Removal of Heavy Metals from Aqueous Solutions by Precipitation-Filtration Using Novel Organo-Phosphorus Ligands

Abstract

An organophosphorus mixture of sodium mono- and di-(n-hexa-decyl) phosphinate was synthesized and purified, and then used as a ligand to remove heavy metals by precipitation from aqueous nitrate, chloride, and sulfate solutions. The new ligand offers more advantages over the previously studied sodium dioctyl and dodecyl phosphinates. The sodium form of the mono- and di-(n-hexa-decyl) phosphinate has a much lower solubility in water, which contributed to much lower back contamination and much lower loss of the reagent, even when excess amount of ligand was employed. Moreover, an excess amount of the ligand did not alter the filtration characteristics of the resultant precipitate. The heavy metals: lead, cadmium, mercury, cobalt, and nickel were precipitated with the sodium mono- and di-(n-hexa-decyl) phosphinate, NaL, in the form of Pb L _2(s), Cd L _2(s), Hg L _2(s), Co L _2(s), and Ni L _2(s). In the absence of free acid in the feed, a maximum removal of each metal corresponded to the stoichiometric ratio. The residual concentrations of each of the metals at the optimum conditions were measured for the different media and found to be lower than 10 ppb, lower than the acceptable levels for most regions. Lead, as a model heavy metal, was studied in more detail. Adding an acid to the feed solution reduced the removal of lead as some of the phosphinate ligand was converted to the acid form. The presence of chloride and sulfate in the feed solution; up to mole ratios to lead of 5000, and of calcium in the feed solution; up to mole ratio to lead of 200, had no effect on the removal of lead. The ligand was more selective to lead than the other four metals, and the selectivity was in the order Pb > Cd > Co & Ni > Hg. The ligand was regenerated up to 99.99% and the metals were recovered in 100 times more concentrated aqueous solutions.     

Organic reagents for removing heavy metals from a 10-34-0 (N-P2O5-K2O) grade fertilizer solution and wet-process phosphoric acid

Fertilizer solutions and wet-process phosphoric acid (WPA) contain heavy metal impurities such as cadmium, zinc, lead, copper, manganese, and chromium. Trisodium trithiocyanuric acid (TMT-15), sodium trithiocarbonate (5% Na₂CS₃), and sodium polythiocarbonate (Thio-Red II) were evaluated as precipitating agents for heavy metals in a 10-34-0 (N-P₂O₅-K₂O) grade fertilizer solution and WPA. A water-insoluble starch xanthate was also evaluated as an adsorbent for the heavy metals in 10-34-0 (N-P₂O₅-K₂O) and WPA. Arsenic (24–99+%), cadmium (36–97+%), copper (98+%), mercury (96+%), lead (83–88+%), and zinc (8–83+%) precipitated from 10-34-0 (N-P₂O₅-K₂O) upon the addition of each organic reagent, while levels of manganese and chromium were unaffected. Mercury (97+%), lead (75+%), cadmium (11–38%), copper (99+%), and chromium (3–35%) precipitated from WPA upon the addition of 5% Na₂CS₃ and Thio-Red II, while precipitation of manganese and zinc was negligible. The water-insoluble starch xanthate adsorbed mercury (96+%), copper (38–98+%), and lead (24–75%) from 10-34-0 (N-P₂O₅-K₂O) and WPA while adsorption of arsenic, cadmium, manganese, chromium, and zinc was negligible.     

Determination of the competitive adsorption of heavy metal ions on poly(n‐vinyl‐2‐pyrrolidone/acrylic acid) hydrogels by differential pulse polarography

Poly(N‐vinyl‐2‐pyrrolidone) and poly(N‐vinyl‐2‐pyrrolidone/acrylic acid) hydrogels were prepared by gamma irradiation for the removal of heavy metal ions (i.e., lead, copper, zinc, and cadmium) from aqueous solutions containing different amounts of these ions (2.5–10 mg/L) and at different pH values (1–13). The observed affinity order in adsorption of these metal ions on the hydrogels was Zn(II) > Pb(II) > Cu(II) > Cd(II) under competitive conditions. The optimal pH range for the heavy metal ions was from 7 to 9. The adsorption of the heavy metal ions decreased with increasing temperature in both water and synthetic seawater conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2013–2018, 2003     

Development of a Precipitation Based Separation Scheme for Selective Removal and Recovery of Heavy Metals from Cadmium Rich Electroplating Industry Effluents

Abstract

The treatment of electroplating wastes is a serious worldwide problem, because of their high content of many different heavy metals. Chemical precipitation based treatment methods could be an important alternative for fractional selective separation of heavy metals if they are systematically developed by sequencing of pH, adjusting the added portions of precipitating agents, and selecting the optimum time period before removing the precipitate from the solution. In this study, for selective removal and recovery of Cd from real electroplating bath wastewater (containing high amounts of Cd, medium amounts of Zn, Cu, Fe and small amounts of Ni, Co, Mn), a precipitation based separation scheme was developed. The scheme comprised of three consecutive steps: 1) Acid treatment with nitric acid (HNO₃). Cyano‐metal complexes were decomposed in acidification step and complete removal of iron was achieved. 2) Alkali precipitation by sodium hydroxide (NaOH). Large portion of Cd was recovered as pure Cd(OH)₂. 3) As a polishing step sulfide precipitation by sodium sulfide (Na₂S) was applied. pH was the critical parameter in sulfide precipitation. Addition of sodium sulfide in alkali pH range led to cadmium precipitation whereas copper was totally precipitated in acidic pH range. The sulfide precipitation step may be replaced by more environmentally friendly steps (e.g. polymer enhanced ultrafiltration) until the heavy metal concentrations were reduced down to suitable discharge limits.     

The interaction between Cu,Pb, Zn and Ni in their biosorption onto polyurethane‐immobilised Sphagnum moss

The uptake of Cu(II), Pb(II), Zn(II) and Ni(II) was investigated both individually and from mixed metal ion solutions using Sphagnum moss biomass immobilised in a polyurethane support. The data were evaluated using the Langmuir isotherm equation, and sorption capacities were calculated for different concentration ranges. It was concluded that care must be taken in presentation and interpretation of results when this modelling approach is applied at low concentrations. Repeated metal loading cycles also gave lower values for sorption capacity compared with the maximum potential value, due to equilibrium effects. The uptake capacity for the different metals on a weight basis was in the order lead > copper > zinc > nickel, but on a molar basis this changed to copper > lead > nickel > zinc. Sorption from a multi‐component metal system showed that lead and copper competed equally for binding sites and much more effectively than zinc and nickel. Equations were derived to predict the percentage effect on a given metal ion of other metals in a multi‐metal system based their behaviour in the relevant single and binary systems. Copyright © 2005 Society of Chemical Industry     

Synthesis of water‐insoluble functional copolymers containing amide,amine, and carboxylic acid groups and their metal‐ion‐uptake properties

The crosslinked poly[N‐(3‐dimethylamino)propylmethacrylamide] [P(NDAPA)] and poly[N‐(3‐dimethylamino)propylmethacrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] were synthesized by radical polymerization. The resins were completely insoluble in water. The metal‐ion‐uptake properties were studied by a batch equilibrium procedure for the following metal ions: silver(I), copper(II), cadmium(II), zinc(II), lead(II), mercury(II), chromium(III), and aluminum(III). The P(NDAPA‐co‐AA) resin showed a lower metal‐ion affinity than P(NDAPA), except for Hg(II), which was retained at 71% at pH 2. At pH 5, the resin showed a higher affinity for Pb(II) (80%) and Cu(II) (60%), but its affinity was very low for Zn(II) and Cr(III). The polymer ligand–metal‐ion equilibrium was achieved during the first 20 min. By changing the pH, we found it possible to remove between 60 and 70% of Cd(II) and Zn(II) ions with (1M, 4M) HClO₄ and (1M, 4M) HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5232–5239, 2006     

Separation and recovery of heavy metals from concentrated smelting wastewater by synergistic solvent extraction using a mixture of 2-hydroxy-5-nonylacetophenone oxime and bis(2,4,4-trimethylpentyl) -phosphinic acid

Extraction and separation of copper, zinc, nickel, and cadmium from calcium and magnesium in concentrated smelting wastewater by synergistic solvent extraction using a mixture of 2-hydroxy-5-nonylacetophenone oxime (Mextral 84H) and bis(2,4,4 -trimethylpentyl)-phosphinic acid (Cyanex 272) in an aliphatic diluent (DT-100) was studied. The effects of extractant concentrations, equilibrium pH, organic-to-aqueous phase ratios, system temperature, and extraction and stripping efficiencies on the extraction performance of the heavy metals were investigated. Extraction of pH isotherms showed that addition of Cyanex 272 to Mextral 84H causes obvious synergistic shifts for zinc and cadmium and a slightly antagonistic shift for nickel. The separation factor of cadmium over magnesium was 155.7 and the ΔpH₅₀ values between the metals were over 1.00 pH units. Semi-continuous tests for the metals extraction, scrubbing, and stripping were conducted in a continuous extraction apparatus with conditions further optimized for separation of the metals. Nearly 100% of the copper and nickel and over 98% of the zinc and cadmium were recovered with less than 0.1 mg/L copper and nickel, 26 mg/L of zinc, and 10 mg/L of cadmium remaining in the raffinate. A process in which all valuable metals are extracted simultaneously and stripped selectively at optimal conditions is proposed that is entirely feasible for the separation of copper, zinc, nickel, and cadmium from calcium and magnesium in concentrated smelting wastewater. The study determines the fundamental parameters for the treatment of smelting wastewater by solvent extraction.     

Heavy Metals Precipitation in Sewage Sludge

Abstract

There is a great need for heavy metal removal from strongly metal‐polluted sewage sludges. One of the advantages of heavy metal removal from this type of sludge is the possibility of the sludge disposal to landfill with reduced risk of metals being leached to the surface and groundwater. Another advantage is the application of the sludge as soil improver. The use of chemical precipitation to remove dissolved heavy metals from sewage sludge implies a high cost for chemicals. This work shows, for real sewage sludge for the first time that the addition of NaOH as first precipitating agent considerably saves the addition of Na₂S, that is one of the most effective metal precipitating agents and also expensive. After solubilization of heavy metals by chemical leaching with previous aeration, the next step was the separation of the sludge solids from the metal‐rich acidic liquid (leachate) by centrifugation and filtration. Afterwards, the filtered leachate was submitted to the application of NaOH and Na₂S, separately and in combination, followed by filtration. The results showed that when iron and aluminium are present in the leachate, adsorption and/or coprecipitation of Cr, Pb, and Zn with Fe(OH)₃ and Al(OH)₃ might occur at increasing pH conditions. The combination of hydroxide and sulfide precipitation was able to promote an effective removal of heavy metals from leachate. Applying NaOH at a pH of 4–5 as a first precipitation step, followed by filtration and further addition of Na₂S to the filtered liquid at pH of 7–8 as a second precipitation step, decreased considerably the dosage of the second precipitant (almost 200 times), compared to when it was solely applied. This has practical applications, as the claimed costs drawbacks of H₂S addition is considerably reduced by the addition of the less expensive NaOH. The best removal efficiencies obtained were: Pb: ～100%, Cr: 99.9%, Cu: 99.7%, and Zn: 99.9%.     

The solvent extraction of nickel from acidic solutions using synergistic mixtures containing pyridinecarboxylate esters. Part 2: Systems based on alkylsalicylic acids

The synergistic solvent extraction of nickel and cobalt by pyridinecarboxylate esters (2-, 3- or 4-C₅H₄N.CO.OR) in admixture with 3-bromo- or 3-nitro-derivatives of 5-alkylsalicylic acids was studied. Nickel is extracted more strongly than cobalt in all cases and, for systems containing a given pyridinecarboxylate, the pH₅₀ values (pH values for 50% extraction) of both metals decrease in the order: alkylsalicylic acid > bromo-derivative > nitro-derivative. For systems containing a given salicylic acid, the separation between the pH₅₀ values for nickel and cobalt was found to increase in the order: pyridine 2-ester < 4-ester ≈ 3-ester. The extractability of divalent base metals from sulphate solutions by mixtures of isodecyl 3- or 4-pyridinecarboxylate and 3-bromo- or 3-nitro-5-nonylsalicylic acid in Shellsol K decreases through the series: Cu > Ni > Co ≈ Zn > Ca > Mg. In single-stage batch extraction experiments with a simulated leach liquor containing Ni 2·2, Cu 0·5, Ca 0·4 and Mg 5·0 g dm⁻³ (and smaller amounts of other base metals), adjustment of the equilibrium pH value to between 3·3 and 4·0 with magnesium oxide gave extractions of nickel and copper of 97–100%, with co-extractions of calcium and magnesium of <0·5 and <0·1%, respectively. Amongst the metals present in lower concentrations, manganese (2–5%) and lead (5–10%) were extracted only slightly whereas cobalt (40–80%), zinc (15–65%) and iron (100%) were more strongly extracted.     

Selective sorption of heavy metal on phosphorylated sago starch‐extraction residue

The phosphorylated sago starch‐extraction residue (P‐SR) was produced for the removal of heavy metal from wastewater. The phosphoric ester in the phosphorylated residue was evaluated by means of infrared microspectrometry and solid‐state NMR. In this study, the phosphorus contents of produced P‐SR, phosphorylated cellulose (P‐C), and phosphorylated sago starch were 31.7, 34.2, and 4.6 mg/g, respectively. The phosphorus contents of P‐C and sago starch were clearly different because of the difference of each structure. The maximum sorption capacities of heavy metals (cadmium, lead, copper, and zinc) in single heavy metal sorption on P‐SR were 0.20, 0.25, 0.36, and 0.24 mmol/g (Cu > Pb > Zn > Cd), respectively. On the other hand, the amount of sorbed heavy metals in coexisted heavy metal sorption on P‐SR followed the order of Pb > Cu > Cd > Zn that was different from the relations of maximum sorption capacities for individual heavy metals. The heavy metal sorption behavior in single and coexisted heavy metal solution for P‐SR were different and P‐SR showed the intrinsic heavy metal sorption affinity, called as selective sorption. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Modelling Individual and Competitive Adsorption of Cadmium(II) and Zinc(II) Metal Ions from Aqueous Solution onto Bagasse Fly Ash

Abstract

The present study deals with the competitive adsorption of cadmium (Cd(II)) and zinc (Zn(II)) ions onto bagasse fly ash (BFA) from binary systems. BFA is a waste obtained from the bagasse‐fired boilers of sugar mills. The initial pH≈6.0 is found to be the optimum for the individual removal of Cd(II) and Zn(II) ions by BFA. The equilibrium adsorption data were obtained at different initial concentrations (C ₀ = 10–100 mg/l), 5 h contact time, 30°C temperature, BFA dosage of 10 mg/l at pH ₀ = 6. The Redlich–Peterson (R–P) and the Freundlich models represent the single ion equilibrium adsorption data better than the Langmuir model. The adsorption capacities in the binary‐metal mixtures are in the order Zn(II)>Cd(II) and is in agreement with the single‐component adsorption data. The equilibrium metal removal decreases with increasing concentrations of the other metal ion and the combined action of Cd(II) and Zn(II) ions on BFA is found to be antagonistic. Equilibrium isotherms for the binary adsorption of Cd(II) and Zn(II) ions on BFA have been analyzed by non‐modified Langmuir, modified Langmuir, extended‐Langmuir, Sheindorf–Rebuhn–Sheintuch (SRS), non‐modified R–P and modified R–P adsorption models. The isotherm model fitting has been done by minimizing the Marquardt's percent standard deviation (MPSD) error function using MS Excel. The SRS model satisfactory fits for most of the adsorption equilibrium data of Cd(II) and Zn(II) ions onto BFA.     

Electrokinetic remediation of lead‐, zinc‐ and cadmium‐contaminated soil

Electrokinetic remediation of lead‐, zinc‐ and cadmium‐contaminated sand and clayey soils has been investigated under laboratory‐scale conditions. Soil extracts of heavy metals (by 1 M HCl solution) were analysed by optical emission spectrometry. The efficiency of electrochemical remediation was partially dependent on the pH of the soil media. With pH increase, the migration of heavy metal ions toward the cathode was limited. When acetic acid was added to the sandy soil, almost complete remediation was achieved. A clay layer inserted in the cathode area did enhance the remediation rate. The most effective clean‐up was achieved for zinc and cadmium, with less effective clean‐up being achieved for lead. The effectiveness of the electrokinetic remediation of heavy metal‐contaminated clayey soil was low. The appropriate acidity was not achieved using acetic acid because of the high buffering capacity of clay, and metal ion migration was impeded by its sorption onto some clay components. The conclusion was made that clays could be used as immobilizing media for heavy metal ions by electrokinetic remediation of various soils. © 2001 Society of Chemical Industry     

Potential of carbon nanomaterials for removal of heavy metals from water

Heavy metals, such as, cadmium, lead, nickel and zinc can be removed from water using sorbents. The rate and extent of removal may be enhanced by choice of appropriate sorbents. In this study heavy metal sorption was studied on indigenously synthesized carbon nanomaterials (CNMs). Two CNMs differing in surface morphology were synthesized using turpentine oil in a chemical vapour deposition (CVD) setup by varying the process parameters. Activation and catalyst removal were achieved by post-treatment with HNO₃ and KOH. Characterization of the CNMs produced revealed that both comprised of graphitic amorphous carbon, however, while the nanocarbon (NC) produced using cobalt catalyst in N₂ atmosphere comprised of varying grain sizes indicative of soot, the nanoporous carbon (NPC) produced using silica catalyst in H₂ atmosphere had a distinctive uniformly porous surface morphology. Comparative sorption studies with cadmium, lead, nickel and zinc also revealed greater sorption on NPC compared to NC. Batch isotherms for the various heavy metals using NPC and a commercial activated carbon (AC) widely used for metal sorption revealed that NPC is characterized by significantly higher metal sorption capacity and more favourable sorption energetics. The superior performance of NPC as a sorbent may be due to its unique nanoporous structure.     

Sensing of toxic metals through pH changes using a hybrid sorbent material: Concept and experimental validation

This article reports a new hybrid sorbent material that is capable of detecting trace concentration of toxic metals, such as zinc, lead, copper, nickel, etc., through pH changes only. The material is essentially a composite granular material synthesized through rapid fusion of a mixture of amorphous hydrated ferric oxide (HFO) and akermanite or calcium magnesium silicate (Ca₂MgSi₂O₇). When a water sample is rapidly passed through a mini‐column containing this hybrid material, effluent pH at the exit always remains alkaline (≈9.0) because of slow hydrolysis of akermanite and steady release of hydroxyl (OH^?) ions. This exit solution turns pink through the addition of a phenolphthalein indicator. Commonly encountered electrolytes containing sodium, calcium, chloride, and sulfate have no impact on the exit pH from the mini‐column. However, when trace concentration of a heavy metal (say lead) is present in the sample water, a considerable drop in pH (>2 units) is observed for the exiting solution. At this point, the solution turns colorless through the addition of a phenolphthalein indicator. Moreover, the change in the slope of pH, i.e., ?dpH/dBV, provides a sharp, noticeable peak for each toxic metal where BV is the bed volumes of solution fed. The technique allowed detection of zinc and lead through pH swings in synthesized samples, spiked Bethlehem City water, and also in Lehigh River water in the presence of phosphate and natural organic matter (NOM). Using a simple preconcentration technique, lower than 10 μg/l of lead was detected with a significant peak. From a mechanistic viewpoint, high sorption affinity of HFO surface sites toward toxic metal cations, ability of akermanite to maintain near‐constant alkaline pH for a prolonged period through slow hydrolysis and labile metal‐hydroxy complex formation causing dissipation of OH^? ions from the aqueous phase provide a synergy that allows detection of toxic metals at concentrations well below 100 μg/l through pH changes. Nearly all previous investigations pertaining to toxic metals sensing use metal‐selective enzymes or organic chromophores. This simple‐to‐operate technique using an inexpensive hybrid material may find widespread applications in the developing world for rapid detection of toxic metals through pH changes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Synthesis,Characterization, and swelling behaviors of acrylic acid/carboxymethyl cellulose superabsorbent hydrogel by glow‐discharge electrolysis plasma

This article exploits a new approach for synthesis of acrylic acid/carboxymethyl cellulose (AA/CMC) superabsorbent hydrogel in aqueous solution by a simple one‐step using glow‐discharge electrolysis plasma, in which N,N′‐methylenebisacrylamide (MBA) was used as a crosslinking agent. The reaction parameters affecting the equilibrium swelling, that is, discharge voltage, discharge time, mass ratio of AA to CMC, content of crosslinker, and degree of neutralization, were systematically optimized to achieve a superabsorbent hydrogel with a maximum equilibrium swelling. The structure, thermal stability, and morphology of AA/CMC superabsorbent hydrogel were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction analysis, thermogravimetric analysis, and scanning electron microscopy. The swelling kinetics in distilled water and swelling behaviors in various pH solutions and salts solutions (NaCl, KCl, MgCl₂, CaCl₂, AlCl₃, and FeCl₃) were investigated in detail. The effect of six cationic salt solutions on the equilibrium swelling had the following order K⁺ > Na⁺ > Mg²⁺ > Ca²⁺ > Al³⁺ > Fe³⁺. In addition, the pH‐reversibility was preliminarily investigated with alternating pH between 6.5 and 2.0. The results showed that the equilibrium swelling of AA/CMC was achieved in 90 min. The hydrogel was responsive to the pH and salts, and was reversible swelling and deswelling behavior. POLYM. ENG. SCI., 54:2310–2320, 2014. © 2013 Society of Plastics Engineers     

Modelling Cd(II) removal from aqueous solutions by adsorption on a highly mineralized peat. Batch and fixed‐bed column experiments

This paper evaluates the potential use of a locally available organic soil amendment as a low‐cost adsorbent. The removal of cadmium from aqueous solutions was studied by means of kinetic, batch and fixed‐bed experiments. Batch experiments were conducted to evaluate the process kinetics and the removal equilibrium over a broad pH range. Pseudo‐second‐order kinetics and Freundlich equilibrium parameters were obtained. Six column experiments were carried out at different flow‐rates and feed concentrations. Breakthrough curves showed higher metal retention than expected from the batch adsorption isotherms. Column modelling assuming rate‐controlled pore diffusion was successfully performed. The adsorption process was reversed, regenerating the columns by eluting the cadmium using 0.1 mol dm^?3 hydrochloric acid. The high retention capacity together with the favourable structural characteristics indicated that this material could be used as an effective and low‐cost adsorbent for treatment of wastewaters containing heavy metals. Copyright © 2006 Society of Chemical Industry     

Micellar-Enhanced Ultrafiltration of Heavy Metals Using Lecithin

Abstract

Conventional treatment methods for removal of heavy metals from metal finishing operations are usually energy-intensive and costly. Micellar-enhanced ultrafiltration (MEUF) with synthetic surfactants is a recently developed technique which can remove heavy metals and other small molecular weight ions from wastestreams at relatively lower costs and without a phase change. Lecithin, a natural, inexpensive, nontoxic, and biodegradable surfactant exhibits emulsifying characteristics which can be used in a MEUF. The binding of various lecithins to cadmium, copper, lead, nickel, and zinc—in a mixture and individually—was studied using a continuous diafiltration method. This technique uses small volumes of toxic waters and produces an entire isotherm with just one experiment. In the presence of all five heavy metals, the lecithin in this study showed the following affinity: Cu > Cd ～ Zn > Ni. In experiments when only one metal was present, lecithin exhibited the following affinity: Ni > Cu ～ Zn > Cd. Lead was not bound significantly in either scenario.     

Removal of Cadmium from Aqueous Solution using Wheat Stem,Corncob, and Rice Husk

Three kinds of agricultural by-products, wheat stem, corncob, and rice husk, were tested as biosorbents for cadmium removal from aqueous solution. The study was focused on the evaluation and comparison of the potential of the agriculture by-products as biosorbents of cadmium with the sorption isotherms determination. The impact of solution pH and kinetic study was also discussed. The result indicated that cadmium removal was strongly dependent on solution pH and the optimum pH range is 4.5 ～ 6.0. The sorption process was fast, and the sorption equilibrium can be attained within 60 min. The kinetic process fit well with the pseudo-second-order kinetic model. For the three kinds of biosorbents, the initial sorption rate as well as the maximum sorption capacity q _max calculated from the Langmuir isotherm equation showed the following tendency: rice husk > wheat stem > corncob. The maximum sorption capacity of the three kinds of biosorbents enhanced after being base treated, especially for wheat stem and corncob. This study indicated that wheat stem, corncob, and rice husk displayed the potential to be used as biosorbents for cadmium removal from aqueous solution.     

Sorption characteristics of heavy metal ions by a natural zeolite

Zeolites have been shown to be effective adsorbents for the removal of heavy metals from aqueous solutions. A natural material from Cuba, containing zeolite, has been used for the removal of several metal ions, namely Cu²⁺, Zn²⁺, and Ni²⁺, to evaluate its potential use as a low‐cost adsorbent. Batch experiments have been conducted to evaluate the process kinetics and the removal equilibrium at different pH values, metal and zeolite concentrations. Pseudo‐second order kinetics and Freundlich equilibrium parameters have been obtained. Results suggested that this natural zeolite has a high potential for heavy metal retention. The selectivity of the studied metals was determined as Cu²⁺ ? Zn²⁺ > Ni²⁺, related to the first hydrolysis equilibrium constant. The metal removal efficacy was strongly dependent on pH, and to a lesser extent on metal/zeolite ratio. Copyright © 2005 Society of Chemical Industry     

Biosorption of heavy metals (Cd,Cu, Ni,Pb, Zn) by chemically-reinforced biomass of marine algae

Particles of two different sizes (0·105–0·295 mm and 0·84–1.00 mm diameter) of two marine algae, Sargassum fluitans and Ascophyllum nodosum, were crosslinked with formaldehyde (FA), glutaraldehyde (GA) or embedded in polyethylene imine (PEI), followed by glutaraldehyde crosslinking. They were used for equilibrium sorption uptake studies with cadmium, copper, nickel, lead and zinc. The metal uptake by larger particles (0·84–1·00 mm) was higher than that by smaller particles (0·105–0·295 mm). The order of adsorption for S. fluitans biomass particles was Pb > Cd > Cu > Ni > Zn, for A. nodosum copper and cadmium change places. Uptakes of metals range from q_max = 378 mg Pb g^?1 for S. fluitans (FA, big particles), to q_max = 89 mg Zn g^?1 for S. fluitans (FA, small particles) as the best sorption performance for each metal. Generally, S. fluitans is a better sorbent material for a given metal, size and modification, although there were several exceptions in which metal sorption by A. nodosum was higher. The metal uptake for different chemical modifications showed the order GA > FA > PEI. A comparison of different sorption models revealed that the Langmuir sorption model fitted the experimental data best.