Effect of metallic cations on the sorption of pesticides on soil

We studied the adsorption and desorption of two pesticides, namely isoproturon and dimetomorph, onto a model soil sample. We first show that the adsorption of isoproturon depends on pH, from 1 mg g⁻¹ at pH 4 to 2 mg g⁻¹ at pH 10, contrary to the adsorption of dimetomorph (5.8 mg g⁻¹). We also studied the influence of metallic cations, copper(II), iron(III), manganese(II), and chromium(III), on the sorption of isoproturon and dimetomorph. We found that in the case of isoproturon, the presence of metallic cations does influence the retention capacity of the soil sample. The sorption becomes very weak in the presence of copper and chromium, whereas in the case of iron and manganese the sorption properties are slightly modified.     

Lead(II) and cadmium(II) removal from aqueous solution using processed walnut shell: kinetic and equilibrium study

The biosorption potential of processed walnut shell for Pb(II) and Cd(II) ions from aqueous solutions was explored. The effects of pH, contact time, initial ion concentration, and amount of dried adsorbent were studied in batch experiments. The maximum adsorption was achieved within the pH range 4.0–6.0. The equilibrium data were well fitted by the Langmuir isotherm model. The maximum monolayer adsorption capacities were found to be 32?g?kg^?1 and 11.6?g?kg^?1 for Pb(II) and Cd(II) ions, respectively. Kinetic data were best described by the pseudo-second-order model. The structural features of the adsorbent were characterized by Fourier transform infrared spectroscopy, which confirmed the involvement of hydroxyl (–OH), carboxyl (–COO^–), and carbonyl (C=O) groups in metal sorption. This readily available adsorbent is efficient in the uptake of Pb(II) and Cd(II) ions from an aqueous solution and could be used for the treatment of wastewater streams bearing these metal ions.     

Cd2+ adsorption on alkaline-pretreated diatomaceous earth: equilibrium and thermodynamic studies

Naturally occurring diatomaceous earth was modified by alkaline pretreatment, and its effectiveness for Cd²⁺ removal from contaminated water was investigated. Batch experiments were carried out to determine Cd²⁺ adsorption capacity and the efficiency of the sorption process under different experimental conditions. Experimental data showed good fitting to Langmuir and Freundlich isotherms models. The Cd²⁺ maximum adsorption capacity was 0.058 mmol g⁻¹ for raw diatomite and increased to 0.195 mmol g⁻¹ for alkaline-pretreated diatomite with efficiency higher than 96% (diatomite dose 2.5 g L⁻¹, pH 6). Adsorption of Cd²⁺ to alkaline-pretreated diatomite increased as the temperature increased. Thermodynamic parameters were calculated to evaluate the feasibility of the adsorption process at different temperatures. The adsorption process was spontaneous and endothermic. The interaction between Cd²⁺ ions and diatomite surface was weak enough to be considered as physical sorption, confirmed by the low value of activation energy.     

Heavy metals uptake from aqueous solutions using marine algae (Colpomenia sinuosa): kinetics and isotherms

The adsorption of copper, zinc, cobalt, lead and cadmium ions onto Colpomenia sinuosa was studied as a function of contact time, initial metal ion concentration and initial pH. In addition, desorption studies were performed. Characterisation of this adsorbent was also confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) analysis. Batch adsorption experimental data were analysed using Langmuir, Freundlich and Dubinin–Raduschkevich (D–R) adsorption isotherms. The results indicated that the biosorption equilibrium was well described by both the Freudlich and D–R isotherms. Moreover, sorption kinetics was performed and it was observed that equilibrium was reached in<60 min, which could be described by the pseudo-second-order kinetic model for all heavy metals. The sorption of heavy metals onto the biomass was largely dependent on the initial solution pH. The elution efficiency for heavy metal ions desorption from C. sinuosa was determined for 0.1 M HCl, 1.0 M HCl and 1.0 M HNO₃. Desorption efficiency and also adsorption capacity were highest for Pb(II). The results indicate that C. sinuosa has great potential for the removal of heavy metals in an ecofriendly process.     

Preconcentration of tin in environmental and biological samples by ion exchange using modified Amberlite XAD-2

Utilization of Amberlite XAD-2 surface modified by covalent immobilization of brilliant green through an azo spacer for adsorptive enrichment of Sn(II) from environmental and biological samples was highlighted. The resulting resin was characterized by Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, and scanning electron microscopy. The resin retained Sn(II) ions at an optimum pH of 9.5 with a sorption capacity of 40 mg g^?1. The modified sorbent could be reused for 10 cycles without significant changes in sorption capacity. The recovery of Sn(II) was 98% when eluted with 0.1 mol L^?1 ethylenediaminetetraacetic acid. Scatchard analysis revealed that binding sites in the modified resin were homogeneous. The equilibrium adsorption data were analyzed using the Langmuir, Freundlich, Temkin, and Redlich–Peterson isotherm models. The method was applied with satisfactory results for determination of Sn(II) ions in human plasma and sea water.     

The effect of selenium on fluoride — clay interactions: Possible environmental health implications

Previous epidemiological studies have shown that dental fluorosis is endemic in the lowland, dry zone of Sri Lanka, which is considered to be an area in which excessive quantities of fluorides are present in the drinking water supplies. It has been found that kaolinitic clay forms a suitable raw material in the defluoridation of water.It is shown that there is a noticeable effect of selenium and media pH on the reactions involved in the interaction of fluoride with clay. In this study, 1 mM fluoride solutions containing SeO ₃ ^2– (selenite) concentrations of 0 mM, 0.1 mM, 0.5 mM and 1 mM were used in the reactions with kaolinitic clay. The effect of pH was monitored in the range 4 to 8. It was observed that fluoride adsorption was maximum at a pH of 5.6 without either SeO ₃ ^2– or SeO ₄ ^2– , the adsorption capacity being 15.2 mol F^– g^–1 clay. However, when the SeO ₃ ^2– concentration was increased up to 0.5 mM at this optimum pH, the adsorption capacity reduced to 12.8 mol F^– g^–1 clay. Monitoring of the effect of SeO ₄ ^2– and media pH on fluoride adsorption showed that when the SeO ₄ ^2– concentration increases from zero to 0.1 mM, there is a reduction of fluoride adsorption capacity. However, when the SeO ₄ ^2– concentration is further increased from 0.1 mM to 1.0 mM, there was an increase in the fluoride adsorption capacity, indicating a more consistent effect of SeO ₃ ^2– on fluoride-kaolinitic clay interaction than SeO ₄ ^2– .Fluoride concentrations in drinking water supplies have a marked effect on dental health and the geochemistry of selenium appears to play an important role in the geochemical mobility of fluoride ions.     

Trichoderma harzianum: a green sorbent for Pb(II) uptake from aqueous solutions

This investigation describes the use of specially cultivated, nonliving biomass of Trichoderma harzianum as a biosorbent for the batch removal of Pb(II) from a stirred system under different experimental conditions. The metal removal depended upon pH, sorbent particle size, initial Pb(II) concentration, shaking speed, and sorption time. The optimal experimental conditions for the removal of Pb(II) by T. harzianum with an initial metal concentration of 100 mg L^?1 were obtained at a particle size of 53 μm, a pH of 4.5, a shaking speed of 200 rpm, and a contact time of 720 min. The results were analyzed in terms of adsorption isotherms and kinetic models. The Freundlich isotherm model and pseudo second-order model fitted well in the data. T. harzianum proved to be a good biomaterial for accumulating Pb(II) from aqueous solutions (q = 460 mg g^?1).     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Metallothionein induction inMytilus edulis exposed to cadmium

The exposure of mussels,Mytilus edulis, collected from Whitsand Bay, southwest England, in August 1988, to sublethal concentrations of cadmium (400µg l^–1) for 65 d resulted in the induction of metallothionein (MT) synthesis in the soft tissues. In cadmium-exposed mussels, metallothionein concentrations, measured by differential pulse polarography, increased by a factor of three, from 2 to 3 mg g^–1 to a maximum of 9 mg g^–1 after 30 d. No significant changes could be detected in controls. Cadmium accumulated in the soft tissues of mussels correlated significantly with metallothionein concentrations and can be described by the relationship: MT (mg g^–1)=0.045 Cd (µg g^–1)+3.03 (r=0.803,P<0.001). Gel chromatography of heat-treated cytosolic extracts showed that the accumulated cadmium is bound principally to the newly formed metallothioneins. Copper and zinc were also analysed in the whole soft-tissues and in subcellular fractions of cadmium-exposed mussels. Although copper concentrations were not affected by cadmium-exposure, zinc levels were significantly reduced. The results demonstrate that the induction of metallothioneins inM. edulis is a quantifiable biological response to sublethal levels of cadmium exposure.     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

1,3,5-triazine-triethylenetetramine polymer: an efficient adsorbent for removal of Cr(VI) ions from aqueous solution

The synthesis of 1,3,5-triazine-triethylenetetramine (TATETA), its characterization by infrared spectroscopy and elemental analysis, and its application for removal of Cr(VI) ions from aqueous solution is reported. The effects of pH, contact time, initial concentration of Cr(VI), sorbent dose, and temperature on adsorption were investigated and optimized by batch adsorption experiments. Adsorption was highest at acidic conditions with an equilibration time of 25 min. The adsorption followed a Langmuir model, with an adsorption capacity of 303 mg g^?1, was second order in its kinetics, and exothermic and thus spontaneous.     

Suitability of various chemically prepared activated carbons for the removal of copper(II) ions

Studies on the suitability of various chemically prepared activated carbons (CPACs) like straw carbon (SC), sawdust carbon (SDC), dates nut carbon (DNC) and commercial activated carbon (CAC) for the removal of copper(II) ions by adsorption from simulated wastewater have been carried out under batch mode at 30?±?1°C and the results are compared. The percentage removal of Cu(II) ions increased with a decrease in initial concentration, particle size and added electrolytes (ionic strength) and increased with an increase in contact time, dose of adsorbent and initial pH of the solution. The adsorption data were fitted with the Langmuir isotherm. The applicability of the first order kinetic equation viz. Lagergren equation was tested by correlation analysis. The adsorption process is concluded to be a spontaneous, first order reaction, occurring with increased randomness at the solid–liquid interface. Studies on the desorption of Cu²⁺-loaded activated carbons (ACs) were carried out with nitric acid (0.2–1?N). The possibility of reuse of the regenerated ACs in cycle (in cue-one after another) was tested. SC was found to be a suitable adsorbent alternative to CAC among CPACs for the removal of metal ions, in general, and Cu²⁺ ions, in particular.     

Efficient removal of heavy metals from electroplating wastewater using polymer ligands

Poly(hydroxamic acid)-poly(amidoxime) chelating ligands were synthesized from poly(methyl acrylate-co-acrylonitrile) grafted acacia cellulose for removing toxic metal ions from industrial wastewaters. These ligands showed higher adsorption capacity to copper (2.80 mmol?g⁻¹) at pH 6. In addition, sorption capacities to other metal ions such as iron, zinc, chromium, and nickel were also found high at pH 6. The metal ions sorption rate (t_1/2) was very fast. The rate of adsorption of copper, iron, zinc, chromium, nickel, cobalt, cadmium and lead were 4, 5, 7, 5, 5, 8, 9 and 11 min, respectively. Therefore, these ligands have an advantage to the metal ions removal using the column technique. We have successfully investigated the known concentration of metal ions using various parameters, which is essential for designing a fixed bed column with ligands. The wastewater from electroplating plants used in this study, having chromium, zinc, nickel, copper and iron, etc. For chromium wastewater, ICP analysis showed that the Cr removal was 99.8% and other metal ions such as Cu, Ni, Fe, Zn, Cd, Pb, Co and Mn removal were 94.7%, 99.2%, 99.9%, 99.9%, 99.5%, 99.9%, 95.6% and 97.6%, respectively. In case of cyanide wastewater, the metal removal, especially Ni and Zn removal were 96.5 and 95.2% at higher initial concentration. For acid/alkali wastewater, metal ions removing for Cd, Cr and Fe were 99.2%, 99.5% and 99.9%, respectively. Overall, these ligands are useful for metal removal by column method from industrial wastewater especially plating wastewater.     

Uptake of Ni2+ and rhodamine B by nano-hydroxyapatite/alginate composite beads: batch and continuous-flow systems

Alginate encapsulated nano-hydroxyapatite beads were synthesized and characterized by Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface analysis, and X-ray diffraction. Their adsorptive potential for Ni²⁺ and rhodamine B was explored in batch mode and by fixed-bed column passage. In the batch system, maximum uptake capacity for Ni²⁺ was 360 mg g^?1 and 480 mg g^?1 for rhodamine B. In the presence of humic acid, sorption was enhanced. For the continuous-flow system, adsorption was effective at low flow rate. For both pollutants, mass transport resistance increased during adsorption. The overall rates of rhodamine B and Ni²⁺ uptake were found to be controlled by external mass transfer.     

Effect of Ca(II), Fe(II), and Fe(III) on Cu(II) adsorption by a polyvinylidene fluoride-based chelating membrane from Cu(II)–EDTA complex solution

A polyvinylidene fluoride-based membrane bearing the diethylenetriaminepentaacetic acid chelating group was employed to recover Cu(II) from the Cu(II)-ethylenediaminetetraacetic acid complex aqueous solution. Effects of Ca(II), Fe(II), and Fe(III) on Cu(II) uptake were investigated by static batch adsorption tests and dynamic adsorption filtration. Isotherms, kinetics, and breakthrough curves of Cu(II) uptakes in the presence of the three cations at concentrations of 1 mmol L^?1 were elucidated. The three cations showed a positive effect on the Cu(II) uptake; the stimulative roles were in the order of Fe(III) > Fe(II) > Ca(II). They did not alter the adsorption behavior of the membrane; adsorption isotherms and kinetics could be described by Langmuir and Lagergren second-order models, and Cu(II) adsorption was a spontaneous and exothermic process. The presence of Ca(II), Fe(II), and Fe(III) increased the sorption capacity of the membrane stack by 1.3, 1.9, and 3 times. Breakthrough time and the exhaustion time of membrane stacks were also extended.     

Preconcentration of samarium with modified yeast cells for its determination by atomic emission spectroscopy

A chelating-modified biosorbent is produced by coupling of a dye, procion red, to yeast cells. The resulting modified cells have been characterized by Fourier transform infrared, elemental analysis and thermogravimetric analysis and studied for preconcentration and determination of trace Sm(III). The optimum pH value for sorption of the samarium ions is 6.2. The sorption capacity of functionalized modified yeast cells is 7.2 mg g^?1. Recovery was 99% when Sm(III) was eluted with an aqueous solution of 0.1 mol L^?1 ethylenediaminetetraacetic acid. Scatchard analysis suggested that binding sites were homogeneous. The equilibrium data were analyzed using Langmuir, Freundlich, Temkin, and Redlich–Peterson isotherm models, and the respective constants were determined as 1.0 (L mg^?1), 2.9 [(mg g^?1) (L mg^?1)^1/n], 2.4 × 10⁸ (L g^?1), and 30 (dm³ g^?1) at 20 °C. The method was applied for an Sm(III)-containing sample of ceramic industry effluent.     

Improved Cu and Zn sorption on oxidized wheat lignocellulose

We studied the effect an oxidizing treatment of a lignocellulosic substrate, extracted from wheat bran, on the sorption of Cu and Zn. Oxidizing agents, such as potassium permanganate (KMnO₄) or sodium periodate (NaIO₄), creates oxygenated functions, e.g. alcohol and carboxylic acid, which increase the density of functional sites and the binding capacity of lignocellulose towards copper and zinc. We found that the treatment with KMnO₄ is the most efficient, with an increase of about 30–40% metal ion binding, compared to 15–25% using NaIO₄. The investigation of the oxidation process shows that the efficiency of KMnO₄ can be attributed to its affinity towards insaturated double bonds of lignin entities. Oxidized lignocellulose is thus a promising, efficient, and cheap biomaterial for the decontamination of wastewater.