Metals removal from aqueous solution by iron-based bonding agents

GOAL AND SCOPE AND BACKGROUND: The application of a promising method, termed sorptive flotation, for the removal of chromium(VI) and zinc ions was the aim of the present paper. A special case of sorptive flotation is adsorbing colloid flotation. Suitable sorbent preparation techniques have been developed in the laboratory. METHODS: Sorptive flotation, consisting of the sorption and flotation processes combined in series, has proved to give fast and satisfactory treatment of the industrial streams and effluents bearing dilute aqueous solutions of zinc and chromium(VI). RESULTS AND DISCUSSION: Goethite has proved to be effective for the removal of chromium(VI) and zinc ions. Also, adsorbing colloid flotation with ferric hydroxide (as the co-precipitant) could be an alternative method to the above-mentioned separation of metal ions. In both cases, chromium(VI) (pH=4) and zinc (pH=7) removal was about 100%. CONCLUSION: The reasons for selecting the iron-based bonding materials, like goethite and/or in-situ produced ferric hydroxide, are that they are cheap, easily synthesized, suitable both for cation and anion sorption, and, furthermore, that they present low risks for adding a further pollutant to the system. Promising results were obtained. RECOMMENDATION AND OUTLOOK: The application of goethite and in-situ produced ferric hydroxide has demonstrated their effectiveness in the removal of heavy metal ions, such as chromium anions and zinc cations. A proposed continuation of current work is the utilization of similar iron oxides, for instance synthesized akaganeite. The comparison between the results reported in this paper with the results reported in the literature, also deserves attention.     

Anion and cation leaching or desorption from activated carbons from municipal sludge and poultry manure as affected by pH.

The conversion of municipal sludge and poultry manure to activated carbon results in a significant ash fraction that contains several different anions and cations. The objectives of this study were to determine whether the select ions are released or leached from virgin carbon into the sorption medium at different pH values. Activated carbon was placed in solutions of pH 1, 5, or 7, and the leaching of six cations (cadmium, chromium, copper, nickel, lead, and zinc) and two anions (arsenate and selenate) was recorded. Considerable quantities of zinc and copper were removed at pH 1 from all carbon sources. However, the amounts leached at pH 5 and 7 were small or undetectable. Our results indicate that leaching or desorption from carbons made from municipal sludge or poultry manure is pH-dependent and occurs readily under highly acidic conditions but minimally under pH conditions typically seen in contaminated water or wastewater.     

Sorption of arsenate and arsenite anions by iron(III)-poly(hydroxamic acid) complex

Iron(III)-poly(hydroxamic acid) resin complex has been studied for its sorption abilities with respect to arsenate and arsenite anions from an aqueous solution. The complex was found effective in removing the arsenate anion in the pH range of 2.0 to 5.5. The maximum sorption capacity was found to be 1.15 mmol/g. The sorption selectivity showed that arsenate sorption was not affected by chloride, nitrate and sulphate. The resin was tested and found effective for removal of arsenic ions from industrial wastewater samples.     

Factors affecting EDTA extraction of lead from lead-contaminated soils

The effects of solution:soil ratio, major cations present in soils, and the ethylenediaminetetraacetic acid (EDTA):lead stoichiometric ratio on the extraction of lead using EDTA were studied for three different Superfund site soils, one rifle range soil, and one artificially lead-contaminated soil. Extraction of lead from the lead-contaminated soils was not affected by a solution:soil ratio as low as 3:1 but instead was dependent on the quantity of EDTA present. Results of the experiments showed that the extraction efficiencies were different for each soil. If sufficiently large amount of EDTA was applied (EDTA-Pb stoichiometric ratio greater than 10), most of the lead were extracted for all soils tested except for a Superfund site soil from a lead mining area. The differences in extraction efficiencies may be due to the major cations present in soils which may compete with lead for active sites on EDTA. For example, iron ions most probably competed strongly with lead for EDTA ligand sites for pH less than 6. In addition, copper and zinc may potentially compete with lead for EDTA ligand sites. Experimental results showed that addition of EDTA to the soil resulted in a very large increase in metals solubility. The total molar concentrations of major cations extracted were as much as 20 times the added molar concentration of EDTA. For some of the soils tested, lead may have been occluded in the iron oxides present in the soil which may affect lead extraction. While major cations present in the soil may be one of the factors affecting lead extraction efficiency, the type of lead species present also play a role.     

Comparison of biochar- and activated carbon-supported zerovalent iron for the removal of Se(IV) and Se(VI): influence of pH,ionic strength,and natural organic matter

Biochar (BC) and activated carbon (AC) were both produced from corn straw. Biochar-supported zerovalent iron (BC-ZVI) and activated carbon-supported zerovalent iron (AC-ZVI) were synthesized and applied for Se(IV)/Se(VI) removal. The sorption capacity of BC-ZVI for Se(IV) and Se(VI) was reported at 62.52 and 35.39 mg g^?1, higher than that of AC-ZVI (56.02 and 33.24 mg g^?1), respectively, due to its higher iron content and more positive charges. The spectroscopic analyses showed that Se(IV)/Se(VI) were reduced to Se(0)/Se(-II) of less toxicity and solubility. The effects of various factors such as pH, ionic strength, co-existing cations and anions, and natural organic matter (NOM) were also investigated. Ionic strength showed no significant effect on Se(IV)/Se(VI) removal, but pH was critical. The presence of NO₃^? and SO₄^2? did not cause obvious inhibition to the removal, while PO₄^3? inhibited the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI) significantly. Common cations (K⁺, Ca²⁺, and Mg²⁺) were found to slightly enhance the removal, while NOM significantly decreased the sorption capacity of BC-ZVI and AC-ZVI for Se(IV)/Se(VI). Besides, NOM showed stronger inhibition effect on AC-ZVI than that on BC-ZVI. These results indicated that BC-ZVI, compared with AC-ZVI, could be a promising sorbent to remove Se(IV)/Se(VI) due to its low cost and high efficiency.

     

Efficient removal of uranium(VI) from aqueous systems by heat-treated carbon microspheres

In this study, uranium(VI) was successfully removed from aqueous solutions using heat-treated carbon microspheres based on a batch adsorption technique. Influence of the parameters, such as solution pH, contact time, initial uranium(VI) concentration, and temperature on the removal efficiency have been investigated in detail. The results reveal that the maximum adsorption capacity of the heat-treated carbon microspheres toward uranium(VI) is 92.08 mg g^?1, displaying a high efficiency for the removal of uranium(VI) from aqueous solution. The experimental data are analyzed using sorption kinetic models. It is revealed that the process obey the pseudo-second-order kinetic model, the determining step might be chemical sorption. The thermodynamic parameters, such as ΔH°, ΔS°, and ΔG° show that the process is endothermic and spontaneous. This work provides an efficient, fast, and convenient approach for the removal of uranium(VI) from aqueous solutions.     

Fixed-bed study for lanthanide (La, Eu, Yb) ions removal from aqueous solutions by immobilized Pseudomonas aeruginosa: experimental data and modelization

A fixed-bed study was carried out by using cells of Pseudomonas aeruginosa immobilized in polyacrylamide gel as a biosorbent for the removal of lanthanide (La, Eu, Yb) ions from aqueous solutions. The effects of superficial liquid velocity based on empty column, particle size, influent concentration and bed depth on the lanthanum breakthrough curves were investigated. Immobilized biomass effectively removed lanthanum from a 6 mM solution with a maximum adsorption capacity of 342 micromolg(-1) (+/-10%) corresponding closely to that observed in earlier batch studies with free bacterial cells. The Bohart and Adams sorption model was employed to determine characteristic parameters useful for process design. Results indicated that the immobilized cells of P. aeruginosa enable removal of lanthanum, europium and ytterbium ions from aqueous effluents with significant and similar maximum adsorption capacities. Experiments with a mixed cation solution showed that the sequence of preferential biosorption was Eu3+ > or = Yb3+ > La3+. Around 96+/-4% of the bound lanthanum was desorbed from the column and concentrated by eluting with a 0.1 M EDTA solution. The feasibility of regenerating and reusing the biomass through three adsorption/desorption cycles was suggested. Neural networks were used to model breakthrough curves performed in the dynamic process. The ability of this statistical tool to predict the breakthrough times was discussed.     

Removal of aqueous lead by poorly-crystalline hydroxyapatites

The use of a phosphorus amendment in altering Pb to a chemically less mobile phase is a promising strategy based on minimizing ecotoxicological risk and improving time and cost efficiency. This study evaluated crystalline and poorly-crystalline hydroxyapatite sorbents on removal of aqueous Pb in response to reaction time, solution pH, and Pb concentration. Batch experiments were conducted using a commercially-available crystalline hydroxyapatite (HA), and two poorly-crystalline hydroxyapatites synthesized from gypsum waste (CHA) and incinerated ash of poultry waste (MHA). Poorly-crystalline hydroxyapatites had greater capacity for Pb removal from a solution with a wider pH range as compared to a crystalline hydroxyapatite. The maximum sorption capacity of Pb determined by the Langmuir model was 500 mg g⁻¹ for CHA, 277 mg g⁻¹ for MHA and 145 mg g⁻¹ for HA. Removal of aqueous Pb by CHA was not dependent on solution pH, with a 98.8% reduction throughout the solution pH range of 2–9, whereas aqueous Pb removal by HA and MHA was pH-dependent with less removal in the neutral solution pH. Poorly-crystalline hydroxyapatites may provide an effective alternative to existing remediation technologies for Pb-contaminated sites.     

Sorption of Zn(II) in aqueous solutions by scoria

We conducted kinetic and equilibrium sorption experiments on removal of Zn(II) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The batch-type kinetic sorption tests under variable conditions indicated that the percentage of Zn(II) removal by scoria increases with decreasing initial Zn(II) concentration, particle size, and sorbate/sorbent ratio. However, the sorption capacity decreases with the decrease of the initial Zn(II) concentration and sorbate/sorbent ratio. Equilibrium sorption tests show that Jeju scoria has a larger capacity and affinity for Zn(II) sorption than commercial powdered activated carbon (PAC); at initial Zn(II) concentrations of more than 10mM, the sorption capacity of Jeju scoria is about 1.5 times higher than that of PAC. The acquired sorption data are better fitted to the Langmuir isotherm than the Freundlich isotherm. Careful examination of ionic concentrations in sorption batches suggests that the sorption behavior is mainly controlled by cation exchange and typically displays characteristics of 'cation sorption'. The Zn(II) removal capacity decreases when solution pH decreases because of the competition with hydrogen ions for sorption sites, while the Zn(II) removal capacity increases under higher pH conditions, likely due to hydroxide precipitation. At an initial Zn(II) concentration of 5.0mM, the removal increases from 70% to 96% with the increase of initial pH from 3.0 to 7.0. We recommend Jeju scoria as an economic and efficient sorbent for Zn(II) in contaminated water.     

Removal of cationic dyes from aqueous solutions using microspherical particles of fly ash

Batch sorption experiments were carried out for the removal of cationic dyes (methylene blue and malachite green) from their aqueous solutions using sorbent made from fly ash-a waste material. Effects of various experimental parameters: initial dye concentration, contact time, pH, adsorbent dosage, solution temperature, surfactant addition and ionic strength on the fly ash sorption of dyes were evaluated. The isothermal data for sorption followed the Langmuir model. The maximum sorption capacity obtained for methylene blue and malachite green was 36.05 mg/g and 40.65 mg/g, respectively. Kinetic studies indicate that sorption on fly ash follows the pseudo-second order kinetics. Present research suggests that fly ash could be an appropriate adsorbent for the removal of basic dyes from aqueous solutions.     

Waste green sands as reactive media for the removal of zinc from water

Waste green sands are industrial byproducts of the gray iron foundry industry. These green sands are composed of fine silica sand, clay binder, organic carbon, and residual iron particles. Because of their potential sorptive and reactive properties, tests were performed to determine the feasibility of using green sands as a low cost reactive medium in permeable reactive barriers (PRBs). Serial batch kinetic tests and conventional batch sorption tests were conducted to determine the removal characteristics for zinc in aqueous solutions. Removal characteristics for zinc in the presence of green sands are comparable to those of Peerless iron, a common reactive medium used in PRBs. High removal capacities for zinc of green sands are attributed to clay, organic carbon, and residual iron particles, which are known sorptive media for heavy metals. Furthermore, high pH values in the presence of clay and residual iron particles enhanced sorption and precipitation of zinc.     

Palygorskite as a feasible amendment to stabilize heavy metal polluted soils

The sorption behaviour of palygorskite has been studied with respect to lead, copper, zinc and cadmium in order to consider its application to remediate soils polluted with these metals. The Langmuir model was found to describe well the sorption processes offering maximum sorption values of 37.2 mg/g for lead, 17.4 mg/g for copper, 7.11 mg/g for zinc and 5.83 mg/g for cadmium at pH 5-6. In addition the effect of palygorskite amendment in a highly polluted mining soil has been studied by means batch extractions and leaching column studies. The soluble metal concentrations as well as the readily-extractable metal concentrations were substantially decreased at any concentration of palygorskite applied to soil (1, 2, 4%), although the highest decrease is obtained at the 4% dose. The column studies also showed a high reduction in the metal leaching (50% for lead, 59% for copper, 52% for zinc and 66% for cadmium) when a palygorskite dose of 4% was applied.     

Effective sorption of perfluorooctane sulfonate (PFOS) on hexadecyltrimethylammonium bromide immobilized mesoporous SiO2 hollow sphere

The hexadecyltrimethylammonium bromide (HDTMAB) immobilized hollow mesoporous silica spheres were prepared for the efficient removal of perfluorooctane sulfonate (PFOS) from aqueous solution. Besides the traditional sorption behavior including sorption kinetics as well as effect of solution pH and temperature, the effect of increasing volume which simulated the natural river where the rate of solute and solvent was relatively constant and solution volume was always changing was investigated. The result indicated that the residual PFOS concentrations in aqueous phase decreased with increasing solution pH and ionic strength, whereas they increased with increasing temperature. The HDTMAB immobilized material still maintained high efficiency after increasing volume, that is, the removal kept more than 99% after the treatment when the initial PFOS concentration was 1 mg L^?1. The uptake behavior and morphology of spheres which was characterized by transmission electron microscopy (TEM) revealed that the additional HDTMAB and mesoporous shell were responsible for the enhanced sorption of PFOS. It was concluded that electrostatic interaction and Ca-bridge role played an important role in the sorption of PFOS on the mesoporous SiO₂ hollow spheres, whereas, hydrophobic interaction contributed to the nice sorption performance of PFOS on the HDTMAB immobilized sorbent.     

Lead sorption by a Mexican,clinoptilolite-rich tuff

Goal, Scope and Background The retention of lead by a Mexican, clinoptilolite-rich tuff from Oaxaca (Mexico) at different pH values was evaluated and the lead sorption mechanisms on the zeolitic material in this work were discussed. Methods Isotherms were determined using lead nitrate solutions (initial pH values between 2 and 5) at 303 K. After the equilibrium was reached, the content of lead in the liquid phases was determined by atomic absorption spectrometry. The elemental composition of the clinoptilolite-rich tuff before and after the lead sorption process was evaluated by electron microscopy. Results The maximum ion exchange capacity of the Mexican, clinoptilolite-rich tuff for lead was 1.4 meq/g at pH 3, considering an ion exchange mechanism in the absence of any precipitated or hydrolyzed lead species in the sorption process or any change in the zeolite network. Langmuir and Freundlich isotherms were also considered in this work for comparison purposes. Discussion It is important to consider the nature of the sorption processes before choosing a model to describe the interaction between the metal ions and the sorbent. Conclusions The chemical lead speciation, the pH, as well as the characteristics of the clinoptilolite-rich tuff are important factors to be considered on the lead sorption process by natural zeolites. The chemical species involved in that process are Na⁺ from the zeolite and Pb²⁺ from the aqueous solution at pH 2 and 3, so that the ion exchange mechanism explains the lead sorption processes by the clinoptilolite-rich tuff through the ion exchange isotherms. The sodium, Mexican, clinoptilolite-rich tuff is a potential adsorbent for lead from aqueous solutions. Recommendations and Perspectives The natural zeolite-rich tuffs are very important as ion exchangers for the treatment of polluted water due to their sorption properties and low cost. The sorption behavior of each natural material depends on their composition. Mexican, clinoptilolite-rich tuff from Oaxaca (Mexico) could be used for the treatment of waste water contaminated with lead. It would be important to propose this material as an alternative as waste water treatment, because it shows good selectivity for the removal of heavy metals from water.     

Removal of aqueous lead by poorly-crystalline hydroxyapatites

The use of a phosphorus amendment in altering Pb to a chemically less mobile phase is a promising strategy based on minimizing ecotoxicological risk and improving time and cost efficiency. This study evaluated crystalline and poorly-crystalline hydroxyapatite sorbents on removal of aqueous Pb in response to reaction time, solution pH, and Pb concentration. Batch experiments were conducted using a commercially-available crystalline hydroxyapatite (HA), and two poorly-crystalline hydroxyapatites synthesized from gypsum waste (CHA) and incinerated ash of poultry waste (MHA). Poorly-crystalline hydroxyapatites had greater capacity for Pb removal from a solution with a wider pH range as compared to a crystalline hydroxyapatite. The maximum sorption capacity of Pb determined by the Langmuir model was 500 mg g⁻¹ for CHA, 277 mg g⁻¹ for MHA and 145 mg g⁻¹ for HA. Removal of aqueous Pb by CHA was not dependent on solution pH, with a 98.8% reduction throughout the solution pH range of 2–9, whereas aqueous Pb removal by HA and MHA was pH-dependent with less removal in the neutral solution pH. Poorly-crystalline hydroxyapatites may provide an effective alternative to existing remediation technologies for Pb-contaminated sites.     

Chromium(VI) sorptive removal from aqueous solutions by nanocrystalline akaganèite

In this study, akaganeite (beta-FeO(OH)) an ironoxyhydroxide material, was used as a low-cost potential adsorbent for the removal of hexavalent chromium from aqueous solutions. The influence of agitation speed, solution pH, initial chromium concentration, sorbent concentration and temperature were evaluated at batch kinetic runs. It was shown that the solid diffusion model, in comparison to simple reaction kinetic models, described better the sorption kinetics. Freundlich and Frumkin isotherm best fitted the equilibrium results. Akaganeite presented a sorption capacity approximately 80 mg Cr(VI) g(-1), under the conditions studied. Flotation was used as a downstream process for the effective removal of the loaded material.     

Lead removal from synthetic leachate matrices by a novel ion-exchange material

This paper discusses the application of a novel polyacrylate-based ion-exchange material for the removal of Pb ions from water. Preliminary testing includes the establishment of the operating pH range, capacity information, and the effect of Ca2+ and anions in the matrix. Batch testing with powder indicates slightly different optimal operational conditions from those used for column testing. The ion-exchanger is excellent for removing Pb from aqueous solutions.     

Sorption of basic and acid dyes from aqueous solutions onto oxihumolite

Naturally occurring kind of weathered and oxidised young brown coal called oxihumolite was used for an adsorptive removal of basic (Methylene Blue, Malachite Green) as well as acid (Egacid Orange, Midlon Black) dyes from waters. It was shown that both kinds of dyes can be sorbed onto oxihumolite. The maximum sorption capacities determined from the parameters of Langmuir isotherms ranged from 0.070 mmol g-1 (for Midlon Black) to 0.278 mmol g-1 (for Malachite Green) and did not differ significantly for basic and acid dyes. The dye sorption (except of Midlon Black) increased in the presence of inorganic salt. Non-ionic surfactants, and surfactants bearing the same charge as the dye exhibited only a minor effect on the dye sorption, whereas oppositely charged surfactants enhanced the dye sorption to a certain extent. The pH value of the aqueous phase exhibited rather pronounced effect on the sorption of acid dyes causing a suppression of the sorption with increasing pH. The sorption of basic dyes, on the other hand, remained almost unchanged in the examined pH range. Oxihumolite is recommended for the treatment of acid wastewaters because of its limited stability in alkaline aqueous solutions.     

Multi-step leaching of Pb and Zn contaminated soils with EDTA

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.     

Evaluating of arsenic(V) removal from water by weak-base anion exchange adsorbents

Arsenic contamination of groundwater has been called the largest mass poisoning calamity in human history and creates severe health problems. The effective adsorbents are imperative in response to the widespread removal of toxic arsenic exposure through drinking water. Evaluation of arsenic(V) removal from water by weak-base anion exchange adsorbents was studied in this paper, aiming at the determination of the effects of pH, competing anions, and feed flow rates to improvement on remediation. Two types of weak-base adsorbents were used to evaluate arsenic(V) removal efficiency both in batch and column approaches. Anion selectivity was determined by both adsorbents in batch method as equilibrium As(V) adsorption capacities. Column studies were performed in fixed-bed experiments using both adsorbent packed columns, and kinetic performance was dependent on the feed flow rate and competing anions. The weak-base adsorbents clarified that these are selective to arsenic(V) over competition of chloride, nitrate, and sulfate anions. The solution pH played an important role in arsenic(V) removal, and a higher pH can cause lower adsorption capacities. A low concentration level of arsenic(V) was also removed by these adsorbents even at a high flow rate of 250–350 h^?1. Adsorbed arsenic(V) was quantitatively eluted with 1 M HCl acid and regenerated into hydrochloride form simultaneously for the next adsorption operation after rinsing with water. The weak-base anion exchange adsorbents are to be an effective means to remove arsenic(V) from drinking water. The fast adsorption rate and the excellent adsorption capacity in the neutral pH range will render this removal technique attractive in practical use in chemical industry.