Ion chromatographic determination of transition metals in irradiated nuclear reactor surveillance samples

The determination of transition metal ions in radioactive (+/-25 microCi/g) low-alloy steels (nuclear reactor surveillance samples) by ion chromatography (IC) is described. The analysis has been done directly without prior separation of the iron matrix. The eluted metal ions have been detected with a UV-visible spectrophotometric detector after post-column complexation with 4-(2-pyridylazo)resorcinol. The results are in a good agreement with the certified values for the standard reference material used. The method was applied to nuclear reactor surveillance samples for the determination of Cu, Mn, Co and Ni.     

Separation and determination of some metal ions on new chelating resins containing N, N donor sets

Two new stable chelating resins have been synthesized incorporating the imidazolylazobenzene and 1,4-bis(imidazolylazo)benzene as functional group into Merrifield polymer through CN covalent bond and characterized by elemental analyses, IR and thermal study. A comparison of sorption capacity of newly formed resins towards the cations Ag(I), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) as a function of pH has been studied. Kinetic studies show the time for the completeness of metal ion saturation with the resin phase. Cd(II) in trace quantities has been successfully separated and determined in different biological samples and Zn(II) in medicinal samples. It is also found that Cd(II) can be removed from water at usual pH of natural water. Both the resins can be employed for water purification as the resins reveal sorption ability towards toxic metal ions and exhibit no affinity to alkali or alkaline earth metal ions.     

The INAA of untreated and water-extracted bone samples

Bone samples /of about 5 mg/ were activated in a nuclear reactor for 1 h. Lines of^87mSr,⁵⁶Mn,²⁴Na,⁴²K,³⁸Cl and⁴⁷Sc /daughter of⁴⁷Ca/ were found in the -ray spectrum. Effects of pre-activation boiling with water and affinities of particular ions for the bone mineral are discussed.     

Synthesis and Efficiency of a Spherical Macroporous Epoxy-Polyamide Chelating Resin for Preconcentrating and Separating Trace Noble Metal Ions

A new spherical macroporous epoxy-polyamide chelating resin was synthesized from epoxy resin by simple and rapid means and used for the preconcentration and separation of trace noble metal ions from solution samples. The acidity, flow rate, reusability, capacity and interference with the adsorption of ions on the resin as well as the conditions of desorption of these ions from the resin are discussed. The results show that the relative standard deviations for the determination of 50ng mL^–1 Au(III), Pt(IV) and Pd(IV) by inductively coupled plasma atomic emission spectrometry are in the range of 0.5–3.6%. The procedure was applied to determine metal smelter samples with satisfactory results.     

Sorption–Desorption of Copper and Strontium Ions by the Soil. The Influence of Microorganisms on the State of Metals

Sorption of heavy metal (copper and strontium) ions by the meadow chernozem and grey forest soils differing in the content of organic substance was described using the Langmuir equation. The analysis of characteristic sorption coefficients demonstrated that copper possesses the enhanced affinity for the studied soil samples compared to strontium. Maximal values of the sorption of copper (0.085 mmol/g) and strontium (0.045 mmol/g) obtained for the colloidal fraction of meadow chernozem soil (particle diameter d < 1 m) are approximately 1.5 times larger than for the same fraction of grey forest soil; this ratio remains almost the same even when using the coarser fraction (d < 50 m). It was established that up to 90% of metal ions could be present in the soil in an immobile form. An increase in the concentration of heavy metal ions in the soil causes their redistribution between the components of absorbing soil complex and an increase in the fraction of metal in mobile forms (water-soluble, exchange, soluble in weakly acidic medium). Upon the microbiological treatment (bioleaching in the suspension variant) of the soils containing copper or strontium ions, the total content of metal, including its mobile forms, decreases by an order of magnitude.     

Analyse von Schichten und Schichtsystemen mit hochenergetischen Ionenstrahlen

Summary The utility of energetic ion beams for thin film analysis is reviewed briefly. The different methods for analysis are based on the different interactions of the fast ions with atomic nuclei and electrons of the solid state samples to be analysed. These interactions include not only ion scattering, but also emission of x-rays and nuclear reactions. Quantitative chemical analysis with good depth resolution by Rutherford-backscattering analysis (RBS) is demonstrated for the suicide formation at the interface between Si and metal. Particle induced x-ray emission (PIXE) can be used for the detection of small amounts of impurities (atomic number Z 6). In addition, light elements can be detected within a heavy matrix using ion beams for nuclear reaction analysis (NRA). The different ion beam methods are compared and their advantages are discussed with respect to different analytical problems. In addition, channeling experiments on epitaxial superlattices are presented which allow the determination of the strain individual interfaces.     

2-Pyridylaldehydebenzoylhydrazone derivatives as highly selective precolumn chelating reagents for nickel (II) ion in kinetic differentiation mode high-performance liquid chromatography

2-Pyridylaldehydearoylhydrazones have been examined as reagents for precolumn derivatization of metal ions in the HPLC-spectrophotometry system. With the simplest analog, 2-pyridylaldehydebenzoylhydrazone (PAB), among 11 metal ions only Ni(II) ion gives the peak while the other metal chelates seem to be dissociated on an HPLC column where no added PAB is present in the eluent solutions. All other PAB analogs exhibit the peak for Ni(II) ion as well as Co(III) ion. In one reagent system, V(V) and Fe(II) chelates also appear in the chromatograms. It has been stressed that the selectivity principle is the kinetic differentiation (KD) towards metal chelates associated with the HPLC processes. The specificity for Ni(II) ion is in close relation to a key structure of the ligand molecules which provides an N,N,O coplanar coordination environment to form two five-membered chelate rings. An extremely selective and sensitive KD-HPLC method for the quantitation of Ni(II) ion at the ultra-trace levels was assessed; the detection limit (3 _Blank) for Ni(II) ion was down to 5.34 × 10^–9 mol l^–1 (31.5 pg in a 100 l injection) and the excellent applicability was checked using coal fly ash samples.     

Metal ion-coupled and decoupled electron transfer

Effects of metal ions on thermal and photoinduced electron-transfer reactions from electron donors (D) to electron acceptors (A) are reviewed in terms of metal ion-coupled electron transfer (MCET) vs. metal ion-decoupled electron transfer (MDET). When electron transfer from D to A is coupled with binding of metal ions to A^?, such an electron transfer is defined as MCET in which metal ions accelerate the rates of electron transfer. A number of examples of electron-transfer reactions from D to A, which are energetically impossible to occur, are made possible by strong binding of metal ions to A^? in MCET. The structures of metal ion complexes with A^? are also discussed in relation with the MCET reactivity. The MCET reactivity of metal ions is shown to be enhanced with an increase in the Lewis acidity of metal ions. In contrast to MCET, strong binding of metal ions to A^? results in deceleration of back electron transfer from metal ion complexes of A^? to D⁺ in the radical ion pair, which is produced by photoinduced electron transfer from D to A in the presence of metal ions, as compared with back electron transfer without metal ions. The deceleration of back electron transfer in the presence of metal ions results from no binding of metal ions to A. This type of electron transfer is defined as metal ion-decoupled electron transfer (MDET). The lifetimes of CS state (D⁺–A^?) produced by photoinduced electron transfer from D to A in the D–A linked systems are also elongated by adding metal ions to the D–A systems because of the stabilization of the CS states by strong binding of metal ions to A^? and the resulting slow MDET processes.     

Simultaneous ion-chromatography of alkali, alkaline earth and heavy metal ions with conductivity and indirect UV detection: Comparison of eluents containing organic complexing acids and copper sulfate

Summary The simultaneous ion-chromatography of mono-and divalent metal ions on the weak cation-exchange column Nucleosil-PBDMA (polymer coated silica with polybutandiene-maleic acid) with conductivity and indirect UV-detection is presented. The influences of eluents containing organic complexing acids (-hydroxy-isobutyric, tartaric, citric, oxalic, pyridine-2,6-dicarbonic acid and EDTA etc.) as well as UV-absorbing, displacing counterions [Cu(II), Ce(III) etc.] on the retention times of metal ions was investigated in detail. With the combination of citric acid-PDCA as eluent all alkali and alkaline earth ions could be completely separated within 12 min. Alkali, alkaline earth and heavy metal ions [Cu/Zn/Co/Fe(II)] were separated by the combination of tartaric and oxalic acid as eluent in a single run. Trace amounts of Na, K and Ca were successfully separated from the Mg-matrix by an EDTA-PDCA eluent. For the IC with indirect UV-detection the eluent consisting of CuSO₄ or CuCl₂ was used to separate Na, K, Mg and Ca with baseline resolution within 10 min.The detection limits of metal ions with conductivity detection were found beween 0.5 g/l for Li and 8 g/l for Cs. They were 10 times more sensitive than those with indirect UV-detection.This IC-method was applied to determine alkali, alkaline earth and Mn ions in the water, food, ore-cinder and sole-brine samples with satisfactory results.Dedicated to Prof. Dr. G. Schulze on the occasion of his 60th birthday     

Coulometric determination of uranium in perchloric acid medium and its applications

Amorphous samples of a new inorganic ion exchanger, cerium(IV) selenite have been prepared under varying conditions. The material prepared by mixing 0.025M ceric sulfate and 0.025M sodium selenite in the ratio of 11 was studied in detail for its ion-exchange capacity, chemical stability, IR, thermogravimetry and K_d values. Separations of metal ions have been performed on columns of this ion exchanger.     

Fluorometric determination of cadmium(II) and mercury(II) using nanoclusters consisting of a gold-nickel alloy

A one-pot route has been developed for the preparation of bovine serum albumin-templated nickel-doped bimetallic gold-nickel nanoclusters (BSA-Au-Ni NCs) at a 10:1 M ratio of the precursor salts in a BSA matrix under alkaline conditions. The metal ions are reduced to the metal alloys by BSA. The resulting NCs display strong fluorescence and dual emission with peaks at 405 and 640 nm, respectively, under excitation at 340 nm. Fluorescence is strongly enhanced on addition of Cd(II) ions, but quenched on addition of Hg(II) ions. The findings have been exploited to design a fluorometric method for the separate determination of Cd(II) and Hg(II), respectively. The optimized analytical nanosystem displays relatively good dynamics between enhancement and quenching. Cd(II) and Hg(II) can be quantified in the 0 to 200 and 0 nM to 24 μM, respectively. The limits of detection are ~1.8 nM in both cases, which indicates the highest sensitivity to Cd(II) and Hg(II) ions for a fluorescent probe. This new kind of nanocrystal probe is hardly interfered by a range of commonly encountered metal ions. Its advantages were demonstrated by determining Cd(II) and Hg(II) ions in spiked serum samples.

Dually emitting nanoclusters composed of gold-nickel alloys are shown to act as very sensitive fluorescent probes for the detection of Cd(II) and Hg(II) ions.

     

Thermodynamics of interactions between lead(II) and cadmium(II) ions and azulene-based complexing polymer films

In order to understand the essential processes/interactions between the metal ions and modified electrodes which are based on complexing polymeric films, access to thermodynamic characteristics is compulsory. The paper enlarges the information concerning the sorption of metal ions within complexing polymer films, particularly based on azulene, which can be involved in metal detection sensors. Interactions between lead(II) or cadmium(II) ions and complexing polymer films have been studied using chemical preconcentration–anodic stripping method. The films have been obtained by controlled potential electrolysis in millimolar solutions of 4-azulen-1-yl-2,6-bis(2-thienyl)pyridine (L) in acetonitrile. PolyL films affinities towards these metal ions have been quantified at different temperatures by means of sorption isotherms. Parameters for sorption of lead(II) and cadmium(II) ions within polyL films have been calculated for Freundlich, Langmuir and Redlich–Peterson isotherms. The best fit was obtained when using Langmuir isotherm. The results evidence that lead ions are better sorbed than cadmium within polyL film. Thermodynamic parameters for the chemical sorption of lead(II) and cadmium(II) ions within polyL films have been calculated.     

Extractive spectrophotometric determination of palladium using 2-(2-hydroxyimino-1-oxoethyl)furan

A rapid, simple, selective and sensitive method for the determination of palladium in trace amounts has been developed, based on the reaction of 2-(2-hydroxyimino-1-oxoethyl)furan [-isonitroso-2-acetyl-furan] with the metal ion in acetic acid. The intense yellow complex is quantitatively extractable into chloroform, whose absorbance is measured at 425 nm. The method is free from the interference of a large number of other metal ions. It obeys Beer's law in the range 0.0–3.8 g Pd mL^–1 with Sandell's sensitivity of 0.003 g Pd cm^–2. The ratios of metal to ligand in the extracted complex are 1:1 and 1:2. The analysis of various samples has been carried out with satisfactory and reproducible results.     

Neutron irradiation of candidate ceramic breeder materials of fusion reactors; Gamma-spectrometry of the activation nuclides and evaluation of the tritium produced by (n, α) reaction on6Li

In the context of the European programs for the future fusion reactors, the Process Chemistry Department of ENEA, Casaccia Center (Rome), has been involved in preparing ceramic blanket materials as tritium breeders; a special consideration has been addressed to the nuclear characterization of LiAlO₂ and Li₂ZrO₃. In this paper are reported: (a) neutron irradiation of ceramic specimens in TRIGA reactor and -spectrometric measurements for INAA purposes, and (b) isothermal annealing of the irradiated samples and tritium extraction, by using an out of pile system.     

Mixed metal hydroxycarboxylic acid complexes. Spectrophotometric study of complexes of U(VI) with In(III), Cu(II), Zn(II) and Cd(II)

The formation of mixed metal complexes between uranium (VI), as the central metal ion, and aluminium (III), indium (III), copper (II), zinc (II) and cadmium (II), as the additional metal ions, with a hydroxycarboxylic acid chosen between citric, tartaric or malic, has been studied using spectrophotometric methods.The effect of pH has been examined, and the results show that at pH=4 stable complexes are formed for most of the systems. At this pH the method of mole ratio and Job's method of continuous variations, were employed to determine the stoichiometry of the mixed metal complexes. Al(III), In(III) and Cu(II) showed a high tendency to form mixed metal complexes with U(VI), while the formation of complexes is uncertain for Cd(II) and Zn(II). The ratio of the ligand to the total metal ion has been found to be 21 and metal:metal ratios of 11 and 12 have been observed.Represents part of the Ph.D. thesis submitted by Emanuel Manzurola to Ben Gurion University of the Negev.     

Competitive Sorption of Copper and Nickel Ions from Aqueous Solution Using Peat

Bicomponent aqueous solutions of copper and nickel ions have been used to investigate the sorption of metal ions onto peat. Peat, a low cost sorbent, has shown a high capacity for the sorption of single component metal ions attributed to extensive carboxylic acids within its structure. Copper and nickel ions were selected as typical metals in the effluents of electroplating industries. The effects of competitive sorption in batch systems were studied at various metal ion concentrations. In this study the Butler and Ockrent model was modified using a coefficient, . Two models were developed based on the interaction coefficient . The first model incorporates a constant fixed factor for each metal ion into the Butler-Ockrent equation. The second model incorporates a variable factor into the Butler-Ockrent equation; this interaction factor varies as a function of sorbent surface coverage. Predicted equilibrium data are found to be in excellent agreement with experimental values using both modified models for various mole ratios of copper and nickel ions in competitive sorption.     

Application of a Chelate Forming Calix[4]arene-o-vanillinthiosemicarbazone Resin to the Separation,Preconcentration and Trace Determination of Cu(II), Cd(II) and Pb(II) in Natural Water Samples

A very stable calixarene-based polymeric chelating resin has been synthesized by covalently linking calix[4]arene-o-vanillinthiosemicarbazone through its lower rim to Merrifield resin. It was characterized by FT IR, ¹H NMR and elemental analysis. The resin was efficiently employed to separate and preconcentrate toxic metal ions such as Cu(II), Cd(II) and Pb(II) in a column prior to their determination by UV-Vis spectrophotometry and atomic absorption spectrophotometry (GFAAS) with a relative standard deviation ranging between 1.0–1.4%. Various physico-chemical parameters such as pH, concentration of eluting agents, flow rate, total sorption capacity, metal-ligand stoichiometry, exchange kinetics, preconcentration factor, distribution coefficient, breakthrough capacity, resin stability, effect of electrolytes and associated metal ions have been studied. Uptake and stripping of these metal ions on the resin were fast, indicating better access of the metal ions to the chelating sites. Detection limits (3_B) of 4.22µgL^–1, 11.89µgL^–1 and 19.61µgL^–1, along with preconcentration factors of 100, 125 and 111 for Cu(II), Cd(II) and Pb(II), respectively, were achieved. The proposed method was successfully applied to the separation and trace determination of Cu(II), Cd(II) and Pb(II) from natural water samples of Ahmedabad city.     

Cationic and anionic contributions to the crystal lattice energy and the heat of solution of salts

Up to now values of H, S, and G have been determined for individual ions in the gaseous state and in aqueous solution at infinite dilution. Values of S have also been determined for individual ions entering into a crystal lattice. The Born-Mayer-Huggins crystal lattice theory has been used to calculate the enthalpy of individual ions in the crystal lattice of alkali metal halides. A formula has been derived on the basis of this theory for the difference between the enthalpies of the cation and anion in the crystal lattice. This difference depends on the van der Waals forces resulting from dipole-dipole and dipole-quadrupole interactions and on the quantum mechanical repulsive forces between the electron clouds of the ions. The enthalpy difference between ions in the lattice varies from +3.1 (LiCl) to -10.1 (KCl) kJ/g-ion. Values of H and G for ions in the crystal lattices of twenty alkali metal halides are presented in tabular form. It is found that the lattice energy is almost equally divided between the cations and anions.The heats of hydration and entropies of solution of ions were calculated from the data obtained and from the known heats of solution of electrolytes. They are presented in tables of H and G of solution, i.e., of the change from a crystal lattice to the aquated state, for the individual ions of twenty alkali metal halides.     

Determination of arsenic in the presence of high copper concentrations using flow-injection analysis-hydride atomic absorption spectrometry

Summary Arsenic is determined in environmental samples containing metal ions up to 10,000 mg/l copper, 200 mg/l lead, 200 mg/l iron and 200 mg/l nickel by using the FIA-hydride-AAS technique. In the presented sample preparation method arsenic is prereduced and the interfering metal ions are precipitated. As signal depressions from metal ions are excluded, a detection limit of 1 g/l arsenic is achieved.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Amperometric detection of heavy metal ions in ion pair chromatography at an array of water/nitrobenzene micro interfaces

A novel amperometric detector for heavy metal ions has been developed and successfully applied for ion pair chromatography. The detector is based on the electrochemical transfer of the metal ions across an array of water/nitrobenzene micro interfaces. The ion transfer is facilitated by the neutral ionophores methylenebis(diphenylphosphineoxide) and methylenebis(di- phenylphosphinesulfide). More than eight metals are separated in less than 15 min on an RP18 column using octyl sulfonate as ion pair reagent. For the heavy metals, the limits of decision are 19(Pb²⁺), 9(Zn²⁺), 9l (Co²⁺), 8(Cd²⁺) and 1.6(Mn²⁺) g/L. The applicability of the new method for water samples is demonstrated.