Highly efficient removal of diazinon pesticide from aqueous solutions by using coconut shell-modified biochar

This study evaluates the adsorption of diazinon from aqueous solutions onto coconut shell-modified biochar using a batch system. The amount of dosage and initial pH are the main parameters being studied to obtain maximum adsorption capacity of the probe molecules. The carbonized coconut shell biochar (BC1), activated coconut shell biochar (BC2), chemically modified phosphoric acid (BC3) and sodium hydroxide coconut shell biochar (BC4) were prepared and tested as variables in the adsorption experiment. The characteristic of biochar via SEM, EDX and BET analysis revealed the large porous of surface morphology and slight changes in the composition with high surface area (405.97 – 508.07 m²/g) by following the sequence of BC3 > BC2 > BC4. Diazinon removal percentage as high as 98.96% was achieved at pH 7 with BC3 as adsorbent dosing at 5.0 g/L. The high coefficient of determination, R² with a small value of ERRSQ and χ² error analysis present the BC1 (0.9971) and BC2 (0.9999) are best fitted with Freundlich isotherm indicates multilayer sorption onto heterogeneous surface whereby the Langmuir isotherm model is the best fitting is described of monolayer adsorption process onto the homogenous surface of BC3 and BC4. The results indicated the maximum adsorption capacity (q_m) was achieved by BC3 with 10.33 mg/g, followed by BC2 (9.65 mg/g) in accordance to the Langmuir isotherm while Freundlich isotherm showed the highest adsorption capacity (k_F) with 1.73 mg/g (L/mg)^1/n followed by BC4 with 0.63 mg/g (L/mg)^1/n at favorable adsorption isotherm (1 ≤ n ≤ 10). Thus, the results obtained depicted that BC2 and BC3 are highly efficient adsorbents and both exhibit great potential in removing diazinon from aqueous solutions.     

Removal of Cr (VI) from aqueous solution using magnetic biochar synthesized by a single step method

Magnetic biochar, as an adsorbent, was synthesized by a single step method, where iron salt was directly mixed with pinewood sawdust by chemical co-precipitation and subsequently pyrolyzed at 700°C for Cr (VI) removal from aqueous solution. The effects of some important parameters including adsorbent dosage (0.4–2.8?g/L), pH (1–10) of the solution, contact time (0–1440 minutes), initial concentration (30–120?mg/L), and temperature (20–40°C) were investigated in batch experiments. Both pre- and post-adsorbents were characterized by SEM-EDX and XPS to investigate the adsorption mechanism. The maximum adsorption capacity of the tested magnetic biochar under the certain experimental conditions determined as optimal was 42.7?mg/g for Cr (VI). The adsorption data were proved to be suitable for the pseudo-second order model for kinetics and the Langmuir model for isotherms with correlation R²?=?0.9996 andR²?>?0.9980, respectively, after fitting with four kinetic models (pseudo-first order, pseudo-second order, W-M model, and Elovich) and three isotherm models (Langmuir, Freundlich, and Temkin). The characteristic analyses further verified that the efficient particle was a mixture of iron oxides in essence, and it had a strong effect on the spontaneous and endothermic adsorption process.     

Effective sequestration of Congo red dye with ZnO/cotton stalks biochar nanocomposite: MODELING,reusability and stability

Widespread application of dyes and disposal of their untreated effluents into water bodies adversely affect the ecosystem due to their complex aromatic structures and persistent nature. The present study aims to utilize the cotton stalks biochar (CSB) and its composite with zinc oxide nanoparticles (CSB/ZnONPs) to evaluate for the decontamination their batch scale potential of Congo red dye from wastewater. The characterization of CSB and CSB/ZnONPs was performed with Fourier-transform infra-red (FTIR) spectroscopy, scanning electron microscopy, energy-dispersive X-ray (EDX) and point of zero charge (PZC) to get insight of their potential for the decontamination of CR. The effects of initial CR concentration (25–500 mg/L), dosage of CSB and CSB/ZnONPs (0.5–2 g/L), solution pH (2–10) and contact time (0–180 min) were evaluated on CR removal at temperature (25 ± 1.5 °C). The results disclosed that CSB/ZnONPs showed excellent adsorption potential (556.6 mg/g) in comparison with CSB (250 mg/g) and most of the other adsorbents previously studies in the literature. The equilibrium experimental data were equally explained with Freundlich and Langmuir isotherm models (R² > 0.98) while kinetic data demonstrated the best fit with pseudo second order model. The CSB/ZnONPs composite exhibited excellent reusability (89.65%) after five adsorption/desorption cycles for the sequestration of CR from contaminated systems. The present study demonstrated that metallic nanocomposite of CSB (CSB/ZnONPs) is an excellent candidate for the cost effective and environment friendly decontamination of CR from industrial wastewater and is suggested to be considered for the decontamination of other pollutants from the wastewater.     

Isotherm modelling and optimization of oil layer removal from surface water by organic acid activated plantain peels fiber

This research aimed to optimize and model the adsorption process of oil layer removal using activated plantain peels fiber (PPF), a biomass-based material. The adsorbent was activated by thermal and esterification methods using human and environmentally friendly organic acid. Effects of process parameters were examined by one factor at a time (OFAT) batch adsorption studies, revealing optimal conditions for oil removal. Also, RSM, ANN and ANFIS were used to adequately predict the oil removal with correlation coefficient > 0.98. RSM modelling revealed the best conditions as 90 °C, 0.2 mg/l, 1.5 g, 6 and 75 mins, for temperature, oil–water ratio, adsorbent dosage, pH and contact time respectively. Under these simulated conditions, the predicted oil removal was 96.88 %, which was experimentally validated as 97.44 %. Thermodynamic studies revealed the activation energy, change in enthalpy and change in entropy for irreversible pseudo-first order and pseudo-second order model as (15.82, 24.17, ?0.614 KJ/mols) and (33.21,40.31, ?0.106 KJ/mols) respectively, indicating non-spontaneous process; while modeling studies revealed that the adsorption process was highly matched to Langmuir’s isotherm, with maximum adsorption capacity of 50.34 mg/g. At the end of the overall statistical modelling, ANFIS performed marginally better than the ANN and RSM. It can be concluded from these results that our biomass-based material is an efficient, economically viable and sustainable adsorbent for oil removal, and has potentials for commercialization since the process of adsorption highly matched with standard models, and its capacity or percentage oil removal also compares favorably to that of commercially available adsorbents.     

CoFe2O4@Methylcellulose/AC as a New,Green, and Eco-friendly Nano-magnetic adsorbent for removal of Reactive Red 198 from aqueous solution

Methylcellulose (MC) is the most common commercial cellulose ether and the most attractive biopolymer due to its cheap cost of biodegradability, biocompatibility, hydrophilicity, and lack of toxicity. In this study, CoFe₂O₄@MC/activated carbon (AC) was synthesized as a unique magnetic nano-adsorbent in the presence of MC biopolymer for Reactive Red 198 (RR198) dye removal. The nano-magnetic adsorbent was characterized by FESEM (Field emission scanning electron microscopy), EDS (Energy-dispersive X-ray spectroscopy), Mapping, Linescan, BET (Brunauer–Emmett–Teller), FTIR (Fourier Transform Infrared Spectroscopy), XRD (X-Ray Diffraction), and VSM (Vibrating-Sample magnetometer). For simple separation by external magnetic fields, the Ms value was 57.91 emu/g. According to XRD analysis, the nano-adsorbent maintains its crystal structure, with an average crystal size of 11 nm. The maximum removal efficiencies of RR198 for synthetic and real wastewater samples under optimal conditions (an initial concentration of 10 mg/L, pH 3, contact time of 10 min, nanocomposite dose of 1.5 g/L, and a temperature of 25 °C) were 92.2% and 78%, respectively. The adsorption experiments were fitted well with the Freundlich isotherm (R² = 0.989) and pseudo-second-order kinetic (R² = 0.995). The values of entropy changes (ΔS = 35.087 kJ/mol.k), enthalpy changes (ΔH = -9.862 kJ/mol), and negative Gibbs free energy changes (ΔG) showed that the adsorption process was exothermic. Finally, the reusability findings showed that after six recovery cycles, the efficiency decreased slightly (90.1%). In the end, it can be concluded that the prepared CoFe₂O₄@Methylcellulose/AC can be used as an efficient adsorbent for the removal of RR198 from an aqueous solution.     

Modelling and optimization of crude oil removal from surface water via organic acid functionalized biomass using machine learning approach

Banana peel fiber adsorbent (BPF) with well-arranged substructure of pores was fabricated via esterification reaction with organic acid and biomass. The emerged adsorbent (BPF) was employed in taking away crude oil from water surface. Three machine learning tools such as RSM, ANN and ANFIS was employed for the modelling and optimization of the process. From results, the optimal oil layer removal of 98.2% was achieved at oil water ratio of 0.2 g /100 cm³. For now, BPF displayed high adsorptive prospect at a very low pH of 4 with 96.8% oil removal. On the other hand, the activation energy, enthalpy change and entropy change of the system are (18.56, 25.44, ?0.751 KJ/mols) and (25.77, 29.16, ?0.813 KJ/mols) designating a non-spontaneous system. The process of removal by BPF really matched the Langmuir isotherm model as proved by statistical error analysis with highest adsorption capacity of 49.33 mg/g as shown through equilibrium modeling. RSM displayed the optimum conditions of the key variables such as temperature, oil concentration, adsorbent dosage, pH and time as 100 °C, 0.2 g/100 cm³, 1.5 g, 2 and 75 mins, respectively. Analysis of the three generic algorithm indicated significant oil removal prediction with quite remarkably similar coefficient of correlation of 0.999. Additional statistical analysis suggested that RSM was marginally better than ANN and ANFIS for the modelling of crude oil removal via esterified banana peels fiber.     

Adsorptive scavenging of cationic dyes from aquatic phase by H3PO4 activated Indian jujube (Ziziphus mauritiana) seeds based activated carbon: Isotherm,kinetics, and thermodynamic study

In the present work, a cost-effective Indian jujube seeds derived activated carbon (IJSAC) prepared via o-phosphoric acid chemical activation, is studied for the sequestration of acriflavine (AF) and Victoria blue B (VB) from the aquatic environment. The activated carbon is characterized by Fourier transform infrared spectroscopy, N₂-adsorption/desorption isotherm, scanning electron microscopy techniques and point of zero-charge measurement. The specific surface area (S_BET) of 571 m²/g with a pore radius of 22.45 Å specifies mesoporous nature of the IJSAC. The implication of operational conditions on the adsorption of both dyes onto IJSAC assessed by batch methodology, establish the optimal conditions as dosage (1.5 and 2.5 g/L), contact time (60 min), pH (8 and 10), and initial concentration (130 and 140 mg/L) for AF and VB uptake, respectively. The Freundlich adsorption isotherm model (R² = 0.99) appropriates the equilibrium data suggesting multilayer adsorption onto heterogeneous surface sites, while pseudo-second order (R² = 0.95–0.99) is the best fit kinetic model. The liquid film and intraparticle diffusion modelling demonstrate that the adsorption process of these dyes is governed by both the steps. Maximum Langmuir adsorption capacity is 113.6 mg/g for acriflavine and 92.78 mg/g for Victoria blue B. Thermodynamic studies indicate endothermic and spontaneous adsorption of dyes. The adsorption mechanism for the uptake of AF and VB by IJSAC most probably involves hydrogen bonding, electrostatic and π-π interactions. Based on its high adsorption capacity, relatively faster kinetics, and reusability, IJSAC can be perceived as a proficient and effective adsorbent for cationic dyes removal from the liquid waste.     

Cadmium removal from aqueous solution by biochar obtained by co-pyrolysis of sewage sludge with tea waste

Resource utilization is a critical pathway for sustainable solid waste treatment. Biochar was prepared from the co-pyrolysis of sewage sludge and tea waste. Brunauer–Emmett–Teller measurement, scanning electron microscopy and Fourier transform infrared analysis were employed to characterize the biochar. Then, the interface behavior between biochar and Cd from aqueous solution was investigated. The effect of adsorbent dose and pH on Cd adsorption was evaluated. Adsorption kinetics and the adsorption isotherm were studied, and the adsorption mechanism was explored. The results showed that the suitable adsorbent dose was 4 g L^?1 and the optimal pH of the Cd solution remained at 6.0. Cadmium sorption on the biochar could be well described by the pseudo-second order kinetic model (R ² > 0.98). The adsorption process was described using the Langmuir (R ² > 0.86), Freundlich (R ² > 0.86), Temkin (R ² > 0.84) and Dubinin–Radushkevich (R ² > 0.86) isotherm models. The proportion of organic constituents in biochar was 69.2–72.4%. Minerals that originated in biochar played an important role during the Cd adsorption process, and the contribution of minerals accounted for 27.6–30.8% of the total adsorption. The main mechanism of the Cd adsorption process by biochar involved ion exchange, surface complexation, electrostatic interaction, surface co-precipitation, and other mechanisms. Therefore, biochar created by the co-pyrolysis of sewage sludge and tea waste could be used as an adsorbent for the removal of metal ions from contaminated water.     

Adsorption of tetracycline using CuCoFe2O4@Chitosan as a new and green magnetic nanohybrid adsorbent from aqueous solutions: Isotherm,kinetic and thermodynamic study

Utilizing a new microwave-assisted method, CuCoFe₂O₄@Chitosan (Ch) was synthesized as a very strong, magnetically separable nano-adsorbent. The magnetic nanohybrid adsorbent was characterized by FESEM (Field emission scanning electron microscopy), EDS (energy dispersive X-ray), Mapping & Linescan, BET (Brunauer-Emmett-Teller), FTIR (Fourier-transform infrared spectroscopy), XRD (X-ray diffraction analysis), TGA (Thermogravimetric analysis), and VSM (Vibrating Sample Magnetometer) techniques. Then, the adsorption process of Tetracycline (TC) was investigated. The highest percentage of pollutant adsorption on the synthetic and real samples was recorded at an initial concentration of 5 mg/L, pH 3.5, contact time of 20 min, the dose of 0.4 g/L, and temperature of 25 °C, 93.07 %, and 67%, respectively. The TC adsorption process via the synthesized magnetic nanocomposite was consistent with the Freundlich isotherm model (R² = 0.992) and pseudo-second-order kinetic (K₂ = 0.267). The outcomes of thermodynamic analyses, which included entropy changes (ΔS = 10.122 J/mol.k), enthalpy changes (ΔH = ?1.975 kJ/mol), and the Gibbs negative free energy (ΔG = ?4.992 kJ/mol), revealed that the adsorption process was spontaneous, favorable, and exothermic. The good magnetic properties allow easy separation after the adsorption operation. Finally, the efficiency of the nano-adsorbent in the removal process was 82.16% after four adsorption–desorption cycles. Some advantages of this research are a fast and green method for synthesis of adsorbent, fast kinetic, and magnetic properties to easy separation.     

Post Synthetic Modification of NH2-(Zr-MOF) via Rapid Microwave-promoted Synthesis for Effective Adsorption of Pb(II) and Cd(II)

Excessive heavy metals in the water constitute a health hazard to humans, yet it may be efficiently purified using adsorbents. Herein, for the first time, UiO-66-NH₂ was modified by Glycidyl methacrylate (GMA) via microwave heating method to investigate its potential for adsorption of Pb(II) and Cd(II) metal ions. Synthesized MOF was characterized by TGA, XRD, BET, FE-SEM-EDX, and FTIR. The MOF has a huge surface area of 1144 m²/g, a mean pore diameter of 2.84 nm, and a total pore volume of 0.37 cm³/g. The effect of UiO-66-GMA performance was evaluated by investigating the impact of pH (1–9), contact time (0–200 min), initial metal ions concentration (20–1000 mg/L), temperature (25–55 °C), adsorbent dosage (0.5–3 g/L), and co existences of other metals was investigated on Pb(II) and Cd(II) percentage removal. Following an analysis of the adsorption isotherms, kinetics, and thermodynamics, the Temkin isothermal model showed an excellent fit with the adsorption data (R² = 0.99). The adsorption process was a spontaneous endothermic reaction and kinetically followed the pseudo-second-order kinetics model. Microwave heating method produced highly crystalline small Zr-MOF nanoparticles with a short reaction time. It promoted the simple yet highly efficient synthesis of Zr-based MOFs, as shown by the reaction mass space-time yield. The adsorption capability of Pb to the presence of several polar functional groups, including as primary and secondary amines, ester, alkene, and hydroxyl groups. This adsorbent is a potential candidate for wastewater treatment due to its outstanding structural stability in acidic and basic solutions, high removal efficiency, and recyclability.     

Design,synthesis of new novel quinoxalin-2(1H)-one derivatives incorporating hydrazone,hydrazine, and pyrazole moieties as antimicrobial potential with in-silico ADME and molecular docking simulation

A series of 6-(morpholinosulfonyl)quinoxalin-2(1H)-one based hydrazone, hydrazine, and pyrazole moieties were designed, synthesized, and evaluated for their in vitro antimicrobial activity. All the synthesized quinoxaline derivatives were characterized by IR, NMR (¹H /¹³C), and EI MS. The results displayed good to moderate antimicrobial potential against six bacterial, and two fungal standard strains. Among the tested derivatives, six quinoxalin-2(1H)-one derivatives 4a, 7, 8a, 11b, 13, and 16 exhibited a significant antibacterial activity with MIC values (0.97–62.5 µg/mL), and MBC values (1.94–88.8 µg/mL) compared with Tetracycline (MICs = 15.62–62.5 µg/mL, and MBCs = 18.74–93.75 µg/mL), and Amphotericin B (MICs = 12.49–88.8 µg/mL, and MFC = 34.62–65.62 µg/mL). In addition, according to CLSI standards, the most active quinoxalin-2(1H)-one derivatives demonstrated bactericidal and fungicidal behavior. Moreover, the most active quinoxaline derivatives showed a considerable antibacterial activity with bactericidal potential against multi-drug resistance bacteria (MDRB) strains with MIC values ranged between (1.95–15.62 µg/mL), and MBC values (3.31–31.25 µg/mL) near to standard Norfloxacin (MIC = 0.78–3.13 µg/mL, and MBC = 1.4–5.32 µg/mL. Further, in vitro S. aureus DNA gyrase inhibition activity were evaluated for the promising derivatives and displayed potency with IC₅₀ values (10.93 ± 1.81–26.18 ± 1.22 µM) compared with Ciprofloxacin (26.31 ± 1.64 µM). Interestingly, these derivatives revealed as good immunomodulatory agents by a percentage ranging between 82.8 ± 0.37 and 142.4 ± 0.98 %. Finally, some in silico ADME, toxicity prediction, and molecular docking simulation were performed and showed a promising safety profile with good binding mode.     

Adsorption of uranium from aqueous solution using biochar produced by hydrothermal carbonization

The ability of biochar produced by hydrothermal carbonization (HTC) has been explored for the removal and recovery of uranium from aqueous solutions. The micro-morphology and structure of HTC were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The HTC showed the highest uranium sorption capacity at initial pH of 6.0 and contact time of 50 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, △G°(298 K), △H° and △S° were determined to be ?14.4, 36.1 kJ mol^?1 and 169.7 J mol^?1 K^?1, respectively, which demonstrated the sorption process of HTC towards U(VI) was feasible, spontaneous and endothermic in nature. The adsorbed HTC could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 2.0 g HTC.     

Adsorptive removal of phenol by bagasse fly ash and activated carbon: Equilibrium,kinetics and thermodynamics

Present study deals with the adsorption of phenol on carbon rich bagasse fly ash (BFA) and activated carbon-commercial grade (ACC) and laboratory grade (ACL). BFA is a solid waste obtained from the particulate collection equipment attached to the flue gas line of the bagasse-fired boilers of cane sugar mills. Batch studies were performed to evaluate the influences of various experimental parameters like initial pH (pH₀), contact time, adsorbent dose and initial concentration (C₀) on the removal of phenol. C₀ varied from 75 to 300 mg/l for the adsorption isotherm studies and the effect of temperature on adsorption. Optimum conditions for phenol removal were found to be pH₀ ≈ 6.5, adsorbent dose ≈10 g/l of solution and equilibrium time ≈5 h. Adsorption of phenol followed pseudo-second order kinetics with the initial sorption rate for adsorption on ACL being the highest followed by those on BFA and ACC. The effective diffusion coefficient of phenol is of the order of 10⁻¹⁰ m²/s. Equilibrium isotherms for the adsorption of phenol on BFA, ACC and ACL were analysed by Freundlich, Langmuir, Temkin, Redlich–Peterson, Radke–Prausnitz and Toth isotherm models using non-linear regression technique. Redlich–Peterson isotherm was found to best represent the data for phenol adsorption on all the adsorbents. The change in entropy (ΔS°) and heat of adsorption (ΔH°) for phenol adsorption on BFA were estimated as 1.8 MJ/kg K and 0.5 MJ/kg, respectively. The high negative value of change in Gibbs free energy (ΔG°) indicates the feasible and spontaneous adsorption of phenol on BFA. The values of isosteric heat of adsorption varied with the surface loading of phenol.     

Surface modification of date palm activated carbonaceous materials for heavy metal removal and CO2 adsorption

In this study, high surface area activated carbon (AC) was prepared from a local palm tree (Phoenix Dactylifera) using a variety of metal carbonates activators and finally achieved an excellent S_BET of 2700 m²/g when Cs₂CO₃ was used as an activating agent at a temperature of 600 °C. Surface modification of AC was carried out using various nitrogen transporting agents, resulting in N-doped ACs with nitrogen content varying from 4.0 to 11.4 %, depending on the functionalizing agents and activators used. The bimodal (presence of micro- as well as meso-porosity) ACs with such excellent surface properties were studied for their CO₂ uptake capacity at two different temperatures (0 and 25 °C) by isotherms recorded at pressure 1 bar and showed a remarkable uptake ability of 3.52 mmol/g (at 25 °C) and 5.6 mmol/g (at 0 °C), respectively. Also, batch experiments with variable pH, contact time, adsorbate concentrations, adsorbent dose, and temperatures were evaluated to understand the mechanism of sorption phenomena of Cr(VI) and Pb(II) achieving > 99.9 % removal capacity by the prepared ACs. Depending on the heavy metal ions being investigated, it was revealed that the pH of the solution and the amount of adsorbent had a direct impact on the total adsorption ability. Nitrogen atoms doped into the carbon frameworks were found to enhance the adsorption in the case of Pb(II) while the removal of Cr(VI) appeared to be unaffected. Maximum adsorption for Cr(VI) was observed at pH 2 and was determined to follow Freundlich isotherm while that of Pb(II) was observed at pH 7 and follows Langmuir isotherm. Best adsorption was found at an adsorbate concentration of 10 ppm and an adsorbent dose of 10 g/L. Kinetic modeling parameters showed the applicability of pseudo-second-order model perfectly.     

Elucidating dominant factors of PO43–, Cd2+ and nitrobenzene removal by biochar: A comparative investigation based on distinguishable biochars

Biochars produced from crab shell (CSB), oak sawdust (OB), Jerusalem artichoke tuber (JAB) and sorghum grain (SB) displayed distinguishable adsorption-related characteristics, such as specific surface area (SSA), ash content and acidic oxygen-containing functional groups (AFGs), which linked to the biochar adsorption mechanisms of most pollutants. Herein, PO₄^3–, Cd²⁺, and nitrobenzene (NB) were employed for adsorption by these biochars to elucidate the dominant factors for the adsorption. Adsorption performance of the three pollutants onto these four biochars varied considerably, as exemplified by the excellent adsorption of PO₄^3– and Cd²⁺ onto CSB (225.3 and 116.0 mg/g, respectively) as compared with onto the other three biochars (4.2–37.1 mg/g for PO₄^3– and 9.7–41.0 mg/g for Cd²⁺). OB displayed the best adsorption of NB (72.0 mg/g), followed by SB (39.5 mg/g), JAB (31.1 mg/g), and CSB (23.6 mg/g). The kinetics and isotherm adsorption assessments couple with material characterization suggested that the sorption of selected pollutants on biochars was attributed to the multiple mechanisms involved, including coprecipitation, chemical bonds, cation exchange, physical absorption, and complexation. Further path analysis suggested that AFGs and ash content in biochars were more important than SSA with regards to pollutant removal, especially, with ash playing a crucial role in the removal of Cd²⁺ and PO₄^3–, and AFGs being mainly responsible for NB adsorption. These findings might offer guidance on the preparation or modification of biochar with a targeted function for pollutant removal through an understanding the dominant factors.     

Photogenic MnO2/Ag metal nanocomposites and their dye adsorbing activities

• Manganese dioxide/silver (MnO₂/Ag) nanoparticles were fabricated by using KMnO₄-NaBH₄ redox reaction at room temperature. The optical and structural properties of MnO₂/Ag were determined using UV–visible and Fourier transform infrared spectroscopies. The morphology was established with scanning and transmission electron microcopies, and X-ray diffraction. MnO₂/Ag showed excellent adsorbing activity to the removal of Congo red. The various kinetic models were used to determine the rate of dye removal. Congo red adsorption onto MnO₂Ag proceeds through the pseudo-second-order kinetic model. Langmuir adsorption capacity (Q⁰_max = 97.1 mg/g), and sorption intensity (n = 1.6) were estimated with Langmuir and Freundlich adsorption isotherm models for 250 mg/L Congo red. Elovich model suggest the adsorption of Congo red with the MnO₂Ag proceeds through the film diffusion. The positive values of enthalpy changes (ΔH⁰), entropy changes (ΔS⁰), and negative Gibbs free energy changes (ΔG⁰) showed that the Congo red adsorption process was endothermic, spontaneous, and chemisorption process followed with physical mechanism. The results showed that the removal efficiency decreases from 98% to 89% after the six consecutive experiments.

     

Preparation of hydrophilic molecularly imprinted solid‐phase microextraction fiber for the selective removal and extraction of trace tetracyclines residues in animal derived foods

The present work reported a novel hydrophilic and selective solid‐phase microextraction fiber by improved multiple co‐polymerization method immobilization of tetracycline molecularly imprinted polymer on a stainless steel wire and directly coupled with high‐performance liquid chromatography for sensitive determination of trace tetracyclines residues in animal derived foods. The developed molecularly imprinted polymer coated solid‐phase microextraction fibers were characterized through scanning electron microscopy, Fourier transfer infrared spectroscopy, thermogravimetric analysis, and adsorption experiments, the fiber with cross‐linked and porous structure was observed and high thermal and chemical stability. The maximum adsorption capacity of this fiber with good selectivity reached 2.35 µg/mg in aqueous matrices, and showed good repeatability (relative standard deviation ≤ 6.6%, n = 5) and satisfying reproducibility between fiber to fiber (relative standard deviation ≤ 7.8%, n = 5). Under the optimized solid‐phase microextraction conditions, satisfactory linearity (5–1000 µg/L) and detection limits (0.38–0.72 µg/kg, S/N = 3) for all the tetracyclines were obtained. The practicality of this method was proved by adding tetracycline, oxytetracycline at three levels to milk, chicken, and fish samples with good recoveries of 77.3–104.4%.     

Field‐amplified sample injection combined with capillary electrophoresis for the simultaneous determination of five chlorophenols in water samples

A sensitive method of CZE‐ultraviolet (UV) detection based on the on‐line preconcentration strategy of field‐amplified sample injection (FASI) was developed for the simultaneous determination of five kinds of chlorophenols (CPs) namely 4‐chlorophenol (4‐CP), 2‐chlorophenol (2‐CP), 2,4‐dichlorophenol (2,4‐DCP), 2,4,6‐trichlorophenol (2,4,6‐TCP), and 2,6‐dichlorophenol (2,6‐DCP) in water samples. Several parameters affecting CZE and FASI conditions were systematically investigated. Under the optimal conditions, sensitivity enhancement factors for 4‐CP, 2‐CP, 2,4‐DCP, 2,4,6‐TCP, and 2,6‐DCP were 9, 27, 35, 43, and 43 folds, respectively, compared with the direct CZE, and the baseline separation was achieved within 5 min. Then, the developed FASI‐CZE‐UV method was applied to tap and lake water samples for the five CPs determination. The LODs (S/N = 3) were 0.0018–0.019 µg/mL and 0.0089–0.029 µg/mL in tap water and lake water, respectively. The values of LOQs in tap water (0.006–0.0074 µg/mL) were much lower than the maximum permissible concentrations of 2,4,6‐TCP, 2,4‐DCP, and 2‐CP in drinking water stipulated by World Health Organization (WHO) namely 0.3, 0.04, and 0.01 µg/mL, respectively, and thereby the method was suitable to detect the CPs according to WHO guidelines. Furthermore, the method attained high recoveries in the range of 83.0–119.0% at three spiking levels of five CPs in the two types of water samples, with relative standard deviations of 0.37–8.58%. The developed method was proved to be a simple, sensitive, highly automated, and efficient alternative to CPs determination in real water samples.     

An efficient biosorption‐based dispersive liquid‐liquid microextraction with extractant removal by magnetic nanoparticles for quantification of bisphenol A in water samples by gas chromatography‐mass spectrometry detection

In this work, a simple, fast, sensitive, and environmentally friendly method was developed for preconcentration and quantitative measurement of bisphenol A in water samples using gas chromatography with mass spectrometry. The preconcentration approach, namely biosorption‐based dispersive liquid‐liquid microextraction with extractant removal by magnetic nanoparticles was performed based on the formation of microdroplet of rhamnolipid biosurfactant throughout the aqueous samples, which accelerates the mass transfer process between the extraction solvent and sample solution. The process is then followed by the application of magnetic nanoparticles for easy retrieval of the analyte‐containing extraction solvent. Several important variables were optimized comprehensively including type of disperser solvent and desorption solvent, rhamnolipid concentration, volume of disperser solvent, amount of magnetic nanoparticles, extraction time, desorption time, ionic strength, and sample pH. Under the optimized microextraction and gas chromatography with mass spectrometry conditions, the method demonstrated good linearity over the range of 0.5–500 µg/L with a coefficient of determination of R² = 0.9904, low limit of detection (0.15 µg/L) and limit of quantification (0.50 µg/L) of bisphenol A, good analyte recoveries (84–120%) and acceptable relative standard deviation (1.8–14.9%, n = 6). The proposed method was successfully applied to three environmental water samples, and bisphenol A was detected in all samples.     

Effect of Direct yellow 50 removal from an aqueous solution using nano bentonite; adsorption isotherm,kinetic analysis and also thermodynamic behavior

The developing countries are suffering from the toxicity of different industrial effluents, especially dyes that contaminate water systems. This study successfully explained the preparation and characterization of nano bentonite to extract Direct Yellow Fifty (DY50). Direct Yellow 50 is an organic contaminant that may affect the quality of water. The characterization of prepared nanoparticles was done using Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR). The impact of different operating conditions was studied using different pH, dose, temperature, contact time, and initial DY50 concentrations. The obtained results indicated that nano bentonite could adsorb about 94 % at initial concentrations of 40 mg/L, respectively. The optimum removal conditions were observed at an acidic pH (pH 3) using a sorbent material dosage of 0.05 g for 4 h at 30 °C. The adsorption isotherm, kinetic analysis, and thermodynamic behavior were studied using linear equation form, and the adjusted R² was compared to detect the preferred models. The adsorption behavior pseudo-second order kinetics, and fitted Langmuir isotherm model, respectively, showed the chemisorption interactions between adsorbed and sorbed molecules. Thermodynamic behavior indicated that the reaction was exothermic. Finally, this study strongly recommended using nano bentonite for DY50 removal from an aqueous solution.