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.     

Biosorption of heavy metals and uranium by starfish and Pseudomonas putida

Biosorption of heavy metals and uranium from contaminated wastewaters may represent an innovative purification process. This study investigates the removal ability of unit mass of Pseudomonas putida and starfish for lead, cadmium, and uranium by quantifying the adsorption capacity. The adsorption of heavy metals and uranium by the samples was influenced by pH, and increased with increasing Pb, Cd, and U concentrations. Dead cells adsorbed the largest quantity of all heavy metals than live cells and starfish. The adsorption capacity followed the order: U(VI)>Pb>Cd. The results also suggest that bacterial membrane cells can be used successfully in the treatment of high strength metal-contaminated wastewaters.     

Coal ash conversion into effective adsorbents for removal of heavy metals and dyes from wastewater

Fly ash was modified by hydrothermal treatment using NaOH solutions under various conditions for zeolite synthesis. The XRD patterns are presented. The results indicated that the samples obtained after treatment are much different. The XRD profiles revealed a number of new reflexes, suggesting a phase transformation probably occurred. Both heat treatment and chemical treatment increased the surface area and pore volume. It was found that zeolite P would be formed at the conditions of higher NaOH concentration and temperature. The treated fly ash was tested for adsorption of heavy metal ions and dyes in aqueous solution. It was shown that fly ash and the modified forms could effectively absorb heavy metals and methylene blue but not effectively adsorb rhodamine B. Modifying fly ash with NaOH solution would significantly enhance the adsorption capacity depending on the treatment temperature, time, and base concentration. The adsorption capacity of methylene blue would increases with pH of the dye solution and the sorption capacity of FA-NaOH could reach 5 x 10(-5) mol/g. The adsorption isotherm could be described by the Langmuir and Freundlich isotherm equations. Removal of copper and nickel ions could also be achieved on those treated fly ash. The removal efficiency for copper and nickel ions could be from 30% to 90% depending on the initial concentrations. The increase in adsorption temperature will enhance the adsorption efficiency for both heavy metals. The pseudo second-order kinetics would be better for fitting the dynamic adsorption of Cu and Ni ions.     

Characteristics and heavy metal leaching of ash generated from incineration of automobile shredder residue

Bottom and fly ash collected from automobile shredder residue (ASR) incinerator have been characterized in terms of particle size, compositions, and heavy metal leaching by the standard TCLP method. Two alternative methods were also examined for the treatment of heavy metals in ASR incinerator ash from the aspect of recycling into construction or lightweight aggregate material. It was remarkable that the concentration of Cu was very high compared to common MSWI bottom and fly ash, which was probably originated from copper wires contained in ASR. As a whole, the results of characterization of ASR fly ash were in good agreement with common MSWI fly ash in terms of particle size, pH, and water-soluble compounds. It was clearly found that heavy metals could be removed thoroughly or partly from ASR fly ash through acid washing with dilute HCl solution so that the remaining fly ash could be landfilled or used as construction material. It was also found that the amount of heavy metal leachability of lightweight aggregate pellet prepared with ASR incineration ash could be significantly decreased so that the application of it to lightweight aggregate would be possible without pre-treatment for the removal of heavy metals.     

Comparative study of adsorption properties of Turkish fly ashes. II. The case of chromium (VI) and cadmium (II)

The purpose of the study described in this paper was to compare the removal of Cr(VI) and Cd(II) from an aqueous solution using two different Turkish fly ashes; Afsin-Elbistan and Seyitomer as adsorbents. The influence of four parameters (contact time, solution pH, initial metal concentration in solution and ash quality) on the removal at 20+/-2 degrees C was studied. Fly ashes were found to have a higher adsorption capacity for the adsorption of Cd(II) as compared to Cr(VI) and both Cr(VI) and Cd(II) required an equilibrium time of 2h. The adsorption of Cr(VI) was higher at pH 4.0 for Afsin-Elbistan fly ash (25.46%) and pH 3.0 for Seyitomer fly ash (30.91%) while Cd(II) was adsorbed to a greater extent (98.43% for Afsin-Elbistan fly ash and 65.24% for Seyitomer fly ash) at pH 7.0. The adsorption of Cd(II) increased with an increase in the concentrations of these metals in solution while Cr(VI) adsorption decreased by both fly ashes. The lime (crystalline CaO) content in fly ash seemed to be a significant factor in influencing Cr(VI) and Cd(II) ions removal. The linear forms of the Langmuir and Freundlich equations were utilised for experiments with metal concentrations of 55+/-2mg/l for Cr(VI) and 6+/-0.2mg/l for Cd(II) as functions of solution pH (3.0-8.0). The adsorption of Cr(VI) on both fly ashes was not described by both the Langmuir and Freundlich isotherms while Cd(II) adsorption on both fly ashes satisfied only the Langmuir isotherm model. The adsorption capacities of both fly ashes were nearly three times less than that of activated carbon for the removal of Cr(VI) while Afsin-Elbistan fly ash with high-calcium content was as effective as activated carbon for the removal of Cd(II). Therefore, there are possibilities for use the adsorption of Cd(II) ions onto fly ash with high-calcium content in practical applications in Turkey.     

Use of fly ash,phosphogypsum and red mud as a liner material for the disposal of hazardous zinc leach residue waste

Increasing amounts of residues and waste materials coming from industrial activities in different processes have become an increasingly urgent problem for the future. The release of large quantities of heavy metals into the environment has resulted in a number of environmental problems. The present study investigated the safe disposal of the zinc leach residue waste using industrial residues such as fly ash, phosphogypsum and red mud. In the study, leachability of heavy metals from the zinc leach residue has been evaluated by mine water leaching procedure (MWLP) and toxicity characteristic leaching procedure (TCLP). Zinc removal from leachate was studied using fly ash, phosphogypsum and red mud. The adsorption capacities and adsorption efficiencies were determined. The adsorption rate data was analyzed according to the pseudo-second-order kinetic, Elovich kinetic and intra-particle diffusion kinetic models. The pseudo-second-order kinetic was the best fit kinetic model for the experimental data. The results show that addition of fly ash, phosphogypsum and red mud to the zinc leach residue drastically reduces the heavy metal content in the leachate and could be used as liner materials.     

Effect of water-extraction on characteristics of melting and solidification of fly ash from municipal solid waste incinerator

This study was conducted to investigate the effect of water-extraction process on the removal of major elements and heavy metals in the fly ash from Municipal Solid Waste Incinerator (MSWI), and their thermal stability in the following melting process. The water-extraction was first applied to extract soluble elements and heavy metals from the fly ash from MSWI at different liquid-to-solid rates (L/S) of 2, 5, and 10, respectively. The extracted fly ash and the raw fly ash were then melted at the temperatures of 1000-1350 degrees C in an electrically heated furnace. The results showed that the compounds of Ca, Na, K, and Cl achieved high removal rates of 30.7-72.8% at L/S=10, respectively, Cr was the most extractable heavy metal with removal rate of 12.3% among the several heavy metals tested. The water-extracted fly ash had better stability as compared to raw one, which was indicated by lower weight loss and better immobilization ability of heavy metals such as Zn, Cu, and Pb in the melting process. The results showed that combing water-extraction and melting process could provide one of the alternatives for treating MSWI fly ash in China for reutilization.     

Equilibrium studies for the sorption of zinc and copper from aqueous solutions using sugar beet pulp and fly ash

In the present work, the abilities of native sugar beet pulp (SBP) and fly ash (FA) to remove copper (Cu(2+)) and zinc (Zn(2+)) ions from aqueous solutions were compared. The SBP and FA, an industrial by-product and solid waste of sugar industry, were used for the removal of copper and zinc from aqueous water. Batch adsorption experiments were performed in order to evaluate the removal efficiency of SBP and lignite-based FA. The effect of various operating variables, i.e. initial pH, adsorbent dose, initial metal ion concentration, and time on adsorption of copper and zinc onto the SBP and FA, has been studied. The sorption process was relatively fast and equilibrium was reached after about 60 min of contact. As much as 60-97% removal of copper and zinc for SBP and FA are possible in about 60 min, respectively, under the batch test conditions. Uptake showed a pH-dependent profile. The overall uptake for the SBP is at a maximum at pH 5.5 and gives up to 30.9 mg g(-1) for copper and at pH 6.0 and gives 35.6 mg g(-1) for zinc for SBP, which seems to be removed exclusively by ion exchange and physical sorption. Maximum adsorption of copper and zinc occurred 7.0 and 7.84 mg g(-1) at a pH value of 5.0 and 4.0 for FA, respectively. A dose of 8 g l(-1) of SBP and 8 g l(-1) FA were sufficient for the optimum removal of both the metal ions. The sorption data were represented by the Freundlich for SBP and the Langmuir and Freundlich for FA. The sorption data were better represented by the Langmuir isotherm than by the Freundlich one for FA in the adsorption of zinc ion, suggesting that the monolayer sorption, mainly due to ion exchange. The presence of low ionic strength or low concentration of Na and Cl ions does not have a significant effect on the adsorption of these metals by SBP and FA. The SBP and FA are shown to be effective metal adsorbents for these two metals.     

Removal mechanism of phosphate from aqueous solution by fly ash

This work studied the effectiveness of fly ash in removing phosphate from aqueous solution and its related removal mechanism. The adsorption and precipitation of phosphate by fly ash were investigated separately in order to evaluate their role in the removal of phosphate. Results showed that the removal of phosphate by fly ash was rapid. The removal percentage of phosphate in the first 5min reached 68-96% of the maximum removal of phosphate by fly ash. The removal processes of phosphate by fly ash included a fast and large removal representing precipitation, then a slower and longer removal due to adsorption. The adsorption of phosphate on fly ash could be described well by Freundlich isotherm equation. The pH and Ca2+ concentration of fly ash suspension were decreased with the addition of phosphate, which suggests that calcium phosphate precipitation is a major mechanism of the phosphate removal. Comparison of the relative contribution of the adsorption and precipitation to the total removal of phosphate by fly ash showed that the adsorption accounted for 30-34% of the total removal of phosphate, depending on the content of CaO in fly ash. XRD patterns of the fly ash before and after phosphate adsorption revealed that phosphate salt (CaHPO4 x 2H2O) was formed in the adsorption process. Therefore, the removal of phosphate by fly ash can be attributed to the formation of phosphate precipitation as a brushite and the adsorption on hydroxylated oxides. The results suggested that the use of fly ash could be a promising solution to the removal of phosphate in the wastewater treatment and pollution control.     

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.     

Electrodialytic removal of heavy metals from different fly ashes. Influence of heavy metal speciation in the ashes

Electrodialytic remediation, an electrochemically assisted extraction method, has recently been suggested as a potential method for removal of heavy metals from fly ashes. In this work, electrodialytic remediation of three different fly ashes, i.e. two municipal solid waste incinerator (MSWI) fly ashes and one wood combustion fly ash was studied in lab scale, and the results were discussed in relation to the expected heavy metal speciation in the ashes. The pH-dependent desorption characteristics for Cr differed between the two MSWI ashes but were similar for Cd, Pb, Zn and Cu. Thus, it was expected that the speciation of Cd, Pb, Zn and Cu was similar in the two ashes. However, in succeeding electrodialytic remediation experiments significant differences in removal efficiencies were observed, especially for Pb and Zn. In analogous electrodialytic remediation experiments, 8% Pb and 73% Zn was removed from one of the MSWI ashes, but only 2.5% Pb and 24% Zn from the other. These differences are probably due to variations in pH and heavy metal speciation between the different ashes. Cd, the sole heavy metal of environmental concern in the wood ash, was found more tightly bonded in this ash than in the two MSWI ashes. Approximately 70% Cd was removed from both types of ashes during 3 weeks of electrodialytic remediation, although the total concentration was a factor of 10 lower in the wood ash. It was suggested that complex Cd-silicates are likely phases in the wood ash whereas more soluble, condensed phases are dominating in the MSWI ashes.     

A study on the chemical and mineralogical characterization of MSWI fly ash using a sequential extraction procedure

The presence of heavy metals in municipal solid waste incineration (MSWI) fly ash is of environmental concern due to their leaching potential in landfill environments. Sequential chemical extraction was performed on fly ash samples from a large-scale municipal solid waste incineration plant in East China. The transformation of the mineralogical species of fly ash during the sequential extraction was studied using X-ray fluorescence (XRF) and X-ray powder diffraction (XRD). The leaching behavior of heavy metals such as zinc, lead, cadmium and copper in MSWI fly ash was considered to have a dependency relationship with the components of calcium, such as aphthitalite, calcite, anhydrite and calcium aluminate or calcium aluminosilicate.     

Effect of ionic strength on the adsorption of copper and chromium ions by vermiculite pure clay mineral

It is important to assess the effects of ionic strength when studying adsorption of metal ions on clay mineral because the background salt may complex metals and compete for adsorption sites. The sorption behavior of vermiculite pure clay mineral has been studied with respect to copper and chromium as a function of ionic strength in single metal ion solutions. Background electrolytes used in these experiments were KCl, NaCl and NH₄Cl. The studies were conducted by a batch method at temperature 25 °C. The adsorption capacity and adsorption energy for each metal ion were calculated from the Langmuir adsorption isotherm.Also the competitive adsorption behavior of some heavy metal ions such as Cr(III), Cu(II), Ni(II) and Co(II) by vermiculite pure clay mineral was studied. The result shows the competition between coexisting heavy metal cations for the same adsorption sites of an adsorbent. However, when trivalent metal was added to the solution it competitively replaced divalent ions that had been previously adsorbed onto the vermiculite pure clay mineral, resulting in the desorption of these metals into the solution.     

Removal of heavy metal ions from aqueous solutions using various low-cost adsorbents

The removal of single heavy metals Co and Zn from aqueous solutions using various low-cost adsorbents (Fe(2)O(3), Fe(3)O(4), FeS, steel wool, Mg pellets, Cu pellets, Zn pellets, Al pellets, Fe pellets, coal, and GAC) was investigated. Experiments were performed at different solution pH values (1.5-9) and metal concentrations (0.67-333 mg/l). The effect of solution pH on metal adsorption using Fe(2)O(3) and Fe(3)O(4) was significant, but was negligibly small using steel wool, Mg pellets, Fe pellets, and Al pellets over the entire pH range. Steel wool and Mg pellets were the most excellent adsorbents; for example, the removal of Zn and Co from dilute solutions (<35 mg/l) was greater than 94% at an adsorbent dose of 1.7 g/l. A mass transfer model, which involves two parameters tau (50% breakthrough time) and k (proportionality constant), was proposed to describe breakthrough data of Co in the fixed beds packed with steel wool and Mg pellets. The calculated breakthrough curves agreed well with the measured data (standard deviation < 6%). The value of tau decreased with increasing the flow rate. The effects of flow rates on the value of k and adsorption capacity are discussed.     

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.     

Factorial experimental design for recovering heavy metals from sludge with ion-exchange resin

Wastewaters containing heavy metals are usually treated by chemical precipitation method in Taiwan. This method can remove heavy metals form wastewaters efficiently, but the resultant heavy metal sludge is classified as hazardous solid waste and becomes another environmental problem. If we can remove heavy metals from sludge, it becomes non-hazardous waste and the treatment cost can be greatly reduced. This study aims at using ion-exchange resin to remove heavy metals such as copper, zinc, cadmium, and chromium from sludge generated by a PCB manufacturing plant. Factorial experimental design methodology was used to study the heavy metal removal efficiency. The total metal concentrations in the sludge, resin, and solution phases were measured respectively after 30 min reaction with varying leaching agents (citric acid and nitric acid); ion-exchange resins (Amberlite IRC-718 and IR-120), and temperatures (50 and 70 degrees C). The experimental results and statistical analysis show that a stronger leaching acid and a higher temperature both favor lower heavy metal residues in the sludge. Two-factors and even three-factor interaction effects on the heavy metal sorption in the resin phase are not negligible. The ion-exchange resin plays an important role in the sludge extraction or metal recovery. Empirical regression models were also obtained and used to predict the heavy metal profiles with satisfactory results.     

Comparative study of adsorption properties of Turkish fly ashes. I. The case of nickel(II), copper(II) and zinc(II)

The objective of this study was to compare two different Turkish fly ashes (Afsin-Elbistan and Seyitomer) for their ability to remove nickel [Ni(II)], copper [Cu(II)] and zinc [Zn(II)] from an aqueous solution. The effect of contact time, pH, initial metal concentration and fly ash origin on the adsorption process at 20+/-2 degrees C were studied. Batch kinetic studies showed that an equilibrium time of 2h was required for the adsorption of Ni(II), Cu(II) and Zn(II) on both the fly ashes. The maximum metal removal was found to be dependent on solution pH (7.0-8.0 for Ni(II), 5.0-6.0 for Cu(II) and 6.0-7.0 for Zn(II)) for each type of fly ash. With an increase in the concentrations of these metals, the adsorption of Ni(II) and Zn(II) increased while the Cu(II) adsorption decreased on both the fly ashes. Adsorption densities for the metal ions were Zn(II)>Cu(II)>Ni(II) for both the fly ashes. The effectiveness of fly ash as an adsorbent improved with increasing calcium (CaO) content. Adsorption data in the range of pH values (3.0-8.0) using Ni(II) and Cu(II) concentrations of 25+/-2mg/l and Zn(II) concentration of 30+/-2mg/l in solution were correlated using the linear forms of the Langmuir and Freundlich equations. The adsorption data were better fitted to the Langmuir isotherm since the correlation coefficients for the Langmuir isotherm were higher than that for the Freundlich isotherm. The fly ash with high calcium content (Afsin-Elbistan) was found to be a metal adsorbent as effective as activated carbon and, therefore, there are good prospects for the adsorptions of these metals on fly ash with high calcium content in practical applications in Turkey.     

Determination of solid waste sorption capacity for selected heavy metals in landfills

The adsorption process is largely a surface-action phenomenon. In this study, sorption capacities for heavy metals on a solid waste matrix were investigated. Five heavy metals (iron, copper, zinc, nickel and cadmium) were chosen because of their availability in any landfill site. The conditions during all the experimental runs were pH 7.0, temperature 32 degrees C and suppressed microbial degradation. For adsorption isotherm (Freundlich and Langmuir) calculations, fixed quantities of heavy metal ions were mixed with variable quantities of solid waste. The ratio of mass of adsorbate per unit mass of adsorbent was changed five times, by changing only the adsorbent amount. The results showed that the time required to reach equilibrium varied from metal to metal but all reached equilibrium within the first 32 h. The relative potential of sorption of the individual metals and mixed metals on the solid waste matrix is Fe > Zn > Cu > Ni > Cd. The sorption capacity of domestic solid waste matrix for heavy metals is quite significant and this property might prove helpful for the in situ removal of heavy metals in landfill operation.     

Removal of copper and cadmium from the aqueous solutions by activated carbon derived from Ceiba pentandra hulls

Activated carbon prepared from Ceiba pentandra hulls, an agricultural solid waste by-product, for the removal of copper and cadmium from aqueous solutions has been studied. Parameters such as equilibrium time, effect of pH and adsorbent dose on removal were studied. The adsorbent exhibited good sorption potential for copper and cadmium at pH 6.0. C=O and S=O functional groups present on the carbon surface were the adsorption sites to remove metal ions from solution. The experimental data was analysed by both Freundlich and Langmuir isotherm models. The maximum adsorption capacity of copper and cadmium was calculated from Langmuir isotherm and found to be 20.8 and 19.5 mg/g, respectively. The sorption kinetics of the copper and cadmium have been analysed by Lagergren pseudo-first-order and pseudo-second-order kinetic models. The desorption studies were carried out using dilute hydrochloric acid solution and the effect of HCl concentration on desorption was also studied. Maximum desorption of 90% for copper and 88% for cadmium occurred with 0.2 M HCl.     

THE EFFECT OF TARTRATE, A WEAK COMPLEXING AGENT, ON THE REMOVAL OF HEAVY METALS BY SULFIDE AND HYDROXIDE PRECIPITATION

Industrial vastevaters generated in the electroplating and metal finishing industries typically contain toxic heavy metals. Depending on their origin, these wastewaters may also contain chelating agents, such as EDTA, NTA, citrate, tartrate, and gluconic acid. Although the major effect of complexation is an increase in the solubility of complexed metal ions, significant changes in the precipitation kinetics and particle size distribution may also contribute to the observed precipitation behavior.

This paper addresses the effect of a weak complexing agent, tartrate, on the removal of zinc and cadmium using both hydroxide and sulfide treatment. Results are presented on the removal of heavy metals from synthetic plating wastewaters. Poor zinc removals were observed in the presence of tartrate, particularly when larger filter pore sizes were employed. The results suggest that tartrate severely hinders both zinc hydroxide and zinc sulfide precipitation, resulting in the formation of very fine precipitates; this was confirmed when no zinc removal occurred even with a settling time of 30 min. For removal of cadmium, virtually no change in residual cadmium concentration was observed in the presence of tartrate (compared to the case of no complexing agents present) due to the formation of low-stability complexes.