and magnesium hydrogen phosphate with calcium sulfate. The precursors were then transformed into biphasic and single-phase Mg-WH granules by means of immersion in magnesium- and phosphate-containing solutions under controlled conditions. The X-ray diffraction results demonstrated that biphasic materials containing Mg-WH and either calcium-deficient hydroxyapatite (CDHA) or dicalcium phosphate anhydrous (DCPA) formed after 24 h of synthesis, depending on the synthesis conditions. Prolonging the reaction time to 48 h resulted in complete transformation into single-phase Mg-WH granules. Fourier-transform infrared spectroscopy confirmed the presence of functional groups characteristic of Mg-WH, CDHA, and DCPA in the intermediate products. The spectra also indicated the absence of precursor phases and the progressive elimination of secondary phases as the reaction time increased. Scanning electron microscopy analyses revealed notable morphological transformations from the raw granules to the product granules, with the latter exhibiting interlocked spherical and rod-like particles composed of fine Mg-WH rhombohedral crystals. N₂ adsorption–desorption analyses exposed significant differences in the surface properties of the synthesized granules. By varying precursor, reaction solution compositions, and reaction times, the study elucidated the phase evolution mechanisms and demonstrated their impact on the structural, morphological, and surface properties of Mg-WH granules. Full article

Although constructed wetlands (CWs) are a viable solution for wastewater treatment, substrate selection significantly affects their performance. This study evaluated the adsorption behavior of ammonium and orthophosphate on natural zeolite (coarse- and fine-grained) and coarse gravel using kinetic and isotherm experiments. Coarse materials are intended for use as filler media in CWs to address problems such as clogging. Ammonium removal due to adsorption reached 96.20% and 96.49% for coarse and fine zeolite, respectively, and 16.84% for gravel. For orthophosphate, the removal was 11.46% and 12.81% for coarse and fine zeolite, respectively, and 6.70% for gravel. Kinetic analysis showed that the adsorption of both nutrients followed the pseudo-second-order model. Zeolite exhibited high ammonium adsorption capacities (181.87 and 174.23 mg/kg), with granulometry showing minimal effect. The orthophosphate adsorption capacities were lower (11.76 and 12.35 mg/kg for zeolite; 6.44 mg/kg for gravel). Isotherm modeling indicated that ammonium adsorption fitted better to the Langmuir model (monolayer adsorption), while orthophosphate followed the Freundlich model (heterogeneous surface adsorption). Ζeolite adsorbed six times more ammonium and twice as much phosphate as gravel. These findings suggest that natural zeolite is an effective and sustainable CW substrate, enhancing nutrient removal and serving as an economical and environmentally friendly alternative to traditional filler media. Full article

This study focuses on the chemical synthesis of nano-titanium dioxide (nano-TiO₂) via ammonium fluorotitanate ((NH₄)₂TiF₆) precipitation with ammonia solution, aiming to elucidate the effects of experimental parameters—including reaction temperature, duration, molar ratio of (NH₄)₂TiF₆ to ammonia, and (NH₄)₂TiF₆ concentration—on the particle size of synthesized nanoparticles, as well as the correlation between particle size and photocatalytic performance. The synthesized nanoparticles predominantly exhibited spindle-shaped morphology. Direct TEM imaging revealed the crystallization and growth mechanisms during synthesis: higher molar ratios, combined with lower temperatures and shorter durations, facilitated the formation of ultrafine particles, whereas lower molar ratios, with elevated temperatures and prolonged reaction times, yielded larger particles. Notably, nanorod structures emerged under low-temperature conditions with F⁻ ion adsorption. To investigate the relationship between particle size and photocatalytic performance, a Taguchi method-inspired experimental design was employed to evaluate the positive or negative impacts of particle size on photocatalytic activity. An experimental matrix was constructed using coded values for each factor, and regression coefficients were calculated to quantify input-output correlations. Results demonstrate that titanium dioxide catalysts with a particle size range of 50–75 nm exhibit optimal photocatalytic efficiency. Full article

Research on using biochar as an adsorbent of contaminants in aqueous matrices has gained significant relevance in recent years due to the surface chemistry and porous structure of biochar, which facilitate the retention of a wide range of pollutants. This study explores the adsorption performance of a novel biochar produced from agave bagasse—a readily available agro-industrial waste in Mexico—through low-temperature pyrolysis. The biochar was evaluated for its capacity to remove conventional water quality parameters (chemical oxygen demand (COD), nitrates (NO₃⁻), total nitrogen (TN), total phosphorus (TP), ammonium (NH₄⁺), turbidity, apparent color, and true color) from water samples collected from the polluted Bustillos Lagoon in Chihuahua, Mexico. Additionally, the removal of emerging pharmaceutical contaminants, specifically acetaminophen (Act) and diclofenac (Dfc), was assessed in synthetic aqueous solutions. Potentiometric titration analyses revealed a significant contribution of surface acidity in the adsorption of pharmaceutical derivatives, highlighting the relevance of functional groups retained during low-temperature pyrolysis. The biochar derived from agave bagasse (BBAF1) was tested in a fixed-bed column system and compared with two commercial activated carbons (CACCF2 and CVCF3). The BBAF1 biochar achieved average removal efficiencies ranging from 50% to 90% for all conventional parameters. In contrast, those of ACT and DFC were between 0.43 and 0.67 mg g⁻¹ (59–85%) and 0.34 and 0.62 mg g⁻¹ (37–79%), respectively, demonstrating their potential as an adsorbent material for improving water quality. This work supports the development of circular economic strategies by valorizing agricultural residues while offering an effective solution to environmental pollution challenges. Full article

Excess phosphorus (P) and nitrogen (N) in wastewater contribute to eutrophication, driving the need for low–cost and sustainable recovery technologies. This study presents a novel adsorbent synthesized from spent coffee grounds biochar (CB) chemically modified with Mn²⁺/Zn²⁺/Fe³⁺ (oxy)hydroxide nanoparticles (CB–M) for simultaneous removal of phosphate and ammonium. Batch adsorption experiments using both synthetic solution and municipal wastewater were conducted to evaluate the material’s adsorption performance and practical applicability. Kinetic, isotherm, thermodynamic, and sequential extraction analyses revealed that CB–M achieved maximum phosphate adsorption capacities ranging from 42.6 to 72.0 mg PO₄³⁻·g⁻¹ across temperatures of 20–33 °C, reducing effluent phosphate concentrations to below 0.01 mg·L⁻¹. Ammonium removal was moderate, with capacities ranging between 2.8 and 2.95 mg NH₄⁺·g⁻¹. Thermodynamic analysis indicated that phosphate adsorption was spontaneous and endothermic, dominated by inner–sphere complexation, while ammonium uptake occurred primarily through weaker, reversible ion exchange mechanisms. Sequential extraction showed over 70% of adsorbed phosphate was associated with Fe-Mn-Zn phases, indicating the potential for use as a slow–release fertilizer. The CB–M retained structural integrity and exhibited partial desorption, supporting its reusability for nutrient recovery. Compared to other biochars, CB–M demonstrated superior phosphate selectivity at a neutral–pH, avoided the use of hazardous metals, and transformed coffee waste into a multifunctional material for wastewater treatment and soil amendment. These findings underscore the potential of CB–M as a circular economy solution for nutrient recovery without introducing secondary contamination. Full article

Poly(3,3-bis(azidomethyl)oxetane(BAMO)-tetrahydrofuran(THF)) copolymer (PBT) and ammonium perchlorate (AP) are critical components of solid rocket propellants, where their interfacial bonding mechanisms and temperature-dependent mechanical properties are pivotal to propellant reliability. In this study, density functional theory (DFT) calculations were employed to evaluate the adsorption energies between common AP crystal surfaces and PBT units, identifying the most energetically favorable adsorption configurations. The atomic configurations and charge transfer characteristics at the PBT-AP interface were systematically analyzed. Molecular dynamics (MD) simulations were further conducted to determine the thermally stable operating range of the PBT-AP system. The results reveal a strong temperature dependence of mechanical performance, with viscous failure mechanisms and damage thresholds during static tensile processes investigated across varying temperatures. Notably, mechanical properties remain stable below 60 °C but deteriorate significantly above this temperature. This study elucidates the influence of a PBT-AP interfacial microstructure and temperature on mechanical performance and tensile fracture damage boundaries, providing crucial insights for the design, formulation, and safe application of PBT-based solid rocket propellants. Full article

The aim of this research is to optimize the process parameters for nitrate adsorption from aqueous solutions using ammonium modified calabash gourd shell (CGS). Two types of experimental design (DoE) methodology were implemented in the optimization. A full factorial design (FFD) assessed the influence of the main factors on the process response. The efficiency of nitrate adsorption at the predicted optimal conditions by FFD was 78.93%. The study was extended to a central composite design (CCD) within the response surface methodology (RSM) to capture the factors nonlinear effects and optimize the adsorption parameters. The quadratic polynomial model using CCD proved to be useful for understanding the adsorption system’s behavior, locating the optimal process factors, and predicting the adsorption efficiency (R² > 0.95). The significance of the model terms (A, B, C, D, B², and C²) is confirmed by F = 74.95 and p < 0.0001. According to the CCD, the optimal adsorption conditions were estimated in the range: initial nitrate concentration 10–20 mg/L, pH 6–7, temperature 20–25 °C, and contact time 25–30 min (desirability 0.996). The predicted and obtained values using FFD and CCD models are very close, which confirms their practical applicability. The repeated test found the nitrate adsorption efficiency (84.9%) using CCD model in the predicted range (80.1–89.6%), which confirms the adequacy and significance of the model. This model could find potential application in real processes for the treatment of nitrate-contaminated water using the environmentally friendly CGS cationic adsorbent. Full article