Pre-treatment processes of Azolla filiculoides to remove Pb(II), Cd(II), Ni(II) and Zn(II) from aqueous solution in the batch and fixed-bed reactors

Intact and treated biomass can remove heavy metals from water and wastewater. This study examined the ability of the activated, semi-intact and inactivated Azolla filiculoides (a small water fern) to remove Pb(2+), Cd(2+), Ni(2+) and Zn(2+) from the aqueous solution. The maximum uptake capacities of these metal ions using the activated Azolla filiculoides by NaOH at pH 10.5 +/- 0.2 and then CaCl(2)/MgCl(2)/NaCl with total concentration of 2 M (2:1:1 mole ratio) in the separate batch reactors were obtained about 271, 111, 71 and 60 mg/g (dry Azolla), respectively. The obtained capacities of maximum adsorption for these kinds of the pre-treated Azolla in the fixed-bed reactors (N(o)) were also very close to the values obtained for the batch reactors (Q(max)). On the other hand, it was shown that HCl, CH(3)OH, C(2)H(5)OH, FeCl(2), SrCl(2), BaCl(2) and AlCl(3) in the pre-treatment processes decreased the ability of Azolla to remove the heavy metals in comparison to the semi-intact Azolla, considerably. The kinetic studies showed that the heavy metals uptake by the activated Azolla was done more rapid than those for the semi-intact Azolla.     

Studying effect of cell wall's carboxyl-carboxylate ratio change of Lemna minor to remove heavy metals from aqueous solution

The pre-treated Lemna minor can remove Hg(II), Cr(III), Cr(VI) and Cu(II) from the aqueous solution. The concentration determination of carboxyl and carboxylate groups and its rule to change the metal ions uptake was done by the curves of the potentiometric titration. It was shown that the removal percent of the heavy metal ions (Co=1.00 mM) increased 25.1, 26.0, 17.2 and 24.1% for these ions, respectively, with increasing the carboxylate from 0.92 to 2.42 mmol/g L. minor and then activating by the activator chloride salts. The removal percent of these ions was decreased 33.1, 27.5, 20.7 and 15.01%, respectively, with increasing the carboxyl from 1.50 to 2.41 mmol/g L. minor, inspite of activating by the chloride salts. The enthalpy change (DeltaH) was -27.43, -25.94, -28.12 and -22.27 kJ/mol and the entropy change (DeltaS) was 81.3, 79.9, 86.1 and 67.7 J/mol K, by activated biomass, respectively. L. minor removed these heavy metals corresponding to pseudo-second-order kinetic model that the activation energy (E(a)) was obtained 18.59, 15.93, 20.36 and 21.12 kJ/mol by the activated and 23.02, 22.27, 23.98 and 24.46 kJ/mol by the reference biomass to uptake Hg(II), Cr(III), Cr(VI) and Cu(II), respectively.     

Characteristics of equilibrium, kinetics studies for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modified magnetic chitosan microspheres

Magnetic chitosan microspheres were prepared and chemically modified with thiourea (TMCS) for adsorption of metal ions. TMCS obtained were investigated by means of X-ray diffraction (XRD), IR, magnetic properties and thermogravimetric analysis (TGA). The adsorption properties of TMCS toward Hg(2+), Cu(2+), and Ni(2+) ions were evaluated. Various factors affecting the uptake behavior such as contact time, temperature, pH and initial concentration of the metal ions were investigated. The kinetics was evaluated utilizing the pseudo-first-order, pseudo-second-order, and the intra-particle diffusion models. The equilibrium data were analyzed using the Langmuir, Freundlich, and Tempkin isotherm models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, evidencing chemical sorption as the rate-limiting step of adsorption mechanism and not involving a mass transfer in solution. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 625.2, 66.7, and 15.3mg/g for Hg(2+), Cu(2+), and Ni(2+) ions, respectively. TMCS displayed higher adsorption capacity for Hg(2+) in all pH ranges studied. The adsorption capacity of the metal ions decreased with increasing temperature. The metal ion-loaded TMCS with were regenerated with an efficiency of greater than 88% using 0.01-0.1M ethylendiamine tetraacetic acid (EDTA).     

Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: kinetic modelling

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75-100 mg L(-1). The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9-39.5, 18.6-32.0 and 32.3-50.4 mg g(-1), respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.     

Heavy metal removal from aqueous solutions by activated phosphate rock

The use of natural adsorbent such as phosphate rock to replace expensive imported synthetic adsorbent is particularly appropriate for developing countries such as Tunisia. In this study, the removal characteristics of lead, cadmium, copper and zinc ions from aqueous solution by activated phosphate rock were investigated under various operating variables like contact time, solution pH, initial metal concentration and temperature. The kinetic and the sorption process of these metal ions were compared for phosphate rock (PR) and activated phosphate rock (APR). To accomplish this objective we have: (a) characterized both (PR) and (APR) using different techniques (XRD, IR) and analyses (EDAX, BET-N(2)); and, (b) qualified and quantified the interaction of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) with these sorbents through batch experiments. Initial uptake of these metal ions increases with time up to 1h for (PR) and 2h for (APR), after then, it reaches equilibrium. The maximum sorption obtained for (PR) and (APR) is between pH 2 and 3 for Pb(2+) and 4 and 6 for Cd(2+), Cu(2+) and Zn(2+). The effect of temperature has been carried out at 10, 20 and 40 degrees C. The data obtained from sorption isotherms of metal ions at different temperatures fit to linear form of Langmuir sorption equation. The heat of sorption (DeltaH degrees), free energy (DeltaG degrees) and change in entropy (DeltaS degrees) were calculated. They show that sorption of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) on (PR) and (APR) an endothermic process. These findings are significant for future using of (APR) for the removal of heavy metal ions from wastewater under realistic competitive conditions in terms of initial heavy metals, concentrations and pH.     

Equilibrium, thermodynamic and kinetic studies for the biosorption of aqueous lead(II), cadmium(II) and nickel(II) ions on Spirulina platensis

The biosorption of lead(II), cadmium(II) and nickel(II) ions from aqueous solution by Spirulina platensis was studied as a function of time, concentration, temperature, repetitive reactivity, and ionic competition. The kinetic results obeyed well the pseudo second-order model. Freundlich, Dubinin Radushkevich and Temkin isotherm models were applied in describing the equilibrium partition of the ions. Freundlich isotherm was applied to describe the design of a single-stage batch sorption system. According to the thermodynamic parameters such as DeltaG degrees, DeltaH degrees and DeltaS degrees calculated, the sorption process was endothermic and largely driven towards the products. Sorption activities in a three metal ion system were studied which indicated that there is a relative selectivity of the biosorbent towards Pb2+ ions. The measurements of the repetitive reusability of S. platensis indicated a large capacity towards the three metal ions.     

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.     

A study on removal characteristics of copper from aqueous solution by sewage sludge and pomace ashes

In the present work, the abilities of sewage sludge and pomace ashes to remove copper (Cu(2+)) ions from aqueous solutions are compared. Batch adsorption experiments were performed in order to evaluate the removal efficiency of these materials. Effect of contact time, solution pH, ash concentration and temperature on the removal of Cu(2+) was investigated. The results of batch equilibrium studies showed that the solution pH was the key factor affecting the adsorption characteristics. In general, the amount of Cu removed increased as the solid concentration and pH increased, and then it remained constant over a wide pH region. The adsorption test of applying sewage sludge and pomace ashes into synthetic wastewater revealed that the adsorption data of these materials for copper 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 copper adsorbed by sewage sludge and pomace ashes were 5.71 and 6.98 mg g(-1), respectively. Experimental results indicated that the adsorption was favorable at higher pH and higher temperature. Values of DeltaG degrees ranging from -4.64 to -5.13 kcal mol(-1) for sewage sludge ash and from -4.97 to -5.53 kcal mol(-1) for pomace ash suggest that the adsorption reaction is a physical process enhanced by the electrostatic effect. The values of DeltaH degrees and DeltaS degrees are, respectively, 4.27 kcal mol(-1) and 30.6 cal K(-1)mol(-1) for sewage sludge ash and 4.33 kcal mol(-1) and 31.3 cal K(-1)mol(-1) for pomace ash. The mechanisms of copper removal by these materials included adsorption and precipitation. The sewage sludge and pomace ashes are shown to be effective adsorbents for this metal.     

Biosorption of Pb(II) and Cd(II) from aqueous solution using green alga (Ulva lactuca) biomass

The biosorption characteristics of Pb(II) and Cd(II) ions from aqueous solution using the green alga (Ulva lactuca) biomass were investigated as a function of pH, biomass dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by U. lactuca biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The monolayer biosorption capacity of U. lactuca biomass for Pb(II) and Cd(II) ions was found to be 34.7mg/g and 29.2mg/g, respectively. From the D-R isotherm model, the mean free energy was calculated as 10.4kJ/mol for Pb(II) biosorption and 9.6kJ/mol for Cd(II) biosorption, indicating that the biosorption of both metal ions was taken place by chemisorption. The calculated thermodynamic parameters (DeltaG degrees , DeltaH degrees and DeltaS degrees ) showed that the biosorption of Pb(II) and Cd(II) ions onto U. lactuca biomass was feasible, spontaneous and exothermic under examined conditions. Experimental data were also tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the biosorption processes of both metal ions followed well pseudo-second-order kinetics.     

Removal of Zn(II), Cu(II), Ni(II), Ag(I) and Cr(VI) present in aqueous solutions by aluminium electrocoagulation

The performance of an electrocoagulation system with aluminium electrodes for removing heavy metal ions (Zn2+, Cu2+, Ni2+, Ag+, Cr2O7(2-)) on laboratory scale was studied systematically. Several parameters - such as initial metal concentration, numbers of metals present, charge loading and current density - and their influence on the electrocoagulation process were investigated. Initial concentrations from 50 to 5000 mg L(-1) Zn, Cu, Ni and Ag did not influence the removal rates, whereas higher initial concentrations caused higher removal rates of Cr. Increasing the current density accelerated the electrocoagulation process but made it less efficient. Zn, Cu and Ni showed similar removal rates indicating a uniform electrochemical behavior. The study gave indications on the removal mechanisms of the investigated metals. Zn, Cu, Ni and Ag ions are hydrolyzed and co-precipitated as hydroxides. Cr(VI) was proposed to be reduced first to Cr(III) at the cathode before precipitating as hydroxide.     

Nitro and Nitroso Metathesis Reactions with Monomeric Zirconium Imido Complexes

The bis(cyclopentadienyl)(tert-butylimido)zir-conium complex 1 undergoes ambient-temperature metathesis reactions with nitro- and nitrosoarenes, providing a rare nonphotochemical synthesis of cis-azoxy and cis-azo compounds, respectively. 2-Nitro-2-methylpropane also undergoes metathesis to give trans-(tert-butylazoxy)-2-methylpropane. This reaction was studied kinetically, and the rate was found to be first order in both 1 and substrate and inversely proportional to the concentration of tetrahydrofuran, with activation parameters DeltaH(double dagger) = 15 +/- 2 kcal mol(-1) and DeltaS(double dagger) = -26 +/- 3 cal mol(-1) K(-1).     

Studies on sorption properties of zeolite derived from Indian fly ash

Indian fly ash has been completely converted to crystalline porous 13X zeolite by NaOH fusion at 600 degrees C followed by hydrothermal treatment at 105 degrees C for 20 h. Obtained materials were characterized by XRD, SEM and surface area measurement. Prepared material was used for the sorption study of different metal ions (Cu(2+), Co(2+) and Ni(2+)) at different pH, temperature. Thermodynamic data (DeltaS, DeltaH and DeltaG) corresponding to different metal ion uptake were evaluated from Langmuir equation. In all the experiment sorption capacity of prepared zeolite was found to be quite high than that of fly ash at acidic pH. However, the uptake selectivity order for both the materials is Cu(2+)>Co(2+)>Ni(2+).     

Sorption profile of Cd(II) ions onto beach sand from aqueous solutions

Sorption of traces of Cd(II) ions onto beach sand is investigated as a function of nature and concentration of electrolyte (10(-4) to 10(-2)M nitric, hydrochloric and perchloric acids, pH 2-10 buffers and deionized water), shaking time 5-40min, shaking speed 50-200strokes/min, dosage of sand (50-1000mg/15cm(3)), concentration of sorbate (1.04x10(-6) to 1.9x10(-4)M) and temperature (293-323K). Maximum sorption of Cd(II) ions (approximately 66%) is achieved from deionized water using 300mg/15cm(3) sand in 20min. The data are successfully tested by Langmuir, Freundlich and Dubinin-Redushkevich (D-R) sorption isotherms. The values for characteristic Langmuir constants Q=13.31+/-0.20micromol/g and of b=(6.56+/-0.53)x10(3)dm(3)/mol, Freundlich constants A=2.23+/-1.16mmol/g and 1/n=0.70+/-0.05 of (D-R) constants beta=-0.005068+/-0.000328kJ(2)/mol(2), X(m)=46.91+/-11.91micromol/g and energy E=9.92+/-0.32kJ/mol have been estimated. Kinetics of sorption has been studied by applying Morris-Weber, Richenberg and Lagergren equations. The sorption follows first order rate equation resulting 0.182+/-0.004min(-1) The thermodynamic parameters DeltaH=32.09+/-2.92kJ/mol, DeltaS=111.0+/-9.5J/molK and DeltaG=-1.68+/-0.02kJ/mol are evaluated. The influence of common ions on the sorption of Cd(II) ions is also examined. Some common ions reduce the sorption while most of the ions have very little effect. It can be concluded that beach sand may be used as an alternative for the expensive synthetic sorbents.     

An adsorption study of Al(III) ions onto chitosan

The adsorption of Al(III) from aqueous solutions onto chitosan was studied in a batch system. The isotherms and the kinetics of adsorption with respect to the initial Al(III) concentration and temperature were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms. Equilibrium data fitted very well to the Langmuir model in the entire concentration range (5-40 mg/L). The negative values of free energy (DeltaG degrees ) and enthalpy (DeltaH degrees ) for the adsorption of Al(III) onto chitosan indicated that the adsorption process is a spontaneous and exothermic one. Two simplified kinetic models, based on pseudo first-order and pseudo second-order equations, were tested to describe the adsorption mechanism. The pseudo second-order kinetic model resulted in an activation energy of 56.4 kJ/mol. It is suggested that the overall rate of Al(III) ion adsorption is likely to be controlled by the chemical process. The values of the enthalpy (DeltaH(#)) and entropy (DeltaS(#)) of activation were 53.7 kJ/mol and -164.4 J/molK, respectively. The free energy of activation (DeltaG(#)) at 30 degrees C was 103.5 kJ/mol.     

Biosorption of copper(II) and lead(II) from aqueous solution by chaff in a fixed-bed column

In this article, the ability of chaff to adsorb heavy metal ions from aqueous solution was investigated in a fixed-bed column. The effect of important parameters, such as the value of pH, the flow rate, the influent concentration of solution and the effect of coexistence ions, was studied. Also the adsorption/desorption recycles of chaff were shown, and the results indicated that chaff could be recycled to remove heavy metal ions. The Thomas model was applied to adsorption of copper and lead at different flow rate and different influent concentration to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The model was found suitable for describing the biosorption process of the dynamic behavior of the chaff column. All the results suggested that chaff as adsorbent to removal heavy metal ions from solution prove efficient, and the rate of biosorption process is speedy. Furthermore, the efficiency of adsorption is high. When the flow rate was 3.6 ml min(-1) and the influent concentration of copper and lead was 14.82 mg l(-1) and 50.12 mg l(-1) respectively, the equilibrium adsorption biomass reached 1.98 mg g(-1) and 6.72 mg g(-1), respectively. The competitive adsorption for lead and copper was studied. Moreover the total adsorbing capability of chaff did not decrease when there were both copper(II) and lead(II) in solution.     

Adsorption characteristics of Cu(II) and Pb(II) onto expanded perlite from aqueous solution

The adsorption characteristics of Cu(II) and Pb(II) onto expanded perlite (EP) from aqueous solution were investigated with respect to the changes in pH of solution, adsorbent dosage, contact time and temperature of solution. For the adsorption of both metal ions, the Langmuir isotherm model fitted to equilibrium data better than the Freundlich isotherm model. Using the Langmuir model equation, the monolayer adsorption capacity of EP was found to be 8.62 and 13.39 mg/g for Cu(II) and Pb(II) ions, respectively. Dubinin-Radushkevich (D-R) isotherm model was also applied to the equilibrium data and the mean free energies of adsorption were found as 10.82 kJ/mol for Cu(II) and 9.12 kJ/mol for Pb(II) indicating that the adsorption of both metal ions onto EP was taken place by chemical ion-exchange. Thermodynamic functions, the change of free energy (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees ) of adsorption were also calculated for each metal ions. These parameters showed that the adsorption of Cu(II) and Pb(II) ions onto EP was feasible, spontaneous and exothermic at 20-50 degrees C. Experimental data were also evaluated in terms of kinetic characteristics of adsorption and it was found that adsorption process for both metal ions followed well pseudo-second-order kinetics.     

Removal of copper(II) from aqueous solution by Jordanian pottery materials

The aim of this work was to assess the possibility of removing some heavy metals from water by a low-cost adsorbent, like Jordanian raw pottery. Five types of raw and modified pottery materials have been investigated. The effects of initial metal concentration, agitation time, pH and temperature on the removal of Cu(II) were studied. A pseudo-first order was used to test the adsorption kinetics. In order to investigate the sorption isotherm, two equilibrium models, the Freundlich and Langmuir isotherms, were analyzed. The effect of solution pH on the adsorption onto pottery was studied in the pH range 1-5. The adsorption was exothermic at ambient temperature and the computation of the parameters, DeltaH, DeltaS and DeltaG, indicated the interactions to be thermodynamically favorable.     

Adsorption of Pb(II) from aqueous solution by Azadirachta indica (Neem) leaf powder

An adsorbent was developed from the mature leaves of the Neem (Azadirachta indica) tree for removing Pb(II) from water. Adsorption was carried out in a batch process with several different concentrations of Pb(II) by varying amount of adsorbent, pH, agitation time and temperature. The uptake of the metal was very fast initially, but gradually slowed down indicating penetration into the interior of the adsorbent particles. Both first-order and second-order kinetics were tested and it was found that the latter gave a better explanation. The experimental data closely followed both Langmuir and Freundlich isotherms. The adsorbent had a considerably high Langmuir monolayer capacity of 300 mg/g. A small amount of the adsorbent (1.2 g/L) could remove as much as 93% of Pb(II) in 300 min from a solution of concentration 100mg/L at 300 K. The adsorption continuously increased in the pH range of 2.0-7.0, beyond which the adsorption could not be carried out due to the precipitation of the metal. The adsorption was exothermic at ambient temperature and the computation of the parameters, DeltaH, DeltaS and DeltaG, indicated the interactions to be thermodynamically favourable.     

Isotherm studies of lead(II), manganese(II), and cadmium(II) adsorption by Nigerian bentonite clay in single and multimetal solutions

This study was aimed at evaluating the isotherm of lead(II), manganese(II), and cadmium(II) adsorption in single and multimetal solutions using Nigerian bentonite. The natural and calcined clays were characterized for specific surface area, surface morphology, elemental composition, and cation exchange capacity (CEC). The adsorption data were analyzed and interpreted using isotherm models. The natural bentonite exhibits a specific surface area of 23.5?m²/g and a CEC value of 47.7 mEq/100?g and displays a higher adsorption capacity of all heavy metals in both single and multimetal solutions than the calcined bentonite. The removal of lead(II) by natural bentonite in single-component system is 0.0448?mmol/g. The order of selectivity is lead(II)?>?cadmium(II)?>?manganese(II). Result also shows that both clays demonstrate a preferable adsorption toward lead(II). Lead(II) adsorption is less affected by the presence of counter cations in multimetal solution. The adsorption of heavy metals onto Dijah-Monkin bentonite is site selective and site specific, and the adsorption data are well presented by the Langmuir model. The CEC could be the primary mechanism for the uptake of heavy metals, and the removal capacity was shown to depend on the ionic radius of metal ions.