Cellulose/chitin beads for adsorption of heavy metals in aqueous solution

We successfully prepared the biodegradable cellulose/chitin beads by coagulating a blend of cellulose and chitin in 6 wt% NaOH/5 wt% thiourea aqueous solution with 5% H2SO4 as coagulant, and investigated the adsorption of heavy metals (Pb2+, Cd2+, Cu2+) from an aqueous solution on the beads by atomic absorption spectrophotometer. Batch adsorption experiments were carried out as a function of ion concentrations, initial pH, ionic strength, temperature, adsorption time and desorption time. The results revealed that the cellulose/chitin beads could adsorb effectively Pb2+, Cd2+ and Cu2+ ions, and the uptakes of Pb2+, Cd2+ and Cu2+ ions on cellulose/chitin beads were 0.33 mmol/g at pH0 4, 0.32 mmol/g at pH0 5 and 0.30 mmol/g at pH0 4, respectively. Experimental results also showed that the adsorption of these heavy metals was selective to be in the order of Pb2+ > Cd2+ > Cu2+ in a low ion concentration solution. The adsorption equilibrium time of these heavy metals on beads was 4-5 h, but the desorption time was 5-15 min. Moreover, these beads could be regenerated up to about 98% by treating with 1 mol/L HCl aqueous solution. The mechanisms for the removal of free heavy metal ions by cellulose/chitin beads was based on mainly complexation adsorption model, as well as a affinity of hydroxyl groups of the materials on metals. Therefore, we developed new environment-friendly beads prepared by a simple produce process for removal and recovery of heavy metals.     

Estuarine capacity in removal of trace metals from contaminated river water, Southern Caspian Sea

In the present investigation, the flocculation of dissolved Cd, Cu, Ni, Pb, Mn and Zn with initial concentrations of 1, 2.5 and 5 mg/L in Tadjan River water during mixing with the Caspian Sea water has been studied in order to determine estuarine capacity to remove dissolved metals in the accidental contamination of the river. The flocculation process was investigated on a series of mixtures with salinities ranging from 0.1 to 11 p.p.t. The flocculation rates were indicative of the nonconservative behaviour of Cd, Cu, Ni, Pb, Mn and Zn during estuarine mixing. The order of the final flocculation rate of dissolved metals at 1, 2.5 and 5 mg/L of initial metal concentrations in the river water is as follows:Cu (99%)>Cd (95%)>Zn (88%)>Mn (85%)>Pb (83%)>Ni (73%), Cu(95.6%)>Pb(92.4%)>Cd (90%)>Zn(88.4%)>Mn (81.6%)>Ni(78.8%) and Cd (100%)>Cu(88%)>Ni (85.2%)>Pb (84%)>Zn (83.2%)>Mn (81.2%), respectively. The results also revealed that removal of dissolved metals is not influenced by pH changes and precipitation processes. The flocculation rates revealed that the overall dissolved metal pollution loads may be reduced to about 70% up to about more than 90% during estuarine mixing of Tadjan River with the Caspian Sea water.     

Displacement mechanism of binary competitive adsorption for aqueous divalent metal ions onto a novel IDA-chelating resin: isotherm and kinetic modeling

Adsorptive properties for Cu (II), Pb (II) and Cd (II) onto an iminodiacetic acid (IDA) chelating resin were systematically investigated at the optimal pH-value in both single and binary solutions using batch experiments. The Langmuir isotherm model and the pseudo second-order rate equation could explain respectively the isotherm and kinetic experimental data for sole-component system with much satisfaction. The maximum adsorption capacity in single system for Cu (II), Pb (II) and Cd (II) was calculated to be 2.27 mmol/g, 1.27 mmol/g and 0.65 mmol/g individually. The initial adsorption rate followed the order as Cu (II) > Pb (II) > Cd (II) at the fixed initial concentration, and for each metal the initial sorption rate increased as the initial concentration increased. In addition, the modified Langmuir model could describe the binary competitive adsorption behavior successfully, with which the interaction coefficient was obtained to follow the order as Cu (II) < Pb (II) < Cd (II). Furthermore, in every case of the investigated three binary systems, the reduction in both the uptake amounts and distribution coefficients testified the antagonistic competitive phenomena. Obviously, this novel IDA-chelating resin possessed of a good selectivity toward Cu (II) over Pb (II) and Cd (II) for the obtained highest separation factor values were up to 21.30 and 133.91 in the range of tested. This interaction mechanism between the favorable component and other metal ions could mainly contribute to the direct displacement impact which be herewith illustrated schematically.     

A simplified equilibrium model for sorption of heavy metal ions from aqueous solutions on chitosan

The amounts of sorption of Cu2 , Ni2+, and Zn2+ from water on cross-linked chitosan were measured. Experiments were performed as a function of initial pH (2-5), total metal concentration (0.77-17 mol/m3), and metal concentration ratio (0.25-4) at 25 degrees C in single- and binary-metal systems. The sorption was so highly pH dependent that the isotherm could not be described by one specific equation. A simplified equilibrium model was thus proposed considering competitive sorption of proton and metal ions. The number of active sites on chitosan bound with one metal ion was adjustable and model parameters could be graphically determined. Given initial metal concentrations and solution pH, the proposed model could predict the amounts of sorption of proton and metals as well as the equilibrium pH. In general, application of the model parameters calculated in single-metal systems to the prediction of sorption in binary-metal systems was not satisfactory due to a remarkable effect of competitive sorption.     

Purification of metal electroplating waste waters using zeolites

The sorption behaviour of natural (clinoptilolite) and synthetic (NaP1) zeolites has been studied with respect to Cr(III), Ni(II), Zn(II), Cu(II) and Cd(II) in order to consider its application to purify metal finishing waste waters. The batch method has been employed using metal concentrations in solution ranged from 10 to 200 mg/l and solid/liquid ratios ranged from 2.5 to 10 g/l. The Langmuir model was found to describe well all sorption processes, allowing to establish metal sorption sequences from which the main retention mechanism involved for each metal has been inferred. Synthetic zeolite exhibited about 10 times greater sorption capacities (b_Cr=0.838 mmol/g, b_Ni=0.342 mmol/g, b_Zn=0.499 mmol/g, b_Cu=0.795 mmol/g, b_Cd=0.452 mmol/g) than natural zeolite (b_Cr=0.079 mmol/g, b_Ni=0.034 mmol/g, b_Zn=0.053 mmol/g, b_Cu=0.093 mmol/g, b_Cd=0.041 mmol/g), appearing, therefore, as most suitable to perform metal waste water purification processes. This mineral showed the same high sorption capacity values when used in the purification of metal electroplating waste waters.     

Removal of copper,nickel, cobalt and manganese from aqueous solution by kaolinite

The removal of some heavy metals such as Mn(II), Co(II), Ni(II), and Cu(II) from aqueous solution is studied using a raw kaolinite. The sorption of these metals on kaolinite conformed to linear form of Langmuir adsorption equation. Langmuir C(m) constants for each metal were found as 0.446 mg/g (Mn), 0.919 mg/g (Co), 1.669 mg/g (Ni), 10787 mg/g (Cu) at 25 degrees C, respectively. Also, kinetic and thermodynamic parameters such as enthalpy (deltaH), free energy (deltaG) and entropy (deltaS) were calculated and these values show that adsorption of heavy metal on kaolinite was an endothermic process and the process of adsorption was favoured at high temperatures.     

Removal of divalent heavy metal mixtures from water by Saccharomyces cerevisiae using crossflow microfiltration

The removal of heavy metal ions, Ni2+, Cu2+ and Pb2+ using yeast (Saccharomyces cerevisiae) as carriers in a crossflow microfiltration is investigated. The effects of yeast cell and electrolyte concentrations on the transient and steady-state permeate flux and metal ion rejections are established. It is found that the metal ion rejection reaches a plateau if yeast cell concentration is greater than approximately 2 g/l as a result of cell aggregation. The binding affinity of the metals to yeast cell is Pb2+ > Cu2+ > Ni2+, which is also reflected in the metal ion rejection under identical process conditions. Because of the formation of yeast cell flocks in the presence of Pb2+, permeate flux is also higher for this metal. The presence of NaCl decreases both rejection and permeate flux for Ni2+ and Cu2+ but not for Pb2+. When binary or ternary metal mixtures are used, the rejection of the individual metals is reduced except that of Pb2+. It is found that the pseudo-gel concentration is unaffected by the presence of metal ions.     

Anodic stripping voltammetric study of the lability of Cd, Pb, Cu ions sorbed on humic acid particles

The sorption of Cd, Pb and Cu by humic acid particles has been studied at μg l⁻¹ levels using A.S.V. on a Hg film electrode as the measuring technique. The variables examined included amount of solid present (0.01–0.2% w/v), initial metal ion concn (10–100 μg l⁻¹), systems pH (5.3, 6.35, 8.15) and base electrolyte composition. The calculated capacity for specific adsorption of the metal ions was a few mmol M²⁺ kg⁻¹, or less. The apparent lability of part of the sorbed material was examined by analysing the base solution before and after filtering, and by adding Chelex 100 particles to the suspension. Some sorbed Cd²⁺ was A.S.V. labile, another fraction transferred to the resin. The effect of solution reactions on uptake was studied by making the 1 M CH₃COONa base solution 0.2 M in a range of Na⁺ salts (8 different anions), or in carboxylic acid content (5 acids) or in compounds having S-type bonding groups. Formation of complex ions in solution altered the extent of metal ion uptake, and in the case of Cu A.S.V. peak size, shape and position were varied. It is suggested that natural waters containing suspended matter should be analysed by A.S.V. “as received”, as well as after filtration since response differences provide guidance in respect to the lability of sorbed ions.     

Heavy metal biosorption by gellan gum gel beads

The Ni(2+) accumulation in batch mode from diluted solutions by gel beads of gellan gum (GG), alginate, kappa-carrageenan, agar, agarose, silica gel, polyacrylamide and two mixtures of GG+agar was investigated. All polymeric materials studied accumulated Ni(2+), but gel beads of GG were stable, easily obtainable and showed the highest Ni(2+) accumulation. The pH of the Ni(2+) solution was not critical for Ni(2+) accumulation. Accumulation of metals Cu(2+), Co(2+), Ni(2+), Pb(2+), Cd(2+) and Zn(2+) by GG gel beads reached the equilibrium after 24h. The removal of Pb(2+) and Cu(2+) from the aqueous solution was very efficient, with maximum metal uptake (q(max)) of 0.85 and 0.75 mmol/g dw GG, respectively. The general q(max) sequence was Pb>Cu>Ni approximately Zn=Co>Cd. In an equimolar metal mixture sorption experiment a clear reduction in accumulation was observed, except for Pb(2+) (30%). Heavy metals were desorbed with 100mM sodium citrate.     

Removal of Co(II) and Pb(II) from aqueous solutions by Zn/Al-layered double hydroxide intercalated with hexacyanoferrate (II)-ions

We have studied the possibility of using zinc–aluminum layered double hydroxide intercalated hexacyanoferrate (II)-ions for sorption removal of Cu(II), Co(II) and Pb(II) from aqueous solutions. The article showed high efficiency of a sorbent for removal from aqueous solutions of Cu(II) and P(II). It was found that a model of kinetics of the pseudosecond order the most precisely describes the sorption process of studied ions of heavy metals (R ² > 0.99).     

Phragmites australis: a novel biosorbent for the removal of heavy metals from aqueous solution

Reed (Phragmites australis), a commonly used macrophyte in the wetlands constructed for water purification, was investigated as a new biosorbent for the removal of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) from aqueous solution. The metal adsorption capacity of reed biomass was improved significantly by water-wash, base- and acid-treatment. The maximum sorption of NaOH-pretreated reed biomass was observed near neutral pH for Cu(2+), Cd(2+), Ni(2+) and Zn(2+), while that for Pb(2+) was from an acidic range of pH 4.0 or higher. The maximum metal adsorption capacity on a molar basis assumed by Langmuir model was in the order of Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Pb(2+). Reed biosorbent showed a very high adsorption affinity value, which helps predict its high ability to adsorb heavy metals at low concentration. Desorption of heavy metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after three cycles of adsorption-elution, the adsorption capacity was regained completely and the desorption efficiency of metal was maintained at around 90%.     

Adsorption of heavy metals by a sorbent based on pine bark

Sorption properties of the pine bark treated with a 5% urea solution have been studied with respect to heavy metals Cu(II), Ni(II), Zn(II), and Pb(II). The bark subjected to treatment has higher sorption properties and retains several times as many metals as the untreated bark. Parameters of the Langmuir and Freundlich sorption isotherms were obtained. The possible mechanisms of the bark interaction with urea and reasons for an enhanced metal adsorption on the bark treated with urea solution have been also discussed.     

Adsorption of heavy metals on Na-montmorillonite. Effect of pH and organic substances

Clays (especially montmorillonite and bentonite) are widely used as barriers in landfills to prevent contamination of subsoil and groundwater by leachates containing heavy metals. For this reason it is important to study the adsorption of metals by these clays. The sorption of seven metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) on Na-montmorillonite was studied as a function of pH and in the presence of ligands, forming complexes of different stabilities with the metals of interest. The continuous column method was used as it better simulates natural conditions. The total capacity of Na-montmorillonite towards these metals was determined. The pH variations influence to a higher extent the concentrations of Cu, Pb and Cd in the effluent. Moreover the results suggest that complex formation hinders the sorption of the metals on the clay, with an increasing influence in the order: Mn < or = Pb < or = Cd < or = Zn < Ni < Cu < Cr. The evaluation of the total capacity of Na-montmorillonite shows that this clay is a good sorbent towards all examined metals.     

Pb(II)、Cu(II)、Cd(II)在黄土上二元竞争吸附特性研究

铅、铜、镉是3种具有代表性的重金属污染物,可用于模拟多重离子复合污染情况。研究了离子浓度、土水比等因素对3种元素在黄土上二元竞争吸附特性的影响。等温吸附模型Langmuir、Freundlich和D-R模型都能在一定程度上解释Pb(II)-Cu(II)、Pb(II)-Cd(II)、Cu(II)-Cd(II)在黄土上的竞争吸附性能。黄土对Pb(II)、Cu(II)、Cd(II)的选择顺序为Pb(II)>Cu(II)>Cd(II)。相比单一吸附,黄土对每种离子的吸附容量均有不同程度的下降。溶液的初始浓度越大,3种离子在单位黄土上的最大吸附量也随之增大,吸附效率随之降低;适当增大土水比可提高离子的去除效率。试验结果为黄土作为防污屏障和污水处理材料提供了依据。     

Uptake of heavy metals from synthetic aqueous solutions using modified PEI-silica gels

The decontamination of synthetic Pb(II), Zn(II), Cd(II), Ni(II) solutions was investigated, using silica gels chemically modified with poly(ethyleneimine) (PEI) as sorbents. Two families of sorbents, i.e. silica/PEI and crosslinked silica/PEI, were prepared and characterized. Then the removal of metal ions from synthetic aqueous solutions was studied by static tests. They revealed that the sorption capacities depend on the pH, the initial concentration and to some extent on the nature of the metal. The recovery of the metal cations from the saturated sorbents was possible with diluted acid, only for the crosslinked supports. In this case, the regeneration and reuse without sorption decrease, was demonstrated. The presence of other cations (as Na(+), Ca(2+)) and metals does not affect the sorption capacities.     

Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents: equilibrium and kinetic studies

Natural Jordanian sorbent (consisting of primary minerals, i.e., quartz and aluminosilicates and secondary minerals, i.e., calcite and dolomite) was shown to be effective for removing Zn(II), Pb(II) and Co(II) from aqueous solution. The major mineral constitutions of the sorbent are calcite and quartz. Dolomite was present as minor mineral and palygorskite was present as trace mineral. The sorbent has microporous structure with a modest surface area of 14.4 m(2)g(-1). pH(zpc) (pH of zero point charge) of the sorbent was estimated by alkaline-titration methods and a value of 9.5 was obtained. The sorption capacities of the metals were: 2.860, 0.320, 0.076 mmol cation g(-1) for Zn(II), Pb(II) and Co(II) at pH 6.5, 4.5 and 7.0, respectively. The shape of the experimental isotherm of Zn(II) was of a "L2" type, while that of Pb(II) and Co(II) was of a "L1" type according to Giles classification for isotherms. Sorption data of metals were described by Langmuir and Freundlich models over the entire concentration range. It was found that the mechanism of metal sorption was mainly due to precipitation of metal carbonate complexes. The overall sorption capacity decreased after acid treatment, as this decreased the extent of precipitation on calcite and dolomite. The effect of Zn(II) ions concentration on sorption kinetics was investigated. Kinetic data were accurately fitted to pseudo-first order and external diffusion models which indicated that sorption of Zn(II) occurred on the exterior surface of the sorbent and the contribution of internal diffusion mechanism was insignificant. Furthermore, the sorption rate of Zn(II) was found to be slow, where only 10-20% of the maximum capacity was utilized in the first 30 min of interaction.     

Divalent metal accumulation in freshwater bivalves: an inverse relationship with metal phosphate solubility

Whole soft tissue concentrations of Mn, Co, Ni, Cu, Zn, Pb, Cd and U were measured in two species of freshwater (unionid) bivalves (Hyridella depressa and Velesunio ambiguus) from a minimally polluted site in the Hawkesbury-Nepean River, south-eastern Australia. Although the mean concentrations of metals in the tissue were similar for each bivalve species, their patterns of accumulation were dissimilar. For each metal, positive linear relationships between tissue concentration and shell length (r2 = 0.37-0.77; P < or = 0.001) and tissue dry weight (r2 = 0.29-0.51; P < or = 0.01) were found in H. depressa, but not in V. ambiguus. However, for both species, positive linear relationships were found between the tissue concentration of each divalent metal and Ca tissue concentration (r2 = 0.59-0.97; P < or = 0.001). For both bivalve species, the normalised rates of accumulation of the metals relative to increasing Ca concentration and/or size, were U approximately = Cd > or = Pb > or = Mn > Co > or = Zn > Cu > Ni. The differential rates of accumulation of divalent metals are interpreted as being predominantly governed by their varying loss rates, which are controlled by the differing solubilities (log Ksp values) of the metals in the phosphatic extracellular granules, the demonstrated major sites of metal deposition in the tissue of H. depressa and V. ambiguus. The rates of accumulation of Mn, Co, Zn, Cu and Ni were linearly and inversely related (r2 = 0.91-0.97; P < or = 0.001) to their solubilities as hydrogen phosphates, a finding consistent with the bioaccumulation model previously developed for the alkaline-earth metals. However, for U, Cd and Pb, this linear inverse relationship did not continue to hold, i.e. their rates of accumulation did not increase with decreasing solubility. However, these results are still consistent with the model if U, Cd and Pb are so insoluble in the granules of H. depressa and V. ambiguus over their lifetime (up to approx. 50 years) that there is effectively no loss of these metals, and hence, no differential between their rates of accumulation. The present results reaffirm the use of Ca tissue concentration to predict the tissue concentrations of other divalent metals by explaining up to 94 and 97% of the variability between individual bivalves of H. depressa and V. ambiguus, respectively. The use of Ca tissue concentration to effectively minimise the inherent variability between individuals in their metal tissue improves the ability of an investigator to discern smaller spatial and/or temporal differences in the metal tissue concentrations of these bivalves, and thus to detect metal pollution.     

Flow-injection sample preconcentration for ion-pair chromatography of trace metals in waters

Selected trace transition metal ions have been determined in an FIA/HPLC hyphenated system using on-line preconcentration on cellulose functionalised sorbent Cellex P. For HPLC separation ion-pair chromatography was employed with spectrophotometric detection at 510 nm using post-column derivatisation with PAR. Favourable kinetic conditions of sorption and elution as well as optimisation of hyphenated system allowed to obtain detection limits at sub-microgL(-1) level at 25 min preconcentration time. The developed method was employed for determination of Co(II), Ni(II), Cd(II) and Mn(II) in river water with reasonable agreement of obtained results with electrothermal AAS determination.     

Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric acid-containing wastewater

Heavy metal-contaminated soil and wastewater have been attracting an increasing amount of attention due to the potential threat to the surrounding environment and human health. Thus, in this study, citric acid (CA) and citric acid-containing wastewater (CACW) were selected for an evaluation of the influence of the contamination level of the soil, the concentration of citric acid, the contact time, the soil pH, and the ionic interaction on the desorption characteristics of three heavy metals (i.e., Cr(III), Mn(II), and Ni(II)). According to the experimental results, a high concentration of citric acid, an acidic condition, a low level of contamination, and a lengthy contact time were found to be beneficial for desorbing the heavy metals from the contaminated soil. Based on the experimental and calculated results, the H⁺ ions and organic ligands made substantial contributions to the release and adsorption of the heavy metals. The metal ions on the low selectivity sorption sites were leached out earlier than those on the high selectivity sorption sites. The removal percentages of Cr(III), Mn(II), and Ni(II) using CA with a contact time of 6?h were 39.9%, 77.0%, and 62.8%, respectively. By using the CACW as a desorbent, the removal percentages of Cr(III), Mn(II), and Ni(II) with a contact time of 6?h reached 21.4%, 26.9%, and 63.4%, respectively. This suggests a promising practical application of CACW for removing heavy metals from contaminated soil.     

Quantities and associations of lead, zinc, cadmium, manganese, chromium, nickel, vanadium, and copper in fresh Mississippi delta alluvium and New Orleans alluvial soils

The topic of this study is the effect of anthropogenic metals on the geochemical quality of urban soils. This is accomplished by comparing the metal contents and associations between two alluvial soils of the lower Mississippi River Delta, freshly deposited alluvial parent materials and alluvial soils collected from a nearby urban environment. Fresh alluvium samples (n = 97) were collected from the Bonnet Carré Spillway. The urban alluvial soil samples (n = 4026) were collected from New Orleans and stratified by census tracts (n = 286). The Spillway samples tend to have less Pb and Zn than generally noted for the baseline of natural soils. Except for Mn and V, Spillway alluvium contains significantly less metal than urban soils. For Spillway samples, the median metal content (in microg g(-1)) is 4.7 Pb, 11.1 Zn, 0.7 Cd, 164 Mn, 0.8 Cr, 3.9 Ni, 3.2 V, and 3.9 Cu. For urban soils, the median metal content (in microg g(-1)) is 120 Pb, 130 Zn, 3.2 Cd, 138 Mn, 2.1 Cr, 9.8 Ni, 3.8 V, and 12.7 Cu. Metal associations also differ between Spillway alluvium and urban alluvial soils. Fresh alluvium correlation coefficients between individual metals vary from 0.87 to 0.99 (P < 10(-13)) except for Cr which ranges from 0.57 to 0.68 (P < 10(-7)). The urban soil correlation coefficients for metals and the index value are 0.40-0.98. In urban soils, Pb, Zn, Cr, and Cu are dominant metals and highly associated, with a correlation coefficient ranging from 0.83 to 0.98 (P < 10(-25)). Their strong association justifies the use of GIS to map the integrated soil metal index (sum of the medians of metals by census tract) of New Orleans. Although also positively correlated (0.40-0.68, P < 10(-10)), Cd, Mn, Ni and V differ in their distribution in the city compared to Pb, Zn, Cr and Cu. Overall, significantly higher metal values occur in the inner city and lower values occur in outlying areas. The human health impact of the mixture of metals is not well understood. This study provides empirical data about the mixture and distribution of metals in New Orleans alluvial soils. Given common technical development, especially of traffic flows in cities, similar patterns of soil metals are expected for all US cities and probably international cities as well. Primary prevention of urban metal accumulations is necessary to enhance and sustain the development of urban culture.