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.     

Sorption of Cd(II) onto kaolin as a soil component and desorption of Cd(II) from kaolin using rhamnolipid biosurfactant

In this study, a microbial surfactant, rhamnolipid, was investigated for its potential to enhance recovery of Cd(II) from kaolin, a representative soil component. The study was divided into two parts. In the first part, the sorption of Cd(II) ions to kaolin was investigated as a function of pH and initial Cd(II) ion concentration. Kaolin was also shown to be a good sorbent for treatment of Cd(II) ions from waste waters. The equilibrium sorption capacity for Cd(II) ions was measured and extrapolated using the Langmuir, Freundlich, Redlich-Peterson, and Koble-Corrigan sorption models. The best correlation between experimental and model predicted equilibrium uptake was obtained using the Kolbe-Corrigan sorption model. The values of parameters of the Koble-Corrigan model were determined as A=11.13 (mmol(1-b)kg(-1)L(b)); B=0.39 (L(b)mmol(-b)); b=0.48. In the second part, the desorption of Cd(II) from kaolin was investigated as a function of pH, rhamnolipid concentration, and the amount of sorbed Cd(II) by kaolin. The highest Cd(II) desorption efficiency by rhamnolipid biosurfactant from kaolin was obtained at pH 6.8, at an initial Cd(II) ion concentration of 0.87 mM (4.42 mmol Cd(II)/kg kaolin) and at a rhamnolipid concentration of 80 mM and found to be 71.9% of the sorbed Cd(II).     

Synthesis of polyimide from 5,5'-bis(bromomethyl)-2,2':6',2'-terpyridine and investigation of the polymer sorption behavior towards some metal ions

The synthesis of a terpyridine-based polyimide sorbent for solid-phase extraction (SPE) of some metal ions is described. For this purpose, 5,5'-bis(bromomethyl)-2,2':6',2'-terpyridine was polymerized with the corresponding diimide derivatives of dianhyrides to give polyimides utilizing terpyridine unit in the main chain. This polymer was used for its extraction capabilities for Pb(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II), at different pH. Under competitive conditions and at pH<0.6, the selectivity order was Pb approximately Cd approximately Zn. Enhanced selectivity was observed at pH 3.5, the order was Cu>Ni>Zn approximately Cd approximately Pb. Quantitative recoveries>97% were observed for all metals in case loading was stopped before reaching the point of breakthrough. As the synthesized polyimides are insoluble in water, solid-liquid extractions have been carried out and the resins sorption for mixture of basic and/or precious metals have been studied under various experimental conditions (reaction time and hydrochloric acid concentration).     

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.     

Effect of EDTA on divalent metal adsorption onto grape stalk and exhausted coffee wastes

In the present work, two industrial vegetable wastes, grape stalk, coming from a wine producer, and exhausted coffee, coming from a soluble coffee manufacturer, have been investigated for the removal of Cu(II) and Ni(II) from aqueous solutions in presence and in absence of the strongly complexing agent EDTA. Effects of pH and metal-EDTA molar ratio, kinetics as a function of sorbent concentration, and sorption equilibrium for both metals onto both sorbents were evaluated in batch experiments. Metal uptake was dependent of pH, reaching a maximum from pH around 5.5. EDTA was found to dramatically reduce metal adsorption, reaching total uptake inhibition for both metals onto both sorbents at equimolar metal:ligand concentrations. Kinetic results were successfully modelled by means of the pseudo second order model. Langmuir and Freundlich models were used to describe the sorption equilibrium data. Grape stalk showed the best performance for Cu(II) and Ni(II) removal in presence and in absence of EDTA, despite exhausted coffee appears as less sensitive to the presence of complexing agent. The performance of Cu(II) and Ni(II) sorption onto grape stalk in a continuous flow process was evaluated. In solutions containing EDTA, an initial metal concentration in the outlet flow corresponding to the complexed metal fraction was observed from the beginning of the process. A high metal recovery yield (>97%) was achieved by feeding the metal-loaded column with 0.05 M HCl.     

Selective removal of Pb(II), Cd(II), and Zn(II) ions from waters by an inorganic exchanger Zr(HPO3S)2

The present study reported synthesis of a new inorganic exchanger, i.e., zirconium hydrogen monothiophosphate [Zr(HPO₃S)₂, denoted ZrPS] and its selective sorption toward Pb(II), Cd(II) and Zn(II) ions. ZrPS sorption toward all the three metals is dependent upon solution pH due to the ion-exchange nature. As compared to another inorganic exchanger zirconium phosphate [Zr(HPO₄)₂, denoted ZrP], ZrPS exhibits highly selective sorption toward these toxic metals from the background of calcium ions at great levels. Such sorption preference is mainly attributed to the presence of –SH group in ZrPS, as further demonstrated by FT-IR analysis and XPS study. Moreover, ZrPS particles preloaded with heavy metals could be efficiently regenerated with 6 M HCl for multiple use without any noticeable capacity loss. All the experimental results indicated that ZrPS is a promising sorbent for enhanced heavy metals removal from contaminated water.     

A comparative study for the sorption of Cd(II) by soils with different clay contents and mineralogy and the recovery of Cd(II) using rhamnolipid biosurfactant

Recent research has demonstrated that biosurfactants, especially rhamnolipids, can enhance recovery of soil-bound metals. To propose the success of remediation process of soils by rhamnolipids, both sorption and desorption characteristics of soils having different clay mineralogy should be known exactly. To assess sorption of Cd(II), batch equilibrium experiments were performed using three soils characterized with different proportions of clay minerals from Eski?ehir region of Turkey. Soil pH, initial metal concentration and clay mineralogy affected the sorption process. For comparisons between soils, the sorption process was characterized using the Langmuir, Freundlich, Redlich-Peterson, Koble-Corrigan sorption models. The Freundlich model showed the best fit for the Cd(II) sorption data by the soils, while the Langmuir-type models generally failed to describe the sorption data. Soils with higher clay content characterized by having smectite as a dominant component had the greatest sorption capacity and intensity estimated by the KF and n parameters of the Freundlich model. The soil C has the highest sorption efficiency of 83.9%, followed by soils B and A with sorption efficiencies of 76.7% and 57.9%, respectively. After the soils were loaded by different doses of Cd(II), batch washing experiments were used to evaluate the feasibility of using rhamnolipid biosurfactant for the recovery of Cd(II) from the soils. The Cd(II) recovery of the soils were investigated as a function of pH, amount of Cd(II) loaded to the soils, and rhamnolipid concentration. Cd(II) recovery efficiencies from the soils using rhamnolipid biosurfactant decreased in the order of soil A>soil B>soil C. This order was the reverse of the Cd(II) sorption efficiency order on the soils. When 80 mM rhamnolipid was used, the recovery efficiencies of Cd(II) from the soils A, B, and C was found to be 52.9%, 47.7%, 45.5% of the sorbed Cd(II), respectively. Rhamnolipid sorption capacity of the soils in the presence of Cd(II) ions decreased in the order of soil A>soil B>soil C.     

Pb(II) and Cd(II) biosorption on Chondracanthus chamissoi (a red alga)

Chondracanthus chamissoi is an efficient biosorbent for Pb(II) and Cd(II). The sorption efficiency increases with pH and reaches an optimum around pH 4. Maximum sorption capacity reaches 1.37 mmol P bg(-1) and 0.76 mmol C dg(-1). The biosorbent has a marked preference for Pb(II) over Cd(II), though insufficient for separating these metals by a simple sorption step. The uptake kinetics is controlled by the resistance to intraparticle diffusion with a limited impact of particle size, metal concentration and sorbent dosage. In the present case, grinding the biomass does not improve sorption capacity and uptake kinetics. The sorption of metal ions is probably due to their interaction with carrageenan (one of the main constituents of the biosorbent): sulfonic groups (on the sulfated polysaccharide) have a higher affinity for Pb(II) than for Cd(II) according to HSAB rules.     

Immobilization of aqueous Hg(II) by mackinawite (FeS)

As one of the major constituents of acid volatile sulfide (AVS) in anoxic sediments, mackinawite (FeS) is known for its ability to scavenge trace metals. The interaction between aqueous Hg(II) (added as HgCl(2)) and synthetic FeS was studied via batch sorption experiments conducted under anaerobic conditions. Due to the release of H(+) during formation of hydrolyzed Hg(II) species which is more reactive than Hg(2+) in surface adsorption, the equilibrium pH decreased with the increase in Hg(II)/FeS molar ratio. Counteracting the loss of FeS solids at lower pH, the maximum capacity for FeS to remove aqueous Hg(II) was approximately 0.75 mol Hg(II) (mol FeS)(-1). The comparison of X-ray power diffraction (XRPD) patterns of synthetic FeS sorbent before and after sorption showed that the major products formed from the interaction between FeS and the aqueous Hg(II) were metacinnabar, cinnabar, and mercury iron sulfides. With the addition of FeS at 0.4 g L(-1) to a 1 mM Hg(II) solution with an initial pH of 5.6, Fe(2+) release was approximately 0.77 mol Fe(2+) per mol Hg(II) removed, suggesting that 77% of Hg(II) was removed via precipitation reaction under these conditions, with 23% of Hg(II) removed by adsorption. Aeration does not cause significant release of Hg(II) into the water phase.     

FTIR spectrophotometry, kinetics and adsorption isotherms modeling, ion exchange, and EDX analysis for understanding the mechanism of Cd(2+) and Pb(2+) removal by mango peel waste

Mango peel waste (MPW) was evaluated as a new sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution. The maximum sorption capacity of Cd(2+) and Pb(2+) was found to be 68.92 and 99.05mgg(-1), respectively. The kinetics of sorption of both metals was fast, reaching at equilibrium in 60min. Sorption kinetics and equilibria followed pseudo-second order and Langmuir adsorption isotherm models. FTIR analysis revealed that carboxyl and hydroxyl functional groups were mainly responsible for the sorption of Cd(2+) and Pb(2+). Chemical modification of MPW for blocking of carboxyl and hydroxyl groups showed that 72.46% and 76.26% removal of Cd(2+) and Pb(2+), respectively, was due to the involvement of carboxylic group, whereas 26.64% and 23.74% was due to the hydroxyl group. EDX analysis of MPW before and after metal sorption and release of cations (Ca(2+), Mg(2+), Na(+), K(+)) and proton H(+) from MPW with the corresponding uptake of Cd(2+) and Pb(2+) revealed that the main mechanism of sorption was ion exchange. The regeneration experiments showed that the MPW could be reused for five cycles without significant loss in its initial sorption capacity. The study points to the potential of new use of MPW as an effective sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution.     

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.     

Sorption of selenium(IV) and selenium(VI) onto natural iron oxides: goethite and hematite

Selenium is a toxic element with a relatively high mobility in the natural waters. Iron oxy-hydroxides might play an important role in the migration of this element as well as on its removal from contaminated water. In this work we study the interaction of Se(IV), and Se(VI) with natural iron oxides hematite and goethite through two series of batch experiments at room temperature. In the first series, sorption as a function of initial selenium concentration is studied and the results have been fitted with Langmuir isotherms. In a second series of experiments, sorption is studied as a function of pH, being the main trend an increase of the sorption at acidic pH. The variation of the sorption with pH has been modelled with a triple layer surface complexation model and using the FITEQL program. The experimental data have been modelled considering for the Se(IV) the formation of the FeOSe(O)O(-) complex onto the hematite surface, and a mixture of FeOSe(O)O(-), and FeOSe(O)OH onto the goethite surface. For Se(VI) the surface complex considered is FeOH(2)(+)-SeO(4)(2-) on both goethite and hematite.     

Bromine pretreated chitosan for adsorption of lead (II) from water

Pollution by heavy metals like lead (II) is responsible for health hazards and environmental degradation. Adsorption is a prevalent method applied for removal of heavy metal pollutants from water. This study explored adsorption performances of 30% bromine pretreated chitosan for lead (II) abatement from water. Bromine pretreatment alters porosity and specific surface area of chitosan by means of physicochemical interaction with cationic sites of chitosan skeleton, besides imparting anionic alteration at amino linkages of chitosan, to remove lead (II) by chemical interactions on superfluous active sites as characterized by FTIR, SEM, DTA and elemental analysis. Lead adsorptions were studied in batch mode by varying parameters viz. pH, bromine loading, sorbent dosage, initial lead concentration, contact time and temperature. The adsorption equilibrium data was well fitted to Freundlich isotherm and maximum sorption capacity of 30% bromine pretreated chitosan sorbent was 1·755 g/kg with 85–90% lead removal efficiency. Though cost and applicability of sorbent is unproven, yet contrast to raw chitosan derivatives, activated carbons and some resins, 30% bromine pretreated chitosan endow benign and efficient lead abatement technique.     

Pb(II) and Cd(II) removal from aqueous solutions by olive cake

The removal of heavy metals from wastewater using olive cake as an adsorbent was investigated. The effect of the contact time, pH, temperature, and concentration of adsorbate on adsorption performance of olive cake for Pb(II) and Cd(II) ions were examined by batch method. Adsorption of Pb(II) and Cd(II) in aqueous solution onto olive cake was studied in single component. After establishing the optimum conditions, elution of these ions from the adsorbent surface was also examined. The optimum sorption conditions were determined for two elements. Maximum desorption of the Pb(II) and Cd(II) ions were found to be 95.92 and 53.97% by 0.5M HNO(3) and 0.2M HCl, respectively. The morphological analysis of the olive cake was performed by the scanning electron microscopy (SEM).     

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.     

Sorption of selenium(IV) and selenium(VI) to mackinawite (FeS): effect of contact time, extent of removal, sorption envelopes

Higher concentrations (127, 253 μM) of Se(IV) at pH 8 were completely removed by 0.5 g/L FeS within 120 min. Removal of Se(VI) by FeS at pH 8 was less extensive than removal of Se(IV). Only 10% of the Se(VI) was removed by 1 g/L FeS within 1h. Removal patterns for Se by FeS depend on pH. Removal patterns of Se at pH 7 and pH 8 were best described by BET models for Se(IV) and Freundlich models for Se(VI), while removal patterns of both at pH 9 and 10 were best described by Langmuir models. Sulfate at 1 and 10 mM had negligible effect on removal of Se(IV) by FeS, while sulfate had little effect on removal of Se(VI) by FeS, but there was some indication that sulfate promoted removal of Se(VI) at intermediate concentrations. The test for the effect of pH on sorption of Se(IV) by FeS showed nearly complete removal at all but the high initial pH. When pH was raised back to initial value, greater removals were observed than initially. Mixtures of Se(VI) and FeS showed moderate removal at low pH, a minimum removal near pH 6 and nearly complete removal at high pH. Very high stability was observed with negligible release as pH decreased.     

Removal of Cd(II) and Pb(II) ions, from aqueous solutions, by adsorption onto sawdust of Pinus sylvestris

Fixation of heavy metal ions (Cd(II) and Pb(II)) onto sawdust of Pinus sylvestris is presented in this paper. Batch experiments were conducted to study the main parameters such as adsorbent concentration, initial adsorbate concentration, contact time, kinetic, pH solution, and stirring velocity on the sorption of Cd(II) and Pb(II) by sawdust of P. sylvestris. Kinetic aspects are studied in order to develop a model which can describe the process of adsorption on sawdust. The equilibrium of a solution between liquid and solid phases is described by Langmuir model. Scanning electronic microscopy (SEM) coupled with energy dispersive X-ray analysis (EDAX) and X-ray photoelectron spectroscopy (XPS) shows that the process is controlled by a porous diffusion with ion-exchange. The capacity of the metal ions to bind onto the biomass was 96% for Cd(II), and 98% for Pb(II). The sorption followed a pseudo-second-order kinetics. The adsorption of these heavy metals ions increased with the pH and reached a maximum at a 5.5 value. From these results, it can be concluded that the sawdust of P. sylvestris could be a good adsorbent for the metal ions coming from aqueous solutions. Moreover, this material could also be used for purification of water before rejection into the natural environment.     

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.     

Evaluation of iron-based hybrid materials for heavy metal ions removal

The article presents in detail the results of the sorption of heavy metal ions such as Cu(II), Zn(II), Cd(II), and Zn(II) in the presence of ethylenediamine-N,N′-disuccinic acid as well as chromium(VI) on Purolite Arsen X^np and Lewatit FO36. Factors affecting the sorption equilibrium (sorbent dose, contact time, temperature, pH, and the presence of interfering ions) were studied. To compare the surface morphologies of the studied ion exchangers, scans using atomic force microscope were also recorded, and attenuated total reflectance infrared spectroscopy was applied to establish the adsorption mechanism. The main parameters affecting sorption are initial concentration of the solution, pH, and phase contact time. Temperature has only a slight influence. The kinetic data were fitted using the pseudo-first-order and pseudo-second-order models. In the case of Cr(VI) adsorption, the equilibriums on Purolite Arsen X^np and Lewatit FO36 were established within 60 min, in the case of Cu(II) and Zn(II) within 30–40 min and for Cd(II) and Pb(II) even less than 30 min. Moreover, it was found that the effectiveness of adsorption in the case of Cr(VI), Cu(II), Zn(II), Cd(II), and Pb(II) on Purolite ArsenX^np was higher than that on Lewatit FO36.