Kinetic and isotherm studies of cadmium adsorption on manganese nodule residue

The adsorption equilibrium and kinetics studies of cadmium (Cd) ions from aqueous solutions on manganese nodule residue were carried out by considering the influence of various parameters, such as contact time, solution pH and initial metal concentration in solution, temperature and adsorbent quantity. The adsorption of Cd increased with an increase in the concentrations of this metal in solution. Presence of manganese and iron content in manganese nodule residue (MNR) played a significant role in Cd(II) ions removal. The linear forms of the Langmuir and Freundlich equations were utilized for experiments with metal concentrations of 200 mg/L for Cd(II) as functions of solution pH (2.0-6.0). First-order rate equation and pseudo second-order rate equations were applied to study adsorption kinetics. Mass transfer study was also done to know the reaction rate. Thermodynamic parameters, such as standard Gibb's free energy (deltaG(o)), standard enthalpy (deltaH(o)) and standard entropy (deltaS(o)), were also evaluated by Van't Hoff equation. Thus, adsorption of Cd on this adsorbent was found to be spontaneous and exothermic thermodynamically. The adsorption capacity for Cd was found to be 19.8 mg/g of MNR. Under the optimised conditions, cadmium level was brought down from 100 mg/L to Cd less than detection limits and from 200 to 2 mg/L. Thus, the wastewater after cadmium removal could be safely disposed off on to land or sewage. Finally, the metal loaded adsorbent was subjected to desorption using different mineral acids and leaching by using toxicity characteristic leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP) tests for its further treatment or its safe disposal.     

Removal of dieldrin from aqueous solution by a novel triolein-embedded composite adsorbent

In this study, a novel triolein-embedded activated carbon composite adsorbent (CA-T) was prepared and applied for the adsorption and removal of dieldrin from aqueous systems. Experiments were carried out to investigate the adsorption behavior of dieldrin on CA-T, including adsorption isotherms, adsorption kinetics, the influence of initial concentration, temperature, shaking speed, pH and the addition of humic acid (HA) on adsorption. The adsorption isotherms accorded with Freundlich equation. Three kinetics models, including pseudo-first-order, pseudo-second-order and intraparticle diffusion models, were used to fit the experimental data. By comparing the correlation coefficients, it was found that both pseudo-second-order and intraparticle diffusion models were used to well describe the adsorption of dieldrin on CA-T. The addition of HA had little effect on dieldrin adsorption by CA-T. Results indicated that CA-T appeared to be a promising adsorbent for removing lipophilic dieldrin in trace amount, which was advantageous over pure granular activated carbon (GAC). The adsorption rate increased with increasing shaking speed, initial concentration and temperature, and remained almost unchanged in the pH range of 4-8. Thermodynamic calculations indicated that the adsorption reaction was spontaneous with a high affinity and the adsorption was an endothermic reaction.     

Insight into kinetics and thermodynamics properties of multicomponent lead(II), cadmium(II) and manganese(II) adsorption onto Dijah-Monkin bentonite clay

Multicomponent adsorption of lead(II), cadmium(II) and manganese(II) by Nigerian Dijah-Monkin bentonite clay was investigated. The clay samples were characterized for elemental composition, cation exchange capacity and textural properties. Natural bentonite exhibits cation exchange capacity of 47.7?meq/100?g and specific surface area of 23.5?m²/g. Manganese(II) displays higher values of rate constant than lead(II) in multimetals adsorption. However, lead(II) is favorably adsorbed onto bentonite adsorbents at different concentrations studied. The multimetals adsorption onto bentonite clay samples is site selective and site specific. The pseudo-second-order kinetics model gave a better fit to the adsorption data, suggesting ion exchange and/or complex formation. The adsorption mechanism could be described by intraparticle diffusion with some restriction of metals diffusion due to film or boundary layer. Also, the multicomponent adsorption is endothermic and becomes more spontaneous as temperature increased from 303 to 338?K. Nigerian bentonite clay in its natural form is a promising adsorbent for multimetals removal in aqueous solution.     

An investigation into the sorption of heavy metals from wastewaters by polyacrylamide-grafted iron(III) oxide

An adsorbent for heavy metals was synthesized by introducing carboxylate functional group into polyacrylamide-grafted hydrous iron(III) oxide. The product exhibits a very high adsorption potential for Pb(II), Hg(II) and Cd(II). The removal of metal ions by adsorption on adsorbent has been found to be contact time, concentration, pH and temperature dependent. The process follows first-order reversible kinetics. The intraparticle diffusion of metal ions through pores in the adsorbent was shown to be the main rate-limiting step. The optimum pH range for the removal of metal ions was found to be 5.0-6.0. The thermodynamic parameters such as free energy change, enthalpy change and entropy change have been calculated to predict the nature of adsorption. The adsorption data were fitted using the Langmuir equation and maximum adsorption for each metal was estimated using their respective Langmuir equation constants. The method was applied for synthetic wastewaters. NaCl regeneration has been tried for several cycles with a view to recover the adsorbed metal ions and also to restore the sorbent to its original state.     

Equilibrium,kinetic and thermodynamic studies on the adsorption of 2-nitroaniline onto activated carbon prepared from cotton stalk fibre

Activated carbon prepared from cotton stalk fibre has been utilized as an adsorbent for the removal of 2-nitroaniline from aqueous solutions. The influence of adsorbent mass, contact time and temperature on the adsorption was investigated by conducting a series of batch adsorption experiments. The equilibrium data at different temperatures were fitted with the Langmuir, Freundlich, Tempkin, Redlich–Peterson and Langmuir–Freundlich models. The Langmuir–Freundlich isotherm was found to best describe the experimental data. The adsorption amount increased with increasing temperature. The maximum adsorption capacity of 2-nitroaniline was found to be 383 mg/g for initial 2-nitroaniline concentration of 200 mg/L at 45 °C. The kinetic rates were modeled by using the Lagergren-first-order, pseudo-second-order and Elovich models. The pseudo-second-order model was found to explain the adsorption kinetics most effectively. It was also found that the pore diffusion played an important role in the adsorption, and intraparticle diffusion was the rate-limiting step at the first 30 min for the temperatures of 25, 35 and 45 °C. FTIR and ¹³C NMR study revealed that the amino and isocyanate groups present on the surface of the adsorbent were involved in chemical interaction with 2-nitroaniline. The negative change in free energy (ΔG°) and positive change in enthalpy (ΔH°) indicated that the adsorption was a spontaneous and endothermic process.     

Kinetics and equilibrium studies of malachite green adsorption on rice straw-derived char

In this work, the potential feasibility of rice straw-derived char (RSC) for removal of C.I. Basic Green 4 (malachite green (MG)), a cationic dye from aqueous solution was investigated. The isotherm parameters were estimated by non-linear regression analysis. The equilibrium process was described well by the Langmuir isotherm model. The maximum RSC sorption capacity was found to be 148.74 mg/L at 30 degrees C. The kinetics of MG sorption on RSC followed the Lagergren's pseudo-first-order model and the overall rate of dye uptake was found to be controlled by external mass transfer at the beginning of adsorption, while intraparticle diffusion controlled the overall rate of adsorption at a later stage. The results indicated that RSC was an attractive adsorbent for removing basic dye from aqueous solutions.     

Cu2+, Cd2+ and Pb2+ adsorption from aqueous solutions by pyrite and synthetic iron sulphide

In this study, removal of Cu(2+), Cd(2+) and Pb(2+) from aqueous solutions by adsorption onto pyrite and synthetic iron sulphide (SIS) was investigated as a function of pH, contact time, adsorbent dosage, initial metal concentration and temperature. It has been determined that the adsorption of metal ions onto both adsorbents is pH dependent and the adsorption capacities increase with the increasing temperature. The mechanisms governing the metal removal processes were determined as chemical precipitation at low pH (<3) due to H(2)S generation and adsorption at high pH (in the range of 3-6). The metal adsorption yields also increased with the increasing adsorbent dosage and contact time and reached to equilibrium for both adsorbents. The Cu(2+), Cd(2+) and Pb(2+) adsorption capacities of both adsorbents decrease in the order of Pb(2+)>Cu(2+)>Cd(2+). Except for cadmium, little fraction of copper and lead in the solid adsorption residues was desorbed in acidic media.     

Guava (Psidium guajava) leaf powder: novel adsorbent for removal of methylene blue from aqueous solutions

Batch sorption experiments were carried out using a novel adsorbent, guava leaf powder (GLP), for the removal of methylene blue (MB) from aqueous solutions. Potential of GLP for adsorption of MB from aqueous solution was found to be excellent. Effects of process parameters pH, adsorbent dosage, concentration, particle size and temperature were studied. Temperature-concentration interaction effect on dye uptake was studied and a quadratic model was proposed to predict dye uptake in terms of concentration, time and temperature. The model conforms closely to the experimental data. The model was used to find optimum temperature and concentration that result in maximum dye uptake. Langmuir model represent the experimental data well. Maximum dye uptake was found to be 295mg/g, indicating that GLP can be used as an excellent low-cost adsorbent. Pseudo-first-order, pseudo-second order and intraparticle diffusion models were tested. From experimental data it was found that adsorption of MB onto GLP follow pseudo second order kinetics. External diffusion and intraparticle diffusion play roles in adsorption process. Free energy of adsorption (DeltaG degrees ), enthalpy change (DeltaH degrees ) and entropy change (DeltaS degrees ) were calculated to predict the nature of adsorption. Adsorption in packed bed was also evaluated.     

Characterization of mesoporous rice husk ash (RHA) and adsorption kinetics of metal ions from aqueous solution onto RHA

The present study deals with the characterization of low-cost rice husk ash (RHA) for its various physico-chemical properties and adsorption characteristics of metal ions. The average particle size of RHA was 150.47mum. Proximate analysis showed the presence of high amount of ash in RHA. Bulk density and the heating value of RHA were 104.9kg/m(3) and 9.68MJ/kg, respectively. The pore size distribution results showed that the RHA was predominantly mesoporous. The BET surface area was 36.44m(2)/g. The average pore diameter by BET was 42.603A. The BJH pore area showed 80% of the pore area due to the mesopores. The polar groups present on the RHA surface imparted considerable cation exchange capacity to it. RHA was found to be an effective adsorbent for the removal of cadmium (Cd(II)), nickel (Ni(II)) and zinc (Zn(II)) metal ions from aqueous solutions. The pH(0) approximately 6.0 is found to be the optimum for the removal of individual cations from the aqueous solutions by RHA at an optimum dose of 10kg/m(3). The kinetics of adsorption showed that the metal ions adsorption on RHA is a gradual process with quasi-equilibrium being attained in 5h. The pseudo-second-order kinetics represents the equilibrium data well. The effective diffusion coefficient of the cations onto the RHA is of the order of 10(-13)m(2)/s.     

Adsorption studies on Parthenium hysterophorous weed: removal and recovery of Cd(II) from wastewater

The efficiency of parthenium weed as an adsorbent for removing Cd(II) from water has been studied. Parthenium is found to exhibit substantial adsorption capacity over a wide range of initial Cd(II) ions concentration. Effect of time, temperature, pH and concentration on the adsorption of Cd(II) was investigated by batch process. Pseudo-first-order and Pseudo-second-order models were evaluated. The kinetics data for the adsorption process obeyed second-order rate equation. The equilibrium data could be described well by the Langmuir and Freundlich isotherms. Thermodynamic parameters such as DeltaH degrees , DeltaS degrees and DeltaG degrees were calculated. The adsorption process was found to be endothermic and spontaneous. The maximum adsorption of Cd(II) ions (99.7%) in the pH range 3-4 indicated that material could be effectively utilized for the removal of Cd(II) ions from wastewater. The desorption studies showed 82% recovery of Cd(II) when 0.1 M HCl solution was used as effluent.     

Adsorption of reactive dye from an aqueous solution by chitosan: isotherm, kinetic and thermodynamic analysis

The adsorption of Remazol black 13 (Reactive) dye onto chitosan in aqueous solutions was investigated. Experiments were carried out as function of contact time, initial dye concentration (100-300mg/L), particle size (0.177, 0.384, 1.651mm), pH (6.7-9.0), and temperature (30-60 degrees C). The equilibrium adsorption data of reactive dye on chitosan were analyzed by Langmuir and Freundlich models. The maximum adsorption capacity (qm) has been found to be 91.47-130.0mg/g. The amino group nature of the chitosan provided reasonable dye removal capability. The kinetics of reactive dye adsorption nicely followed the pseudo-first and second-order rate expression which demonstrates that intraparticle diffusion plays a significant role in the adsorption mechanism. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption. The positive value of the enthalpy change (0.212kJ/mol) indicated that the adsorption is endothermic process. The results indicate that chitosan is suitable as adsorbent material for adsorption of reactive dye form aqueous solutions.     

The adsorption of basic dye (Astrazon Blue FGRL) from aqueous solutions onto sepiolite, fly ash and apricot shell activated carbon: kinetic and equilibrium studies

In this study, sepiolite, fly ash and apricot stone activated carbon (ASAC) were used as adsorbents for the investigation of the adsorption kinetics, isotherms and thermodynamic parameters of the basic dye (Astrazon Blue FGRL) from aqueous solutions at various concentrations (100-300 mg/L), adsorbent doses (3-12 g/L) and temperatures (303-323 K). The result showed that the adsorption capacity of the dye increased with increasing initial dye concentration, adsorbent dose and temperature. Three kinetic models, the pseudo-first-order, second-order, intraparticle diffusion, were used to predict the adsorption rate constants. The kinetics of adsorption of the basic dye followed pseudo-second-order kinetics. Equations were developed using the pseudo-second-order model which predicts the amount of the basic dye adsorbed at any contact time, initial dye concentration and adsorbent dose within the given range accurately. The adsorption equilibrium data obeyed Langmuir isotherm. The adsorption capacities (Q0) calculated from the Langmuir isotherm were 181.5 mg/g for ASAC, 155.5 mg/g for sepiolite and 128.2 mg/g for fly ash at 303 K. Thermodynamical parameters were also evaluated for the dye-adsorbent systems and revealed that the adsorption process was endothermic in nature.     

Cadmium adsorption by coal combustion ashes-based sorbents--relationship between sorbent properties and adsorption capacity

A very interesting possibility of coal combustion ashes reutilization is their use as adsorbent materials, that can also take advantage from proper beneficiation techniques. In this work, adsorption of cadmium from aqueous solutions was taken into consideration, with the emphasis on the intertwining among waste properties, beneficiation treatments, properties of the beneficiated materials and adsorption capacity. The characterization of three solid materials used as cadmium sorbents (as-received ash, ash sieved through a 25 μm-size sieve and demineralized ash) was carried out by chemical analysis, infrared spectroscopy, laser granulometry and mercury porosimetry. Cadmium adsorption thermodynamic and kinetic tests were conducted at room temperature, and test solutions were analyzed by atomic absorption spectrophotometry. Maximum specific adsorption capacities resulted in the range 0.5-4.3 mg g(-1). Different existing models were critically considered to find out an interpretation of the controlling mechanism for adsorption kinetics. In particular, it was observed that for lower surface coverage the adsorption rate is governed by a linear driving force while, once surface coverage becomes significant, mechanisms such as the intraparticle micropore diffusion may come into play. Moreover, it was shown that both external fluid-to-particle mass transfer and macropore diffusion hardly affect the adsorption process, which was instead regulated by intraparticle micropore diffusion: characteristic times for this process ranged from 4.1 to 6.1d, and were fully consistent with the experimentally observed equilibrium times. Results were discussed in terms of the relationship among properties of beneficiated materials and cadmium adsorption capacity. Results shed light on interesting correlations among solid properties, cadmium capture rate and maximum cadmium uptake.     

The synthesis,activation and characterization of charcoal powder for the removal of methylene blue and cadmium from wastewater

Charcoal prepared from biomass, wastes of the local forest (tree branches), activated with NaOH solution and with Degussa P25 (TiO₂) was used as adsorbent and photocatalyst for the removal of cadmium cations and methylene blue from wastewater. These materials were characterized by using atomic force microscopy for roughness surface. The energy dispersive X-ray (EDX) spectroscopy and X-ray diffraction (XRD) analysis indicate the existence of nano TiO₂ on the charcoal surface. Additionally, the FT-IR spectroscopy measurements indicate that the alkali treatment develops hydroxyl groups on charcoal surface which could adsorb methylene blue, heavy metals and other pollutants via the synergistic effect. The activities of the charcoal (BC), activated charcoal (BCA) and BCA/TiO₂ mixture (BCA-D) depend on the contact time, adsorbent dosage and pH. The adsorption kinetic data were tested using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. The kinetic studies showed that the adsorption is followed by the pseudo-second-order reaction with regard to the intraparticle diffusion rate kinetics.     

Removal of direct blue-86 from aqueous solution by new activated carbon developed from orange peel

The use of low-cost, easy obtained, high efficiency and eco-friendly adsorbents has been investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater. This study investigates the potential use of activated carbon prepared from orange peel for the removal of direct blue-86 (DB-86) (Direct Fast Turquoise Blue GL) dye from simulated wastewater. The effects of different system variables, adsorbent dosage, initial dye concentration, pH and contact time were studied. The results showed that as the amount of the adsorbent increased, the percentage of dye removal increased accordingly. Optimum pH value for dye adsorption was determined as approximately 2.0. Maximum dye was sequestered within 30min after the beginning for every experiment. The adsorption of direct blue-86 followed a pseudo-second-order rate equation and fit well Langmuir, Tempkin and Dubinin-Radushkevich (D-R) equations better than Freundlich and Redlich-Peterson equations. The maximum removal of direct blue-86 was obtained at pH 2 as 92% for adsorbent dose of 6gL(-1) and 100mgL(-1) initial dye concentration at room temperature. The maximum adsorption capacity obtained from Langmuir equation was 33.78mgg(-1). Furthermore, adsorption kinetics of DB-86 was studied and the rate of adsorption was found to conform to pseudo-second-order kinetics with a good correlation (R2>0.99) with intraparticle diffusion as one of the rate determining steps. Activated carbon developed from orange peel can be attractive options for dye removal from diluted industrial effluents since test reaction made on simulated dyeing wastewater show better removal percentage of DB-86.     

Spent tea leaves: a new non-conventional and low-cost adsorbent for removal of basic dye from aqueous solutions

In the present study, spent tea leaves (STL) were used as a new non-conventional and low-cost adsorbent for the cationic dye (methylene blue) adsorption in a batch process at 30 degrees C. Equilibrium sorption isotherms and kinetics were investigated. The experimental data were analyzed by the Langmuir, Freundlich and Temkin models of adsorption. The adsorption isotherm data were fitted well to the Langmuir isotherm and the monolayer adsorption capacity was found to be 300.052mg/g at 30 degrees C. The kinetic data obtained at different initial concentrations were analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equations. The results revealed that the spent tea leaves, being waste, have the potential to be used as a low-cost adsorbent for the removal of methylene blue from aqueous solutions.     

Azadirachta indica (Neem) leaf powder as a biosorbent for removal of Cd(II) from aqueous medium

A biosorbent, Neem leaf powder (NLP), was prepared from the mature leaves of the Azadirachta indica (Neem) tree by initial cleaning, drying, grinding, washing to remove pigments and redrying. The powder was characterized with respect to specific surface area (21.45 m2g(-1)), surface topography and surface functional groups and the material was used as an adsorbent in a batch process to remove Cd(II) from aqueous medium under conditions of different concentrations, NLP loadings, pH, agitation time and temperature. Adsorption increased from 8.8% at pH 4.0 to 70.0% at pH 7.0 and 93.6% at pH 9.5, the higher values in alkaline medium being due to removal by precipitation. The adsorption was very fast initially and maximum adsorption was observed within 300 min of agitation. The kinetics of the interactions was tested with pseudo first order Lagergren equation (mean k(1)=1.2x10(-2)min(-1)), simple second order kinetics (mean k2=1.34x10(-3) gmg(-1)min(-1)), Elovich equation, liquid film diffusion model (mean k=1.39x10(-2)min(-1)) and intra-particle diffusion mechanism. The adsorption data gave good fits with Langmuir and Freundlich isotherms and yielded Langmuir monolayer capacity of 158mgg(-1) for the NLP and Freundlich adsorption capacity of 18.7 Lg(-1). A 2.0 g of NLP could remove 86% of Cd(II) at 293 K from a solution containing 158.8 mg Cd(II) per litre. The mean values of the thermodynamic parameters, DeltaH, DeltaS and DeltaG, at 293 K were -73.7 kJmol(-1), -0.24 Jmol(-1)K(-1) and -3.63 kJmol(-1), respectively, showing the adsorption process to be thermodynamically favourable. The results have established good potentiality for the Neem leaf powder to be used as a biosorbent for Cd(II).     

Study of removal of Direct Yellow 12 by cadmium oxide nanowires loaded on activated carbon

In this research, cadmium oxide nanowires loaded on activated carbon (CdO-NW-AC) has been synthesized by a simple procedure and characterized by different techniques such as XRD, SEM and UV–vis spectrometry. This new adsorbent has been efficiently utilized for the removal of the Direct Yellow 12 (DY-12) from wastewater. To obtain maximum DY-12 removal efficiency, the influences of variables such as pH, DY-12 concentration, amount of CdO-NW-AC, contact time, and temperature have been examined and optimized in a batch method. Following the variable optimization, the experimental equilibrium data (at different concentration of DY-12) was fitted to conventional isotherm models such as Langmuir, Freundlich and Tempkin. The applicability of each method is based on the R² and error analysis for each model. It was found that the experimental equilibrium data well fitted to the Langmuir isotherm model. The dependency of removal process to time and the experimental data follow second order kinetic model with involvement of intraparticle diffusion model. The negative value of Gibbs's free energy and positive value of adsorption enthalpy show the spontaneous and endothermic nature of adsorption process.     

Amino-functionalized magnetic bacterial cellulose/activated carbon composite for Pb2+ and methyl orange sorption from aqueous solution

A new nanostructured amino-functionalized magnetic bacterial cellulose/activated carbon(BC/AC)composite bioadsorbent(AMBCAC)was prepared for removal of Pb~(2+)and methyl orange(MO)from aqueous solution.The results demonstrated that the equilibrium adsorption capacity(q_e)for Pb~(2+)obviously increases by 2.14 times after introduction of amino groups,the optimum p H for Pb~(2+)and MO adsorption was 5.0 and 3.0,respectively,and the q_eof AMBCAC was 161.78 mg g~(-1)for Pb~(2+)and 83.26 mg g~(-1)for MO under the optimal conditions in this investigation.The kinetics and adsorption isotherm data of the sorption process were well fitted by pseudo-second-order kinetic model and Langmuir isotherm respectively.The thermodynamic results(the Gibbs free energy change G0,the enthalpy change H0,the entropy change S0)implied that the adsorption process of Pb~(2+)and MO was feasible,endothermic and spontaneous in nature.These results support that the AMBCAC composite developed in this work can provide a cheap and efficient way for easy removal of both Pb~(2+)and MO as a promising adsorbent candidate for wastewater treatment.     

Adsorption of malachite green from aqueous solution onto carbon prepared from Arundo donax root

Arundo donax root carbon (ADRC), a new adsorbent, was prepared from Arundo donax root by carbonization. The surface area of the adsorbent was determined 158 m²/g by N₂ adsorption isotherm. Batch adsorption experiments were carried out for the removal of malachite green (MG) from aqueous solution using ADRC as adsorbent. The effects of various parameters such as solution pH (3–10), carbon dose (0.15–1.0 g/100 ml) and initial MG concentration (10–100 mg/l) on the adsorption system were investigated. The effective pH was 5–7 and the optimum adsorbent dose was found to be 0.6 g/100 ml. Equilibrium experimental data at 293, 303 and 313 K were better represented by Langmuir isotherm than Freundlich isotherm using linear and non-linear methods. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated. The negative Gibbs free energy change and the positive enthalpy change indicated the spontaneous and endothermic nature of the adsorption. The adsorption equilibrium time was 180 min. Adsorption kinetics was determined using pseudo-first-order model, pseudo-second-order model and intraparticle diffusion model. The results showed that the adsorption of MG onto ADRC followed pseudo-second-order model.