Lead removal from aqueous solution by basaltic scoria: adsorption equilibrium and kinetics

Pb-contaminated water is a dangerous threat occurring near metallurgic and mining industries. This circumstance produces serious environment concern, due to Pb(II) high toxic effects. Several reactive materials have been reported for Pb(II) adsorption, but not all reached final Pb(II) suitable concentrations, or they are expensive and rejected in massive remediation technologies; hence, natural materials are good options. The adsorption behavior of a volcanic scoria (two sieved fractions 1425 and <425 µm) was studied toward synthetic Pb(II) water solutions in batch experiments (170.4–912.3 mg L^?1) with high removal efficiencies (97%). The Langmuir model fits both fractions with high linear correlation coefficients (0.9988 and 0.9949) with high maximum capacity values (588.23 and 555.55 mg g^?1). Separation factor R _L parameter varies with initial concentration, and the empirical equation predicts the limits of the material usefulness, a criterion proposed in this paper for conditions’ selection. The Lagergren pseudo-second-order analysis demonstrates chemisorption; calculated rate constant (416.66 mg g^?1 min^?1). Weber–Morris intraparticle model proves that the adsorption phenomena occur fast on the material surface (k _inst = 72 g mg^?1 min^?0.5). The characterization of the volcanic material afforded the elemental composition (X-ray fluorescence), and the empirical formula was proposed. X-ray diffraction patterns verify the material structure as basalt, with a plagioclase structure that matches anorthite and albite, mostly composed of quartz. The presence of oxides on the material surface explain the high Pb(II) adsorption capacity, observed on the surface by scanning electronic microscopy. The studied volcanic scoria has potential use as a Pb(II) adsorbent in water remediation technologies.     

Insight into adsorption equilibrium,kinetics and thermodynamics of lead onto alluvial soil

In the present study, adsorption of lead (II) ions from aqueous solution by alluvial soil of Bhagirathi River was investigated under batch mode. The influence of solution pH, sorbent dose, initial lead (II) concentration, contact time, stirring rate and temperature on the removal process were investigated. The lead adsorption was favored with maximum adsorption at pH 6.0. Sorption equilibrium time was observed in 60 min. The equilibrium adsorption data were analyzed by the Freundlich, Langmuir, Dubinin–Radushkevich and Temkin adsorption isotherm models. The kinetics of lead (II) ion was discussed by pseudo first-order, pseudo second-order, intra-particle diffusion, and surface mass transfer models. It was shown that the adsorption of lead ions could be described by the pseudo second-order kinetic model. The activation energy of the adsorption process (E _a) was found to be ?38.33 kJ mol^?1 using the Arrhenius equation, indicating exothermic nature of lead adsorption onto alluvial soil. Thermodynamic parameters, such as Gibbs free energy (?G ⁰), the enthalpy (?H ⁰), and the entropy change of sorption (?S ⁰) have also been evaluated and it has been found that the adsorption process was spontaneous, feasible, and exothermic in nature. The results indicated that alluvial soil of Bhagirathi River can be used as an effective and low cost adsorbent to remove lead ions from aqueous solutions.     

Dye adsorption on electrochemical exfoliated graphene oxide nanosheets: pH influence,kinetics and equilibrium in aqueous solution

Graphene oxide nanosheets were synthesized by electrochemical exfoliation. X-ray diffraction, scanning electron microscopy, atomic force microscopy, Raman spectrometry and Fourier transform infrared spectrometry were used to characterize crystal structure, particle size, thickness and function groups of the nanosheets. The nanosheets were examined for adsorption of methyl orange, an anionic dye, in aqueous solution at different pHs and temperatures. The maximum adsorption capacity of methyl orange on graphene oxide nanosheets obtained from the Langmuir isotherm was 138.69 mg/g at pH 2.0, which is larger than that of other carbonaceous adsorbents. The large adsorption affinity of graphene oxide nanosheets to methyl orange might be due to the presence of hydrogen bonding and π–π interaction between methyl orange and graphene oxide nanosheets. Adsorption kinetics followed a pseudo-second-order kinetic model, and the isotherm adsorption results were fitted with Langmuir isotherm model in a monolayer adsorption manner. The thermodynamic studies indicated that the adsorption reaction was a spontaneous physisorption process.     

Adsorption of a cationic dye (methylene blue) by Iranian natural clays from aqueous solutions: equilibrium,kinetic and thermodynamic study

Removal of dyes by low-cost adsorbents is an effective method in wastewater treatment. Iranian natural clays were determined to be effective adsorbents for removal of a basic dye (methylene blue) from aqueous solutions in batch processes. Characterizations of the clays were carried out by X-ray diffraction, Brunauer–Emmett–Teller surface area analysis and field-emission scanning electron microscopy. Effects of the operational parameters such as adsorbent dosage, initial dye concentration, solution pH and temperature were investigated on the adsorption performance. Adsorption isotherms like Langmuir, Freundlich and Temkin were used to analyze the adsorption equilibrium data and Langmuir isotherm was the best fit. Adsorption kinetics was investigated by pseudo-first-order, pseudo-second-order and intraparticle diffusion models and the results showed that the adsorption system conforms well to the pseudo-second-order model. The thermodynamic parameters of adsorption (ΔS°, ΔH° and ΔG°) were obtained and showed that the adsorption processes were exothermic.     

Biogenic silver nanoparticles on carbonaceous material from sewage sludge for degradation of methylene blue in aqueous solution

Silver nanoparticles (Ag NPs) were synthesized in situ, using a one-step green methodology with Camellia sinensis (green tea) aqueous extract as reducing agent, and supported on a carbonaceous material (Ag-CM), originated from the pyrolysis of sewage sludge. UV–Vis spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Brunauer–Emmet–Teller were used to characterize the nanocomposite. Ag-CM composite exhibited very good catalytic activity in the degradation process of methylene blue (MB) dye in aqueous solution without using sunlight or UV radiation. Batch kinetic and isothermal experiments, using 30 mg/L MB solution, showed that Ag-CM composite removed near to 91 % of MB in 9 h, whereas the carbonaceous material alone removed only 60 % in 30 h. Experimental data were adjusted to different kinetic and isotherms models, where both materials fit the second-order and Langmuir–Freundlich models, respectively; therefore, a chemisorption mechanism probably occurs in these heterogeneous materials.     

Removal of diazinon pesticide from aqueous solutions using MCM-41 type materials: isotherms,kinetics and thermodynamics

In this research, ordered mesoporous silica, including MCM-41, was synthesized via sol–gel process and a propyl methacrylate-modified ordered mesoporous silica (MPS-MCM-41) was successfully synthesized via a postsynthesis grafting process. Then both MCM-41 and MPS-MCM-41 were characterized using FTIR, XRD, SEM and BET techniques. The synthesized materials were utilized as adsorbent for removal of diazinon pesticide from aqueous solutions. The effects of pH, contact time, adsorbent dose, initial concentration and temperature have been evaluated using removal efficiencies. Also, the kinetic, thermodynamic and isotherm models of diazinon adsorption were studied for the both MCM-41 and MPS-MCM-41. The results showed that the maximum adsorption capacities are 142 and 254 mg g^?1 for the MCM-41 and MPS-MCM-41, respectively, at the initial concentration of 50 mg L^?1, temperature of 298 K and adsorbent dose of 0.1 g L^?1. The highest percentages of diazinon removal are 56.4 and 87.2 (at adsorbent dose of 2 g L^?1 and the temperature of 318 K) for the MCM-41 and MPS-MCM-41, respectively. The Freundlich and Langmuir models are more compatible for describing equilibrium data of the diazinon adsorption capacity on the MCM-41 and MPS-MCM-41, respectively. Thermodynamic study indicated that the adsorption process of diazinon onto MCM-41 and MPS-MCM-41 is exothermic and has a spontaneous nature. The higher adsorption capacity and higher spontaneous nature of MPS-MCM-41 in comparison with MCM-41 might be due to the presence of the both hydrogen bonding and hydrophobic interaction between surface functional groups of MPS-MCM-41 (hydroxyl and propyl methacrylate) and diazinon functional groups.     

Removal of cationic dye methylene blue (MB) from aqueous solution by ground raw and base modified pine cone powder

The adsorption capacity of raw and sodium hydroxide-treated pine cone powder in the removal of methylene blue (MB) from aqueous solution was investigated in a batch system. It was found that the base modified pine cone exhibits large adsorption capacity compared with raw pine cone. The extent of adsorption capacity was increased with the increase in NaOH concentration. Overall, the extent of MB dye adsorption increased with increase in initial dye concentration, contact time, and solution pH but decreased with increase in salt concentration and temperature for both the systems. Surface characteristics of pine cone and base modified pine cone were investigated using Fourier transform infrared spectrophotometer and scanning electron microscope. Equilibrium data were best described by both Langmuir isotherm and Freundlich adsorption isotherm. The maximum monolayer adsorption capacity was found to be 129.87 mg g^?1 at solution pH of 9.02 for an initial dye concentration of 10 ppm by raw pine cone. The base modified pine cone showed the higher monolayer adsorption capacity of 142.25 mg g^?1 compared with raw pine cone biomass. The value of separation factor, R _L, from Langmuir equation and Freundlich constant, n, both give an indication of favourable adsorption. The various kinetic models, such as pseudo-first-order model, pseudo-second-order model, intraparticle diffusion model, double-exponential model, and liquid film diffusion model, were used to describe the kinetic and mechanism of adsorption process. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on other models. The different kinetic parameters, including rate constant, half-adsorption time and diffusion coefficient, were determined at different physicochemical conditions. A single-stage bath adsorber design for the MB adsorption onto pine cone and modified pine cone has been presented based on the Langmuir isotherm model equation. Thermodynamic parameters, such as standard Gibbs free energy (ΔG ⁰), standard enthalpy (ΔH ⁰) and standard entropy (ΔS ⁰), were also calculated.     

Adsorption of reactive dyes from aqueous solutions by tannery sludge developed activated carbon: Kinetic and equilibrium studies

Adsorption kinetic and equilibrium studies of two reactive dyes, namely, Reactive Red 31 and Reactive Red 2 were conducted. The equilibrium studies were conducted for various operational parameters such as initial dye concentration, pH, agitation speed, adsorbent dosage and temperature. The initial dye concentration was varied from 10 - 60 mg/L, pH from 2–11, agitation speed from 100–140 rpm, adsorbent dosage from 0.5 g to 2.5 g and temperature from 30 °C -50 °C respectively. The activated carbon of particle size 600 μm was developed from preliminary tannery sludge. The dye removal capacity of the two reactive red dyes decreased with increasing pH. The zero point charge for the sludge carbon was 9.0 and 7.0 for the two dyes, respectively. Batch kinetic data investigations on the removal of reactive dyes using tannery sludge activated carbon have been well described by the lagergren plots. It was suggested that the Pseudo second order adsorption mechanism was predominant for the sorption of the reactive dyes onto the tannery sludge based carbon. Thus, the adsorption phenomenon was suggested as a chemical process. The adsorption data fitted well with Langmuir model than the Freundlich model. The maximum adsorption capacity(q⁰) from Langmuir isotherm were found to have increased in the range of 23.15–39.37 mg/g and 47.62–55.87 mg/g for reactive dyes reactive red 31 and reactive red 2, respectively.     

Characteristics of arsenic adsorption from aqueous solution: Effect of arsenic species and natural adsorbents

Batch and column experiments were conducted on As adsorption from aqueous solution by natural solids to test the feasibility of these materials to act as adsorbents for As removal from groundwater and drinking water. The solids considered are natural hematite and natural siderite. The As species studied are As(V), As(III) and dimethylarsinic acid (DMA). Arsenic(III), As(V) and DMA were removed to different extents by the solids studied from water solutions containing these three As species, with the highest efficiency for As(V). In aqueous solutions with a mixture of As species, adsorption kinetics depend on the species. On both materials, As(V) was preferentially adsorbed in the batches and first reached equilibrium, followed by DMA and As(III). The As adsorption took place more slowly on natural hematite and natural siderite compared with ferrihydrite. The results demonstrate that the amount of As removed from As(III) batches was greater than that from As(V) batches due to a surface alteration of the solids caused by As(III) oxidation. Although the highest efficiency for As retention was observed on hematite HIO1 in the batch experiments, siderite used as column filling was more efficient in removing As from water containing the As species studied in comparison with hematite. The coating of fresh Fe(III)-oxides was much more intensive in the siderite-packed column than in the hematite-packed column. The combination of siderite and hematite would promote the column filling performance in removing As from aqueous solution.     

Sequestration of arsenate from aqueous solution using 2-line ferrihydrite: equilibria,kinetics, and X-ray absorption spectroscopic analysis

Arsenic(V), as the arsenate (AsO₄ ^3?) ion and its conjugate acids, has a strong affinity on Fe, Mn, and Al (oxyhydr)oxides and clay minerals. Removal of arsenate from aqueous solution by poorly crystalline ferrihydrite (hydrous ferric oxide) via a combination of macroscopic (equilibria and kinetics of sorption) and X-ray absorption spectroscopic studies was investigated. The removal of arsenate significantly decreased with increasing pH and sorption maxima of approximately 1.994 mmol/g (0.192 mol_As/mol_Fe) were achieved at pH 2.0. The Langmuir isotherm is most appropriate for arsenate sorption over the wide range of pH, indicating that arsenate sorption preferentially takes place at relatively homogenous and monolayer sites rather than heterogeneous and multilayer surfaces. The kinetic study demonstrated that arsenate sorption onto 2-line ferrihydrite is considerably fast, and sorption equilibrium was achieved within the reaction time of 2 h. X-ray absorption near-edge structure spectroscopy indicates no change in oxidation state of arsenate following interaction with the ferrihydrite surfaces. Extended X-ray absorption fine structure spectroscopy supports the efficient removal of arsenate by the 2-line ferrihydrite through the formation of highly stable inner-sphere surface complexes, such as bidentate binuclear corner-sharing (²C) and bidentate mononuclear edge-sharing (²E) complexes.     

Preparation of magnetic microgels for catalytic reduction of 4-nitrophenol and removal of methylene blue from aqueous medium

This work describes the synthesis of poly(acrylic acid) microgels and fabrication of magnetic cobalt nanoparticles in the prepared microgels. Cobalt nanoparticles were fabricated by loading the cobalt (II) ions in microgels from aqueous solution and their subsequent reduction with sodium borohydride (NaBH₄). Bare and composite microgels were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. The catalytic properties of the prepared microgel composites were investigated by using them as catalyst for the reduction of 4-nitrophenol and methylene blue. The effect of temperature and catalyst dose on the rate of reduction of these toxic pollutants was investigated. The reusability of prepared catalysts was also studied for the five consecutive cycles, and an increase in catalytic activity was observed after every cycle. The prepared bare and magnetic microgels were found as very effective adsorbent for the removal of methylene blue from aqueous medium. Very rapid adsorption rate was found for the removal of methylene as its 100 mg was adsorbed on per gram of dried hydrogels in about 25 min. The effects of different parameters like amount of adsorbate and concentration of adsorbent on the adsorption process were studied. Langmuir, Freundlich and Temkin adsorption isotherms were applied, and it was found that adsorption of MB follows Freundlich model better than others. Furthermore, pseudo-first-order and pseudo-second-order kinetic models were also applied and adsorption of MB was found to abide by pseudo-second-order kinetics.     

Removal of zinc(II) from aqueous solutions using modified agricultural wastes: kinetics and equilibrium studies

In recent years, the need for safe and economical methods to eliminate heavy metals from contaminated waters has necessitated research on the production of low-cost alternatives to commercially available activated carbon. In the present work, in order to enhance the removal of heavy metals from contaminated water, Zizyphus vulgaris wastes were modified chemically to produce an adsorbent rich in carboxylic groups to enhance the removal of heavy metals from contaminated water. Adsorption of Zn(II) ions on the produced adsorbent was then optimized. The optimal ratio for esterification involved the treatment of Z. vulgaris wastes (1 g) with 0.0037 mmol malic acid in the presence of a very small amount of water for 2 h at 140 °C. The maximum values for adsorption capacity, q _max, were 28.7 and 164.6 mg/g on native and modified Z. vulgaris wastes, respectively, at pH 5 and 30 °C with a contact time 2 h and an initial metal ion concentration of 400 mg/L. The equilibrium data were well fitted by the Langmuir and Freundlich adsorption models and demonstrated the significant capacity for Z. vulgaris wastes in the removal of Zn(II) ions from aqueous solutions.     

Removal of ibuprofen from aqueous solution by functionalized strong nano-clay composite adsorbent: kinetic and equilibrium isotherm studies

The functionalized nano-clay composite adsorbent was prepared, and its properties were characterized using FT-IR, XRD and SEM techniques. The synthesized nano-clay composite was studied with regard to its capacity to remove ibuprofen under different adsorption conditions such as varying pH levels (5–9), initial ibuprofen concentrations (3, 5 and 10 mg L^?1), contact time, and the amount of adsorbent (0.125, 0.25, 0.5 and 1 g). In order to evaluate the nanocomposite adsorption capacity, the adsorption results were assessed using nine isotherm models. The results showed that the optimum adsorption pH was 6 and that an increase or decrease in the pH reduced the adsorption capacity. The adsorption process was fast and reached equilibrium after 120 min. The maximum efficacy of ibuprofen removal was approximately 95.2%, with 1 g of adsorbent, 10 mg L^?1 initial concentration of ibuprofen, 120 min contact time and pH = 6. The optimal adsorption isotherm models were the Freundlich, Fritz–Schlunder, Redlich–Peterson, Radke–Prausnitz, Sip, Toth and Khan models. In addition, four adsorption kinetic models were employed for adsorption system evaluation under a variety of experimental conditions. The kinetic data illustrated that the process is very fast, and the reaction followed the Elovich kinetic model. Therefore, this nano-clay composite can be used as an effective adsorbent for the removal of ibuprofen from aqueous solutions, such as water and wastewater.     

Evaluation of adsorption potential of bamboo biochar for metal-complex dye: equilibrium,kinetics and artificial neural network modeling

Metal-complex dyes are widely used in textile industry, but harmful to the environment and human health due to aromatic structure and heavy metal ions. The objective of this work was to evaluate the adsorption potential of bamboo biochar for the removal of metal-complex dye acid black 172 from solutions. Freundlich model was more suitable for the adsorption process of bamboo biochar than Langmuir isotherm, indicating multilayer adsorption of acid black 172 on a heterogeneous bamboo biochar surface. Adsorption kinetics analysis of pseudo-second-order and Weber–Morris models revealed that intraparticle transport was not the only rate-limiting step. The bamboo biochar exhibited a good adsorption performance even at high ionic strength. Analysis based on the artificial neural network indicated that the temperature with a relative importance of 29 % appeared to be the most influential parameter in the adsorption process for dye removal, followed by time, ionic strength, pH and dye concentration.     

Adsorption isotherms, kinetics and mechanism for the adsorption of cationic and anionic dyes onto carbonaceous particles prepared from Juglans regia shell biomass

In the present study, Juglans regia shells were used to prepare activated carbon by acid treatment method. J. regia shell-based activated carbon was used for the adsorption of two synthetic dyes namely, a basic dye malachite green and an acid dye amido black 10B. The prepared adsorbent was crushed and sieved to three different mesh sizes 100, 600 and 1,000 μm. The adsorbent was characterized by scanning electron microscopy, surface acidity and zero-point charge. Batch experiments were carried out by varying the parameters like initial aqueous phase pH, adsorbent dosage and initial dye concentration. The equilibrium data were tested with Langmuir, Freundlich, Redlich–Peterson and Sips isotherm at three different temperatures 293, 300 and 313 K and it was found that the Freundlich isotherm best fitted the adsorption of both the dyes. Kinetic data were tested with pseudo first-order model and pseudo second-order model. The mechanism for the adsorption of both the dyes onto the adsorbent was studied by fitting the kinetic data with intraparticle diffusion model and Boyd plot. External mass transfer was found to be the rate-determining step. Based on the ionic nature of the adsorbates, the extent of film diffusion and intraparticle diffusion varied; both being system specific. Thermodynamic parameters were also calculated. Finally, the process parameters of each adsorption system were compared to develop the understanding of the best suitable system.