Heterogeneous Adsorption Research Articles

Heterogeneous oxidation and adsorption of iodide by Bi-Fe-Mn ternary oxide: Roles of different metal oxide

Long-term consumption of groundwater with high iodine content can lead to thyroid damage and other endemic diseases. Hence, there is an urgent need to develop an efficient iodine removal technology suitable for the complex water quality conditions of actual groundwater. In light of the small water treatment capacity and low investment in drinking water in remote areas, we combined Fe-Mn binary oxides (FMBO), which have been widely used in engineering, with bismuth oxides to construct a Bi-Fe-Mn ternary metal oxide (BFMTO) heterogeneous interface that can efficiently remove and regulate the species of iodine. Compared to FMBO and Bi-Mn binary oxides, BFMTO is less affected by coexisting ions, organic matter, and pH during the iodine removal process. When the dosage of BFMTO is 1.0 g/L, the iodide (I-) concentration is 120 μg/L, and the reaction time is 60 min, the removal rates of I- and iodate (IO3-) in groundwater reach 53.82 % and 84.74 %, respectively. The reaction process follows the pseudo-second-order kinetic equation, and the maximum adsorption capacities are 1084.0 μg/g and 1143.4 μg/g, respectively. Based on the results of XPS, HPLC-ICP/MS, and DFT, it can be observed that the metal oxides in BFMTO simultaneously play the function of I- removal. Among them, FeOOH and Bi intrinsic oxides (Bi Ntv Ox) play a crucial adsorption role in the removal of I-, and Mn(IV) and Mn(III) play an oxidation role. In addition to being directly adsorbed and removed, some I- in water is oxidized to I2 and IO3-. This study offers technical support for practical projects such as the control and purification of I- in rural groundwater.

Encapsulation of a 5FU-curcumin hybrid on bacterial nanocellulose for colorectal cancer treatment

The traditional treatment of colorectal cancer (CRC) involves a combination of chemotherapy and synthetic and natural drugs. In this study, a hybrid compound of 5-fluorouracil-curcumin encapsulated in bacterial nanocellulose (BNC) was evaluated for CRC treatment. Bacterial nanocellulose was produced using K. medellinensis and spray-dried. The encapsulation technique involved solvent evaporation. The interactions between cellulose and the hybrid were evaluated using adsorption isotherms and kinetics, and the system was morphologically and physiochemically characterized. The capsules were tested in vitro using Dukes' C and B CRC cells. The results indicated heterogeneous and incomplete adsorption of the hybrid onto the active sites of cellulose. Capsules with a BNC:hybrid mass ratio of 1:1 maintained the encapsulant properties while maximizing the drug load according to desorption in simulated stomach and colon fluids, where desorption in the colon was 1.79 times greater than that in the stomach. Finally, the cancer cell inhibition results indicated that the encapsulated hybrid performed better on Dukes' C-stage cells than on Duke's B-stage cells. In this study, a new system based on a hybrid cellulose compound was proposed for CRC treatment, specifically for metastatic CRC.

Innovative Use of Spirogyra sp. Biomass for the Sustainable Adsorption of Aflatoxin B1 and Ochratoxin A in Aqueous Solutions

This research investigates the efficacy of Spirogyra sp. biomass as an effective adsorbent for the removal of AFB1 and OTA from aqueous solutions. Several factors, including contact time, adsorbent dosage, pH level, and initial mycotoxin concentration, were analyzed to evaluate their impact on adsorption efficacy. The optimal contact time for equilibrium was determined at 60 min, during which the TPA obtained a 91% reduction in AFB1 and 68% removal of OTA. Although increasing the adsorbent dosage improved effectiveness, excessive quantities led to particle aggregation, hence diminishing adsorption performance. The optimal dosage of 5.0 mg/mL optimized the efficacy and use of resources. Adsorption was more efficacious at acidic to neutral pH levels (5–6), enhancing the accessibility of functional groups on the biomass. Kinetic analysis indicated that adsorption process followed a pseudo second-order model, whereas isotherm studies demonstrated a heterogeneous adsorption mechanism, with the Freundlich model providing the optimal fit. The TPB exhibited enhanced adsorption capacities for both mycotoxins, offering a viable solution for mitigating mycotoxin contamination in food and feed. These findings illustrate the significance of biomass treatment techniques in improving mycotoxin removal efficacy and suggest the potential of algal biomass in food safety applications.

Revolutionizing soil and waste treatment: MoS2 nanosheets turbocharge geopolymerization for eco-friendly remediation and self-cementation of arsenic-contaminated soils and municipal solid waste incineration fly ashes

In the face of escalating arsenic pollution and the mounting challenge of municipal solid waste incineration (MSWI) fly ashes, cutting-edge technology has emerged as a game-changer. By harnessing the power of MoS2 nanosheets, a revolutionary approach to double-self-cementation has been unlocked, addressing the limitations of previous methods. Through heterogeneous adsorption, MoS2 nanosheets bolstered the stability of the matrix, leading to a remarkable surge in compressive strengths and a substantial reduction in leaching toxicities of heavy metals. The compressive strengths of the cemented cubes increased as the dosage of nanosheets increased from 0.3 % to 2.4 %, with compressive strengths ranging from 24.34 to 34.21 MPa. The leaching toxicities of Zn, Cu, Cr, Cd, Pb, and As from the solidified matrix correspondingly decreased to 0.32, 0.21, 0.04, 0.01, 0.05, and 0.53 mg/L, respectively. The role played by nanosheets in inhibiting the release and transport of chloride species further underscored their pivotal contribution. Moreover, the study delved into the intricate mechanisms underlying the impact caused by nanoscale materials cementation and geopolymerization systems, shedding light on their dual function as solidification intensifiers and chemical stabilizers. The nanosheet-enhanced double-self process can be appropriately fitted by the JMAK model. The linear nuclei growth of gels controlled the solidification and geopolymerization of the precursor materials and the stabilization of HM contaminants. This groundbreaking research not only elucidates the transformative potential of MoS2 nanosheets but also paves the way for a paradigm shift in the treatment of contaminated soils and waste materials.

Compositional optimization for enhanced oxidation resistance of high-entropy carbide ceramics

Excellent oxidation resistance is essential for the viability of high-entropy carbides (HECs) in high-temperature environments. However, the vast HEC compositional space presents a significant challenge in developing desirable formulations with improved oxidation tolerance. In this work, we establish a computational framework to guide the optimization of oxidation-tolerant HEC compositions and further validate the theoretical predictions through systematic oxidation experiments. Leveraging first-principles calculations, we initially determine the heterogeneous oxygen adsorption ability of different constituent elements in HECs, which is subsequently harnessed to regulate preferential oxidation and suppress the formation of detrimental oxides during the oxidation process. Incorporating this fundamental-level understanding, multi-objective optimization (MOO) was performed to identify a compositional region with potentially intrinsic oxidation immunity, achieving a balance between the compactness of the oxidation product and the thermodynamic stability of the HEC matrix. Based on our analysis, we propose a compositional design strategy involving the strategic reduction of elements with higher oxygen adsorption energies, such as Nb, Ta, and Ti in (NbTaZrHfTi)C, to effectively improve the oxidation performance of HECs. The theoretical findings are robustly corroborated by our comparative oxidation experiments, which demonstrate that the selected NbTa-depletion HEC exhibits superior antioxidant performance compared to the equiatomic counterpart. The integrated computational-experimental approach presented in this work serves as a powerful framework to accelerate the discovery and development of oxidation-resistant HECs, paving the way for their expanded applications in demanding high-temperature, oxygen-rich environments.

An efficient polyaluminum lanthanum silicate coagulant for phosphorus removal and algal bloom control

Due to the advantages of convenient operation and low cost, the use of coagulants is considered a promising method for algae bloom harvesting. However, large dosages, poor algal bloom control rates, and limited phosphorus removal efficiency restrict the usage of most coagulants. In this study, a novel polyaluminum lanthanum silicate (PALS) coagulant was used to remove phosphorus and control algal bloom. The results of isotherm study showed that phosphorus adsorption on PALS fitted Freundlich model, indicating chemisorption and heterogeneous multilayer adsorption were the mechanisms of phosphorus adsorption by PALS. The maximum phosphorus adsorption capacity of PALS by Langmuir model was 485.30mg/g. According to the algal bloom control experiments, the removal of algae and phosphorus was slight at low dosages of PALS (2mg/L and 5mg/L). Short-term control of the algal bloom was observed within 2 days in PALS-10 group, but the bloom recovered afterward, while phosphorus and algae were almost completely removed in PALS-15 and PALS-20. When the dosage of PALS was ≤ 10mg/L, PALS coated the algal cell surfaces and induced mild oxidative stress, showing a little damage to cell integrity. However, the PALS dose over 15mg/L could effectively capture algal cells through charge neutralization, cause severe oxidative stress, strongly upregulate the expression of selected five genes, significantly damage cell integrity, and lead to algae lysis. These findings demonstrated that PALS is a promising coagulant for phosphorus removal and algal bloom control in eutrophic waters, and the minimum threshold of its usage was 15mg/L.

Innovative cellulose-lactone hybrid material for efficient rhodamine 6G dye adsorption: Synthesis and characterization

This study uses a simple solvent casting technique to offer an innovative, cost-effective synthesis of a cellulose-lactone hybrid material for Rhodamine 6G dye adsorption. The modified cellulose revealed superior adsorption competencies, triumphing a maximum dye removal efficiency of 97.8 % under neutral pH. Adsorption isotherms were best defined by the Langmuir model (R2 = 0.999), signifying monolayer adsorption, while the Freundlich model (R2 = 0.9714) suggested the existence of heterogeneous adsorption sites. Characterization methods, including FTIR, TGA, DSC, and SEM, confirmed the structural, thermal, and morphological changes induced by lactone modification, which enhanced the material's mechanical properties and adsorption efficiency. The hybrid material demonstrated excellent long-term stability, recyclability, and potential for large-scale water treatment applications. These findings emphasize the material's potential as a sustainable solution for removing organic pollutants from wastewater.

Sequestration of Ni2+ and Zn2+ utilising agricultural biowaste-based amorphous M−SiO2 and modified green M−SiO2/Fe3O4 nano-adsorbents: Modelling and electroplating wastewater performance

This work reports the synthesis of novel amorphous mesoporous silicon dioxide (M−SiO2) nanoparticles and modified hybrid green mesoporous silicon dioxide embedded magnetite (M−SiO2/Fe3O4) nanocomposite by one-pot co-precipitation green approach. The nano-adsorbents’ ability to sequester Ni2+ and Zn2+ ions was investigated in batch experiments using synthetic solutions. The M−SiO2/Fe3O4, having specific surface area of 171.71 m2/g and mesoporous diameters of 6.281 nm, exhibits soft ferromagnetism with a saturation magnetisation of 35.45 emu/g. Specific surface areas and mesoporous diameters of 909 m2/g and 2.288 nm were recorded for M−SiO2. The Langmuir isotherm, pseudo second order kinetic, and Elovich kinetic were found to be best fitted to explain the highest capability of adsorption. The Langmuir monolayer coverage (qmax) of 108.70 and 96.15 mg/g for Ni2+ and Zn2+ by M−SiO2/Fe3O4, respectively, was notably higher than M−SiO2 (80.65 and 72.46 mg/g). The best-fitted kinetics imply that chemisorption predominates on M−SiO2 and M−SiO2/Fe3O4 heterogeneous adsorption surfaces. Thermodynamic parameters confirm endothermic adsorption of cationic metals, and sequestration improved marginally at elevated temperatures. The lab scale cost estimation, magnetic separability and superior metal ions sequestration efficacy of M−SiO2/Fe3O4 nanocomposite up to five ad-desorption cycles with > 90 % regenerability render it an economically feasible and recyclable nano-adsorbent. The feasibility of cationic metals sequestration from electroplating effluent confirms an effective and cost-efficient environmentally friendly nano-adsorbent (M−SiO2/Fe3O4) for treatment of wastewater contaminated with potentially toxic metals.

Unravelling heterogenous adsorption performance of hydrochar particle and key properties in heavy metal immobilization relative to corresponding residual bulk hydrochar

Immobilization performance of released hydrochar particle (HP) to metal is largely unknown and hinder accurate estimation to immobilization effect in hydrochar application. Herein, HPs derived from typical biomass, food waste (FW), and blue algae (BA), were collected to investigate their adsorption abilities, mechanisms towards typical Cd(II) relative to residual bulk hydrochar (BH) and unravel corresponding properties of this heterogeneity. The results were: 1) the micro-sized HP with poor porous structure, less O-containing functional groups (OFGs) and negative surface charge induced inferior adsorption capacities (0.65-0.81 times) but quicker adsorption rate (3.09-10.08 times) towards Cd(II) compared with BH, 2) cation bridge interaction in coagulation and settling processes unexpectedly facilitated adsorption performance of micro-sized and negative charged FWHPs added with counterions, 3) HP facilitated its electrostatic attraction with Cd(II) rather than common pore filling and surface complexation, especially bare aromatic structure in HP formed another cation-π interaction with Cd(II) highlighted by density functional theory (DFT) method. The special coagulation process and cation-π interaction of HP will facilitate its vertical co-migration ability but weaken immobilization stability towards metals. The distinct heterogeneities of adsorption ability of HP and BH and underlying key properties provide an in-depth understanding of hydrochar application for remediation of metal contaminants in soil/water environment.

Insights into the enhanced adsorption of glyphosate by dissolved organic matter in farmland Mollisol: effects and mechanisms of action.

Dissolved organic matter (DOM) is easy to combine with residual pesticides and affect their morphology and environmental behavior. Given that the binding mechanism between DOM and the typical herbicide glyphosate in soil is not yet clear, this study used adsorption experiments, multispectral techniques, density functional theory, and pot experiments to reveal the interaction mechanism between DOM and glyphosate on Mollisol in farmland and their impact on the environment. The results show that the adsorption of glyphosate by Mollisol is a multilayer heterogeneous chemical adsorption process. After adding DOM, due to the early formation of DOM and glyphosate complex, the adsorption process gradually became dominated by single-layer chemical adsorption, and the adsorption capacity increased by 1.06 times. Glyphosate can quench the endogenous fluorescence of humic substances through a static quenching process dominated by hydrogen bonds and van der Waals forces, and instead enhance the fluorescence intensity of protein substances by affecting the molecular environment of protein molecules. The binding of glyphosate to protein is earlier, of which affinity stronger than that of humic acid. In this process, two main functional groups (C-O in aromatic groups and C-O in alcohols, ethers and esters) exist at the binding sites of glyphosate and DOM. Moreover, the complexation of DOM and glyphosate can effectively alleviate the negative impact of glyphosate on the soil. This study has certain theoretical guidance significance for understanding the environmental behavior of glyphosate and improving the sustainable utilization of Mollisol.

The Use of Organoclays as Excipient for Metformin Delivery: Experimental and Computational Study

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

Magnetic Nanocomposites Revolutionize Heavy Metal Adsorption for Environmental Cleanup

General background: Magnetic nanocomposites have garnered significant attention due to their multifunctional properties, particularly in environmental remediation, where they can be used for the removal of heavy metals from aqueous solutions. Specific background: Polypyrrole (PPy) and poly(p-hydroxyaniline) (P(p-OH An)) are conductive polymers known for their adsorption capabilities, while Fe3O4 nanoparticles exhibit magnetic properties, facilitating separation and recovery. Knowledge gap: Despite the potential of Fe3O4-based composites, few studies have systematically explored the synergistic adsorption properties of PPy and P(p-OH An) in Fe3O4-based nanocomposites under varying environmental conditions. Aims: This study aimed to synthesize and characterize Fe3O4/PPy/P(p-OH An) magnetic nanocomposites and evaluate their adsorption performance under different temperatures and isotherm models. Results: The nanocomposite was synthesized through chemical oxidation polymerization and characterized using FTIR, TEM, AFM, and TGA, confirming its successful formation and nanoscale structure. Adsorption studies indicated an exothermic process, with a decrease in adsorption capacity at higher temperatures. The adsorption data fit the Freundlich isotherm better than the Langmuir model, suggesting heterogeneous surface adsorption. Novelty: This study demonstrates a novel Fe3O4/PPy/P(p-OH An) nanocomposite with superior adsorption properties, showing its potential in heavy metal ion removal and offering an improved understanding of temperature effects on adsorption performance. Implications: The findings underscore the composite's promise for environmental remediation applications, particularly in water treatment, and suggest further optimization of the adsorption conditions and evaluation of the composite's reusability for industrial-scale applications. Highlights: Enhanced Adsorption: Fe3O4/PPy nanocomposites offer combined magnetic and polymer adsorption properties. Temperature Sensitivity: Adsorption decreases as temperature rises, indicating exothermic behavior. Surface Interaction: Freundlich isotherm shows adsorption occurs on heterogeneous surfaces. Keywords: Magnetic nanocomposite, Fe3O4, Polypyrrole, Adsorption, Environmental remediation.

Adsorption and catalytic degradation of Light green SF by magnetic PEI-modified carbon nanotubes composites

Treatment of colored effluent is necessary for the textile industry. In this study, a magnetically recyclable composite (MnFe2O4@cCNTs-PEI) was prepared by coprecipitation and grafting methods, and its efficiency for removal of light green SF (LG) from solution assessed via the adsorption and advanced oxidation techniques. The experimental results indicated that the maximum adsorption capacity of MnFe2O4@cCNTs-PEI towards LG could reach 371 mg‧g−1 at solution pH 3 and 303 K. The adsorption equilibrium results could be well fitted by Koble-Corrigan, Temkin, and Freundlich isotherm models whereas the adsorption kinetic process follows the Elovich equation and Double Constant model. This implies the adsorption process be heterogeneous multimolecular layer adsorption, accompanied by heterogeneous diffusion. The adsorption process was spontaneous, endothermic and entropy increasing which was majorly controlled by the electrostatic attraction and π-π stacking mechanisms. MnFe2O4@cCNTs-PEI can catalyze and activate H2O2 to achieve a heterogeneous Fenton-like degradation of LG. MnFe2O4@cCNTs-PEI as a catalyst could achieve a higher removal rate of LG (90 %) within a broad pH range (3–10) which could be ascribed to the presence of active radical species such as ‧OH and 1O2. After three adsorption and degradation regeneration cycles, the removal rate of LG was still higher than 60 %. It is potential for MnFe2O4@cCNTs-PEI to be economically viable for practical applications.

Molecularly imprinted polymer gel with superior recognition and adsorption capacity for amphenicol antibiotics in food matrices

A molecular-imprinted polymer (MIP) gel with high effective recognition of amphenicol antibiotics was synthesized for the first time based on layered double hydroxide (LDH) as the support and initiator, and functionalized β-cyclodextrin (β-CD) as the functional monomer. The synergistic effect of molecular imprinting recognition and β-CD host-guest affinity enabled MIP gel to exhibit excellent selectivity (imprinted factors: 3.9–9.4) and high adsorption capacity (28.9–75.4 mg g−1) for amphenicol antibiotics. Different adsorption isotherms and kinetics models were followed, suggesting heterogeneous single-layer recognition and chemical adsorption. After 5 cycles of adsorption and desorption, the adsorption capacity of MIP gel retained above 83.6 %, demonstrating favorable reproducibility and stability. Under optimal conditions, the method validation showed a satisfactory limit of detection (5–10 μg L−1), good correlation (r2 > 0.9967), and respectable recovery (82.6–105.3 %). The MIP gel was applied to extract amphenicol antibiotics from food matrices, achieving recoveries in the range of 78.3–104.5 %. Importantly, the recognition mechanism was studied in detail using density functional theory. Therefore, the established method demonstrates high sensitivity and can be applied as a new tactic for detecting amphenicol antibiotics in food matrices.

Antimony removal using zero-valent iron-manganese bimetallic nanomaterial: Adsorption behavior and mechanism

Although the effectiveness of zero-valent iron (ZVI) and zero-valent manganese (ZVMn) in heavy metal removal is well-established, their combined synergistic potential for antimony (Sb) remediation from wastewater has remained largely unexplored. Addressing this gap, this study introduced a magnetic zero-valent iron-manganese bimetallic material (ZVIM), synthesized via the borohydride reduction method, to investigate its capabilities and underlying mechanisms for Sb reduction and adsorption. The ZVIM, characterized by a high specific surface area of 220 m²/g, exhibited a high adsorption capacity (614.6 mg/g for Sb(III) and 241.7 mg/g for Sb(V)), facilitating over 96.7 % removal for both Sb(III) and Sb(V). The adsorption conformed to the pseudo-second-order kinetic model, and the isotherm data aligned with the Freundlich model, indicative of a heterogeneous adsorption process. The removal of Sb(III) predominantly occurred via surface complexation and electrostatic adsorption to the positively charged ZVIM surface, accompanied by a partial oxidation of Sb(III) to Sb(V). In contrast, the elimination of Sb(V) was primarily facilitated through surface complexation mechanism, encompassing both reduction and electrostatic adsorption. The outcomes of this study shed light on the intricate interactions between Sb species and the ZVIM, revealing the material as a promising candidate for the efficacious removal of Sb from wastewater.

Preparation of NH2-MIL-101(Fe) Metal Organic Framework and Its Performance in Adsorbing and Removing Tetracycline.

Tetracycline's accumulation in the environment poses threats to human health and the ecological balance, necessitating efficient and rapid removal methods. Novel porous metal-organic framework (MOF) materials have garnered significant attention in academia due to their distinctive characteristics. This paper focuses on studying the adsorption and removal performance of amino-modified MIL-101(Fe) materials towards tetracycline, along with their adsorption mechanisms. The main research objectives and conclusions are as follows: (1) NH2-MIL-101(Fe) MOF materials were successfully synthesized via the solvothermal method, confirmed through various characterization techniques including XRD, FT-IR, SEM, EDS, XPS, BET, and TGA. (2) NH2-MIL-101(Fe) exhibited a 40% enhancement in tetracycline adsorption performance compared to MIL-101(Fe), primarily through chemical adsorption following pseudo-second-order kinetics. The adsorption process conformed well to Freundlich isotherm models, indicating multilayer and heterogeneous adsorption characteristics. Thermodynamic analysis revealed the adsorption process as a spontaneous endothermic reaction. (3) An increased adsorbent dosage and temperature correspondingly improved NH2-MIL-101(Fe)'s adsorption efficiency, with optimal performance observed under neutral pH conditions. These findings provide new strategies for the effective removal of tetracycline from the environment, thus holding significant implications for environmental protection.

Synthesis of nano zero valent zinc-reduced graphene oxide nanocomposite using a novel electrochemical technique for the adsorptive degradation of methyl orange

Indiscriminate disposal of effluent contaminated with persistent azo dyes has become a significant environmental issue. Since the conventional wastewater treatment processes are ineffective in removing azo dyes completely, many studies are currently being focused on finding effective methods to degrade azo dyes. We herein report a novel in-situ synthesis of a nanocomposite with nano-zero valent zinc (nZVZ) and reduced graphene oxide (rGO) that can effectively remove methyl orange, an azo dye, from an aqueous solution via adsorptive degradation. nZVZ-rGO nanocomposite was synthesized by electrochemical reduction of Zn2+ ions on rGO. The presence of nZVZ particles on rGO with an average metal-loading of 4 % was confirmed by SEM-EDS, TEM, XPS and XRD results. Batch experiments showed that a maximum removal efficiency of 99.6 % of methyl orange can be achieved with 25 mg L−1 initial dye concentration and by optimizing the pH, nanocomposite dosage and contact time. However, a noticeable reduction in removal efficiency was observed in the presence of anions such as Cl-, SO42- and CO32-. The degradation of methyl orange was monitored using UV-Visible spectroscopy, HPLC and FTIR spectroscopy. The peaks corresponding to -NN- group, –C-N bond and –SO3Na group have completely disappeared in the product spectrum of FTIR analysis, indicating the degradation of methyl orange. The adsorptive degradation process of methyl orange obeys the Sips model (R2=0.9820) indicating a complex heterogenous adsorption mechanism while the kinetic model was shown to be pseudo-second-order model (R2=0.9999).

Experimental and numerical study of cadmium fate and transport mechanisms during artificial recharge in agricultural regions

Agricultural Managed Aquifer Recharge (AgMAR) uses agricultural lands and floodwater to enhance groundwater recharge, but its effectiveness can be hindered by heavy metals like cadmium (Cd), which pose risks to groundwater quality. Cd is particularly concerning due to its high mobility and persistence in the environment. This study investigates Cd's fate and transport in agricultural regions during MAR, focusing on sandy loam soils through batch and column experiments. Equilibrium and kinetic batch studies were conducted under varying Cd concentrations and exposure times to quantify the adsorption capacity and rate. HYDRUS-2D was used to simulate Cd's transport in soil under various ponding depths and Cd concentrations. Results showed a maximum Cd adsorption capacity of 439.58 mg/kg, with the Freundlich isotherm providing a better fit (R2 = 0.98) and indicating heterogeneous adsorption sites (n = 0.389). The kinetic experiment indicated chemisorption as the predominant mechanism, with an equilibrium adsorption capacity of 236.49 mg/kg. The pseudo-second-order kinetic model (rate constant 0.0016 h⁻1, R2 = 0.99) suggested that adsorption kinetics are influenced by Cd concentration and available adsorption sites. The column experimental findings supported by HYDRUS-2D modeling successfully explained the fate and transport of Cd within the soil columns. The model fitted parameter values for Freundlich adsorption isotherm coefficient (KF), linearity factor (Nu), and kinetic rate coefficient are (α) 47.37 L/kg, 0.00389 cm³/ppm and 0.0029 min⁻1, respectively. Modeling scenarios further elucidated the transport dynamics of Cd under simulated AgMAR conditions. Modeling scenarios indicated that with constant ponding of 5 cm over a year, Cd at 20 and 40 ppb concentrations in floodwater could potentially migrate below root zone systems. This study highlights the critical role of understanding Cd fate and transport in optimizing AgMAR systems and reducing Cd pollution risks, providing valuable insights for developing effective monitoring and management strategies.

Adsorption of dibenzothiophene sulfone using Fe3+ and Fe6+-impregnated clay adsorbents

In this study, the adsorption of dibenzothiophene sulfone (DBTO) was investigated using clay minerals as adsorbents. Raw bentonite (BR) and raw activated clay (ACR) were impregnated with Fe3+ and Fe6+, creating bentonite-Fe3+ (BF3), bentonite-Fe6+ (BF6), activated clay-Fe3+ (ACF3), and activated clay-Fe6+ (ACF6). The surface functional groups, surface morphology, and surface area of the raw and modified adsorbents were studied through Fourier transform infrared spectroscopy, a scanning electron microscope, and Brunauer, Emmett, and Teller analysis, respectively. Batch experiments on simulated oil were done to test the effect of adsorption time (0.5–24 h), adsorption dosage (0.3–1.5 g), and adsorption temperature (30–50 °C). The results of the experiments showed the suitability of the pseudo-second order kinetic model on the clay adsorbent and sulfone system. This suggests that chemisorption is the rate-limiting step of the reaction. Equilibrium isotherms indicated the adherence of DBTO onto BR and BF3 to the Freundlich model, implying the heterogeneous adsorption of the sulfones onto the adsorbents. The systems of DBTO with BF6, ACR, ACF3, and ACF6 showed a better fit with the Dubinin-Radushkevich model. This denotes that adsorption happens through the filling of sulfones of the micropores on the adsorbent. Lastly, thermodynamic studies revealed the endothermic and non-spontaneous nature of the clay adsorbents and sulfone systems. The experiments showed that the impregnation of Fe3+ and Fe6+ lowered the desulfurization ability of the adsorbents. This could be due to the iron ions being hard acids and the sulfones being soft bases, thus showing lower compatibility than the raw counterparts of the adsorbents. Comparison with related studies showed that the prepared adsorbents, namely BF3 (5.1 mg g−1) and BF6 (6.4 mg g−1), had a higher adsorption capacity than Ni2+-loaded activated carbon (4.9 mg g−1) and activated clay (4.1 mg g−1). The study shows that BR (7.2 mg g−1) is the best-performing adsorbent, which can be set as the direction for future research. This study is a step toward the commercialization of oxidative desulfurization methods.

Tuning surface Mn defects on LaMnO3 perovskite oxides by selective dissolution strategy for enhanced phosphate removal

Selective dissolution is widely used to adjust the surface state of LaMnO3 perovskite oxides. In this study, LaMnO3(LMO) with B-Site vacancies was synthesized using ascorbic acid to selectively remove Mn cations and enhance phosphate adsorption. The optimized LMO with Mn defects (LMO-AA3) presented large surface area, plenty of mesoporosity and suitable electronic structure. Particularly, the adsorption capacity (113.48 mg/g) of LMO-AA3 was about10 times that of LMO. Adsorption experiments showed adsorption occurred both chemically and physically on the heterogeneous adsorption surfaces, as the pseudo-second-order kinetic model and the Redlich-Peterson isotherm model predicted. The stimulated mechanism of LMO-AA3 achieved phosphate absorption through enhancing electrostatic attraction and ligand exchange by –OH groups. Regeneration testing showed that LMO-AA3 can be used for both high and low-concentration purification of phosphate. The selectively remove Mn cations method may offer an appropriate choice for enhancing the material characteristics of effective phosphate capture.