Heavy metal complexation behavior in anaerobically digested sludges

Heavy metal interactions with anaerobically digested sludges have been examined by equilibrating sludge solids with solutions containing acetate salts of zinc, nickel copper, and cadmium over the range of pH from 5.0 to 8.0. The partitioning of the metals with the solids suggested chemisorptive behavior. Currently available adsorption isotherms could be used to describe this behavior if modified to incorporate effects due to hydrogen ion concentration. The Freundlich isotherm was superior to the Langmuir and Temkin isotherms.A comparison of Langmuir inhibition variations and Freundlich results suggests that weakly acidic ligands are involved in heavy metal complexation and that there exists a competition between the metal and hydrogen ions for these sites. Lowering the pH resulted in lower degrees of complexation.Stability constants were calculated from Langmuir isotherm results and are in the range of values calculated by others for heavy metal complexation with soil organic matter.     

Equilibrium chemical modelling of heavy metals in activated sludge

A chemical speciation distribution model of heavy metals, previously developed by Nelson et al. (J. Wat. Pollut. Control Fed. 53, 1323, 1981), was applied to cadmium in activated sludge from a full-scale wastewater treatment plant. In the model, cadmium adsorption to bacterial solids was quantified by the determination of conditional formation constants based on TOC. Adsorption of cadmium strongly pH-dependent. Soluble cadmium speciation was dominated by the free cadmium ion below pH 6, by cadmium-organic ligand complexation at pH 6 and 7 and by inorganic species at pH 8 and 9. Cadmium adsorbed by bacterial solids increased greatly with pH from near 30% at pH 4 to near 90% at pH 9. Cadmium speciation and distribution was also modelled in an indifferent electrolyte suspension of bacterial solids and in activated sludge using adsorption constants from the indifferent electrolyte medium.     

Single- and multi-component adsorption of cadmium and zinc using activated carbon derived from bagasse--an agricultural waste

The use of low-cost activated carbon derived from bagasse, an agricultural waste material, has been investigated as a replacement for the current expensive methods of removing heavy metals from wastewater. With a view to find a suitable application of the material, activated carbon has been derived, characterized and utilized for the removal of cadmium and zinc. The uptake of cadmium was found to be slightly greater than that of zinc and the sorption capacity increases with increase in temperature. The adsorption studies were carried out both in single- and multi-component systems. Adsorption data on derived carbon follows both the Freundlich and Langmuir models. The data are better fitted by the Freundlich isotherm as compared to Langmuir in both the single- and multi-component systems. Isotherms have been used to obtain the thermodynamic parameters. The kinetics of adsorption depends on the adsorbate concentration and the physical and chemical characteristics of the adsorbent. Studies were conducted to delineate the effect of temperature, initial adsorbate concentration, particle size of the adsorbent and solid-to-liquid ratio. On the basis of these studies, various parameters such as mass transfer coefficient, effective diffusion coefficient, activation energy and entropy of activation were evaluated to establish the mechanisms. It was concluded that the adsorption occurs through a film diffusion mechanism at low as well as at higher concentrations.     

Equilibrium and kinetics of metal ion adsorption onto a commercial H-type granular activated carbon: experimental and modeling studies

Systematic studies on metal ion adsorption equilibrium and kinetics by a commercial H-type granular activated carbon were carried out. Titration of the carbon showed that the surface charge density decreased with an increasing pH. Higher copper adsorption was obtained with increasing solution pH and ionic strength. Metal removal was in the descending order: Cu2+ > Zn2+ approximately Co2+. Copper removal was not affected by addition of zinc or cobalt, while copper can reduce both zinc and cobalt removal. Kinetic experiments demonstrated that the copper adsorption rapidly occurred in the first 30-60 min and reached the complete removal in 3-5 h. Removal of zinc and cobalt was slightly slower than that of copper. It was found that the mass transfer is important in the metal adsorption rate. The surface complex formation model was used successfully to describe the surface change density, as well as the single- and multi-species metal adsorption equilibrium. The copper removal was due to adsorption of Cu2+, CuOH+, and CuCl+, while the zinc and cobalt uptake was due to the formation of surface metal complexes of SOM2+ and SOMOH+ (M = Zn and Co). It was found that the diffusion-control model well described the adsorption kinetics with various metal ions and pH values. Finally sensitivity analysis on the kinetic model's parameters was carried out.     

Formation and conditional stability constants of complexes formed between heavy metals and bacterial extracellular polymers

The strength and nature of the binding of heavy metal ions to bacterial extracellular polymers has been investigated. The conditional stability constants (K_t) for complexes formed between extracted Klebsiella aerogenes polymer and copper, cadmium, cobalt and nickel were determined, using a gel chromatographic technique, and log K_t values of 7.69, 5.16, 5.48 and 5.49 respectively were obtained. Adsorption isotherms constructed for copper, cadmium and cobalt indicated that metal uptake occurred after the initial complexation capacity had been exceeded, suggesting the presence of more than one binding site, but nickel adsorption ceased when the complexation capacity was reached. Nickel was found to be associated predominantly with the soluble form of polymer, and copper and cadmium with the colloidal fraction when metals were added to the polymer simultaneously, rather than individually. The overall specific metal uptake by polymers extracted from activated sludge was approximately ten times higher than that by K. aerogenes polymer.     

Role of bacterial extracellular polymers in metal uptake in pure bacterial culture and activated sludge—I. Effects of metal concentration

A gel filtration technique afforded a good separation between metal complexed with bacterial extracellular polymers and free metal ions. The complexation of polymers extracted from cultures of Klehsiella aerogenes and activated sludge with cadmium, nickel, manganese and cobalt was demonstrated. The extraction of extracellular polymers from cultures of K. aerogenes and activated sludge reduced the capacity of the cells and flocs to adsorb metal. Adsorption and complexation of metals by cells of K. aerogenes and extracellular polymers extracted from activated sludge were fitted to Freundlich equilibrium isotherms. Saturation of activated sludge polymer binding sites occurred at 10 mg 1^?1 metal additions for all the metals studied except manganese which was complexed to a very limited extent. Cells of K. aerogenes exhibited no saturation effects in the range of metal concentrations studied.Precipitation of metals below a concentration of 1 mg 1^?1 was minimal, with the exception of cadmium precipitation. At a concentration of 10 mg 1^?1, precipitation of cadmium, cobalt and manganese may have been the major mechanism of metal removal. The more soluble metals generally displayed the lowest removals. Concentrations of extracellular polymers and soluble chelating agents may be important in controlling removals of metals which are largely soluble in activated sludge.     

Removal of Cu(II) and Cd(II) from aqueous solution by seafood processing waste sludge

Dried waste slurry generated in seafood processing factories has been shown to be an effective adsorbent for the removal of heavy metals from dilute solutions. Characterization of the sludge surface with scanning electron microscope and X-ray microanalyzer were carried out to evaluate the components on the sludge surface that are related to the adsorption of metal ions. Aluminum and calcium, as well as organic carbon are distributed on the surface of sludge. Alkalimetric titration was used to characterize the surface acidity of the sludge sample. The surface acidity constants, pKa1s and pKa2s, were 5.80 and 9.55, respectively. Batch as well as dynamic adsorption studies were conducted with 10(-5) to 5 x 10(-3) M Cu(II) and Cd(II). A surface complexation model with the diffuse layer model successfully predicted Cu(II) and Cd(II) removals in single metal solutions. Predictions of sorption in binary-adsorbate systems based on single-adsorbate data fits represented competitive sorption data reasonably well over a wide range of conditions. The breakthrough capacity found from column studies was different for each metal ion and the data reflect the order of metal affinity for the adsorbent material very well.     

Role of bacterial extracellular polymers in metal uptake in pure bacterial culture and activated sludge—II Effects of mean cell retention time

A gel filtration technique afforded a good separation between metal complexed with bacterial extracellular polymers and free metal ions. The complexation of polymers extracted from cultures of Klehsiella aerogenes and activated sludge with cadmium, nickel, manganese and cobalt was demonstrated. The extraction of extracellular polymers from cultures of K. aerogenes and activated sludge reduced the capacity of the cells and flocs to adsorb metal. Adsorption and complexation of metals by cells of K. aerogenes and extracellular polymers extracted from activated sludge were fitted to Freundlich equilibrium isotherms. Saturation of activated sludge polymer binding sites occurred at 10 mg 1⁻¹ metal additions for all the metals studied except manganese which was complexed to a very limited extent. Cells of K. aerogenes exhibited no saturation effects in the range of metal concentrations studied.Precipitation of metals below a concentration of 1 mg 1⁻¹ was minimal, with the exception of cadmium precipitation. At a concentration of 10 mg 1⁻¹, precipitation of cadmium, cobalt and manganese may have been the major mechanism of metal removal. The more soluble metals generally displayed the lowest removals. Concentrations of extracellular polymers and soluble chelating agents may be important in controlling removals of metals which are largely soluble in activated sludge.     

Cadmium adsorption by oxic sediment

To understand the strong pH dependency of cadmium adsorption by oxic sediment, we investigated the surface charge of sediment particles by potentiometric titration with acid and base. Metal adsorbed by sediment can occur by complexation of metal ions with weakly acidic functional groups or by ion exchange of metal ions. A multi-site binding model, which incorporates the effect of pH, has been applied to describe the adsorption of cadmium onto sediment. The model has been used to satisfactorily predict the extent of adsorption over the pH range of 4.5–7.0.     

Adsorption of copper, lead and cobalt by activated carbon

The phenomena of lead, copper and cobalt adsorption by activated carbon from aqueous solution was studied in detail. Laboratory studies were conducted to evaluate and optimize the various process variables (i.e. carbon type, solution pH, equilibrium time and carbon dose). A quantitative determination of the adsorptive capacity of activated carbon to remove these metals was also determined.Significant differences were found in the ability of different types of activated carbons to adsorb lead, copper and cobalt from aqueous solution. Solution pH was found to be the most important parameter affecting the adsorption. It was found that there was practically no adsorption of lead, copper and cobalt by activated carbon below a well defined solution pH value for each metal. This critical solution pH value was found to be lower than the pH value associated with the formation of hydrolysis products. Of the ten commercially available activated carbons evaluated in these experiments, Barney Cheney NL 1266 was found to adsorb the largest percentage of lead, copper and cobalt. The adsorption of any single metal (lead, copper and cobalt) was hindered by the presence of the other metals; the metals apparently competed for adsorption sites.     

Derivation and application of a new model for heavy metal biosorption by algae

An equilibrium model for describing the relationships between important parameters for heavy metal sorption by algae was derived through a thermodynamics approach. In this model, both the removal efficiency of heavy metal and metal adsorption per unit algal biomass are considered to be simple functions of the ratio of algal biomass concentration to the initial metal concentration for selected conditions, i.e. as at constant pH and temperature. The model was found to fit the experimental results well (judged by the correlation-regression coefficient, R2), for the adsorption of cadmium, copper, lead and zinc by two algal species, Oocystis sp. (both living and non-living) and Chlorococcum sp. The applicability of the model was also supported by the reprocessed results of experimental data given in the literature, i.e. for the metal species, Cd, Pb, Cu and Ag, the algal species, Chlorella vulgaris, Scenedesmus quadricauda and Cladophora crispata, and both batch and continuous fixed-bed reactors. It was also demonstrated that the model could be applied over a broad range of pH for cadmium and copper adsorption by Oocystis sp. However, the model was not applicable at very low and high pH levels, due to negligible adsorption and precipitation, respectively.     

Predicting metals partitioning in wastewater treatment plant influents

Interactions of heavy metals with primary sludge particulates were investigated using batch equilibrium metal uptake experiments. Results showed that metal uptake by primary sludge is significantly affected by pH. A mathematical model was developed to describe metals partitioning as a function of pH. The metal adsorption constants were determined. Results showed that for the same metal ion, the values of metal adsorption constants for primary sludge samples collected from different locations and at different times were in the same order of magnitude. Therefore, the adsorption constants were normalized and calibrated using field data. For Ag(I), Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II), the calibrated values of adsorption constants (logK(S)) are, respectively, 4.4, 5.1, 3.6, 4.5, 4.6, 3.6, 6.0, and 6.0. These constants can be used to predict the metal partitioning in plant influents and metal removal in primary treatment processes.     

Copper(II) removal from aqueous solutions by fly ash

The removal of Cu(II) by adsorption on fly ash has been found to be concentration, pH and temperature dependent. The kinetics of adsorption indicates the process to be diffusion controlled. The Langmuir constants have been calculated at different temperatures, and the adsorption has been found to be endothermic (ΔH = 15.652 kcal mol^?1). The maximum removal is observed at pH 8.0, and variation in adsorption with pH has been explained on the basis of surface ionisation and complexation.     

Removal of cadmium and nickel from wastewater using bagasse fly ash--a sugar industry waste

The bagasse fly ash, an industrial solid waste of sugar industry, was used for the removal of cadmium and nickel from wastewater. As much as 90% removal of cadmium and nickel is possible in about 60 and 80 min, respectively, under the batch test conditions. Effect of various operating variables, viz., solution pH, adsorbent dose, adsorbate concentration, temperature, particle size, etc., on the removal of cadmium and nickel has been studied. Maximum adsorption of cadmium and nickel occurred at a concentration of 14 and 12 mg x l(-1) and at a pH value of 6.0 and 6.5, respectively. A dose of 10 g x l(-1) of adsorbent was sufficient for the optimum removal of both the metal ions. The material exhibits good adsorption capacity and the adsorption data follow the Langmuir model better then the Freundlich model. The adsorption of both the metal ions increased with increasing temperature indicating endothermic nature of the adsorption process. Isotherms have been used to determine thermodynamic parameters of the process, viz., free energy change, enthalpy change and entropy change.     

Adsorption and desorption of polydimethylsiloxane, PCBs, cadmium nitrate, copper sulfate, nickel sulfate and zinc nitrate by river surface sediments

An investigation into the adsorption and desorption of polydimethylsiloxane, PCBs, cadmium nitrate, copper sulfate, nickel nitrate and zinc nitrate by river sediments was carried out using either a flow-through system or a semi-static system. The material balance in the sediment compartment could be explained by the equation, dCs/dT= K1Cw-K2Cs. The adsorption rate constants (K1), desorption rate constants (K2) and concentration factors (K1/K2) were calculated. For hydrophobic chemicals, the K1's were independent of water solubility, but the K2's were relatively related to water solubility. For both hydrophobic chemicals and heavy metals, the concentration factors per fraction organic carbon were similar to the soil sorption coefficients (Koc), expressed on a organic carbon basis.     

Simultaneous removal of As, Cd, Cr, Cu, Ni and Zn from stormwater: experimental comparison of 11 different sorbents

The potential of using alumina, activated bauxsol-coated sand (ABCS), bark, bauxsol-coated sand (BCS), fly ash (FA), granulated activated carbon (GAC), granulated ferric hydroxide (GFH), iron oxide-coated sand (IOCS), natural zeolite (NZ), sand, and spinel (MgAl(2)O(4)) as sorbents for removing heavy metals from stormwater are investigated in the present study. The ability of the sorbents to remove a mixture of As, Cd, Cr, Cu, Ni and Zn from synthetic stormwater samples were evaluated in batch tests at a starting pH of 6.5. The metal speciation and saturation data is obtained using the PHREEQ-C geochemical model and used to elucidate the sorption data. It is found that BCS, FA, and spinel have significantly higher affinity towards heavy metals mainly present as cationic or non-charged species (i.e. Cd, Cu, Ni and Zn) compared to those present as anionic species (i.e. As and Cr). However, IOCS, NZ and sand have higher affinity towards As and Cr, while alumina has equally high affinity to all tested heavy metals. The Freundlich isotherm model is found to fit the data in many cases, but ill fitted results are also observed, especially for FA, BCS and GAC, possibly due to leaching of some metals from the sorbents (i.e. for FA) and oversaturated conditions making precipitation the dominant removal mechanism over sorption in batches with high heavy metal concentrations and pH. Calculated sorption constants (i.e. K(d)) are used to compare the overall heavy metal removal efficiency of the sorbents, which in a decreasing order are found to be: alumina, BCS, GFH, FA, GAC, spinel, ABCS, IOCS, NZ, bark, and sand. These findings are significant for future development of secondary filters for removal of dissolved heavy metals from stormwater runoff under realistic competitive conditions in terms of initial heavy metal concentrations, pH and ionic strength.     

Hexavalent chromium removal from aqueous solution by adsorption on aluminum magnesium mixed hydroxide

A series of sols consisting of aluminum magnesium mixed hydroxide (AMH) nanoparticles with various Mg/Al molar ratios were prepared by coprecipitation. The use of AMH as adsorbent to remove Cr(VI) from aqueous solution was investigated. Adsorption experiments were carried out as a function of the Mg/Al molar ratio, pH, contact time, concentration of Cr(VI) and temperature. It was found that AMH with Mg/Al molar ratio 3 has the largest adsorption efficiency due to the smallest average particle diameter and the highest zeta potential; AMH was particularly effective for the Cr(VI) removal in a pH range from acid to slightly alkaline, even though the most effective pH range was between 2.5 and 5.0. The adsorption of Cr(VI) on AMH reached equilibrium within 150 min. The saturated adsorption capacities of AMH for Cr(VI) were 105.3-112.0 mg/g at 20-40 °C. The interaction between the surface sites of AMH and the Cr(VI) ions may be a combination of both anion exchange and surface complexation. The pseudo-second-order model best described the adsorption kinetics of Cr(VI) onto AMH. The results showed that AMH can be used as a new adsorbent for Cr(VI) removal which has higher adsorption capacity and faster adsorption rate at pH values close to that at which pollutants are usually found in the environment.     

Removal of toxic metals from aqueous solutions by fungal biomass of Agaricus macrosporus

Fungi such as Agaricus macrosporus show potential for the removal of heavy metals from aqueous solutions contaminated by zinc, copper, mercury, cadmium or lead. This study investigated biosorption of these metals by living or non-living biomass of A. macrosporus from an acid solution, an acid solution supplemented with potassium and phosphorus, and an alkaline solution. Uptake showed a pH-dependent profile. Maximum percentage uptake of all metals was found to occur at alkaline pH (Cu 96%, Pb 89%). With living biomass, metal biosorption was greater and faster in K/P-supplemented acid medium than in non-supplemented acid medium, with equilibrium reached within 15 min for all metals, and the highest percentage uptake being of cadmium (96%). In general, the greatest differences in biosorption capacity were seen for living biomass, between supplemented and non-supplemented acid medium; the smallest differences were between living and dead biomass in alkaline medium. These results support the potential utility of A. macrosporus for heavy metal removal.     

Multi-component adsorption of Ag(I), Cd(II) and Cu(II) by natural carbonaceous materials

Adsorption of silver, cadmium and copper from aqueous solutions by natural carbonaceous materials was investigated. The studied series of natural materials (spruce wood, pine bark, cork, peat, fusinite, lignite, oxidised lignite, bituminous coal and anthracite) was extended to include industrial carbon-rich materials: coke, activated carbon F-400 and Multisorb 100. Adsorption was tested on a single-component system and on the binary and ternary mixtures. All the materials used differ in their ability to adsorb selected metals. The adsorption of metals is significantly affected by the presence of other ions in solution. Total metal uptake was considerably higher in a mixture than single-ion adsorption. Chemical reactions, such as precipitation and reduction of metallic silver, play a role in metal uptake by bituminous coal, coke and activated carbon.