Mechanisms of metal adsorption from aqueous solutions by waste tyre rubber

The mechanisms of adsorption of cadmium(II), mercury(II) and lead(II) on to shredded rubber from old automobile types have been studied and it is shown that at least two distinct processes can be involved depending upon the metal being adsorbed. Mercury and cadmium uptake are accompanied by displacement of zinc and therefore probably involve an ion exchange type mechanism. Lead adsorption, in contrast, involves no zinc displacement and is not competitive with cadium or mercury uptake, suggesting that a completely separate mechanism and site of binding are used by lead(II).     

Cu(II) binding by dried biomass of red, green and brown macroalgae

Dried biomass of the marine macroalgae Fucus spiralis and Fucus vesiculosus (brown), Ulva spp. (comprising Ulva linza, Ulva compressa and Ulva intestinalis) and Ulva lactuca (green), Palmaria palmata and Polysiphonia lanosa (red) were studied in terms of their Cu(II) biosorption performance. This is the first study of its kind to compare Cu(II) uptake by these seaweeds in the South-East of Ireland. Potentiometric and conductimetric titrations revealed a variety of functionalities on the seaweed surface including carboxyl and amino groups, which are capable of metal binding. It was also found that, of the seaweeds investigated, F. vesiculosus contained the greatest number of acidic surface binding sites while Palmaria palmata contained the least. The metal uptake capacities of the seaweeds increased with increasing pH and kinetic behaviour followed a similar pattern for all seaweeds: a rapid initial sorption period followed by a longer equilibrium period. P. palmata reached equilibrium within 10min of exposure while F. vesiculosus required 60min. Correlation was found between the total number of acidic binding sites and the time taken to reach equilibrium. Fourier transform infra-red (FTIR) analysis of the seaweeds revealed the interaction of carboxyl, amino, sulphonate and hydroxyl groups on the seaweed surface with Cu(2+) ions while time course studies established the relative contribution of each of these groups in metal binding.     

Bioremoval of cadmium from aqueous solution by black gram husk (Cicer arientinum)

Husk of black gram (Cicer arientinum), a waste of no commercial value, was investigated as a new biosorbent of cadmium from low concentration aqueous solutions. With 99.99% sorption efficiency from 10mg l(-1) cadmium solution, the biomass required at saturation was 0.8 g mg(-1) cadmium. Biosorption was rapid and equilibrium was achieved in 30 min. Among the various desorbing agents tested, 99.89% cadmium recovery was achieved with 0.1M HCl. Sorption efficiency of cadmium during six biosorption-desorption cycles in batch operations declined, which was traceable to 39.0% black gram husk (bgh) weight loss. This decline was only 9.71% when compensated for biomass loss, which is comparable to 10.45% decline during six cycles in fixed bed column bioreactor in which biomass loss was only 5.98%. On plotting breakthrough curves it was noted that bgh in the fixed bed column was capable of bringing down cadmium concentration from 10 to 0.1 mg l(-1) in 35.5 l volume. Biosorption of cadmium was not effected in the presence of other cations. Comprehensive characterization of parameters indicate bgh to be an excellent material for biosorption of cadmium to treat wastewaters containing low concentration of the metal. As an agrowaste, the advantage of application of this material as a metal biosorbent in a fixed bed column bioreactor system, in comparison with those based on immobilized algae or biomass of algal, fungal and bacterial origin, is considered.     

Adsorption of Cu(II), Cd(II) and Pb(II) from aqueous single metal solutions by succinylated twice-mercerized sugarcane bagasse functionalized with triethylenetetramine

This study describes the preparation of two new chelating materials, MMSCB 3 and 5, derived from succinylated twice-mercerized sugarcane bagasse (MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two different methods as described by Gurgel and Gil (2009). In the first method MMSCB 1 was activated with 1,3-diisopropylcarbodiimide and in the second with acetic anhydride (to form an internal anhydride) and later both were reacted with triethylenetetramine in order to obtain MMSCB 3 and 5. New obtained materials were characterized by mass percent gain, concentration of amine groups, FTIR, and elemental analysis. MMSCB 3 and 5 showed mass percent gain of 19.9 and 57.1%, concentration of amine groups of 2.0 and 2.1 mmol/g, and nitrogen content of 5.8 and 4.4%. The capacity of MMSCB 3 and 5 to adsorb Cu²⁺, Cd²⁺, and Pb²⁺ from aqueous single metal ion solutions was evaluated at different contact times, pHs, and initial metal ion concentrations. Adsorption isotherms were well fitted by Langmuir model. Maximum adsorption capacities of MMSCB 3 and 5 for Cu²⁺, Cd²⁺, and Pb²⁺ were found to be 59.5 and 69.4, 86.2 and 106.4, 158.7 and 222.2 mg/g, respectively.     

Removal of metal ions from aqueous solution by polysaccharide produced from Bacillus firmus

This paper deals with adsorption of Pb, Cu and Zn on the polysaccharide produced by Bacillus firmus. The adsorption of metal ions was significantly affected by the initial pH of solution, initial metal ion and polysaccharide concentrations, and presence of other ions in solution. At optimum pH, the uptakes of Pb, Cu and Zn were 98.3%, 74.9% and 61.8%, respectively. The metal ions removal was lower at neutral and generally the initial adsorption rate was rapid and reached equilibrium after 10 min. The process of uptake obeys both Langmuir and Freundlich isotherms.     

Dynamic and static adsorption and desorption of Hg(II) ions on chitosan membranes and spheres

The adsorption and desorption of Hg(II) ions was studied using static and dynamic methods, employing membranes and spheres of chitosan as the adsorbent. The quantity of adsorption was influenced by chitosan crosslinking and by the adsorbent shape. The Langmuir model was applied to fit the experimental equilibrium data. Glutaraldehyde-crosslinked membranes presented a lower desorption capacity, when compared to natural membranes, but could be regenerated for use in successive cycles. Dynamic adsorption experiments suggested that the adsorption capacity depended mainly on adsorbent geometry, due to differences between surface area to mass ratio and initial concentration of Hg(II) ions. The adsorption capacity determined by the dynamic method was 65% and 77% for membranes and spheres, respectively of the value obtained static method results. A process combining dynamic adsorption and static desorption can be used to concentrate the Hg(II) ions by a factor of nearly seven (7x), when compared to the initially treated volume.     

Heavy metal removal from waste water from wet lime(stone)—gypsum flue gas desulfurization plants

Waste water from wet lime(stone) gypsum flue gas desulfurization processes for coal-fired boilers contains suspended solids (gypsum, silica, hydroxides of iron and aluminum) and soluble salts (chlorides and sulfates of calcium, sodium and magnesium). Furthermore, small amounts of heavy metals such as As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se and Zn are present in these waste water streams. A treatment method has been developed to remove these heavy metals very efficiently. This method has been based on coprecipitation of metal hydroxides and sulfides. The hydroxide and sulfide precipitates are removed by a coagulation/flocculation technique followed by gravity settling. The coprecipitation can be carried out with sodium hydroxide or with lime. Both cases were investigated in two different pilot plants with synthetically composed waste water and with actual waste water from three different types of wet lime(stone)—gypsum flue gas desulfurization plants (lime—gypsum FGD plants without a prescrubber, one using seawater and another using river water as process water; a limestone—gypsum FGD plant with a prescrubber using river water as process water).     

Sorption of Cd(II) from multicomponent nitrate solutions by functional organosilicas

The paper has investigated the impact of hardness salts modeling soft and hard waters on sorption of trace amounts of Cd(II) by β-cyclodextrin-containing silicas, which differ by chemical nature of sorption centers. The paper has demonstrated high affinity of organosilicas to Cd(II) in its sorption from multicomponent solutions. Equilibrium sorption of cations from aqueous nitrate solutions within a broad interval of concentrations has been described by means of the Langmuir and Freundlich models and was interpreted in terms of the theory of hard and soft acids and Pearson bases.     

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 oxovanadium(IV) from aqueous solutions by using commercial crystalline calcium hydroxyapatite

The interaction of oxovanadium(IV) (VO(2+)) in aqueous solution with commercial calcium hydroxyapatite (CAP) has been studied. VO(2+) ions are adsorbed on the surface of CAP by coordination to OH groups, without modification of the crystalline lattice. The extent of the adsorption is followed by chemical analysis, ESR and IR spectroscopy. Results are compared with those obtained for VO(2+)/synthetic calcium hydroxyapatite (HAP), reported by us in previous works. The uptake is better than the observed for HAP. The maximum adsorption is observed at pH 3.5 and 288 K. We conclude that VO(2+) is indeed adsorbed on CAP and the extent of adsorption depends on the pH and temperature.     

Comparative and competitive adsorption of Cu(II), Cd(II) and Pb(II) onto Sepia pharaonis endoskeleton biomass from aqueous solutions

In this research, the possibility of simultaneous removal of lead, cadmium and copper divalent ions from water samples through the use of Sepia pharaonis endoskeleton powder (SPEB) as bio‐material, was investigated. The bio‐sorbent was characterised by Fourier transform infrared spectrum (FT‐IR), atomic force microscopy (AFM) and X‐ray fluorescence (XRF). The different factors affecting the bio‐sorption process were studied. Langmuir and Freundlich isotherm models were applied to analyse the experimental data. The kinetic studies showed that the pseudo‐second order model kinetics were compatible with the investigated systems. It was found that under optimal conditions, this bio‐sorbent was efficient in the uptake of these heavy metal ions from both mono and multi‐metal solutions, and high removal percentages were achieved. This study verified the potential ability of SPEB as an efficient natural adsorbent for removal of Pb(II), Cd(II) and Cu(II) ions from river, tap and mineral water samples.     

Production and detailed characterization of bean husk-based carbon: efficient cadmium (II) removal from aqueous solutions

We report the production of a modified carbon by heat treating bean husk (Phaseolus vulgaris) at 270 degrees C in Ar, followed by chemical activation using HNO(3). The material was studied using thermogravimetric analysis (TGA), infrared spectroscopy (IRS), high-resolution transmission electron microscopy (HRTEM), elemental mapping, energy dispersive X-ray spectroscopy (EDX), X-ray powder diffraction and scanning electron microscopy (SEM). Cd(2+) sorption studies with this material were carried out at different concentrations. It was found that cadmium (II) is effectively removed by the modified material obtained from bean husk (180 mg/g). The sorption mechanism is discussed in terms of the activated surface properties. A relationship between the oxygen content and sorption was found in this novel material. Commercial activated carbon (AC) (F400) was used for comparison.     

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.     

Scavenging cadmium,copper, lead,nickel and zinc ions from aqueous solution by modified cellulosic sorbent

The adsorption of cadmium, copper, lead, nickel and zinc ions on maize Zea mays stalk meal was examined by equilibrium studies at 29°C. The amounts of the metal ions removed from solution depended on the metal ion type, the ionic size of the metals and were enhanced by EDTA (% N = 12.05) modification of the cellulosic sorbent. The sorption coefficient, K_d, of the metal ions between the adsorbent phase and the bulk aqueous phase was found. The sorption on the unmodified sorbent of lead ions from solutions containing zinc ions shows that lead ions are preferentially removed from solution.     

Kinetic modeling of pyruvic acid ozonation in aqueous solutions catalyzed by Mn(II) and Mn(IV) ions

The ozonation of pyruvic acid (2-ketopropionic acid) in aqueous solutions, catalyzed by Mn(II) and Mn(IV) ions, has been studied at three different pH values (pH = 1.1, 2.0 and 3.0). A mathematical model of the unsteady operation of the experimental reactor has been developed, which takes into account the reactions occurring in the liquid phase and the ozone mass transfer from the gas bubbles. Those reactions have been described with two alternative kinetic models, both made out of four elementary steps. The two kinetic models correlate the experimental data with a fair accuracy, respectively at the lowest and at the highest pH examined. In particular, at pH = 3.0, the ozonation results are inhibited by the acetate ions produced by the reaction itself. This effect has been correctly described in the terms of a complex formed with the low oxidation-state manganese, which successively reacts with the dissolved ozone.     

Characterization of barley straw biochar produced in various temperatures and its effect on lead and cadmium removal from aqueous solutions

Conversion of agricultural wastes into a carbon rich material (i.e. biochar) using pyrolysis process could be an appropriate approach for their management. This study was carried out to convert barley straw to biochar in different temperatures (300, 400 and 500°C) and to investigate the potential of the produced biochar as a sorbent of heavy metals (Pb and Cd). Considering the pretest results of Pb and Cd sorption, the biochar produced at 500°C (BS500) was selected to find effect of pH, the sorbent dose, the initial concentration of Pb and Cd and the contact time on metal removal efficiency. The results showed that the optimum conditions of adsorption were pH = 6, the sorbent dose 1 g/L and the contact time of 45 min. The adsorption kinetics and isotherms had the best fit to the pseudo‐second order and Langmuir models, respectively.     

Removal of rhodamine B (a basic dye) and thoron (an acidic dye) from dilute aqueous solutions and wastewater simulants by ion flotation

The present work deals with removal, by ion flotation, of two dyes: a basic dye (rhodamine B (RB)) and an acidic one (thoron (TH)) from dilute aqueous solutions and simulated wastewaters. These dyes are widely used for analytical and biological staining purposes. Besides, RB is commonly used in dyeing of various industrial products. Therefore, wastewaters emanating from chemical and radiochemical laboratories, and biomedical and biological research laboratories may be contaminated with RB and TH. Ion flotation of these dyes has been investigated over a wide range of pH using the anionic surfactant, sodium lauryl sulfate (NaLS) and the cationic surfactant, cetyltrimethylammonium bromide (CTAB) as collectors. Successful removals could be achieved for RB and TH with the anionic collector, NaLS, and the cationic collector, CTAB, respectively. In addition to the effects of pH and type of collector on the efficiency of removal of each dye, the effects of collector and dye concentrations, frother dosage, ionic strength, bubbling time period and presence of foreign salts were investigated and the optimal removal conditions have been established. Removals exceeding 99.5 % and 99.9% could be achieved for RB and TH, respectively. The results obtained are discussed with respect to dissociation of dye, type of collector, ionic strength and sign and magnitude of charge of added foreign ions. Kinetics of flotation were also studied. Further studies demonstrate that under optimum conditions the developed flotation processes can be applied for the treatment of dye-contaminated wastewaters simulated to those generated at dyeing industries and radiochemical laboratories.     

The removal of nickel,copper and cadmium from aqueous solution using liver moss (Dumortiera hirsute Sw. nees)

The aim of this study was to investigate the use of liver moss (Dumortiera hirsute Sw. nees) as an alternative adsorbent for the removal of nickel, copper and cadmium from aqueous solution. The results showed that equilibrium contact time was 60?min and acidic pH was favourable for removal of metal ions. Higher initial metal ion concentrations led to lower removal. The data were fitted well both Langmuir and Freundlich isotherms. The monolayer adsorption capacities were 30.675, 35.971 and 53.476?mg/g for nickel, copper and cadmium, respectively. The presence of metal ions such as sodium, potassium and magnesium at concentration of 10?mM was found to have no significant effect on the removal of nickel, copper and cadmium. The removal of nickel, copper and cadmium was markedly inhibited, however, in the presence of calcium ion and heavy metal ions mixture in solutions. The kinetic data for removal processes were described by the pseudo-second-order model. The liver moss shows high potential as an economic and abundant material for the removal of metal ions from aqueous solution.     

Removal of arsenic(III) from aqueous solutions using fresh and immobilized plant biomass

The ability of Garcinia cambogia, an indigenous plant found in many parts of India, to remove trivalent arsenic from solution was assessed. Batch experiments were carried out to characterize the As(III) removal capability of fresh and immobilized biomass of G. cambogia. It was found that the kinetic property and uptake capacity of fresh biomass were significantly enhanced by the immobilization procedure. The uptake of As(III) by fresh and immobilized biomass was not greatly affected by solution pH with optimal biosorption occurring at around pH 6--8. The presence of common ions such as Ca and Mg at concentrations up to 100mg/l had no effect on As(III) removal. However, the presence of Fe(III) at 100mg/l caused a noticeable drop in the extent of As(III) removal but the effect was minimal when Fe(III) was present at 10mg/l. The adsorption isotherms quantitatively predicted the extent of As(III) removal in groundwater samples collected from an arsenic-contaminated site in India. Immobilized biomass loaded with As(III) was amenable to efficient regeneration with NaOH solution. Column studies showed that immobilized biomass could be reused over five cycles of loading and elution. The excellent As(III) sequestering capability of fresh and immobilized G. cambogia biomass could lead to the development of a viable and cost-effective technology for arsenic removal in groundwater.     

Characterization of PEI-modified biomass and biosorption of Cu(II), Pb(II) and Ni(II)

The objective of this work is to develop a surface-modified biosorbent with enhanced sorption capacity for heavy metal ions. The biomass of Penicillium chrysogenum was modified with polyethylenimine (PEI) and then crosslinked with glutaraldehyde. The crosslinked PEI was chemically bonded on the biomass surface through the amine and carboxylate groups on the pristine biomass. The presence of the amine group was confirmed by X-ray photon spectroscopy (XPS) and Fourier transform infrared (FTIR) analysis, and the concentration of the amine groups on the biomass surface was found to be 2 mmol/g through potentiometric titration. The rugged morphology of the biomass surface after the modification was observed by scanning electron microscope (SEM). Compared with the pristine biomass, the modified biomass with amine groups showed a significant increase in sorption capacity for three metal ions, namely, copper, lead and nickel. The sorption isotherms of the biomass for three metals were well described by Langmuir equation, with a maximum sorption at 92 mg copper, 204 mg lead and 55 mg nickel per g biomass. The binding sites for the three metals attributed to the amine groups on the biomass surface were verified by FTIR analysis.