Search Results (657)

Phosphate tailings (PTs), a solid waste generated from phosphate flotation, are a low-grade phosphate resource rich in quartz and dolomite. Their long-term accumulation leads to both resource loss and environmental risks, making valorization increasingly important for the sustainable development of the phosphorus chemical industry. In this study, calcareous–magnesian PTs were used as raw materials, and selective hydrothermal leaching with weakly acidic AlCl₃ solution was employed to separate the dolomite phase and directly construct a Ca-Mg-Al precursor solution for layered double hydroxides (LDHs). The LDHs were subsequently synthesized by co-precipitation and evaluated for phosphate removal from wastewater. The results showed that the precipitation pH markedly affected the phase composition and platelet morphology of the LDHs, while appropriate aging conditions further improved their adsorption performance. Under the optimal conditions of pH 12, aging at 40 °C for 2 h, the obtained LDHs exhibited the best phosphate uptake. Adsorption kinetics followed the pseudo-second-order model, and the maximum adsorption capacity calculated from the Langmuir model reached 38.61 mg-P/g. Characterization by XRD, FTIR, TG-DTA, point of zero charge, and XPS indicated that phosphate removal was dominated by surface complexation, accompanied by anion exchange, ionic precipitation, and electrostatic attraction. Full article

Removing mercury (Hg²⁺) from aqueous environments remains a major environmental challenge due to its high toxicity and bioaccumulation. Graphene quantum dots (GQDs) are adsorbents that show promise in removing these contaminants, but their yield is low in their pristine form. This study investigates the effect of phosphorus (P) doping on vacancy-containing GQDs to enhance Hg²⁺ absorption using density functional theory (DFT) calculations. These were performed at the M06-2X/def2-TZVP level of theory to optimize the structures of GQDs, 1P-GQDs, and 2P-GQDs to evaluate adsorption energies, frontier molecular orbitals, and dipole moments. The results show that GQDs with vacancy have an adsorption energy of −65.21 kcal mol⁻¹, which increases to −104.54 kcal mol⁻¹ for 1P-GQDs, indicating the strongest Hg²⁺ binding. However, 2P-GQD shows a lower value of −73.47 kcal mol⁻¹, suggesting lower efficiency due to electronic competition between dopants. Dipole moments increase from 0.8192 D (GQD) to 4.6729 D (1P-GQD) and 5.7557 D (2P-GQD), confirming strong polarization induced by P incorporation. The HOMO-LUMO gap decreases from 2.204 eV to 1.937 eV after single doping. At the same time, after Hg²⁺ adsorption, the values increase to 5.153 eV (GQD), 3.462 eV (1P-GQD), and 2.068 eV (2P-GQD), indicating configuration-dependent electronic stabilization. PDOS analysis confirms weak cation-π interaction in GQD and strong orbital hybridization in 1P-GQD, consistent with a coordination-type bond. Doping a single phosphate atom optimizes the electronic structure of GQDs with a vacancy site, thereby improving charge transfer and adsorption strength through electronic balance. Full article

Adsorption is a promising technology for phosphate removal to alleviate eutrophication. In this study, thermally modified calcium aluminate decahydrate (TCAH) was prepared via low-temperature thermal treatment of calcium aluminate decahydrate (CAH₁₀) to develop a cost-effective and high-performance phosphate adsorbent. The optimal modification temperature was determined to be 120 °C, which reduced the crystallinity of CAH₁₀, enhanced its porosity, and induced the formation of amorphous calcium aluminate phases. Batch adsorption experiments showed that TCAH exhibited a maximum adsorption capacity of 199.80 mg P/g at 25 °C. The adsorption kinetics followed the pseudo-second-order model, while the adsorption isotherms were well fitted by the Redlich–Peterson model. TCAH maintained high removal efficiency over a wide pH range of 3.0–11.0 and showed high selectivity against common coexisting anions. Characterizations using SEM-EDS, XRD, FTIR and XPS suggested that phosphate removal by TCAH was dominated by synergistic amorphous precipitation and inner-sphere complexation. In tests with real phosphorus-releasing liquor derived from excess sludge, TCAH achieved nearly complete phosphate removal at a dosage of 5 g/L within 6 h. Owing to its readily available raw materials, low preparation temperature, and outstanding phosphate capture performance, TCAH is a promising candidate for efficient phosphate capture and recovery from wastewater. Full article

Tetracycline-class antibiotics are persistent contaminants in aquatic environments and are difficult to remove by conventional treatment processes. In this study, a recoverable granular MIL-101(Fe)/γ-Al₂O₃ catalyst was prepared through ligand anchoring followed by secondary Fe-MOF growth on spherical γ-Al₂O₃ and applied to catalytic ozonation of tetracycline (TC) under ordinary-bubble and microbubble-assisted operation. Structural characterization supported the formation of Fe-containing MOF domains on the alumina support, accompanied by an increase in BET surface area from 164.28 to 210.05 m² g⁻¹ and enhanced Lewis-acid-related pyridine-IR signals. Under conventional bubbling ozonation, the optimized catalyst achieved 67.93% apparent UV–Vis-based TC removal during an overall 50 min run consisting of 30 min dark adsorption followed by 20 min ozonation. In a 12 L microbubble reactor, the catalyst-assisted system reached 93.74% apparent UV–Vis-based TC removal at pH 6 with 100 g catalyst and 6 mg min⁻¹ fed ozone, showing higher apparent removal than ordinary ozonation, microbubble ozonation, and ordinary-bubble catalytic ozonation under the tested configuration. Phosphate-blocking and radical-quenching experiments were consistent with the involvement of Lewis-acid-related sites, hydroxyl radicals, and superoxide-related pathways, but these tests are interpreted as indirect mechanistic evidence. LC-MS analysis suggested possible hydroxylation, demethylation, deamidation, ring opening, and low-molecular-weight product formation. The system also transformed chlortetracycline, oxytetracycline, and doxycycline and reduced COD and TOC in a simulated mixed-antibiotic matrix. Because parent-compound HPLC/LC-MS time-series quantification, ozone utilization/off-gas ozone measurement, bubble-size/kLa analysis, and ICP-based Fe loading/leaching data were not available, the present work is positioned as an apparent catalyst–reactor coupling study rather than a complete catalytic, hydrodynamic, or process-level demonstration. Full article

Wastewater containing such inorganic contaminants, especially phosphate and nitrate ions, has to be treated thoroughly before disposal into natural environments. This is a precautionary measure to avoid adverse effects on public health, which are exacerbated when these two pollutants are present in an aqueous system. The present research investigated how the adsorption process is influenced by factors such as the effect of ion composition, contact time, temperature and competitive adsorption behavior in multi-anion systems using Ternary Biopolymer–Bentonite Beads. This study used five isotherms and four kinetic models to investigate phosphate ions removal on prepared natural Clay-Bio-polymer composite beads. The results indicate that the pseudo-second-order (PSO) kinetic model provides the most accurate description of the adsorption process. Moreover, the correlation coefficients (R²) obtained for both the Langmuir and Freundlich isotherm models are nearly equal to 1, confirming their strong reliability in fitting the experimental data. The strong fit of both the Langmuir and Freundlich models indicates that the adsorption process exhibits mixed behavior, with both monolayer adsorption on relatively homogeneous sites and multilayer adsorption on heterogeneous sites. This mixed-behavior system is typical of composite adsorbents with diverse surface properties. The Redlich-Peterson model, a hybrid of Langmuir and Freundlich, showed the best overall correlation (R² = 0.990 for H₂PO₄⁻ and 0.998 for NO₃⁻). The applicability of the Sips and Toth isotherm models, which account for both uniform and non-uniform adsorption behaviors, validated the experimental results. In the competitive binary system, the maximum adsorption capacities achieved by the composite were 121.844 mg/g for H₂PO₄⁻ and 27.979 mg/g for NO₃⁻. The results indicate strong competition between H₂PO₄⁻ and NO₃⁻ ions for the available active sites, reflecting an antagonistic adsorption. A positive value of ∆H° verifies that the adsorption process is endothermic and primarily physical, consistent with the experimental observations. The negative ∆G° values demonstrate that the adsorption occurs spontaneously, whereas the positive ∆S° indicates an increase in randomness at the solid–liquid interface during the uptake of phosphate ions. Full article

La-MOFs exhibit strong affinity toward anions such as F⁻ and phosphate. However, conventional La-MOFs show limited regeneration performance when used as CDI electrodes, posing a major challenge for practical applications. In this study, a high-performance sulfur and nitrogen co-doped La-BDC-140-derived carbon electrode (La-CNS₃) was fabricated via a coupled carbonization and doping strategy. The optimized La-CNS₃ electrode possessed abundant defects, a mesoporous structure, favorable hydrophilicity, and rapid charge-transfer capability, which collectively enhanced fluoride electrosorption. At 1.4 V, La-CNS₃ achieved a fluoride removal capacity of 31.86 mg·g⁻¹ for 10 mg·L⁻¹ F⁻ solution and up to 195 mg·g⁻¹ at an initial F⁻ concentration of 100 mg·L⁻¹. More importantly, partial fluoride desorption was realized solely under reverse voltage, and the electrode maintained favorable defluoridation performance over 50 adsorption–desorption cycles. In actual groundwater treatment, the effluent fluoride concentration decreased to below 1.0 mg·L⁻¹ after 120 min. XPS analysis and DFT calculations revealed that fluoride removal was mainly governed by La-F coordination, surface hydroxyl/water ligand exchange, and interfacial charge redistribution. The La₂O₂S/g-C₃N₄ structure provided a favorable balance between fluoride adsorption strength and desorption reversibility. This work offers a promising strategy for designing efficient, selective, and electrically regenerable rare-earth-based CDI electrodes for fluoride-contaminated water treatment. Full article

The wet recovery of spent lithium iron phosphate (LFP) batteries is severely hindered by the low efficiency of copper removal. Here, a new process has been developed using a copper-removing chelating resin with pyridine nitrogen, carboxyl, and hydroxyl groups for the selective separation of copper ions. This copper chelating resin achieved a copper removal efficiency of 96.99% and reduced the residual copper content to below 10 milligrams per liter, significantly outperforming the traditional iron powder method. The adsorption process is highly sensitive to pH, with the highest efficiency at pH 1.75. A concentration of 2.0 moles per liter of H₂SO₄ can achieve a desorption rate of approximately 95%. The adsorption process follows the Langmuir isothermal equation and the pseudo-second-order kinetic model, corresponding to single-layer chelated chemical adsorption. Mechanism studies have confirmed that the synergistic coordination effect of the multifunctional groups helps in the efficient capture of copper ions. This copper chelating resin exhibits excellent stability, reversibility, and reusability, providing a promising method for efficient copper removal and recovery in the wet metallurgical recycling of LFP. Full article

Hydrogen-fueled internal combustion engines (H₂-ICEs) impose unique challenges on engine lubrication because water is an inevitable combustion product. This review summarizes the current understanding of water-induced degradation mechanisms in engine oils for H₂-ICEs, with emphasis on physicochemical property variation, additive depletion, tribofilm evolution, and tribological performance. Water present in dissolved, emulsified, or free states can significantly alter lubricant viscosity, destabilize additive systems, and accelerate oxidative aging. In particular, water promotes the depletion of zinc dialkyldithiophosphate (ZDDP) through tribofilm removal and competitive adsorption at rubbing interfaces, while also inducing additive hydrolysis that transforms long-chain phosphates into shorter-chain species with inferior film-forming capability. These processes inhibit tribofilm growth and reduce the mechanical integrity of protective films, thereby deteriorating anti-wear performance. Although substantial progress has been made in understanding the role of liquid water in lubrication, the tribochemical effects of high-temperature water vapor under realistic H₂-ICE operating conditions remain largely unexplored. Future research should therefore focus on water vapor-dominated lubrication environments representative of hydrogen combustion, aiming to elucidate the underlying tribochemical mechanisms and support the development of dedicated lubricants for durable and reliable H₂-ICE operation. Full article

Nitrogen and phosphorus are the primary pollutants responsible for eutrophication in water bodies, and their effective removal is crucial for water environmental protection. Biochar, owing to its porous structure and surface functional groups, exhibits excellent adsorption performance for nitrogen and phosphorus, which can be significantly enhanced through metal modification. In this study, magnetic biochar (MBC) was prepared from spent mushroom substrate via FeCl₃ impregnation and microwave pyrolysis, and its adsorption performance for NH₄⁺ and PO₄³⁻ was systematically evaluated. The physicochemical properties of MBC were characterized using scanning electron microscopy, thermogravimetric analysis, specific surface area and pore structure analysis, vibrating sample magnetometry, and Fourier transform infrared spectroscopy. The results showed that the saturated magnetization of MBC was 7.86 emu/g, the specific surface area was 37 m²/g, and the material exhibited a mesoporous structure with high thermal stability. The adsorption process followed pseudo-second-order kinetics, and the mechanisms involved electrostatic interactions, surface complexation, and pore filling. Isotherm studies indicated that the maximum adsorption capacities of MBC for NH₄⁺ and PO₄³⁻ were 16.25 mg/g and 14.99 mg/g, respectively. Thermodynamic analysis revealed that the adsorption of NH₄⁺ was exothermic, whereas that of PO₄³⁻ was endothermic. Furthermore, MBC maintained an adsorption efficiency of up to 93% after ten adsorption–desorption cycles, demonstrating excellent reusability. Full article

Green roofs offer significant potential for urban stormwater management, yet their capacity to improve runoff water quality is constrained by the limited pollutant retention of conventional substrates and inherent nutrient leaching risks. This critical review synthesizes recent advances in substrate engineering and phytoremediation to establish an integrated framework for transforming green roofs into active bio-filtration systems. Our analysis reveals that amending conventional substrates with waste-derived biosorbents substantially enhances heavy metal and nutrient retention through complementary mechanisms of surface complexation, ion exchange, and microprecipitation. When strategically coupled with hyperaccumulator plant species and rhizospheric microbial communities, these amended substrates significantly reduce contaminant loads in urban runoff while maintaining hydraulic functionality. We critically evaluate standard growing media versus substrates amended with targeted biosorbents: biochar, which enhances heavy metal retention and hydraulic conductivity via surface complexation; seaweed biomass, which provides superior water retention and cation exchange while reducing synthetic fertilizer dependence; and chitin-rich crab shell waste, which promotes microprecipitation of metals and phosphates while valorizing marine waste. The novelty resides not in the materials themselves, but in their synergistic combination and the systematic comparative analysis of their retention mechanisms under green roof hydrological conditions. This review further identifies critical engineering trade-offs, including biosorbent-induced hydraulic conductivity reductions and long-term adsorption site saturation, and provides actionable design thresholds for amendment dosing, substrate depth, and species selection. Ultimately, this work establishes a mechanistic and practical roadmap for next-generation green roofs that simultaneously optimize stormwater retention, runoff quality, and circular economy valorization, highlighting priority research directions for long-term field validation and climate-adaptive standardization. Full article

Aquaculture wastewater containing tetracycline hydrochloride (TCH) poses significant environmental problems and health risks. We investigated the adsorption of TCH onto phosphoric acid-activated corncob biochar (PCC) as a sustainable and efficient removal strategy. PCC was synthesized from cob feedstock activated by phosphoric acid under a pyrolysis temperature of 300 °C in a limited-air atmosphere. It was characterized extensively, revealing a high specific surface area (1071.75 m²/g), high porosity with total pore volume of 0.912 cm³/g, and abundant surface functional groups including phosphate, carboxylic, and amine groups. Batch adsorption experiments demonstrated an ultrahigh adsorption capacity for TCH, with a maximum theoretical capacity (Langmuir model) of 953.62 mg/g at 313 K. Its adsorption isotherms transfer from Langmuir type to Freundlich type as temperature rises, indicating a transition from monolayer to multilayer adsorption. The adsorption kinetics were governed by a synergistic mechanism involving surface adsorption and a pore-filling effect (intra-particle diffusion). Critically, the adsorption dynamics exhibit an intra-particle diffusion-controlled process at a low pH (3.0) during the final stage of adsorption. Strong hydrogen bonding led to high initial adsorption rates, and the adsorption converted to diffusion-controlled mode eventually. In contrast, at higher pH (≥7.0), electrostatic repulsion between PCC adsorbents and TCH molecules hindered intra-particle diffusion, causing the final adsorption stage to deviate from diffusion control. This work provides comprehensive insights into the pH-dependent interfacial interactions and kinetics governing TCH removal by corncob-derived, phosphoric acid-activated biochar. Full article

Although amorphous calcium phosphate (ACP) has been extensively employed as a biomaterial in dental and orthopedic fields, its exploration for environmental applications—particularly in potentially toxic element remediation—remains notably limited in the scientific literature. This study reports the rational design of a multifunctional adsorbent by integrating sodium citrate-stabilized ACP (Cit-ACP) nanoparticles into calcium-crosslinked sodium alginate (SA) hydrogel beads for selective Cu²⁺ sequestration from aqueous systems. Comprehensive sorption assessments revealed that equilibrium uptake aligned with the Freundlich isotherm (indicating heterogeneous surface interactions), while kinetic profiles adhered to pseudo-second-order behavior, characteristic of chemisorption-driven processes. Under optimized operational parameters (pH 5.0, 45 °C), the Cit-ACP/SA composite attained an exceptional maximum adsorption amount of 307.76 mg/g. Thermodynamic analysis further confirmed the spontaneity (ΔG° < 0) and endothermic nature (ΔH° > 0) of the process. Multi-technique characterization (XPS, FTIR, XRD, pH trajectory) elucidated a dual-mode adsorption mechanism: (i) ion exchange between aqueous Cu²⁺ and structural Ca²⁺ within both the alginate matrix and ACP framework; and (ii) in situ surface precipitation yielding copper-substituted hydroxyapatite. Owing to its facile aqueous-phase synthesis, superior adsorption performance, biodegradability, macroscopic bead morphology enabling rapid separation, and robust selectivity in complex matrices, the Cit-ACP/SA composite presents a sustainable, scalable, and eco-compatible platform for practical remediation of copper-contaminated wastewater. Full article

The electrochemical and surface behaviour of implant-grade commercially pure titanium (cp-Ti), Ti6Al7Nb, and Ti6Al4V clinically used alloys was investigated in phosphate-buffered saline (PBS), with and without albumin, at 37 °C using electrochemical techniques and SEM/EDS analysis. In PBS, the corrosion resistance followed the order Ti6Al4V < Ti6Al7Nb < cp-Ti, with cp-Ti serving as the benchmark reference material. The addition of albumin improved the corrosion resistance of all materials under the investigated static in vitro conditions, with the most pronounced effect observed for Ti6Al4V. Over time, the oxide layer stabilised and the differences between the materials decreased, with Ti6Al4V approaching the behaviour of more stable systems. Surface analysis revealed a comparatively more uniform (but not fully homogeneous) protein distribution on Ti6Al7Nb, whereas Ti6Al4V exhibited localised adsorption associated with greater surface heterogeneity. Protein adsorption acts as a stabilising interfacial factor, contributing to improved protective properties under static conditions. These findings highlight the key role of surface heterogeneity in governing protein adsorption and electrochemical behaviour of titanium alloys under biologically relevant conditions. Full article

In this study, chicken bone biochar (CBC) was prepared from waste chicken bones via oxygen-limited pyrolysis. A magnetic component (Fe₃O₄) was introduced, and the composite was embedded in a sodium alginate (SA) gel network, successfully constructing magnetic chicken bone biochar/sodium alginate composite gel beads (M-CBC/SA). The experimental results showed that under the conditions of pH = 4.5, 25 °C, and an adsorbent dosage of 0.5 g/L, the removal efficiency of M-CBC/SA toward 50 mg/L U(VI) reached 91.67%, corresponding to an adsorption capacity of 91.67 mg/g. The adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model, with a theoretical maximum adsorption capacity of 322.58 mg/g, indicating that the adsorption was dominated by monolayer chemisorption. The material exhibited excellent magnetic separability and good anti-interference ability against coexisting ions such as K⁺, Na⁺, Cl⁻, and SO₄²⁻, and its adsorption behavior was only weakly affected by ionic strength. Characterization by XRD, FTIR, XPS, SEM-EDS and other techniques revealed that the immobilization mechanism of U(VI) involved the synergistic effects of dissolution–precipitation (the formation of a new autunite phase), surface complexation (involving hydroxyl and phosphate groups), ion exchange (exchange with Ca²⁺), and electrostatic attraction. Using waste chicken bones as the raw material, this composite achieves both efficient uranium immobilization and convenient magnetic separation, fully embodying the environmental concept of “treating waste with waste”, and shows promising application prospects in the treatment of uranium-containing wastewater. Full article

In this study, the characteristics of sulfide minerals during the acidic double reverse flotation of phosphate ore and the adsorption mechanisms of sodium oleate (NaOL) and dodecyl trimethyl ammonium bromide (DTAB) were investigated. Micro-flotation test results indicated that NaOL effectively collected galena, sphalerite, and pyrite at a concentration of 1 × 10⁻³ mol/L and pH 4–5.5, whereas DTAB exhibited selectivity for galena at 1 × 10⁻⁴ mol/L. Mixed mineral flotation revealed that NaOL induced a non-selective bulk flotation of sulfides with dolomite, resulting in a high froth yield of 93.23%, while the DTAB system showed superior selectivity with a froth yield of 54.91%. Surface analyses (Zeta potential, FTIR, and XPS) confirmed that NaOL chemisorbs onto sulfide surfaces via metal-oleate complexes, whereas DTAB adsorption is dominated by electrostatic attraction. Bench-scale tests validated the “double-rejection” flowsheet, significantly upgrading the P₂O₅ grade from 23.38% to 31.47% by sequentially partitioning Pb, Zn and Fe into the froth tailings. Size-by-assay analysis indicated that the sulfide separation was primarily controlled by the extent of mineral liberation. These findings provide a robust theoretical framework and practical guidance for the simultaneous management of sulfide minerals during phosphate beneficiation. Full article