Myriophyllum alterniflorum DC., biomonitor of metal pollution and water quality. Sorption/accumulation capacities and photosynthetic pigments composition changes after copper and cadmium exposure

Watermilfoil genus Myriophyllum could be used in ecological surveys as in-situ biomonitors of metal pollution and water quality due to its ability to accumulate chemicals. The copper and cadmium sorption characteristics of Myriophyllum alterniflorum have been investigated. The Langmuir and Freundlich isotherms were used to model the metal sorption isotherms and the monolayer sorption capacities, as obtained by the Langmuir isotherm, were determined to be 13.9 mg/g and 11.1 mg/g for Cu2+ and Cd2+ respectively. Results have been compared with previous works on watermilfoils and are in accordance with those obtained on Myriophyllum spicatum. The sorption of the two metals was time-dependent and the kinetics fitted the pseudo-second-order equation well. The data were discussed in terms of ionic radii and HSAB concept. The phytotoxic effects assessed by classical (i.e. changes in biomass, node length) and photosynthetic pigments content endpoints have been investigated using chemometric techniques leading to an effect of cadmium onto photosynthetic pigments.     

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.     

Manganese-oxide-coated alumina: a promising sorbent for defluoridation of water

In this study, adsorption potential of a new sorbent manganese-oxide-coated alumina (MOCA) was investigated for defluoridation of drinking water using batch and continuous mode experiments. The effects of different parameters such as pH, initial fluoride concentration and co-existing ions (usually present in groundwater sample) were studied to understand the adsorption behavior of the sorbent under various conditions. Optimum removal of fluoride ions occurred in a pH range of 4-7. Results of the present study indicate that fluoride adsorption rate and adsorption capacity of MOCA are far superior to that of activated alumina (AA), which was used as the base material for MOCA preparation. The MOCA can be effectively regenerated using 2.5% NaOH as eluent. The Langmuir equilibrium model was found to be suitable for describing the fluoride sorption on AA and MOCA. The maximum fluoride uptake capacity for MOCA and AA was found to be 2.85 and 1.08 mg g(-1), respectively. The kinetic results showed that the fluoride sorption to MOCA followed pseudo--second-order kinetics with a correlation coefficient greater than 0.98. The fluoride sorption capacity at breakthrough point for both the adsorbents was greatly influenced by bed depth. A bed depth service time (BDST) approach was adopted to describe the continuous flow system. The batch and column studies demonstrated the superiority of MOCA over AA in removing fluoride from the drinking water system.     

Selective heavy metals removal from waters by amorphous zirconium phosphate: behavior and mechanism

Selective removal of heavy metals from water has been of considerable concern for several decades. In the present study, the amorphous zirconium phosphate (ZrP) was synthesized and characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron micrography (SEM), thermogravimetric analysis (TGA) as well as pH-titration experiments. Uptake of heavy metals including lead, cadmium, and zinc onto ZrP was studied by using a polystyrene sulfonic-acid exchanger D-001 as a reference sorbent and Ca(2+) as a competing cation due to its ubiquity in natural or industrial waters. The results indicated that the uptake of heavy metals onto ZrP is essentially an ion-exchange process and dependent upon solution pH. In comparison with D-001, ZrP exhibited more favorable sorption of heavy metals particularly in terms of high selectivity, as indicated by the distribution coefficients of ZrP even several orders higher than D-001 towards heavy metals when calcium ion coexisted at a high level in solution. The Fourier transform-infrared (FT-IR) spectroscopic investigation indicated that the uptake of calcium, cadmium, and zinc ions onto ZrP is only driven by the electrostatic interaction, while that of lead ion is possibly dependent upon the inner-sphere complex formation with ZrP. XPS results further elucidated that ZrP displays different sorption affinity towards heavy metals in the same order as selectivity sequence of Pb(2+)>Zn(2+) approximately Cd(2+)>Ca(2+), which can be explained by hard and soft acids and bases (HASB) theory. Moreover, uptake of heavy metals onto ZrP approached to equilibrium quickly and the used ZrP could be readily regenerated for reuse by the dilute HCl solution. Thus, all the results suggest that amorphous ZrP has excellent potential as a sorption material for water treatment.     

Sorption kinetic analysis for the removal of cadmium ions from effluents using bone char

The adsorption of cadmium ions onto bone char has been studied using a batch adsorber. The experimental data was analyzed using four sorption kinetic models--the pseudo-first order, the Ritchie second order, the modified second order and the Elovich equations--to determine the best-fit equation for the sorption of metal ions onto bone char. The best-fit equation was identified using the sum of the errors squared (SSE). Finally, equilibrium studies were used to evaluate the sorption capacity of bone char for cadmium ions and experimental results showed this to be 0.57 mmol g-1 at an equilibrium solution concentration of 3.0 mmol dm-3. Since the sorption capacity is relatively high, bone char can be considered as a suitable sorbent for the adsorption of cadmium in wastewater treatment systems.     

Mercury(II) sorption by waste rubber

Studies were connected to assess the capability of waste tire rubber for removing inorganic mercury from solution. Samples of vulcanized tire rubber were ground to a suitable sorbent size and utilized in batch sorption studies. Research parameters included aqueous mercury concentration, rubber sorbent particle size, solution temperature, and hydrogen ion concentration. Alternate sulfur-free rubber materials were also evaluated in an attempt to identify the sorption mechanism. The studies showed tire rubber to be an efficient sorbent material for mercury removal from waste solutions. Of the parameters investigated, pH was determined to be most crucial, with an optimum pH range of 5.5 to 6.0 for good mercury removal. The diffusion of mercury through pores in the rubber sorbent was shown to be the rate limiting step regarding mercury uptake. Finally, sulfur-free rubber materials were shown to be equally efficient for inorganic mercury removal.     

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.     

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.     

Bismuth recovery from acidic solutions using Cyphos IL-101 immobilized in a composite biopolymer matrix

Impregnated resins prepared by the immobilization of an ionic liquid (IL, Cyphos IL-101, tetradecyl(trihexyl)phosphonium chloride) into a composite biopolymer matrix (made of gelatin and alginate) have been tested for recovery of Bi(III) from acidic solutions. The concentration of HCl slightly influenced Bi(III) sorption capacity. Bismuth(III) sorption capacity increased with IL content in the resin but non-linearly. Maximum sorption capacity reached 110-130mgBig(-1) in 1M HCl solutions. The mechanism involved in Bi recovery was probably an ion exchange mechanism, though it was not possible to establish the stoichiometric exchange ratio between BiCl(4)(-) and IL. Sorption kinetics were investigated through the evaluation of a series of parameters: metal concentration, sorbent dosage, type and size of sorbent particles and agitation speed. In order to reinforce the stability of the resin particles, the IL-encapsulated gels were dried; this may cause a reduction in the porosity of the resin particle and then diffusion limitations. The intraparticle diffusion coefficients were evaluated using the Crank's equation. Additionally, the pseudo-first-order and pseudo-second-order equations were systematically tested on sorption kinetics. Metal can be desorbed from loaded resins using either citric acid or KI/HCl solutions. The sorbent could be recycled for at least three sorption/desorption cycles.     

Highly efficient removal of heavy metals by polymer-supported nanosized hydrated Fe(III) oxides: Behavior and XPS study

The present study developed a polymer-based hybrid sorbent (HFO-001) for highly efficient removal of heavy metals [e.g., Pb(II), Cd(II), and Cu(II)] by irreversibly impregnating hydrated Fe(III) oxide (HFO) nanoparticles within a cation-exchange resin D-001 (R-SO₃Na), and revealed the underlying mechanism based on X-ray photoelectron spectroscopy (XPS) study. HFO-001 combines the excellent handling, flow characteristics, and attrition resistance of conventional cation-exchange resins with the specific affinity of HFOs toward heavy metal cations. As compared to D-001, sorption selectivity of HFO-001 toward Pb(II), Cu(II), and Cd(II) was greatly improved from the Ca(II) competition at greater concentration. Column sorption results indicated that the working capacity of HFO-001 was about 4-6 times more than D-001 with respect to removal of three heavy metals from simulated electroplating water (pH ∼4.0). Also, HFO-001 is particularly effective in removing trace Pb(II) and Cd(II) from simulated natural waters to meet the drinking water standard, with treatment volume orders of magnitude higher than D-001. The superior performance of HFO-001 was attributed to the Donnan membrane effect exerted by the host D-001 as well as to the impregnated HFO nanoparticles of specific interaction toward heavy metal cations, as further confirmed by XPS study on lead sorption. More attractively, the exhausted HFO-001 beads can be effectively regenerated by HCl-NaCl solution (pH 3) for repeated use without any significant capacity loss.     

Remediation of waters contaminated with ionic herbicides by sorption on polymerin

This study investigated the sorption of paraquat and 2,4-D on polymerin, the humic acid-like fraction of olive mill wastewater. Effects of pH, contact time, initial concentration and sorbent dosage on the sorption of both herbicides were studied. The sorption mechanism of paraquat on polymerin was consistent with the ion exchange of this herbicide with Ca, Mg and K natively occurring in the sorbent; in contrast, 2,4-D was bound to polymerin by hydrogen bonding. Simulated wastewaters contaminated with paraquat were purified after three sorption cycles on polymerin renewed at each cycle, at a solid/liquid ratio of 0.5, whereas those containing 2,4-D showed a maximal residue removal of 44% after two sorption cycles at the same ratio. The possible application of this model to other water-soluble herbicides, as well as the possible exploitation of polymerin as a bio-filter for the decontamination of pollution point sources is briefly discussed.     

Arsenic removal using a polymeric/inorganic hybrid sorbent

A fixed-bed sorption process can be very effective in removing trace concentrations of arsenic from contaminated groundwater provided: the sorbent is very selective toward both As(III) and As(V) species; the influent and treated water do not warrant any additional pre- or post- treatment; pH and composition of the raw water with respect to other electrolytes remain unchanged besides arsenic removal, and the sorbent is durable with excellent attrition resistance properties. In addition, the sorbent should be amenable to efficient regeneration for multiple reuse. This study reports the results of an extensive investigation pertaining to arsenic removal properties of a polymeric/inorganic hybrid sorbent. Each hybrid sorbent particle is essentially a spherical macroporous cation exchanger bead within which agglomerates of nanoscale hydrated Fe oxide (HFO) particles have been uniformly and irreversibly dispersed using a simple chemical-thermal treatment. The new sorbent, referred to as hybrid ion exchanger or HIX, combines excellent mechanical and hydraulic properties of spherical polymeric beads with selective As(III) and As(V) sorption properties of HFO nanoparticles at circum-neutral pH. Comparison of the results of fixed-bed column runs between the new sorbent and the polymeric anion exchanger confirmed that both As(V) and As(III) were removed very selectively with HIX. Equally important, no pH adjustment, pre- or post-treatment was warranted. Besides the absence of arsenic, the treated water composition was identical to that of influent water. HIX was amenable to efficient in situ regeneration with caustic soda and could subsequently be brought into service following a short rinse with carbon dioxide sparged water. During fixed-bed column runs, intraparticle diffusion was identified as the primary rate-limiting step for both As(III) and As(V) sorption. Repeated use of the same HIX particles during various laboratory investigations provided strong evidence that the new sorbent possesses excellent attrition resistance properties and retains its arsenic removal capacity over cycles.     

Cadmium kinetics in freshwater clams (Unionidae) under field and laboratory conditions.

Cadmium dosing experiments were carried out with the freshwater clam Unio pictorum in flow-through micro-streams in order to obtain additional information on the kinetics of cadmium accumulation and elimination. Accumulation of cadmium in the kidney was rapid and within 3 weeks a concentration factor of 6000 was found. During elimination (29 weeks), the organs lose about one-third of their cadmium content rather rapidly, but no further elimination occurs. It can be concluded that the process of Cd accumulation is rapid and almost irreversible.     

Sorption of cadmium(II) and zinc(II) ions from aqueous solutions by cassava waste biomass (Manihot sculenta Cranz)

The sorption of two divalent metal ions, Cd(II) and Zn(II), onto untreated and differentially acid-treated cassava waste biomass over a wide range of reaction conditions was studied at 30°C. The metal ion removal from the spent biomass was also measured. The batch experiments show that pH 4.5–5.5 was the best range for the sorption of the metal ions for untreated and acid-treated biomass. Time-dependent experiments for the metal ions showed that for the two metals examined, binding to the cassava waste biomass was rapid and occurred within 30 min and completed within 1 h. High sorption capacities were observed for the two metals. The binding capacity experiments revealed the following amounts of metal ions bound per gram of biomass: 86.68 mg/g Cd, 55.82 mg/g Zn and 647.48 mg/g Cd, 559.74 mg/g Zn for untreated and acid-treated biomass, respectively. It was further found that the rate of sorption was particle-diffusion controlled, and the sorption rate coefficients were determined to be 2.30×10⁻¹ min⁻¹ (Cd²⁺), 4.0×10⁻³ min⁻¹ (Zn²⁺) and 1.09×10⁻¹ min⁻¹ (Cd²⁺), 3.67×10⁻² min⁻¹ (Zn²⁺) for 0.5 and 1.00 M differential acid treatment, respectively. Desorption studies showed that acid treatment inhibited effective recovery of metal ions already bound to the biomass as a result of stronger sulfhydryl-metal bonds formed. Less than 25% of both metals were desorbed as concentration of acid treating reagent increases. However, over 60% Cd and 40% Zn were recovered from untreated biomass during the desorption study. The results from these studies indicated that both untreated and acid-treated cassava waste biomass could be employed in the removal of toxic and valuable metals from industrial effluents.     

Modeling the sorption kinetics of divalent metal ions to hematite

The sorption kinetics of the divalent metals Zn, Co, Ni, and Cd to hematite were studied in single sorbate systems with high sorbate/sorbent ratios (from 1.67 to 3.33mol sorbate/mol sorption sites) in 10mM Na-piperazine N,N'-bis 2-ethane sulfonic acid (Na-PIPES) solution at pH 6.8. The experimental data showed a rapid initial sorption (half-time about 1min) followed by slower sorption that continued for 1-5 days. The sequence of fast to slow sorption kinetics was modeled by slow inner-sphere (IS) complexation in equilibrium with outer-sphere (OS) complexes. Although the OS reaction was fast and considered to be in equilibrium, the extent of OS complexation changed over time due to increased surface potential from the IS complexes. For example, the model showed that the dimensionless OS complexation function, K(os), decreased from 0.014 initially to 0.0016 at steady state due to sorption of 4x10(-5)M Zn(II) to 2gL(-1) hematite. Sorption rate constants, k(ads), for the various divalent metals ranged from 6.1 to 82.5M(-1)s(-1). Desorption rate constants, k(des), ranged from 5.2x10(-7) to 6.7x10(-5)s(-1). This study suggests that the conversion from OS to IS complex was the rate-determining step for the sorption of divalent metals on crystalline adsorbents.     

The availability of cadmium to perfused rainbow trout gills in different water qualities

The uptake of cadmium in perfused gills from rainbow trout (Salmo gairdneri, Rich.) in different water qualities has been studied.In the naturally hard alkaline Uppsala tap water, the calcium concentration was the dominating factor controlling the cadmium transfer through the gills. A strong inverse relationship was measured between the external Ca²⁺ concentration up to 3 mmol l^?1 (< 120 mg Ca²⁺ l^?1), and the Cd transfer. A higher Ca²⁺ concentration (10 mmol l^?1) did not further affect the transfer. Magnesium decreased the transfer, but only at concentrations 4 to 5 times as high as calcium. At a constant Ca²⁺/Mg²⁺ hardness, the transfer was a function of the free cadmium ion activity (Cd²⁺). Ca²⁺ and Mg²⁺ selectively reduced the transfer by a biological mechanism, probably by changing the permeability of the gill epithelium.Cd transfer was not dependent on pH in the range pH 5–7. A lower transfer at pH 7.6 was related to a lower Cd²⁺ activity, probably due to the formation of non-available bicarbonate/carbonate complexes.Cd transfer decreased in the presence of 121 mmol l^?1 NaCl (0.7% salinity). This decrease was not caused by the altered osmotic gradient over the gills. The transfer was proportional to the Cd²⁺ activity. CdCl⁺ and CdCl₂ were not available for the gills.The retention of Cd in perfused gill tissue was proportional to the Cd²⁺ activity in all water qualities tested. Tissue accumulation of Cd was not sensitive to external Ca and Mg and in this respect different from the transfer.     

Immobilization of heavy metals from aqueous solutions using polyacrylamide grafted hydrous tin (IV) oxide gel having carboxylate functional groups

A new adsorbent containing a carboxylate group has been prepared by the surface modification of a polyacrylamide grafted hydrous tin (IV) oxide gel. The product exhibits a very high adsorption potential for Pb(II), Hg(II) and Cd(II). The effect of initial metal ion concentration, adsorbent dose, pH, concentration of light metal ions, and temperature on metal removal has been studied. The process follows a first-order rate kinetics. The intraparticle diffusion of metal ions through pores in the adsorbent was shown to be the main rate limiting step. The equilibrium data fit well with the Langmuir adsorption isotherm. The selectivity order of the adsorbent is Pb(II) > Hg(II) > Cd(II). Adsorption rate constants and thermodynamic parameters were also presented to predict the nature of adsorption. The method was applied on synthetic wastewaters. Acid regeneration has been tried for several cycles with a view to recover the adsorbed metal ions and also to restore the sorbent to its original state.     

Kinetics of cadmium uptake by chitosan-based crab shells

Crushed crab shells were chemically treated to transform the chitin present into chitosan. Three particle sizes with average diameters of 0.65, 1.43 and 3.38 mm, average pore diameters ranging from approximately 300 to 540 A, and a specific surface area of approximately 30 m2/g were obtained. Batch experiments were performed to study the uptake equilibrium and kinetics of cadmium by chitosan. Adsorption equilibrium followed a Freundlich relationship and was found to be independent of particle size indicating that adsorption takes place largely in the pore space. A high initial rate of cadmium uptake was followed by a slower uptake rate suggesting intraparticle diffusion as the rate-limiting step. The kinetic uptake data were successfully modeled using a pore diffusion model incorporating nonlinear adsorption. The effect of boundary layer resistance was modeled through inclusion of a mass transfer expression at the outside boundary. Two fitting parameters, the tortuosity factor (tau) and the mass transfer coefficient at the outside boundary (k(c)) were used. These parameters were unique for all solute and sorbent concentrations. The tortuosity factors varied from 1.5 for large particles to 5.1 for small particles. The mass transfer coefficient varied from 2 x 10(-7) m/s at 50 rpm to 2 x 10(-3) m/s at 200 rpm. At agitation rates below 100 rpm, boundary layer resistance reduced the uptake rate significantly. Its very high sorption capacity and relatively low production cost make chitosan an attractive sorbent for the removal of heavy metals from waste streams.     

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.     

Sorption of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) to synthetic resins

Methyl tert-butyl ether (MTBE) is a widely used gasoline oxygenate. Contamination of MTBE and its major degradation product tert-butyl alcohol (TBA) in groundwater and surface water has received great attention. However, sorption affinity and sorption mechanisms of MTBE and TBA to synthetic resins, which can be potentially used in removal of these contaminants from water, in passive sampling, or in enrichment of bacteria, have not been studied systemically. In this study, kinetic and equilibrium sorption experiments (single solute and binary mixtures) on four synthetic resins were conducted. The sorption affinity of the investigated sorbents for MTBE and TBA decreases in the order Ambersorb 563>Optipore L493>Amberlite XAD4>Amberlite XAD7, and all show higher sorption affinity for MTBE than for TBA. Binary experiments with o-xylene, a major compound of gasoline as co-contaminant, imply that all resins preferentially sorb o-xylene over MTBE or TBA, i.e., there is sorption competition. In the equilibrium aqueous concentration (Ceq) range (0.1-139.0 mg/L for MTBE, and 0.01-48.4 mg/L for TBA), experimental and modeling results as well as sorbent characteristics indicate that micropore filling and/or some other type of adsorption process (e.g., adsorption to specific sites of high sorption potential at low concentrations) rather than partitioning were the dominant sorption mechanisms. Optipore L493 has favourable sorption and desorption characteristics, and is a suitable sorbent, e.g., in bacteria enrichment or passive sampling for moderately polar compounds. However, for highly polar compounds such as TBA, Ambersorb 563 might be a better choice, especially in water treatment.