Separation and Preconcentration of Boron with a Glucamine Modified Novel Magnetic Sorbent

A novel, simple method based on magnetic separation was developed for analytical purposes. In this method, N‐methyl‐D‐glucamine (NMDG) modified magnetic microparticles that were synthesized by using the sol‐gel method were used for the selective extraction and preconcentration of boron from aqueous solutions. This method combines the simplicity and selectivity of solvent extraction with the easy separation of magnetic microparticles from a solution with a magnet without any preliminary filtration step. The structure of the prepared γ‐Fe₂O₃‐SiO₂‐NMDG (magnetic sorbent) composites were characterized by using X‐ray diffraction (XRD), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). The influence of different parameters on the sorbent capacity, such as the sorption/desorption of boron, magnetic sorbent dosage, pH, equilibrium time, type, and amount of stripping solution, were evaluated by using the magnetic sorbent. Any equilibrium pH greater than 6 can be used for sorption. Desorption from the sorbent was carried out by using 1.0 M HCl. The sorption and desorption efficiency of the γ‐Fe₂O₃‐SiO₂‐NMDG was found as 92.5 ± 0.5% and 99.8 ± 6%, respectively.     

Removal of Congo Red from Aqueous Solution by Sorption on Organified Rectorite

Batch sorption technique was carried out for the removal of anionic dye Congo red (CR) from aqueous solution using raw rectorite (R‐REC) and organified rectorite (CTA⁺‐REC) modified by cetyltrimethylammonium bromide (CTAB) as adsorbents. The effects of organification degree of CTA⁺‐REC as well as the process parameters including the pH of dye solution, sorption time, and initial dye concentration on adsorption capacity for CR were investigated and the sorption kinetics was also evaluated. The results showed that the sorption behaviors of R‐REC and CTA⁺‐REC for CR followed pseudo‐second‐order kinetic model and the sorption equilibrium data perfectly obeyed the Langmuir isotherm. The thermodynamic parameters including entropy of sorption (ΔS⁰), enthalpy of sorption (ΔH⁰), and Gibbs free energy of sorption (ΔG⁰) were obtained and analyzed. Fourier transform infrared study revealed that a chemisorption process occurred between CR and CTA⁺‐REC. REC modified by cationic surfactants showed the higher adsorption capacities for CR compared to R‐REC and in theory would be used as an efficient and promising adsorbent for the removal of anionic dyes in wastewater treatment.     

Preparation of Magnetic Hydroxyapatite and Their Use as Recyclable Adsorbent for Phenol in Wastewater

Magnetic hydroxyapatite (HAP), which combined superparamagnetic Fe₃O₄ nanoparticles and HAP, composite materials were prepared by ultrasound method in this paper. It has also been found that these materials have the ability to adsorb phenol in wastewater. The magnetic materials were investigated by scanning electron microscope, X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, thermal gravimetric analysis, vibrating sample magnetometer, and N₂ adsorption in order to elucidate the morphology, structure, and other properties. When the prepared magnetic materials were calcined at 200°C, the prepared Fe₃O₄ was oxidized to Fe₂O₃, possessing loose‐shaped holes with a high specific area of 325.2 m²/g, a magnetization intensity of 12.5 emu/g, and the N₂ adsorption isotherm belongs to porous adsorption type I. Moreover, the magnetic HAP can adsorb 90% phenol in wastewater. This means that it is an excellent recyclable phenol sorbent for sewage treatment. Experiments confirmed that the Freundlich adsorption isotherms model applies to lower phenol concentrations (0–50 mg/L), while for high phenol concentrations (50–500 mg/L) the Langmuir adsorption isotherms model fits. The magnetic sorbents have the capacity to regenerate after reaching adsorption saturation using ethanol as eluant and external magnetic field as separation unit. The efficiency of adsorption was reduced only by 10% over a six time use period.     

Removal of Organic Pollutants from Wastewater Using Wood Fly Ash as a Low‐Cost Sorbent

In this study, untreated and treated wood fly ash (WA) was used as a low‐cost sorbent in batch sorption tests to investigate the removal of organic pollutants from a real wastewater generated by cleaning/washing of machinery in a wood‐laminate floor industry in Sweden. The experiments focused on the effect of the WA dosage and particle size on the removal efficiency for organic compounds. With a WA dosage of 160 g L^?1 and a particle size less than 1 mm, the reductions of chemical oxygen demand (COD), biologic oxygen demand, and total organic carbon were 37 ± 0.4, 24 ± 0.4, and 30 ± 0.3%, respectively. Pre‐treatment of WA with hot water improved the COD removal efficiency by absorption from 37 ± 0.4 to 42 ± 1.6% when the same dosage (160 g L^?1) was applied. Sorption isotherm and sorption kinetics for COD using untreated WA can be explained by Freundlich isotherm and pseudo‐second‐order kinetic models. Intra‐particle diffusion model indicates that pore diffusion is not the rate‐limiting step for COD removal. Based on the experimental data, WA could be used as an alternative low‐cost sorption media/filter for removal of organic compounds from real industrial wastewater.     

Effects of Alkali and Alkaline‐earth Cations on the Removal of Reactive Dyes with Cucurbituril

The sorption of reactive (textile) dyes onto cucurbituril, a cyclic polymer with hydrophobic cavity, was studied. Dye sorption is strongly enhanced by Ca²⁺ or Sr²⁺ concentrations up to 100 mmol/L for all studied dyes. Mg²⁺ and alkaline ions had similar effects for only one dye (Reactive Red 120), and only at higher concentrations. Concentrations above 100 mmol/L – depending on cation and dye – dissolve cucurbituril and prevent dye removal. As shown in previous studies by our group loadings obtained under suitable conditions (calcium concentration between 2 and 100 mmol/L, total salt concentration not exceeding 100 mmol/L) are 1 to 1.7 mol/mol or 0.9 to 1.8 g/g. The chemical mechanism responsible for the ionic influences is still under investigation. Generally, cucurbituril is a potent sorbent for reactive dyes. However, the technical application is still limited by the lack of a support material that would allow use in fixed bed filters.     

Removal of Organic Dyes in Environmental Water onto Magnetic‐Sulfonic Graphene Nanocomposite

A magnetic‐sulfonic graphene nanocomposite (G‐SO₃H/Fe₃O₄) was synthesized and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. It was used for removal of three cationic dyes: safranine T (ST), neutral red (NR), victoria blue (VB), and three anionic dyes: methyl orange, brilliant yellow, and alizarin red, from environmental water. The experimental conditions were optimized, including pH, amount of adsorbent, adsorption kinetics, adsorption isotherms, ionic strength, etc. The results show that G‐SO₃H/Fe₃O₄ can adsorb cationic dyes more efficiently and selectively than anionic dyes at pH 6.0. In the first 10 min of adsorption time, more than 93% of the cationic dyes were removed by the sorbent. Adsorption kinetics follow the pseudo‐second‐order kinetic model well. The adsorption isotherm coincided with Langmuir and Freundlich adsorption models. The maximum adsorption capacities of G‐SO₃H/Fe₃O₄ for ST, NR, and VB dyes were 199.3, 216.8, and 200.6 mg g^?1. The adsorbed cationic dyes were eluted by using different pH values of ethanol as the solvent. The established method was simple, sensitive, and rapid, and was suitable for the adsorption of cationic dyes in environmental water.     

S‐Doped Magnetic Mesoporous Carbon for Efficient Adsorption of Methyl Orange from Aqueous Solution

A simple and rapid soft‐templating coupled with one‐pot solvent thermal method is developed to synthesize S‐doped magnetic mesoporous carbon (S‐doped MMC). In this method, phenolic resin is used as a carbon precursor and Pluronic copolymer P123 is used as a template and 2,5‐dimercapto‐1,3,4‐thiadiazole is used as sulfur source. Prepared S‐doped MMC processes a high specific surface area, the Fe₃O₄ particles are well embedded in the mesoporous carbon walls that exhibit a strong magnetic response, and the hydrated iron nitrate loading amount of 0.808 g is the best. Batch adsorption experiments are carried out at different pH, initial concentration, temperature, and contact time on the adsorption of methyl orange (MO) by S‐doped MMC. The kinetic data of the adsorption process are better fitted with pseudo‐second‐order model than the pseudo‐first‐order model. Langmuir model is more suitable for the equilibrium data than Freundlich model. The thermodynamic parameters including ΔG⁰, ΔH⁰, and ΔS⁰ indicate that the adsorption is a feasible, spontaneous, and endothermic process. Finally, it is found that the coexistence of PO₄^3?, NO₃^?, SO₄^2?, Cl^?, and CO₃^2? does not influence the adsorption process. These results illustrate S‐doped MMC can be an efficient adsorbent for the removal of MO from wastewater.     

Photocatalytic Degradation of Dye C.I. Direct Blue 78 Using TiO2 Nanoparticles Immobilized on Recycled Wool‐Based Nonwoven Material

This paper discusses the possibility of immobilization of TiO₂ nanoparticles onto recycled wool‐based nonwoven material, which can be utilized for removal of dyes from wastewater. The photocatalytic activity of TiO₂ nanoparticles deposited on the nonwoven material was evaluated in the aqueous solution of direct dye C.I. Direct Blue 78 under the UV illumination. Nonwoven material modified with TiO₂ nanoparticles provides complete removal of dye from the solution already after 4–6 h of UV illumination. However, photodegradation of the dye adsorbed on the nonwoven material was obtained within 24 h of UV illumination. The rate of dye adsorption and photodegradation depends on the amount of deposited TiO₂ nanoparticles. The increase of initial dye concentration induced decrease in photocatalytic efficiency of immobilized TiO₂ nanoparticles. The highest photodegradation rate was achieved in acidic conditions. Elevated temperatures positively affected the removal of dye from solution. Photocatalytic activity of TiO₂ nanoparticles deposited on nonwoven material was preserved after three photodegradation cycles.     

Adsorption of Cationic Dyes from Aqueous Solution by Termite Feces,a Non‐Conventional Adsorbent

The adsorption of three cationic dyes (rhodamine B, RB; crystal violet, CV; and malachite green, MG) onto termite feces, a low‐cost adsorbent, was investigated. The adsorbent was characterized by IR spectroscopy, point of zero charge measurement, and the Boehm titration method. The adsorption follows the pseudo‐second‐order kinetic model and the Langmuir–Freundlich isotherm with maximum adsorption capacities of 95.53 mg g^?1 (RB), 75.71 mg g^?1 (CV), and 44.78 mg g^?1 (MG). The study of thermodynamics showed that the adsorption is a spontaneous and endothermic process. This works suggest that termite feces can be used as a new low‐cost adsorbent for cationic dye removal.     

Regeneration and Reuse of a Seaweed‐Based Biosorbent in Single and Multi‐Metal Systems

A seaweed‐waste material resulting from the processing of Ascophyllum nodosum was previously shown to be very efficient at removing Zn(II), Ni(II) and Al(III) both in single and multi‐metal waste streams. In this study, the regeneration of the biosorbent using an acid wash resulted in the release of high metal concentrations during multiple desorption cycles. Maximum desorption efficiencies (DE) of 183, 122 and 91% were achieved for Zn(II), Ni(II) and Al(III), respectively, for subsequent metal loading cycles, significantly exceeding the desorption rates observed for conventional sorbents. The regeneration of the sorbent was accomplished with very little loss in metal removal efficiency (RE) for both single and multi‐metal systems. Values of 92, 96 and 94% RE were achieved for Zn(II), Ni(II) and Al(III), respectively, for the 5^th sorption cycle in single metal aqueous solutions. A slight decrease was observed for the same metals in multi‐metal systems with maximum REs of 85, 82 and 82% for Zn(II), Ni(II) and Al(III), respectively. This study showed that the novel sorbent derived from a seaweed industrial waste would be suitable for multiple metal sorption cycles without any significant loss in RE.     

Adsorption Characteristics of Reactive Black 5 from Aqueous Solution onto Chitosan

Adsorption of reactive black 5 (RB5) from aqueous solution onto chitosan was investigated in a batch system. The effects of solution pH, initial dye concentration, and temperature were studied. Adsorption data obtained from different batch experiments were modeled using both pseudo first‐ and second‐order kinetic equations. The equilibrium adsorption data were fitted to the Freundlich, Tempkin, and Langmuir isotherms over a dye concentration range of 45–100 µmol/L. The best results were achieved with the pseudo second‐order kinetic and Langmuir isotherm equilibrium models, respectively. The equilibrium adsorption capacity (q_e) was increased with increasing the initial dye concentration and solution temperature, and decreasing solution pH. The chitosan flakes for the adsorption of the dye was regenerated efficiently through the alkaline solution and was then reused for dye removal. The activation energy (E_a) of sorption kinetics was estimated to be 13.88 kJ/mol. Thermodynamic parameters such as changes in free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) were evaluated by applying the van't Hoff equation. The thermodynamics of reactive dye adsorption by chitosan indicates its spontaneous and endothermic nature.     

Sorption and Chemical Reactions of PAHs with Dissolved Humic Substances and Related Model Polymers

Sorption coefficients measured for PAHs on dissolved humic substances by SPME and FQT were found to be inevitably different and method‐dependent – SPME provides activity‐based and FQT concentration‐based sorption coefficients. Poly(acrylic acid) esters as well‐defined model polymers were used in sorption experiments, leading to the conclusion that short aliphatic chains are more effective in binding PAHs than aromatic moieties. FQT was inappropriate to measure sorption coefficients for the interaction of pyrene with poly(acrylic acid) esters but the experiments revealed a characteristic shift in the fluorescence spectrum. Using pyrene as a probe for the molecular environment in the sorbed state, the observed spectral shift indicated a highly hydrophobic microenvironment. The empirical relationships between lg K_DOC and lg K_OW were generalized on the basis of a modified Flory‐Huggins concept. Introducing only one sorbent‐specific parameter, the solubility parameter δ_DOM, the calculation of sorption coefficients became possible for a wide range of HOCs using fundamental data readily available from the literature. Long‐term experiments showed that reactive PAHs (such as acenaphthylene and 9‐methylanthracene) are able to react with HAs under strictly abiotic and anoxic conditions, whereas less reactive PAHs (such as naphthalene and dihydroanthracene) do not form bound residues. The HA reveals two functions in the interaction, behaving as a reaction partner and as a protecting ligand.     

Removal of Heavy Metals from Synthetic Mixture as well as Pharmaceutical Sample Via Cation Exchange Resin Modified with Rhodamine B: Its Thermodynamic and Kinetic Studies

A new sorbent was prepared by loading rhodamine B on Amberlite IR‐120. Various physico‐chemical parameters such as effects of adsorbate concentration, contact time, pH, and temperature on the sorption of the dye have been studied. Thermodynamic parameters (ΔH° and ΔS°) were also evaluated for the sorption of dye. Kinetic studies revealed that the sorption of the dye was best fit for pseudo‐second‐order kinetic. The metal ion uptake in different solvent systems has been explored through column studies. On the basis of distribution coefficient (K_d), some heavy metal ions of analytical interest from binary mixtures have been separated. The limit of detection (LOD) for the Ni²⁺ and Fe³⁺ metal ions was 0.81 and 0.60 µg L^?1, and the limit of quantification (LOQ) was found to be 2.72 and 2.0 µg L^?1. This sorbent has also been successfully applied in the analysis of multivitamin formulation. The applicability of the modified resin in the separation of heavy metals constituting real and synthetic samples has been explored.     

Packed‐Column of Granular Activated Carbons for Removal of Chemical Oxygen Demand from Industrial Wastewater

In the present study, chemical oxygen demand (COD) removal by packed‐columns of activated carbon (AC) derived from two different materials (coal activated carbon, CAC and wood activated carbon, WAC) is reported as part of an on‐site wastewater treatment system for handling small volumes of wastewater generated at wood‐floor industries for which there are no proper on‐site treatment options available in the market. The performance of the sorbents, the effect of bed depth (0.19 and 0.57 m) and volumetric load (0.10 and 0.24 m h^?1) on the breakthrough curve of sorption systems were studied. The results indicated the feasibility of using both ACs to treat these wastewaters. At the bed depth (0.57 m), volumetric load (0.24 m h^?1), and 30% breakthrough, CAC and WAC showed treatment capacity of 40.5 L kg^?1 in 250 h and 23.8 L kg^?1 in 63 h, respectively. This indicated that CAC requires longer retention times to reach a performance similar to WAC. The experimental data was fit into the bed depth‐service time model showing that under the same conditions, CAC had higher maximum sorption capacity (N₀) than WAC. Moreover, thermal regeneration at 500°C temperature could be a cost‐effective procedure since the reuse of spent AC through such regeneration process for further treatment could still achieve 90% of the initial sorption capacity, reducing then costs for the use of new sorbents and also the need for waste disposal.     

Removal of Ni(II) Using Cation Exchange Resins in Packed Bed Column: Prediction of Breakthrough Curves

Sorptive removal of Ni(II) from electroplating rinse wastewaters by cation exchange resin Dueolite C 20 was investigated at the temperature of 30°C under dynamic conditions in a packed bed. The effects of sorbent bed length 0.1–0.2 m, fixed flow rate 6 dm³ min^?1, and the initial rinse water concentration (C₀) 53.1 mg L^?1 on the sorption characteristics of Dueolite C 20 were investigated at an influent pH of 6.5. More than 94.5% of Ni(II) was removed in the column experiments. The column performance was improved with increasing bed height and decreasing the flow rate. The Thomas, Yoon–Nelson, Clark, and Wolborska models were applied to the experimental data to represent the breakthrough curves and determine the characteristic design parameters of the column. The sorption performance of the Ni(II) ions through columns could be well described by the Thomas, Yoon–Nelson, and Wolborska models at effluent‐to‐influent concentration ratios (C/C₀) >0.03 and <0.99. Among the all models, the Clark model showed the least average percentage time deviation. The sorptive capacity of electroplating rinse water using Ni(II) was found to be 45.98 mg g^?1.     

Optimization of a Photo‐assisted Fenton Oxidation Process: A Statistical Model for MDF Effluent Treatment

In the present study, the effects of initial COD (chemical oxygen demand), initial pH, Fe²⁺/H₂O₂ molar ratio and UV contact time on COD removal from medium density fiberboard (MDF) wastewater using photo‐assisted Fenton oxidation treatment were investigated. In order to optimize the removal efficiency, batch operations were carried out. The influence of the aforementioned parameters on COD removal efficiency was studied using response surface methodology (RSM). The optimal conditions for maximum COD removal efficiency from MDF wastewater under experimental conditions were obtained at initial COD of 4000 mg/L, Fe²⁺/H₂O₂ molar ratio of 0.11, initial solution pH of 6.5 and UV contact time of 70 min. The obtained results for maximum COD removal efficiency of 96% revealed that photo‐assisted Fenton oxidation is very effective for treating MDF wastewater.     

Assessment of the Biosorption Characteristics of a Spent Cottonseed Husk Substrate for the Decolorization of Methylene Blue

This study concentrates on the possible application of the spent cottonseed husk substrate (SCHS), an agricultural waste used after the cultivation of white rot fungus Flammulina velutipes, to adsorb methylene blue (MB) from aqueous solutions. Batch studies were carried out with variable initial solution pH, adsorbent amount, reaction time, temperature, and initial MB concentration. MB uptake was favorable at pH ranging from 4.0 to 12.0, and the equilibrium adsorption capacity of 143.5 mg g^?1 can be reached promptly within about 240 min. The combination analysis of FTIR and BET techniques revealed that the massive functional groups on the biosorbent surface, such as hydroxyl and carboxyl, were responsible for the biosorption of MB. It was found that adsorption data matched the pseudo‐second order kinetic and Langmuir isotherm models. Thermodynamic parameters of free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°), obtained from biosorption MB ranging from 293 to 313 K, showed that the sorption experiment was a spontaneous and endothermic process. The study highlighted a new pathway to develop a new potential utilization of SCHS as a low‐cost sorbent for the removal of MB pollutants from wastewater.     

Biodegradation by Co‐inoculated Bacteria and Fungi Alleviates Adverse Effects of Red‐S3B on Growth and Nitrogen Uptake of Wheat

Textile wastewater contains huge quantities of nitrogen (N)‐containing azo‐dyes. Irrigation of crops with such wastewater adds toxic dyes into our healthy soils. One of the ways to prevent their entry to soils could be these waters after the dyes' biodegradation. Therefore, the present study was conducted to evaluate the impact of textile dyes on wheat growth, dye degradation efficiency of bacteria‐fungi consortium, and alleviation of dye toxicity in wheat by treatment with microbial consortium. Among dyes, Red‐S3B (3.19% N) was found to be the most toxic to germination and growth of seven‐day‐old wheat seedlings. Shewanella sp. NIAB‐BM15 and Aspergillus terreus NIAB‐FM10 were found to be efficient degraders of Red‐S3B. Their consortium completely decolorized 500 mg L^?1 Red‐S3B within 4 h. Irrigation with Red‐S3B‐contaminated water after treatment with developed consortium increased root length, shoot length, root biomass, and shoot biomass of 30‐day‐old wheat seedlings by 47, 18, 6, and 25%, respectively, than untreated water. Moreover, irrigation after microbial treatment of dye‐contaminated water resulted in 20 and 51% increase in shoot N content and N uptake, respectively, than untreated water. Thus, co‐inoculation of bacteria and fungi could be a useful bioremediation strategy for the treatment of azo‐dye‐polluted water.     

Dye Removal,Energy Consumption and Operating Cost of Electrocoagulation of Textile Wastewater as a Clean Process

In this research, the efficiency of electrocoagulation treatment process using aluminum electrodes to treat synthetic wastewater containing Reactive Red198 (RR198) was studied. The effects of parameters such as voltage, time of reaction, electrode connection mode, initial dye concentration, electrolyte concentration, and inter electrode distance on dye removal efficiency were investigated. In addition, electrical energy consumption, electrode consumption, and operating cost at optimum condition have been investigated. The results showed that dye and chemical oxygen demand removals were 98.6 and 84%, respectively. Electrode consumption, energy consumption and operating cost were 0.052 kg/m³, 1.303 kWh/m³ and 0.256 US$/m³, respectively. Dye removal kinetic followed first order kinetics. It can be concluded that electrocoagulation process by aluminum electrode is very efficient and clean process for reactive dye removal from colored wastewater.     

Adsorption of Complex Pollutants from Aqueous Solutions by Nanocomposite Materials

In view of water pollutants becoming more complex, both anionic and cationic pollutants need to be removed. The multi‐pollutants simultaneous removal is paid more and more attention. Hence, development composite materials for treatment complex wastewater are the aim of this study. In this research, iron–nickel nanoparticles deposited onto aluminum oxide (α‐Al₂O₃) and carbon nanotubes (CNTs) to form nanocomposite materials Fe–Ni/Al₂O₃ and Fe–Ni/CNTs, respectively, were used as adsorbents. The adsorption capacities of Fe–Ni/Al₂O₃ and Fe–Ni/CNTs for AO7, HSeO, and Pb²⁺ were observed to be 5.46, 8.28, 27.02, and 25.6 mg/g, 15.29 and 17.12 mg/g, separately. The composite materials with negative charges were superior in adsorption of anionic pollutants. Using orthogonal experimental design and analysis of variance to co‐treat dye AO7, HSeO and Pb²⁺ in aqueous solutions, seven testing factors were included: (1) adsorbent types, (2) amount of iron, (3) solution pHs, (4) AO7 concentrations, (5) Pb²⁺ concentrations, (6) HSeO concentrations and (7) reaction time. The experimental results showed that the removal of complex pollutants AO7, HSeO, and Pb²⁺ on Fe–Ni/CNTs could reach up to 90% in the optimal treatment conditions. When using Fe–Ni/CNTs as the adsorbent, the sorption isothermals were well fitted in the Freundlich isotherm, and R² could reach up to 0.98.