Sorption selectivity of cobalt(II), nickel(II), and copper(II) ions by KB-2E macroreticular carboxylic cation exchanger from aqueous-salt solutions of alkali metals

Sorption selectivity of copper(II), nickel(II), and cobalt(II) ions by KB-2E macroreticular carboxylic cation exchanger in the Na-form from dilute solutions was studied in the target concentration range (0.52.6) 103 M. The equilibrium distribution coefficients of Co²⁺, Ni²⁺, and Cu²⁺ were calculated. The role played by hydration of ions in their sorption by KB-2E cation exchangers is analyzed with consideration for IR spectroscopic, thermal analysis, and scanning electron microscopic data.     

Hexacyanoferrate-based composite ion-sensitive electrodes for voltammetry

Composite electrodes made of graphite, paraffin and metal hexacyanoferrates exhibit a voltammetric response of the hexacyanoferrate ions, the potential of which depends linearly on the logarithm of concentration of alkali and alkaline-earth metal ions. This behaviour has been observed on account of the fact that the electrochemical reaction is accompanied by an exchange of these ions between the solution and the zeolitic lattice of the hexacyanoferrates for charge compensation. The voltammetric determination of the formal potential of these electrodes in a solution allows the quantitative analysis of the ions which are exchanged between the metal hexacyanoferrates and the aqueous solutions. Iron(III), copper(II), silver(I), nickel(II) and cadmium(II) hexacyanoferrates have been studied for the determination of H⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH⁺₄, Mg²⁺, Ca²⁺ and Ba²⁺. In some cases, the selectivity constants are as low as 310^-4, or even so small that their exact value is inaccessible. Electrodes made of iron (III), copper (II), silver (I), nickel (II) and cadmium (II) hexacyanoferrates are most suitable for the determination of potassium ions. Electrodes with nickel (II) and cadmium (II) hexacyanoferrates are also suitable for the determination of caesium ions. The working range of the electrodes also depends on the conductivity of the solutions and can range from 10^-5 to 1 moll^-1. Typical standard deviations of the potential measurements are 3 mV.     

Synthesis of N-Methyl-2-Thioimidazole Resin and Its Complex Behavior for Noble Metal Ions

The functional group capacity and the percentage of functional group conversion of crosslinked polystyrene resin bearing N-methyl-2-thioimidazole (MTIR) synthesized under optimum conditions are as high as 4.08 mmol/g resin and 96.0%, respectively. The apparent activation energies of sorption of MTIR for Au(III) and Pt(IV) are 13.1 and 13.4 kJ/mol, respectively. The sorption behavior of MTIR for Au(III), Pt(IV), and Pd(II) obeys the Freundlich and Langmuir isotherms. The sorption capacities of MTIR for Au(III), Pt(IV), and Pd(II) are as high as 4.33, 2.12, and 2.33 mmol/g resin, respectively. Au(III), Pt(IV), and Pd(II) adsorbed on MTIR can be eluted quantitatively by the eluant. The resin can be regenerated easily and reused without an obvious decrease in the sorption capacity for Au(III) and Pd(II). The resin has high sorption selectivity for noble metal ions. Au(III) can be separated quantitatively in the presence of high concentrations of Cu²⁺, Fe³⁺, Ni²⁺, and Mn²⁺. The recovery of platinum from the spent industrial catalysts is 98.6% by MTIR. The preconcentration and separation of palladium and platinum from the anode deposits of electrolysis of crude copper have been investigated. The resin may have potential industrial uses.     

Removal of Cu(II), Cd(II) and Cr(III) ions from aqueous solution by dam silt

The removal of heavy metals, such as Cu(II), Cd(II) and Cr(III) from aqueous solution was studied using Chorfa silt material (Mascara, Algeria). The main constituents of silt sediment are quartz, calcite and mixture of clays. The experimental data were described using Freundlich, Langmuir, Dubinin–Radushkevich (D–R) and Langmuir–Freundlich models. The adsorbed amounts of chromium and copper ions were very high (95% and 94% of the total concentration of the metal ions), whereas cadmium ion was adsorbed in smaller (55%) amounts. The Langmuir–Freundlich isotherm model was the best to describe the experimental data. The maximum sorption capacity was found to be 26.30, 11.76 and 0.35 mg/g for Cr³⁺, Cu²⁺ and Cd²⁺, respectively. The results of mean sorption energy, E (kJ/mol) calculated from D–R equation, confirmed that the adsorption of copper, chromium and cadmium on silt is physical in nature.     

Liquid—liquid extraction of metal ions by the sulfide podand 1,12-di-2-thienyl-2,5,8,11-tetrathiadodecane

The sulfide podand (an open-chain neutral mutlidentate ligand with six sulfur donor atoms) 1,12-di-2-thienyl-2,5,8,11-tetrathiadodecane (TTD) was synthesized. Its extracting properties were examined with 1,2-dichloroethane and 4-methylpentan-2-one as solvents. The reagent showed high selectivity for silver(I) and copper(I) ions; mercury(II) was extracted (ca. 97%) under certain conditions. Extraction of silver(I) was studied in detail with ^110mAg tracer. Log D values ?2 were obtained for the range from pH 6 (with perchlorate as counter-ion) to 2 M perchloric acid or 6 M nitric acid. The ratio of Ag:TTD in the complex was 1:1. Silver could be back-extracted with 4–6 M hydrochloric acid.     

Some synthesized polymeric composite resins for the removal of Co(II) and Eu(III) from aqueous solutions

Summary The ion-exchange and sorption characteristics of new polymeric composite resins, prepared by gamma radiation were experimentally studied. The composite resins show high uptake for Co(II) and Eu(III) ions in aqueous solutions in a wide range of pH. The selectivity of the resins for Co(II) or Eu(III) species in presence of some competing ions and complexing agents (as Na⁺, Fe³⁺, EDTANa₂, etc.) was compared. Various factors that could affect the sorption behavior of metal ions (Co(II) and Eu(III)) on the prepared polymeric composite resins were studied such as ionic strength, contact time, volume mass ratio.     

Phenoxazine‐based Near‐infrared Fluorescent Probes for the Specific Detection of Copper (II) Ions in Living Cells

Abstract : It is well known that copper ions play a critical role in various physiological processes. However, a variety of human diseases are tightly correlated with copper overload. Although there are numerous fluorescent probes capable of detecting copper ions, most of them are “turn‐off” probes owing to copper (II) ions fluorescence quenching effect, resulting in poor sensitivity. Herein, a novel “turn‐on” near‐infrared (NIR) fluorescent probe PZ‐N based on phenoxazine was designed and synthesized for the selective detection of copper (II) ions (Cu²⁺). Upon the addition of Cu²⁺, the probe could quickly react with Cu²⁺ and emit strong fluorescence, along with colour change from colourless to obvious blue. Moreover, the probe PZ‐N showed good water solubility, high selectivity, and excellent sensitivity with low limit of detection (1.93 nM) towards copper (II) ions. More importantly, PZ‐N was capable of effectively detecting Cu²⁺ in living cells.     

Near-Infrared Fluorimetric Determination of Copper(Ⅱ) Ions Using CdHgTe Nanorods as Probe

Stable water‐soluble CdHgTe nanorods with an emission wavelength at 722 nm, obtained by doping Hg²⁺ into CdTe nanorods, has been used as a near‐infrared region (NIR) probe to investigate their interaction with copper(II) ions. A new fluorimetric method for the determination of copper(II) ions has been developed based on the quenching effect of copper(II) ions on the emission of CdHgTe nanorods. The mechanism studies show that an effective electron transfer from nanorods to the copper(II) ions occurred based on the coordination reaction between copper(II) ions and the carboxyl groups on the nanorods surface, which could be responsible for the emission quenching of CdHgTe nanorods. Under optimum conditions, the linear range of the calibration curve for the determination of Cu²⁺ is from 8.0×10^?9 to 1.0×10^?6 mol/L and the detection limit is 2.0×10^?9 mol/L. Owing to low background interference of NIR measurement, the proposed method displays relative high sensitivity and selectivity. Especially, some physiologically important cations almost do not interfere with the determination of Cu²⁺. The proposed method was also applied to the determination of trace Cu²⁺ in real aqueous samples with satisfactory results.     

Preparation of a new Cd(II)-imprinted polymer and its application to determination of cadmium(II) via flow-injection-flame atomic absorption spectrometry

A new cadmium(II)-imprinted polymer based on cadmium(II) 2,2′-{ethane-1,2-diylbis[nitrilo(E)methylylidene]} diphenolate-4-vinylpyridine complex was obtained via suspension polymerization. The beads were used as a minicolumn packing for flow-injection-flame atomic absorption spectrometry (FI-FAAS) determination of cadmium(II) in water samples. Sorption effectiveness was optimal within pH range of 6.6-7.7. Nitric acid, 0.5% (v/v) was used as eluent. Fast cadmium(II) sorption by the proposed material enabled to apply sample flow rates up to 10 mL min⁻¹ without loss in sorption effectiveness. Enrichment factor (EF), concentration efficiency (CE) and limit of detection (LOD, 3σ) found for 120-s sorption time were 117, 39.1 min⁻¹ and 0.11 μg L⁻¹, respectively. Sorbent stability was proved for at least 100 preconcentration cycles (RSD = 2.9%). When compared to non-imprinted polymer the new Cd(II)-imprinted polymer exhibited improved selectivity towards cadmium(II) against other heavy metal ions, especially Cu(II) and Pb(II), as well as light metal ions. Accuracy of the method was tested for ground water and waste water certified reference materials and fortified water. The method was applied to Cd(II) determination in natural water samples.     

Solution chemistry effects on sorption behavior of 109Cd(II) on Ca-montmorillonite

The sorption of radiocadmium on Ca-montmorillonite as a function of contact time, pH, ionic strength, foreign ions, humic acid (HA) and fulvic acid (FA) was studied using batch technique. The results demonstrated that the sorption of Cd(II) was dependent on ionic strength at pH < 9, and was independent of ionic strength at pH > 9. Outer-sphere surface complexation and/or ion exchange were the main mechanism of Cd(II) sorption on Ca-montmorillonite at low pH, whereas the sorption at high pH was mainly dominated via inner-sphere surface complexation. The sorption of Cd(II) on Ca-montmorillonite was dependent on foreign ions at low pH values, but was independent of foreign ions at high pH values. A positive effect of HA/FA on Cd(II) sorption was found at low pH values, whereas a negative effect was observed at high pH values. The thermodynamic parameters (i.e., ??H ⁰, ??S ⁰, ??G ⁰) were calculated from the temperature dependent sorption isotherms, and the results indicated that the sorption process of Cd(II) on Ca-montmorillonite was spontaneous and endothermic.     

Application of a new nanoporous sorbent for extraction and pre-concentration of lead and copper ions

The authors describe a method for the trace determination of copper (II) and lead (II) in water and fish samples using solid-phase extraction via siliceous mesocellular foam functionalised by dithizone. Siliceous mesocellular was functionalised with dithizone, and the resulting sorbent was characterised by scanning electron microscopy, surface area analysis, thermogravimetric/differential thermal analysis and FTIR. Following solid-phase extraction of target ions by the sorbent, copper and lead ions were quantified by flame atomic absorption spectrometry. Factors affecting the sorption and desorption of target ions by the sorbent were evaluated and optimised. The calibration plot is linear in the 1 – 500 μg L^?1 copper (II) and 3–700 μg L^?1 lead (II) concentration range. The relative recovery efficiency in real sample analysis is in the range from 96 to 102%, and precision varies between 1.7 and 2.8%. It is should be noted that the limits of detection for the copper and lead analysis were 0.8 and 1.6 μg L^?1, respectively. Also, the adsorption capacities for copper and lead ions were 120 and 160 mg g^?1, respectively. The obtained pre-concentration factor for the lead and copper ions by the proposed solid-phase extraction was 75. The method was successfully applied to the determination of low levels of copper (II) and lead (II) in tap, Caspian sea, Persian gulf and lake water and also their detection in fish samples.     

Synthesis and physicochemical properties of chelating sorbents containing functional groups of N-aryl-3-aminopropionic acids

Two types of chelating sorbents with different types of addition of iminodipropionate groups to a polymeric matrix were synthesized: carboxyethylated aminopolystyrene (sorbent 1) based on linear polystyrene and carboxyethylaminomethylpolystyrene (sorbent 2) based on the copolymer of styrene and divinylbenzene. The ionization constants and concentrations of functional groups of the sorbents (exchange capacity for hydrogen ions) were determined. The sorbents exhibit high selectivity for copper(II) ions with the maximum of sorption from ammonia—acetate buffer solutions lying in a range of pH 5.0–7.5. The time needed for a solution of copper(II)—sorbent system with continuous stirring to reach exchange equilibrium is 3.5 and 2 h for sorbents 1 and 2, respectively. The exchange capacity for copper(II) ions is 2.54 and 0.10 mmol g⁻¹, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 800–806, May, 2006.     

Application of artificial neural network to simultaneous potentiometric determination of silver(I), mercury(II) and copper(II) ions by an unmodified carbon paste electrode

The response characteristics and selectivity coefficients of an unmodified carbon paste electrode (CPEs) towards Ag⁺, Cu²⁺ and Hg²⁺ were evaluated. The electrode was used as an indicator electrode for the simultaneous determination of the three metal ions in their mixtures via potentiometric titration with a standard thiocyanate solution. A three-layered feed-forward artificial neural network (ANN) trained by back-propagation learning algorithm was used to model the complex non-linear relationship between the concentration of silver, copper and mercury in their different mixtures and the potential of solution at different volumes of the added titrant. The network architecture and parameters were optimized to give low prediction errors. The optimized networks were able to precisely predict the concentrations of the three cations in synthetic mixtures.     

Sorption of heavy metal ions with activated carbons obtained from polyethylene terephthalate waste

The sorption capacity of activated carbons obtained from polyethylene terephthalate containers and packages with respect to heavy metal ions was examined. Based on the sorption capacities for Co²⁺, Mn²⁺, Ni²⁺, Cu²⁺, and Zn²⁺, the selectivity series were established for the samples prepared by conventional steam and gas activation and by the procedure involving pretreatment with sulfuric acid.     

Ultrasensitive Detection of Cu<Superscript>2+</Superscript> Using a Microcantilever Sensor Modified with L-Cysteine Self-Assembled Monolayer

A microcantilever was modified with a self-assembled monolayer (SAM) of L-cysteine for the sensitively and selectively response to Cu(II) ions in aqueous solution. The microcantilever undergoes bending due to sorption of Cu(II) ions. The interaction of Cu(II) ions with the L-cysteine on the cantilever is diffusion controlled and does not follow a simple Langmuir adsorption model. A concentration of 10^?10 M Cu(II) was detected in a fluid cell using this technology. Other cations, such as Ni²⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ca²⁺, K⁺, and Na⁺, did not respond with a significant deflection, indicating that this L-cysteine-modified cantilever responded selectively and sensitively to Cu(II).     

Study of interaction between nitrogen DBD plasma-treated viscose fibers and divalent ions Ca2+ and Cu2+

Viscose fibers were treated with atmospheric pressure dielectric barrier discharge (DBD) plasma obtained in nitrogen in order to activate the fiber surface prior to sorption of the divalent ions Ca²⁺ and Cu²⁺. Methylene blue sorption was used for estimation of carboxyl group formation on the surface after DBD plasma treatment, through the degree of fabric staining (K/S). Sorption of divalent ions was performed from solutions of each individual ion and from solutions of calcium and copper in succession onto untreated and plasma-treated viscose samples. The quantity of sorbed metal was determined from the neutralization and iodometric titration method. Scanning electron microscopy coupled with energy dispersive X-ray analysis was used for fiber morphology and surface characterization before and after plasma treatment, and after metal ions sorption. Experiments revealed copper microparticles formation on the fiber surface when sorption of copper was performed on samples with bonded calcium. Further analysis confirmed that for growth of copper particles, both calcium ions and nitrogen DBD plasma pretreatments are necessary.     

Preparation of a chelating sorbent based on pyridylethylated polyethylenimine for recovering transition metal ions

A method was developed for preparing a chelating amino polymer, pyridylethylpolyethylenimine with maximal degree of substitution, by polymer-analogous transformations of branched polyethylenimine in reaction with 2-vinylpyridine. The ability of cross-linked pyridylethylpolyethylenimine with the degree of substitution of 0.32 to sorb Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Mn²⁺, and Pb²⁺ ions present simultaneously in solution was evaluated. In an ammonium acetate sorption system (pH 3.5–4.0), the sorbent selectively interacts with Cu(II) ions.     

Sorption of Copper(II) and Silver(I) by Four Bacterial Exopolysaccharides

Metal remediation was studied by the sorption of analytical grade copper Cu(II) and silver Ag(I) by four exopolysaccharides (EPS) produced by marine bacteria. Colorimetric analysis showed that these EPS were composed of neutral sugars, uronic acids (>20 %), acetate, and sulfate (29 %). Metal sorption experiments were conducted in batch process. Results showed that the maximum sorption capacities calculated according to Langmuir model were 400 mg g^?1 EPS (6.29 mmol g^?1) and 333 mg g^?1 EPS (3.09 mmol g^?1) for Cu(II) and Ag(I), respectively. Optimum pH values of Ag(I) sorption were determined as 5.7. Experiment results also demonstrated the influence of initial silver concentration and EPS concentrations. Microanalyzing coupled with scanning electron microscopy demonstrated the presence of metal and morphological changes of the EPS by the sorption of metallic cations. The Fourier transform infrared spectroscopy analysis indicated possible functional groups (e.g., carboxyl, hydroxyl, and sulfate) of EPS involved in the metal sorption processes. These results showed that EPS from marine bacteria are very promising for copper and silver remediation. Further development in dynamic and continuous process at the industrial scale will be established next.     

Syntheses and evaluation of 7-deoxycholic amide-based tweezer-type copper(II) ion-selective ionophores

Seven tweezer-type copper(II) ion-selective ionophores; that is, 3α,12α-bis[[[N-(R)thiocarboxamino]acetyl]oxy]-N,N-dioctyl-5β-cholan-24-amides and 3α,12α-bis[[[N-(R)thiocarboxaminomethyl]acetyl]oxy]-N,N-dioctyl-5β-cholan-24-amides (R = alkyl and phenyl), were newly designed and synthesized. Their potentiometric evaluation of the poly(vinyl chloride) (PVC) membranes showed excellent affinity and selectivity to copper(II) ions over those of other transition metal ions and alkali/alkaline earth metal ions. These membranes exhibited super-Nernstian responses toward copper(II) ions (34-36 mV/decade), with detection limits of 10⁻⁶-10⁻⁷ M.