Batch sorption dynamics and equilibrium for the removal of cadmium ions from aqueous phase using wheat bran

Studies on a batch sorption process using wheat bran as a low cost sorbent was investigated to remove cadmium ions from aqueous solution. The influence of operational conditions such as contact time, cadmium initial concentration, sorbent mass, temperature, solution initial pH, agitation speed and ionic strength on the sorption kinetics of cadmium was studied. Pseudo-second-order model was evaluated using the six linear forms as well as the non-linear curve fitting analysis method. Modeling of kinetic results shows that sorption process is best described by the pseudo-second-order model using the non-linear method. The sorption of cadmium was found to be dependent on initial concentration, sorbent mass, solution pH, agitation speed, temperature, ionic strength and contact time. The value of activation energy (12.38 kJ mol(-1)) indicates that sorption has a low potential barrier corresponding to a physical process. Sorption equilibrium isotherms at different temperatures was determined and correlated with common isotherm equations such as Langmuir and Freundlich models. It was found that the Langmuir model appears to well fit the isotherm data but a worse correlation was obtained by the Freundlich model. The five Langmuir linear equations as well as the non-linear curve fitting analysis method were discussed. Results show that the non-linear method may be a better way to obtain the Langmuir parameters. Thermodynamic parameters such as DeltaH degrees, DeltaS degrees and DeltaG degrees were calculated. These parameters indicate that the sorption of cadmium by wheat bran is a spontaneous process and physical in nature involving weak forces of attraction and is also endothermic.     

Equilibrium and kinetic modelling of cadmium(II) biosorption by nonliving algal biomass Oedogonium sp. from aqueous phase

The biosorption of cadmium(II) ions on Oedogonium sp. is studied in a batch system with respect to initial pH, algal dose, contact time and the temperature. The algal biomass exhibited the highest cadmium(II) uptake capacity at 25 degrees C, at the initial pH value of 5.0 in 55 min and at the initial cadmium(II) ion concentration of 200 mg L(-1). Biosorption capacity decreased from 88.9 to 80.4 mg g(-1) with an increase in temperature from 25 to 45 degrees C at this initial cadmium(II) concentration. Uptake kinetics follows the pseudo-second-order model and equilibrium is well described by Langmuir isotherm. Isotherms have been used to determine thermodynamic parameters of the process, viz., free energy change, enthalpy change and entropy change. FTIR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which are responsible for biosorption of metal ions. Acid pretreatments did not substantially increase metal sorption capacity but alkali like NaOH pretreatment slightly enhanced the metal removal ability of the biomass. During repeated sorption/desorption cycles at the end of fifth cycle, Cd(II) sorption decreased by 18%, with 15-20% loss of biomass. Nevertheless, Oedogonium sp. appears to be a good sorbent for removing metal Cd(II) from aqueous phase.     

Studies on sorption of Cd(II) on Tata chromite mine overburden

Chromite mine overburden containing iron as oxide/hydroxide, a waste material generated in chromite mines was used as sorbent for cadmium. The iron content of material was 43.75% with a specific surface area of 50.8m(2)/g. Batch experiments were conducted to study the sorption behavior of Cd(II) on this material. The variable experimental parameters were: time, pH, temperature, Cd(II) and sample concentration. The point of zero charge (PZC) of the overburden sample was experimentally determined as 6.48 which shifted to a pH of 7.8 when the sample was equilibrated with 100 mg/L Cd(II) solution. Maximum loading capacity of the overburden sample was found to be approximately 19 mg Cd/g of material. It was observed that within 30 min the sorption attains equilibrium. Hence, the sorption data generated at 30 min with various initial Cd(II) concentrations and temperatures were taken to evaluate the thermodynamic parameters, i.e., DeltaG degrees , DeltaH degrees and DeltaS degrees . The DeltaG degrees values reflect the feasibility of the metal removal from aqueous solution. The negative values of DeltaH degrees confirmed the exothermic sorption of cadmium and the positive DeltaS degrees values suggested the increased randomness at the solid-solution interface. The sorption data fitted well to both the Langmuir and Freundlich isotherm models indicating a monolayer sorption. The value of Freundlich parameter 'n' (n is indicative of sorption intensity) lying between 1.46 and 1.59 shows that the surface of the sorbent is heterogeneous in nature.     

Removal of mercury(II) from aqueous media using eucalyptus bark: Kinetic and equilibrium studies

In this study, eucalyptus camaldulensis bark, a forest solid waste, is proposed as a novel material for the removal of mercury(II) from aqueous phase. The operating variables studied were sorbent dosage, ionic strength, stirring speed, temperature, solution pH, contact time, and initial metal concentration. Sorption experiments indicated that the sorption capacity was dependent on operating variables and the process was strongly pH-dependent. Kinetic measurements showed that the process was uniform and rapid. In order to investigate the mechanism of sorption, kinetic data were modeled using the pseudo-first-order and pseudo-second-order kinetic equations, and intraparticle diffusion model. Among the kinetic models studied, the pseudo-second-order equation was the best applicable model to describe the sorption process. Equilibrium isotherm data were analyzed using the Langmuir and the Freundlich isotherms. The Langmuir model yields a much better fit than the Freundlich model. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy, and entropy of sorption. The maximum sorption capacity was 33.11 mg g⁻¹ at 20 °C and the negative value of free energy change indicated the spontaneous nature of sorption. These results demonstrate that eucalyptus bark is very effective in the removal of Hg(II) from aqueous solutions.     

Removal of lead(II) and cadmium(II) from aqueous solutions using grape stalk waste

The sorption of lead and cadmium from aqueous solutions by grape stalk waste (a by-product of wine production) was investigated. The effects of the contact time, pH of the solution, ionic medium, initial metal concentration, other metal ions present and ligands were studied in batch experiments at 20 degrees C. Maximum sorption for both metals was found to occur at an initial pH of around 5.5. The equilibrium process was described well by the Langmuir isotherm model, with maximum grape stalk sorption capacities of 0.241 and 0.248 mmol g(-1) for Pb(II) and Cd(II), respectively, at pH around 5.5. Kinetic studies showed good correlation coefficients for a pseudo-second-order kinetic model. The presence of NaCl and NaClO(4) in the solution caused a reduction in Pb and Cd sorption, the latter being more strongly suppressed. The presence of other metals in the uptake process did not affect the removal of Pb, while the Cd uptake was much reduced. HCl or EDTA solutions were able to desorb lead from the grape stalks completely, while an approximately 65% desorption yield was obtained for cadmium. From the results obtained it seems that other mechanisms, such as surface complexation and electrostatic interactions, must be involved in the metal sorption in addition to ion exchange.     

A comparative study of linear and non-linear regression analysis for ammonium exchange by clinoptilolite zeolite

Ammonium ion exchange from aqueous solution using clinoptilolite zeolite was investigated at laboratory scale. Batch experimental studies were conducted to evaluate the effect of various parameters such as pH, zeolite dosage, contact time, initial ammonium concentration and temperature. Freundlich and Langmuir isotherm models and pseudo-second-order model were fitted to experimental data. Linear and non-linear regression methods were compared to determine the best fitting of isotherm and kinetic model to experimental data. The rate limiting mechanism of ammonium uptake by zeolite was determined as chemical exchange. Non-linear regression has better performance for analyzing experimental data and Freundlich model was better than Langmuir to represent equilibrium data.     

Determination of kinetic and equilibrium parameters of the batch adsorption of Ni(II) from aqueous solutions by Na-mordenite

The potential to remove nickel(II) ions from aqueous solutions using Na-mordenite, a common zeolite mineral, was thoroughly investigated. The effects of relevant parameters solution pH, adsorbent dose, ionic strength, and temperature on nickel(II) adsorption capacity were examined. The sorption data followed the Langmuir, Freundlich, Langmuir-Freundlich and Dubinin-Radushkevich (D-R) isotherms. The maximum sorption capacity was found to be 5.324 mg/g at pH 6, initial concentration of 40 mg/L and temperature of 20 degrees C. Thermodynamic parameters, viz. changes in standard free energy (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees ) have also been evaluated and the results show that the sorption process was spontaneous and endothermic in nature. Dynamics of the sorption process were studied and the values of rate constant of adsorption, rate constant of intraparticle diffusion were calculated. The activation energy (E(a)) was found to be 12.465 kJ/mol in the present study, indicating a chemical sorption process involving weak interactions between sorbent and sorbate. The sorption capacity increased with the increase of solution pH and the decrease of ionic strength and adsorbent dose. The nickel(II) ions sorption by the Na-mordenite is not completely attributable to ion exchange. Compared to the other adsorbents, the nickel(II) ions show a lower affinity towards the clay mineral adsorbents.     

Ultrasound facilitates and improves removal of Cd(II) from aqueous solution by the discarded tire rubber

Some of the heavy metal ions such as cadmium are toxic and represent as hazardous pollutants due to their persistence in the environment. In this study the ground discarded tire rubber was used for the sorption of cadmium from aqueous solution. The batch sorption tests were conducted to investigate the sorption of Cd(II) by discarded tire rubber in the presence and absence of ultrasound. To assess the capability of sorbent, research parameters such as ultrasonic waves, solution temperature, particle size of ground tire and others were investigated. The experimental data were fitted in Langmuir model better than Freundlich one. Therefore, the former model was applied to the sorption equilibrium in order to determine the maximum metal sorption capacity in the presence and absence of ultrasound. The Langmuir constants were also obtained from the isotherms under different conditions. In the presence of ultrasound the tire rubber was a more efficient sorbent for this pollutant than its absence. According to the results, the internal porous and film diffusions were both effective in the sorption process. The porous and film diffusion coefficients of the ground tire rubber were, respectively, about 1.8 and 2.7 times more in the presence of ultrasound than its absence. The effect of ultrasound on the sorption process could be explained by the thermal and non-thermal properties of ultrasonic field.     

Sorption of As(V) from aqueous solution using acid modified carbon black

The sorption performance of a modified carbon black was explored with respect to arsenic removal following batch equilibrium technique. Modification was accomplished by refluxing the commercial carbon black with an acid mixture comprising HNO(3) and H(2)SO(4). Modification resulted in the substantial changes to the inherent properties like surface chemistry and morphology of the commercial carbon black to explore its potential as sorbent. The suspension pH as well as the point of zero charge (pH(pzc)) of the material was found to be highly acidic. The material showed excellent sorption performance for the removal of arsenic from a synthetic aqueous solution. It removed approximately 93% arsenic from a 50mg/L solution at equilibration time. The modified carbon black is capable of removing arsenic in a relatively broad pH range of 3-6, invariably in the acidic region. Both pseudo-first-order and second-order kinetics were applied to search for the best fitted kinetic model to the sorption results. The sorption process is best described by the pseudo-second-order kinetic. It has also been found that intra-particle diffusion is the rate-controlling step for the initial phases of the reaction. Modelling of the equilibrium data with Freundlich and Langmuir isotherms revealed that the correlation coefficient is more satisfactory with the Langmuir model although Freundlich model predicted a good sorption process. The sorption performance has been found to be strongly dependent on the solution pH with a maximum display at pH of 5.0. The temperature has a positive effect on sorption increasing the extent of removal with temperature up to the optimum temperature. The sorption process has been found to be spontaneous and endothermic in nature, and proceeds with the increase in randomness at the solid-solution interface. The spent sorbent was desorbed with various acidic and basic extracting solutions with KOH demonstrating the best result ( approximately 85% desorption).     

Adsorption of nickel and copper onto natural iron oxide-coated sand from aqueous solutions: study in single and binary systems

Natural iron oxide-coated sand (NCS), extracted from the iron ore located in North-West of Tunisia, was employed to investigate its capacity to remove copper and nickel from aqueous solutions. The aim of this work was to characterize the considered sorbent (NCS) and to assess the possibility of removing nickel and copper from aqueous solutions by this sorbent. The effects of agitation time, pH, initial metal ion concentration and temperature on the removal of these metals were studied. In order to study the sorption isotherm, two equilibrium models, the Freundlich and Langmuir isotherms, were analyzed. The effect of solution pH on the adsorption onto NCS was studied in the pH range from 2 to 7 and 2 to 9 for copper and nickel respectively. The adsorption was endothermic and the computation of the parameters, DeltaH degrees, DeltaS degrees and DeltaG degrees, indicated that the interactions were thermodynamically favourable. Experiments with Cu and Ni adsorption measured together showed that Cu severely interfered with Ni adsorption to the NCS and vice versa under the conditions of the two coexisted ions adsorption.     

Sorption equilibrium of mercury onto ground-up tree fern

The sorption behavior of mercury at different temperatures onto ground-up tree fern was investigated. The experimental results were fitted to two two-parameter isotherms, the Freundlich and Langmuir isotherms, as well as to two three-parameter isotherms, the Redlich-Peterson and Sips isotherms to obtain the characteristic parameters of each model. A comparison of best-fitting was performed using the coefficient of determination and Chi-square test. Both the Langmuir and Redlich-Peterson isotherms were found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of mercury ions onto ground-up tree fern was 26.5 mg/g at 298 K. It was noted that an increase in temperature resulted in a higher mercury ion loading per unit weight of the tree fern. In addition, various thermodynamic parameters, such as DeltaG degrees, DeltaH degrees, and DeltaS degrees, were calculated and compared with the sorption of mercury by other sorbents.     

Application of maize tassel for the removal of Pb, Se, Sr, U and V from borehole water contaminated with mine wastewater in the presence of alkaline metals

In this study, the removal of Pb(II) from aqueous solutions by tassel powder was studied and optimised. Batch experiments were conducted on simulated solutions using tassel powder adsorbent and the effects of contact time, pH and concentration on the extent of Pb (II) removal was studied. Equilibrium and kinetic models for Pb(II) sorption were developed by considering the effect of contact time and concentration at optimum pH 4 and fixed temperature(25 degrees C). The Freundlich model was found to describe the sorption energetics of Pb(II) on tassel more fully than the Langmuir. A maximum Pb(II) loading capacity of 333.3mg/g on tassel was obtained. The adsorption process could be well described by both the Langmuir and Freundlich isotherms with R(2) values of 0.957 and 0.972, respectively. The kinetic parameters were obtained by fitting data from the effect of contact time on adsorption capacity into the pseudo-first, pseudo-second-order and intra-particle diffusion equations. The kinetics of Pb(II) on tassel surface was well defined using linearity coefficients (R(2)) by pseudo-second-order (0.999), followed by pseudo-first-order (0.795) and lastly intra-particle diffusion (0.6056), respectively. The developed method was then applied to environmental samples taken from borehole waters contaminated with mine wastewater. The removal of Pb (ND-100%), Se (100%), Sr (5.41-59.0%), U (100%) and V (46.1-100%) was attained using tassel. The uptake of the metals from environmental samples was dependent on pH, ionic strength and levels of other competing species.     

Biosorption of Cr(III) ions by eggshells

The paper presents results of studies carried out on sorption of Cr(III) ions from aqueous solutions by eggshells as a low-cost sorbent. It was found that crushed eggshells possess relatively high sorption capacity, when comparing with other sorbents, that was evaluated as 21-160 mg/g. The effect of process parameters: pH, temperature, initial concentration of Cr(III) ions on the process kinetics was studied. It was found that the equilibrium of the process was reached after 60 min. Also equilibrium studies were performed: the effect of sorbent concentration and equilibrium Cr(III) concentration was studied. The maximum experimentally determined sorption capacity 160 mg/g was obtained at low sorbent concentration at 20 degrees C and pH 5. It was found that sorption capacity increased with the increase of Cr(III) concentration, temperature and sorbent concentration. Mathematical models describing kinetics and equilibrium of sorption were proposed. The process kinetics was described with pseudo-second-order pattern and equilibrium was described with Langmuir-type equation, and the influence of sorbate concentration, with an empirical dependence. The models were positively verified. Eggshells were able to remove the concentration of Cr(III) ions below the acceptable level, i.e. at 40 degrees C, at the initial concentration of metal ions 100 mg/kg, at sorbent concentration 15 g/l.     

Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon

The adsorption characteristics of 2,4,6-trichlorophenol (TCP) on activated carbon prepared from oil palm empty fruit bunch (EFB) were evaluated. The effects of TCP initial concentration, agitation time, solution pH and temperature on TCP adsorption were investigated. TCP adsorption uptake was found to increase with increase in initial concentration, agitation time and solution temperature whereas adsorption of TCP was more favourable at acidic pH. The adsorption equilibrium data were best represented by the Freundlich and Redlich-Peterson isotherms. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The mechanism of the adsorption process was determined from the intraparticle diffusion model. Boyd plot revealed that the adsorption of TCP on the activated carbon was mainly governed by particle diffusion. Thermodynamic parameters such as standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), standard free energy (DeltaG degrees ) and activation energy were determined. The regeneration efficiency of the spent activated carbon was high, with TCP desorption of 99.6%.     

Screening of new sorbent materials for cadmium removal from aqueous solutions

This study compares the abilities of four low-cost materials: peels of peas, broad bean, and medlar, respectively and fig leaves, to remove cadmium from aqueous solutions. Kinetic data and equilibrium sorption isotherms were measured in batch conditions. Kinetics of cadmium sorption was contact time, initial cadmium concentration and sorbent type dependent. The results also showed that the kinetics of cadmium sorption were described by a pseudo second-order rate model. The cadmium uptake of these low-cost materials was quantitatively evaluated using sorption isotherms. Results indicated that Langmuir model gave an acceptable fit to the experimental data. A high cadmium sorption was observed by these materials. The broad bean peel was the most effective to remove cadmium ions with a maximum sorption capacity about 147.71 mg/g followed by peas peel (118.91 mg/g), fig leaves (103.09 mg/g), and medlar peel (98.14 mg/g).     

Equilibrium and kinetic studies of methyl violet sorption by agricultural waste

In this work, sunflower (Helianthus annuus L.) seed hull (SSH), an agricultural waste, was evaluated for its ability to remove methyl violet (MV) from aqueous solutions. Sorption isotherm of MV onto the SSH was determined at 30 degrees C with the initial concentrations of MV in the range of 25-300 mg/L. The equilibrium data were analyzed using the Langmuir, Freundlich and Temkin isotherm models. The equilibrium process was described well by the Freundlich isotherm model. The maximum SSH sorption capacity was found to be 92.59 mg/L at 30 degrees C. The kinetic data were studied in terms of the pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models. The pseudo-second-order model best described the sorption process. A single-stage batch-adsorber design of the adsorption of MV onto SSH was studied based on the Freundlich isotherm equation. The results indicated that sunflower seed hull was an attractive candidate for removing methyl violet from aqueous solution.     

Sorption characteristics of Cu(II) ions onto silica gel-immobilized calix[4]arene polymer in aqueous solutions: batch and column studies

In the present study, Cu(II) removal from aqueous solutions by sorption was investigated. Aminopropyl silica gel-immobilized calix[4]arene polymer (APSIC[4]P) was used in sorption as sorbent. During the experimental part of this study, the effect of parameters, such as pH, initial Cu(II) concentration, temperature on Cu(II) removal was observed. In addition, sorption isotherm studies and column studies were made. Maximum Cu(II) removal was obtained at pH 6 and 25 degrees C. In the isotherm studies, Langmuir and Freundlich isotherm models were applied and it was determined that the experimental data confirmed to Langmuir isotherm model. Batch sorption capacity (q0) was calculated as 5.08 mg/g. The capacity value for column study was obtained by graphical integration as 1.14 mg/g. The Thomas and the Yoon-Nelson models were applied to experimental data to predict the breakthrough curves and to determine the characteristics parameters of the column useful for process design.     

On the zinc sorption by the Serbian natural clinoptilolite and the disinfecting ability and phosphate affinity of the exhausted sorbent

The Serbian natural zeolite is moderately effective in removing the zinc(II) ions from aqueous solutions. At 298 K the sorption capacity varies from 13 to 26% for the initial Zn(II) solution concentration of 100 and 600 mg Zndm(-3), respectively. The sorption isotherm at 298-338 K is best represented by the Langmuir model and the sorption kinetics by the pseudo-second-order model. The sorption involves a combination of film diffusion, intra-particle diffusion, and a chemical cation-exchange between the Na(+) ions of clinoptilolite and Zn(2+) ions. The sorption was found to be endothermic and spontaneous in the 298-338 K range. The exhausted sorbent can remove phosphate ions and it exhibits an excellent antibacterial activity towards Acinetobacter junii. By dehydration at about 500 °C it transforms to a ZnO-containing product featuring nano-sized wurtzite ZnO particles widespread over the clinoptilolite surface.     

Ion-exchange iron sorption by carbon nanotubes and nanofibers

We have studied room-temperature equilibrium in systems containing an aqueous Fe(II) or Fe(III) salt solution and carbon nanofibers or carbon nanotubes with various contents of functional groups. The sorption capacity of the sorbents has been determined as a function of contact time, sorbent weight to solution volume ratio, salt concentrations in solution, solution pH, and sorbent “solubility” (degree of functionalization). Equilibrium data have been described by the Langmuir and Freundlich equations, and the sorption kinetics have been represented by a first-order or pseudo-second-order equation. We have demonstrated that the sorption process can be accelerated by physical activation of the system.     

Heavy metals binding properties of esterified lemon

Sorption of Cd(2+), Cr(3+), Cu(2+), Ni(2+), Pb(2+) and Zn(2+) onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni(2+)>Cd(2+)>Cu(2+)>Pb(2+)>Zn(2+)>Cr(3+). The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb(2+)>Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Cr(3+). The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol(-1) for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The DeltaG degrees and DeltaH degrees values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low DeltaH degrees values revealed that physical adsorption significantly contributed to the mechanism.