The use of exhausted olive cake ash (EOCA) as a low cost adsorbent for the removal of toxic metal ions from aqueous solutions

The removal characteristics of cadmium (Cd(II)) and nickel (Ni(II)) ions from aqueous solution by exhausted olive cake ash (EOCA) were investigated under various conditions of contact time, pH, initial metal concentration and temperature. Batch kinetic studies showed that an equilibrium time of 2 h was required for the adsorption of Ni(II) and Cd(II) onto EOCA. Equilibrium adsorption is affected by the initial pH (pH₀) of the solution. The pH₀ 6.0 is found to be the optimum for the individual removal of Cd(II) and Ni(II) ions by EOCA. The adsorption test of applying EOCA into synthetic wastewater revealed that the adsorption data of this material for nickel and cadmium ions were better fitted to the Langmuir isotherm since the correlation coefficients for the Langmuir isotherm were higher than that for the Freundlich isotherm. The estimated maximum capacities of nickel and cadmium ions adsorbed by EOCA were 8.38 and 7.32 mg g⁻¹, respectively. The thermodynamic parameters for the adsorption process data were evaluated using Langmuir isotherm. The free energy change (ΔG°) and the enthalpy change (ΔH°) showed that the process was feasible and endothermic respectively. As the exhausted olive cake is discarded as waste from olive processing, the adsorbent derived from this material is expected to be an economical product for metal ion remediation from water and wastewater.     

Adsorption of Hg(II) ions from aqueous chloride solutions using powdered activated carbons

Activated carbons were developed from Casurina equisetifolia leaves, by chemically treating with sulfuric acid (1:1) or zinc chloride (25%), at low (425 °C) and high (825 °C) temperatures. The resulting powdered activated carbons were applied for removing mercuric ions from aqueous solution at different agitation times and mercuric ion concentrations. The equilibrium data fitted well the Langmuir adsorption isotherm. The Langmuir adsorption capacities were 12.3 and 20.3 mg g⁻¹ for low temperature carbons and 43.9 and 38.5 mg g⁻¹ for high temperature carbons impregnated with H₂SO₄ and ZnCl₂, respectively. Studies of the effects of carbon dosage, NaCl concentrations and solution pH values were carried out for the more effective, high temperature carbons. Increasing NaCl concentration resulted in a significant decrease in the adsorption efficiency. Adsorption was high from solutions with low and neutral pH values and lower for solutions with alkaline pH values for the high temperature carbons.     

Removal of Cu(II) from aqueous solutions by recycled tire rubber

A batch adsorption system was applied to study the adsorption of Cu(II) ions from aqueous solutions by crumb rubber. The effects of pH ranging from 1.5 to 7.0, contact time ranging from 6 to 96 h and initial metal concentration ranging from 1 mg L^− 1 to 50 mg L^− 1 on the removal of Cu(II) were studied. Results show that adsorption of Cu(II) is pH-dependent and the best results are obtained at pH = 6.0. Results also show that copper uptake is accompanied by displacement of zinc and therefore probably involves an ion exchange type mechanism. Langmuir and Freundlich adsorption models were applied to describe the isotherms and isotherm constants. Equilibrium data agreed very well with the Langmuir model. Results clearly show that crumb rubber is an effective adsorbent for the removal of Cu(II) from aqueous solutions.     

Adsorption of cadmium(II) from aqueous solution by surface oxidized carbon nanotubes

Carbon nanotubes (CNTs) were oxidized with H₂O₂, KMnO₄ and HNO₃. Their physicochemical properties were investigated by BET N₂ adsorption, laser particle examination, Boehm’s titration, zeta potential measurement and cadmium(II) adsorption. The experimental results suggest that cadmium(II) adsorption capacities for three kinds of oxidized CNTs increase due to the functional groups introduced by oxidation compared with the as-grown CNTs. The cadmium(II) adsorption capacity of the as-grown CNTs is only 1.1 mg g⁻¹, while it reaches 2.6, 5.1 and 11.0 mg g⁻¹ for the H₂O₂, HNO₃ and KMnO₄ oxidized CNTs, respectively, at the cadmium(II) equilibrium concentration of 4 mg l⁻¹. Adsorption of cadmium(II) by CNTs was strongly pH-dependent and the increase of adsorption capacities for HNO₃ and KMnO₄ oxidized CNTs is more obvious than that of the as-grown and H₂O₂ oxidized CNTs at lower pH regions. The experiments of CNT dosage effect on the cadmium(II) adsorption show that the adsorption capacity for KMnO₄ oxidized CNTs has a sharper increase at the CNT dosage from 0.03 to 0.08 g per 100 ml than the as-grown, H₂O₂ and HNO₃ oxidized CNTs and its removal efficiency almost reaches 100% at CNT dosage of 0.08 g per 100 ml. Analysis revealed that the KMnO₄ oxidized CNTs hosted manganese residuals, and these surely contributed to cadmium sorption to a yet-undefined extent.     

Arsenic adsorption using copper (II) oxide nanoparticles

Arsenic poisoning is a major problem in today's life. To reduce its concentration in drinking water, different metal based compounds were explored as arsenic adsorbents. In the present study, copper (II) oxide nanoparticles were prepared by thermal refluxing technique and used as an adsorbent for arsenic removal from water. Characterization of the adsorbent using TEM, BET, XRD and FTIR implied that the prepared adsorbent was in nano size and had excellent adsorption behavior with surface area of 52.11 m²/g. Systematic adsorption experiments were carried out with different process parameters such as contact time, adsorbent mass, pH, temperature and stirring speed and found that copper (II) oxide had very good efficiency towards arsenic adsorption. Thermodynamic parameters and adsorption kinetics were studied in detailed to know the nature and mechanism of adsorption. Results showed that the adsorption process followed pseudo second order kinetic and endothermic behavior. Adsorption equilibrium was studied with Langmuir and Freundlich isotherm models. The adsorption process followed Langmuir isotherm with an adsorption capacity of 1086.2 μg/g. A regeneration study was proposed in order to reuse the adsorbent for better economy of the process. Finally, a process design calculation is reported to know the amount of adsorbent required for efficient removal of arsenic from aqueous medium.     

Use of a selective extractant-impregnated resin for removal of Pb(II) ion from waters and wastewaters: Kinetics,equilibrium and thermodynamic study

Adsorption of Pb(II) ion by a novel extractant-impregnated resin, EIR, was studied as a function of various experimental parameters using batch adsorption experiments. The new EIR was prepared by impregnating gallocyanine (GCN) onto Amberlite XAD-16 resin beads. The EIR was characterized by nitrogen analysis and SEM micrographs. The new EIR showed excellent selectivity factor values (α) for Pb(II) adsorption respect to other metal ions. The effects of some chemical and physical variables were evaluated and the optimum conditions were found for Pb(II) removal from aqueous solutions. The equilibrium adsorption isotherm was fitted with the Langmuir adsorption model. The maximum adsorption capacity (q_max) of EIR for Pb(II) ions was found to be 367.92 mg g⁻¹. The kinetic studies showed that the intra-particle diffusion is the rate-controlling step. Also, the intra-particle diffusion coefficients, D_ip values, were of the order of 10⁻¹² m² s⁻¹. The values of enthalpy (ΔH°) were positive, which confirms the endothermic nature of adsorption process. Also, the positive entropy changes (ΔS°) were showed that the randomness increased along with the adsorption process. In addition, the obtained negative values of Gibbs free energy (ΔG°) indicated feasible and spontaneous nature of the adsorption process at different temperatures. The new adsorbent was very stable so that it can be successfully used for many consecutive cycles without significant loss in its adsorption capacity.     

Adsorption of Cd(II), Hg(II) and Zn(II) from aqueous solution using mesoporous activated carbon produced from Bambusa vulgaris striata

Mesoporous activated carbon (surface area of 608 m²/g) has achieved high efficiency in removal of cadmium, mercury and zinc ions from water solution. The proposed low-cost adsorbent was physically activated with water steam from the bamboo species Bambusa vulgaris striata. The batch studies suggested an activated carbon dose of 0.6 g/L, solution pH of 9 and an equilibrium time of 16 h in static conditions. The pseudo-second order equations represented the adsorption kinetics with high correlation. Fitting of the experimental results to the Langmuir, Freundlich, Redlich–Peterson and Toth isotherm models showed an almost homogeneous surface coverage and presence of physical adsorption. The highest adsorption capacities, calculated from the Langmuir model, are 239.45, 248.05 and 254.39 mg/g of cadmium, mercury and zinc, respectively.     

Adsorption characteristics of sericite for cesium ions from an aqueous solution

To efficiently remove cesium ions from aqueous solution, sericite was used as a novel adsorbent. The silanol (SiO₂) and aluminol (Al₂O₃) groups in sericite are likely to play an important role in adsorption process. The maximum adsorption capacity (q_m) and adsorption constant (K_L) for cesium ions obtained from the Langmuir isotherm model were 6.68 mg/g and 0.227 L/mg, respectively and regression curve fit well with the experimental data as the 0.965 of correlation coefficients (r²). However, when the Freundlich isotherm model was used correlation coefficient (r²) was 0.973. Therefore, it was concluded that Freundlich model fits equilibrium data better than Langmuir model. When the 6.0 g/L of sericie concentration was added to aqueous solution, cesium ions were removed by about 80% and the increase was not happened above 6.0 g/L of sericite concentration any more. The process was determined as exothermic reaction because the removal efficiency of cesium ions decreased as temperature increased. Furthermore, all adsorption was completed in 120 min and comparing the pseudo first and second-order kinetic models indicates that the adsorption of cesium ions using sericite follows well the pseudo-second-order kinetics.     

Phosphate adsorption characteristics of alunite to be used as a cement additive

The adsorption of phosphate from aqueous solution by alunite has been investigated as a function of calcination temperature, particle size, pH, agitation time and initial phosphate concentration. Phosphate adsorption was seen to increase with increasing calcination temperature, decreasing adsorbent particle size and pH. The adsorption isotherm data were fitted to the Langmuir isotherm. The alunite exhibited the highest phosphate uptake capacity at 1073 K calcination temperature, at a particle size of 90-150 μm, at the initial pH of 5.0, at an equilibrium time of 60 min and at the initial phosphate concentration of 20×10⁻⁴ mol/l. The adsorption capacity, Q, was 4.697×10⁻³ mol/g at initial pH 5.0.     

The defluoridation of water by acidic alumina

Fluoride is considered as a major inorganic pollutant present in drinking water. To remove this excess fluoride, defluoridation was done by alumina. In the present study, alumina used was acidic in nature and hence considered as a good fluoride removing adsorbent. Characterization of the adsorbent was done by XRD, SEM, BET and FTIR with BET surface area of 144.27 m²/g. Systematic adsorption experiments were carried out with different process parameters such as contact time, adsorbent mass, pH, temperature and stirring speed. Fluoride adsorption by alumina was highly pH dependent. Maximum fluoride was removed from water at pH 4.4. At very low and very high pH, fluoride removal efficiency was affected. The study of thermodynamic parameters inferred that physical adsorption was dominant with activation energy of 95.13 kJ/mol and endothermic behavior of the process. The kinetics study concluded that pseudo second order kinetics was followed by the adsorption process. Adsorption equilibrium was studied with Langmuir and Freundlich isotherm models. The adsorption process followed Langmuir isotherm with an adsorption capacity of 8.4 mg/g. A regeneration study was proposed in order to reuse the adsorbent for better economy of the process. Finally, a process design calculation was reported to know the amount of adsorbent required for efficient removal of fluoride from aqueous medium.     

Selective removal mercury (II) from aqueous solution using silica aerogel modified with 4-amino-5-methyl-1,2,4-triazole-3(4H)-thion

Silica aerogel surface modifications with chelating agents for adsorption/removal of metal ions have been reported in recent years. This investigation reported the preparation of silica aerogel (SA) adsorbent coupled with metal chelating ligands of 4-amino-5-methyl-1,2,4-triazole-3(4H)-thion (AMTT) and its application for selective adsorption of Hg(II) ion. The adsorbent was characterized by Fourier transform infrared spectra (FTIR) and thermo gravimetric analysis (TGA) measurements, nitrogen physisorption and scanning electron microscope (SEM). Optimal experimental conditions including pH, temperature, adsorbent dosage and contact time have been established. Langmuir and Freundlich isotherm models were applied to analyze the experimental data. The best interpretation for the experimental data given by the Langmuir isotherm equation and the maximum adsorption capacity of the modified silica gel and silica aerogel was 142.85 and 17.24mgg^?1, respectively. Thermodynamic parameters such as Gibbs free energy (ΔG ^o ), standard enthalpy (ΔH ^o ) and entropy change (ΔS ^o ) were investigated. The adsorbed Hg(II) on the SA-AMTT adsorbents could be completely eluted by 1.0M KBr solution and recycled at least four times without the loss of adsorption capacity. The results of the present investigation illustrate that modified silica aerogel with AMTT could be used as an adsorbent for the effective removal of Hg(II) ions from aqueous solution.     

Comparison with as-grown and microwave modified carbon nanotubes to removal aqueous bisphenol A

This study utilized carbon nanotubes (CNTs) to remove bisphenol A (BPA) from aqueous solution. The surfaces of CNTs were modified by SOCl₂/NH₄OH under microwave irradiation. The surface characteristics of as-grown and modified CNTs were analyzed by measuring zeta potential, and using a scanning electron microscope, a surface area analyzer and a Fourier transform infrared spectroscope. The specific surface area of modified CNTs exceeded that of as-grown CNTs. The pH_iep values of as-grown CNTs and modified CNTs were determined to be 4.3 and 6.5, respectively. Some amine functionalities were formed on the surface of modified CNTs; therefore, the surface of the modified CNTs contained more positive charges than that of the as-grown CNTs. The adsorption kinetics were examined using pseudo first- and second-order models, intraparticle diffusion and Bangham's models. The equilibrium data were simulated using Langmuir, Freundlich, Dubinin and Radushkevich (D-R) and Temkin isotherms. The results reveal that the pseudo second-order model and Langmuir isotherm fit the kinetics and equilibrium data, respectively. The adsorption capacity of BPA on the surface of CNTs fluctuates very little with pH in the range of 3-9, suggesting the high stability of CNTs as an adsorbent for BPA over a rather wide pH range. The values of ΔH⁰ and ΔS⁰ were calculated to be − 11.7 kJ/mol and 46.1 J/mol, respectively. The isotherm and thermodynamic simulations indicate that the adsorption of BPA onto as-grown CNTs proceeds by physisorption process.     

Preparation of an adsorbent by graft polymerization of acrylamide onto coconut husk for mercury(II) removal from aqueous solution and chloralkali industry wastewater

Graft copolymerization of acrylamide onto coconut husk (CH), initiated by the ferrous ammonium sulfate/H₂O₂ redox initiator system, was studied. To determine the optimum conditions of grafting, the effect of the concentrations of ferrous ammonium sulfate, the monomer, and H₂O₂ and the time and temperature on percentage of the graft yield was studied. A new adsorbent media having a carboxylate functional group was synthesized by the surface modification of polymer‐grafted coconut husk (PGCH COOH). The mechanism of graft polymerization and surface functionalization is proposed. The material exhibits a very high adsorption potential for Hg(II). The sorption of Hg(II) was found to be dependent on the contact time, concentration, pH, and temperature. Maximum removal of 99.4% with 2 g/L of the sorbent was observed at 125 μmol L⁻¹ Hg(II) concentration at pH 6.0. The slow step which determines the rate of exchange of Hg(II) ions is diffusion through the adsorbent particles. The diffusion coefficients, energy of activation, and entropy of activation were calculated and used to determine the theoretical behavior of the sorption process. The applicability of the Langmuir isotherm established the endothermic character of the adsorption. Acid regeneration was tried for several cycles with a view to recover the adsorbed metal ions and also to restore the sorbent to its original state. The adsorbent efficiency toward Hg(II) removal was tested using synthetic and chloralkali industry wastewaters. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1261–1269, 2000     

Studies on the removal of Cobalt(II) from aqueous solutions by adsorption with Ficus benghalensis leaf powder through response surface methodology

Suitability of Ficus benghalensis leaf powder for the adsorptive removal of Cobalt(II) from aqueous solutions is exhaustively studied and is reported in this article. Experimentation based on response surface methodology is conducted to understand the interaction among the variables—metal ion concentration, adsorbent dosage, initial solution pH and temperature that are of significance in the treatment. A 20?mg?L^?1 of Cobalt(II) solution, treated with 25?g?L^?1 of adsorbent at a pH of 5.0 and a temperature of 303?K, yielded 98.73% removal of Cobalt(II). Langmuir isotherm proved to be a better model representation of the equilibrium. Adsorption kinetics is of pseudo second rate form. Maximum sorption capacity of F. benghalensis leaf powder, q_max, is found to be 5.65?mg?g^?1. Adsorption is endothermic and spontaneous in nature. Study on surface morphology is included in the study.     

Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste

The adsorption characteristics of Pb(II) and Cd(II) onto colemanite ore waste (CW) from aqueous solution were investigated as a function of pH, adsorbent dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the adsorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The adsorption capacity of CW was found to be 33.6 mg/g and 29.7 mg/g for Pb(II) and Cd(II) ions, respectively. Analyte ions were desorbed from CW using both 1 M HCl and 1 M HNO₃. The recovery for both metal ions was found to be higher than 95%. The mean adsorption energies evaluated using the D-R model indicated that the adsorption of Pb(II) and Cd(II) onto CW were taken place by chemisorption. The thermodynamic parameters (ΔG^o, ΔH^o and ΔS^o) showed that the adsorption of both metal ions was feasible, spontaneous and exothermic at 20-50 °C. Adsorption mechanisms were also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The kinetic results showed that the adsorption of Pb(II) and Cd(II) onto CW followed well pseudo-second order kinetics.     

Adsorption behavior of fluoride ions using a titanium hydroxide-derived adsorbent

The removal behavior of fluoride ions was examined in aqueous sodium fluoride solutions using a titanium hydroxide-derived adsorbent. The adsorbent was prepared from titanium oxysulfate (TiOSO₄·xH₂O) solution, and was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry-differential thermal analysis, Fourier transform infrared spectrum and specific surface area. Batchwise adsorption test of prepared adsorbent was carried out in aqueous sodium fluoride solutions and real wastewater containing fluoride ion. The absorbent was the amorphous material, which had different morphology to the raw material, titanium oxysulfate, and the specific surface area of the adsorbent (96.8 m²/g) was 200 times higher than that of raw material (0.5 m²/g). Adsorption of fluoride on the adsorbent was saturated within 30 min in the solution with 200 mg/L of fluoride ions, together with increasing pH of the solution, due to ion exchange between fluoride ions in the solution and hydroxide ions in the adsorbent. Fluoride ions were adsorbed even in at a low fluoride concentration of 5 mg/L; and were selectively adsorbed in the solution containing a high concentration of chloride, nitrate and sulfate ions. The adsorbent can remove fluoride below permitted level (< 0.8 mg/L) from real wastewaters containing various substances. The maximum adsorption of fluoride on the adsorbent could be obtained in the solution at about pH 3. After fluoride adsorption, fluoride ions were easily desorbed using a high pH solution, completely regenerating for further removal process at acidic pH. The capacity for fluoride ion adsorption was almost unchanged three times after repeat adsorption and desorption. The equilibrium adsorption capacity of the adsorbent used for fluoride ion at pH 3 was measured, extrapolated using Langmuir and Freundlich isotherm models, and experimental data are found to fit Freundlich than Langmuir. The prepared adsorbent is expected to be a new inorganic ion exchanger for the removal and recovery of fluoride ions from wastewater.     

Random forest model for removal of bromophenol blue using activated carbon obtained from Astragalus bisulcatus tree

In this research, activated carbon (AC) simply was prepared from a local, abundant tree in south of Iran. The AC with low cost and toxicity is a good candidate for bromophenol blue (BPB) removal from aqueous media. The AC with nano scale pore diameter is applicable for this dye removal following optimization of the influence of various parameters including contact time, pH, initial dye concentration and amount of adsorbent. Subsequently, experimental data was analyzed by four kinetic models including pseudo first and second-order, Elovich and the intraparticle diffusion equations and subsequently their respective parameters such as rate constants, equilibrium adsorption capacities and correlation coefficients was investigated and based on well known criterion their applicability was judged. The result shows that adsorption of BPB onto proposed adsorbent at all conditions such as versatile adsorbent dosages and initial BPB concentrations sufficiently described by the combination of the pseudo second-order equation and interparticle diffusion model. It was found that equilibrium rate of the BPB adsorption at various adsorbent dosage well fitted by Langmuir. Investigation of experimental result by two approaches (multiple linear regressions (MLR) and random forest (RF)) models show that RF is a powerful tool for prediction of BPB adsorption by activated carbon obtained from Astragalus bisulcatus tree. The optimal tuning parameters for RF model are obtained based on the n_tree = 100, m_try = 2. For the training data set, the MSE values of 0.0006 and the coefficient of determination (R²) values of 0.9895 for RF model and the MSE value of 0.0104 and the R² value of 0.823 for MLR model are obtained.     

Physical and chemical characteristics of polymer-based spherical activated carbon and its ability to adsorb organics

The characterization of a polymeric spherical activated carbon (PAC) was performed by comparing its adsorption, porosity, functional groups and some of the physical properties with a commercial spherical activated carbon (CAC). The PAC was about 4 times superior to the CAC with respect to the mechanical strength. The micropore volume of the PAC was about 5% smaller than that of the CAC. The maximum methylene blue adsorption values of the PAC and the CAC were 32 and 14 mg g⁻¹, respectively, which indicated low mesopore volumes as consistent with the values of BJH volume. This resulted in the low butane working capacity values for both activated carbons. Adsorption parameters for the Langmuir and the Freundlich isotherm models were determined for all organic substances tested. Both isotherms were suitable models to analyze the equilibrium data for the removal of all organics. However, the Langmuir model fitted better than the Freundlich model and the adsorption capacities of the PAC were somewhat higher than those of the CAC. The chemical properties of the activated carbons, the pH of solutions and the substituents on absorbates have an effect on adsorption of the organics tested.     

Kinetic and equilibrium modelling of Cadmium(II) ions sorption onto polymerized tamarind fruit shell

Formaldehyde polymerized tamarind fruit shell (FPTFS) having sulphonic acid groups was prepared and tested as an adsorbent for the adsorption of cadmium(II) ions from water and wastewater. Batch experiments were conducted to determine the adsorption efficiency of the adsorbent. The maximum adsorption of Cd(II) occurred at pH 7.0. The equilibrium was established in 3 h. Kinetic data were modeled using pseudo-first-order, pseudo-second-order and Ritchie modified second-order model. The equilibrium data were described using Langmuir, Freundlich, Sips and Toth isotherm equations. The results of error analysis indicated that the best parameters for kinetic and isotherm equations were obtained by hybrid fractional error function method. The kinetic data could be well described by Ritchie modified second-order expression and the adsorption capacities calculated by the model were close to those determined by experiments. The adsorption isotherm data could be well fitted to the Sips isotherm model. The efficiency of Cd(II) removal by the FPTFS decreased with an increase in ionic strength of the solution. The efficiency of FPTFS was tested using fertilizer industry wastewater. About 98.0% of the adsorbed Cd(II) ions can be released from the spent adsorbent by treatment with 0.1 M HCl solution. Consecutive adsorption/desorption (4 cycles) showed the feasibility of the FPTFS for Cd(II) adsorption.     

Adsorption of Nickel from aqueous solution by the use of low-cost adsorbents

The removal of Ni(II) from aqueous solution by different adsorbents was investigated. Calcined phosphate, red mud, and clarified sludge (a steel industry waste material) were used for the adsorption studies. The influence of pH, contact time, initial metal concentration, adsorbent nature and concentration on the selectivity and sensitivity of the removal process was investigated. The adsorption process was found to follow a first-order rate mechanism and rate constant was evaluated at 30 °C. Langmuir and Freundlich adsorption isotherms fit well in the experimental data and their constants were evaluated. The thermodynamic equilibrium constant and the Gibbs free energy were calculated for each system. The adsorption capacity (q _max ) calculated from Langmuir isotherm and the values of Gibbs free energy obtained showed that calcined phosphate has a higher capacity and affinity for the removal of Ni(II) compared to the other adsorbents used in the study.