The development of an automated HPLC system for the determination of trace-metals in concentrated brines and its application to process monitoring

Methodology based on high performance liquid chromatography (HPLC) has been developed for the determination of trace-metals in concentrated brines. Metal ions, (Al, Ba, Ca, Mg, Sr and Zn) were concentrated quantitatively and isolated from the sodium chloride matrix using a chelating ion-exchange column dynamically coated with the chelating dye xylenol orange. The pH dependence of the uptake of the metals was studied. Using the chelating ion-exchange preconcentration column followed by ion chromatography all the metals studied were determined at the low ng ml^–1 level in concentrated brines and linear/workable calibrations were obtained in the concentration range of interest (<100 ng ml^–1). The methodology developed was successfully transferred to an automated on-line monitoring system for the determination of Ba, Ca, Mg and Sr in concentrated feed brines used in the chlor-alkali industry.     

Distribution of strontium in milk component

The distribution of strontium between the milk components, i.e., serum, casein micelles, whey and hydroxyapatite was determined. The sorption on hydroxyapatite was investigated using batch method and radiotracer technique. The aqueous phase comprised of either milk or whey. The sorption of strontium on hydroxyapatite depended on the method of its preparation and on the composition of the aqueous phase. The sorption of strontium was increased with an increase of pH. The presence of citrate species resulted in decrease of the sorption of strontium on hydroxyapatite. The sorption of ⁸⁵Sr on hydroxyapatite decreased with the increasing concentration of Ca²⁺ ions. Addition of Ca²⁺ ions to milk resulted in milk pH decrease. The decrease in pH value after calcium addition to milk is related to exchanges between added calcium and micellar H⁺. The average value of strontium sorption on casein micelles in milk with presence of hydroxyapatite was (47.3 ± 5.6) %. The average value of sorption of ⁸⁵Sr on casein micelles in milk without the addition of hydroxyapatite was (68.9 ± 2.2) %.     

Sorption of strontium on Slovak bentonites

Sorption of Sr on five Slovak bentonites of deposits has been studied with the use of batch technique. In the experiments there have been used natural, chemically modified and irradiated samples, in three different kinds of grain size. The pH influence on sorption of strontium on bentonites, pH change after sorption and influence of competitive ions have been studied. Distribution ratios have been determined for bentonite–strontium solution system as a function of contact time, pH and sorbate concentration. The data have been interpreted in term of Langmuir isotherm. The uptake of Sr has been rapid and the sorption of strontium has increased by increasing pH. The percentage sorption has decreased with increasing metal concentrations. The pH value after sorption for the natrificated forms of bentonite starts already in the alkaline area and moves to the higher values. For the natural bentonites the values occur in the neutral or in the acidic area. Sorption of Sr has been suppressed by presence of competitive cations as follows: Ba²⁺ > Ca²⁺ > Mg²⁺ > NH₄ ⁺ > K⁺ > Na⁺. By sorption on natrificated samples colloidal particles and pH value increase have been formed. The bentonite exposure as a result of interaction of γ-rays has led to expansion of the specific surface, increasing of the sorption capacity and to the change in the solubility of the clay materials.     

Über Perowskite der Zusammensetzung A2BUIVO6 mit A,B = Ba,Sr, Ca,Mg und Pb

On Perovskites of the Composition A₂BU^IVO₆ with A, B = Ba, Sr, Ca, Mg, and Pb The influence of the A und B ions on the charge transfer O → U are studied by diffuse reflectance measurements. They are completed by vibrational spectroscopic spectroscopic and structural investigations.     

Synthese und XPS-Analyse von nano-skaligen Metall/Metalloxid-Kompositen mit Germanium,Zinn und Blei als metallische Komponente

Synthesis and XPS Analysis of nano-scaled Metal/Metaloxid Composites with Germanium, Tin, and Lead as Metallic Component tert-Butanolates of Germanium(II), tin(II), and lead(II) of the formula {M[O-C(CH₃)₃]₂}_n (M ? Ge, n = 2; M ? Sn, n = 2; M ? Pb, n = 3) as well as the corresponding heterometalalkoxides M′M₂[O? C(CH₃)₃]₆ (M ? Ge, M′ ? Sr, Ba; M ? Sn, M′ ? Ca, Sr, Ba; M ? Pb, M′ ? Ca, Ba) have been subject to a single precursor chemical vapour deposition (CVD) process. In this process the volatile precursor has been pyrolized under reduced pressure (0,1 Torr) on a graphit or metal substrate which has been heated by induction in a microwave field to about 300–500°C. The gases originating from this pyrolisis have been analyzed by means of a quadrupole mass spectrometer whereas the solid coating which contained the micro composite was characterized by X-ray diffraction, electron microscopy, EDX-analysis and XPS-spectra. In all cases the solid material contained two phases, in which the element M ((Ge), Sn, Pb) either had oxidation state 0 or +4 (in the surface of the solids made of germanium containing precursors only Ge^II along with Ge⁰ has been detected by XPS spectroscopy). The group 14-element in the starting material had thus undergone a disproportionation from the +2 oxidation state into a lower and a higher one by two units. The elemental phase and the phase containing the formal +4 cation which is amorphous in most cases and which approaches the formula MO₂ or M′MO³ (M ? (Ge), Sn, Pb; M′ ? Ca, Sr, Ba) are uniformally distributed. The composites consist of ball shaped particles on which other smaller particles are placed in a fractal manner ressembling a black berry. In the case of the composite Sn · BaSnO³ the center of the ball shaped particles has been analyzed as pure elemental tin. The organic substituents of the precursors as well as the dynamic vacuum in the decomposition process seem to be responsible for the ball shaped nature of the solid material. In a test experiment gallium tri-tert-but-oxide has been used as precursor: again ball shaped particles are obtained which have the chemical composition Ga₂O₃ but which contain no elemental gallium.     

Radiochemical studies of the sorption behavior of strontium and barium

The sorption behavior of strontium and barium on kaolinite, bentonite and chlorite-illite mixed clay was studied by radioanalytical techniques using the batch method.⁹⁰Sr (29.1 y) and¹³³Ba (10.5 y) were used as radiotracers. Characterization of the solid matrices was done by FTIR and XRD spectrometries and specific surface area measurements. Synthetic groundwater was used as the aqueous phase. The variation of the distribution ratioR _d, as a function of metal ion loading was examined. The sorption isotherms were fitted to various isotherm models. The sorption energies were calculated to be in the range of 8–10 kJ/mol suggesting an ion exchange type of sorption mechanism. In detailed experiments, chlorite-illite mixed clay was first presaturated with K⁺, Sr²⁺, Ca²⁺ and Al³⁺ ions, respectively, prior to sorption studies with Ba²⁺ ions. The results of Ca²⁺ pretreated chlorite-illite were very similar to those of natural chlorite-illite, suggesting that the Ba²⁺ ion exchanges primarily with the Ca²⁺ ion on the clay minerals.     

Potentialities of fibrous ion-exchange materials in the determination of sulfate ions by color reactions of barium with organic reagents on a solid phase

The possibility of the determination of sulfate ions with the use of fibrous materials filled with ion exchangers on the basis of color reactions of barium with the organic reagents Arsenazo III, Orthanilic B, and Orthanilic K on a solid phase was examined. A polyacrylonitrile fiber filled the cation exchanger KU-2; anion exchangers AB-17, A-5, ANKF-211, and EDE-10p; and polyampholyte ANKB-50 (PANV-ANKB-50) was used as the support. The study of the different techniques of the sorption of the reaction components demonstrated the efficiency of the two systems involving PANV-ANKB-50. The determination of sulfates is possible because of the sorption of the excess barium remaining after the reaction with sulfate ions in the solution and its detection on the solid phase with a solution of Arsenazo III or the detection of the excess barium remaining after the interaction with the solution of sulfate ions on the solid phase with a solution of Orthanilic K. The calibration plots are linear in the concentration range of sulfate ions 10^?4–10^?5 M.     

Solid state and solution structures of alkaline-earth complexes with lariat ethers containing aniline and benzimidazole pendants

Herein we report the synthesis and structural characterization of Mg(II), Ca(II), Sr(II) and Ba(II) complexes with bibracchial lariat ethers derived from 1,7-diaza-15-crown-5 and 1,7-diaza-12-crown-4 containing aniline or benzimidazole pendant arms. The solid state structures of most of them have been determined by using single crystal X-ray crystallography. A coordination number of seven was observed for the Mg(II) complexes in the solid state, while the Ca(II), Sr(II) and Ba(II) complexes are 8-, 9- and 11-coordinate, respectively. The Ca(II), Sr(II) and Ba(II) complexes show a syn conformation, with the two pendant arms of the ligand disposed on the same side of the macrocyclic mean plane. However, the Mg(II) complex with the largest ligand derived from 1,7-diaza-15-crown-5 containing benzimidazole pendants presents an anti conformation in the solid state. ¹H and ¹³C NMR spectroscopy reveal that this conformation is maintained in acetonitrile solution.     

Sorption of aqueous palladium onto synthetic hydroxyapatite

The sorption of Pd(II) on hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) has been studied at 25 °C as a function of pH, in 0.01 M NaClO₄, and 0.01 and 0.025 M Ca(ClO₄)₂ aqueous background electrolytes and Pd(II) concentration (9.3 to 47 ??M), trying to minimize some types of reactions, such as solid dissolution of and metal precipitation. The radiotracer palladium, ¹⁰⁹Pd, obtained by neutron irradiation, has been used to calculate the palladium??s distribution coefficients K _d between aqueous and solid phase. A mathematical treatment of results has been made by ion-exchange theory in order to interpret palladium sorption onto treated solid. For this, we take into account the existence of active sites at the hydroxyapatite surface, and the aqueous solution chemistry of palladium as well as the effect of phosphate anions from solid dissolution. The results can be explained as evidence of sorption of the species PdOH⁺, and of a mixed hydroxo complex of Pd²⁺ like (XCaO^?)?CPdOH⁺·nH₂O fixed onto {??Ca?COH} surface sites of the hydroxyapatite.     

Sorption of the long-lived radionuclides cesium-134, strontium-85 and cobalt-60 on bentonite

The sorption of long-lived radionuclides of cesium, strontium and cobalt (¹³⁴Cs, ⁸⁵Sr and ⁶⁰Co) on bentonite under various experimental conditions, such as contact time, pH, sorbent and sorbate concentrations have been studied. The uptake of Cs and Sr was rapid and equilibrium was reached almost instantaneously in both the cases, while Co sorption was time dependent. The sorption of these nuclides increased by increasing pH. The uptake of Cs, Sr and Co increased with increasing the amount of the bentonite clay. The percentage sorption for Cs, Sr and Co decreased with increasing metal concentrations. The desorption studies with 0.01M CaCl₂ and ground water at low-metal loadings on bentonite showed that about 95% of Cs, 85-90% of Sr and 97% of Co were irreversibly sorbed. These results could be helpful for nuclear waste management, for waste water effluents containing low concentrations of cesium, strontium and cobalt.     

Sorption characteristics of Am(III), Sr(II) and Cs(I) on bentonite and granite

The ability of the back-fill and the host rock materials to take up radioisotopes like ²⁴¹Am, ^85,89Sr and ¹³⁷Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na⁺, K⁺, Ca²⁺ and Mg²⁺ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V _m ,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated.     

Sorption of europium on TiO2 and cement at high Ph in the presence of organic ligands

Summary Organic substances present in radioactive waste lower the sorption of metal ions at the high pH in cement matrices and, hence, enhance their possible migration. The aim of this study was to develop a method to compare organic substances or their degradation products with respect to what extent they affect metal sorption. Batch sorption studies were performed with cement or TiO₂ as solid phase and Eu(III) as a model element for trivalent lanthanides and actinides at pH 12.5 (representative of a cement waste matrix during the first approximately 100,000 years). Different kinds of ligands were studied in a broad concentration range, e.g., organic acids, cement additives, cleaning agents and degradation products from ion-exchange resin.     

Colloidal Regularities of the Interaction between Uranium(VI) and the Cells of Metal-Resistant Bacillus cereus AUMC 4368 Bacterial Culture

Sorption of uranium(VI) by the cells of metal-resistant Bacillus cereus AUMC 4368 bacterium was studied in aqueous solutions as a function of pH, equilibrium concentration of metal, and the presence of co-ions with account of the changes in phase state of metals and biocolloids. Experimental data indicate that the sorption of uranium(VI) by negatively charged biocolloids is maximal at pH 4.2–4.5 (1.2 mM per 1g of dry biomass), when metal is present in the form of positively charged hydroxocomplexes. At pH 8, the interaction between uranium(VI) and the cells is inhibited due to the formation of negatively charged water-soluble hydroxocarbonate complexes and uranate ions. Co, Sr, Cu, Ca, Mg, and Zn ions do not influence the efficiency of sorption of uranium(VI) in a weakly acidic medium, but can cause inhibiting effect in neutral pH region. The most pronounced effect expressed in broadening of sorption range and in the heterocoagulation of uranyl is observed in the presence of Fe³⁺ ions. It was established that the binding of uranium(VI) occurs by the carboxyl surface groups of Bacillus cereuscell surface. Uranium(VI) is irreversibly bound by the carboxyl groups of cell surface and its efficient desorption is possible only during the interaction with citric acid or sodium hydrocarbonate with the formation of water-soluble complexes transferred to aqueous phase. It was shown that uranyl in the form of organocomplexes (citric, humatic, and fulvatic) is not sorbed by biocolloids.     

Solvent Extraction of Alkaline Earths with 1-Phenyl -3-Methyl 4 Stearoylpyrazol - 5 - One and Topo

Abstract

The synergic extraction of Ca, Sr, and Ba ions from aqueous solutions into cyclohexane or benzene containing 1- pheny 1 - 3 - methyl - 4 - stearoylpyrazol - 5 - one (HPMSP) and TOPO has been studied. Quantitative extraction (log D>2) was attained at pH>5.4 for Ca, pH>6.5 for Sr, and pH>7.3 for Ba when cyclohexane containing 0.05 M HPMSP and 0.01 M TOPO was used, and the corresoponding values for benzene were 6.5, 7.8, and 8.4. Extracted species were M(PMSP)₂(TOPO)₃ (M=Ca, Sr, Ba) for cyclohexane and Ca(PMSP)₂(TOPO)₃ and Sr (or Ba) (PMSP)₂(TOPO)₂ for benzene.     

M5(PO4)3F (M=Ca, Sr, Ba)中Sm3+的电荷迁移态及Sm3+和Eu3+的电荷迁移能量关系

采用高温固相反应合成了M_5-2xSm_xNa_x(PO₄)₃F(M=Ca,Sr,Ba)荧光体,研究了其在真空紫外-可见光范围的发光特性。发现在Ca₅(PO₄)₃F中Sm³⁺的电荷迁移带约在191 nm,在Sr₅(PO₄)₃F中约在199 nm,而在Ba₅(PO₄)₃F中约在204 nm,随着被取代碱土离子半径的增大电荷迁移能量逐渐减小。比较了M₅(PO₄)₃F (M=Ca,Sr,Ba)中Sm³⁺和Eu³⁺电荷迁移能量的关系。     

MO?ZrO2 catalysts for nitrogen oxides reduction by hydrocarbons in oxygen excess. Preparation and properties

The physico-chemical and catalytic properties of MO–ZrO₂ systems (where M is Ca, Sr, Ba) have been studied as a function of the synthesis parameters. Finely powdered heterogeneous mixtures of solid solutions with cubic+monoclinic or tetragonal+monoclinic phase composition were found to be formed. These systems possess quite good high-temperature activity in the reaction of NOx selective reduction by propane under oxygen excess. For a given system, the rate constant depends linearly upon the M–O bond dissociation energy in the surface layer, the slope being positive for Ca and Sr and negative for Ba.     

The uptake of strontium by calcium phosphate phase formed at an elevated pH

The sorption of radioactive strontium by poorly crystalline hydroxyapatite (HA) obtained by the transformation of amorphous calcium phosphate (ACP) at initial pH 10.8, was investigated. Morphological analysis, performed by transmission electron microscopy, has demonstrated that the solid phase consists of nanometer size ultra-micro particles connected into spherical aggregates. A maximum sorption capacity, determined as the asymptote of the sorption isotherm was =(3.8±0.3)·10^–2mol Sr/mol P. Based on this result and the structural conditions, a possible theoretical explanation for the incorporation of a strontium ion into the apatite lattice has been proposed.     

Recycling of isotopically modified molybdenum from irradiated CerMet nuclear fuel: part 3—strontium separation from concentrated molybdate solution

This study is aimed at developing a promising method of strontium impurity separation from concentrated molybdenum solutions originating from molybdenum recycling from irradiated CerMet nuclear fuels with an isotopically tailored molybdenum matrix. Strontium sorption onto thirteen inorganic or composite absorbers from a slightly alkaline (pH 9.1) ammonium molybdate surrogate solution was studied. Based on the evaluation of weight distribution ratios, their dependence on molybdenum concentration and pH, and kinetics of sorption, calcium activated barium sulfate (Ba(Ca)SO₄) was identified as the most promising material. In a dynamic column experiment performed with the Ba(Ca)SO₄-PAN absorber, 2700 BV of the solution with c_Sr = 10⁻⁴ mol L⁻¹ could be treated with a breakthrough of lower than 1% and 100% breakthrough was not achieved even after processing almost 7000 BV of the feed.

     

Synthetic calcium aluminosilicates and their sorption properties with respect to Sr<Superscript>2+</Superscript> ions

Sorption characteristics of synthetic calcium aluminosilicates (CAS) obtained in the multicomponent CaCl₂–AlCl₃–KOH–SiO₂–H₂O system are presented. The isotherms of Sr²⁺ sorption on CAS from aqueous solutions containing no additional salts were measured for Sr²⁺ concentration from 0.5 to 11.1 mmol/L and solid to liquid phase ratio S: L = 1: 100. The maximum sorption capacity of synthetic CAS was determined, the phase distribution constants of Sr²⁺ ions at different S: L ratios were found. The recoveries of Sr²⁺ ions from solutions containing 0.01 mol/L Ca(NO₃)₂ and from a solution simulating water of the Mayak plant sewage pond No. 11 were determined.     

Elimination of fluoride ions in water for human consumption using hydroxyapatite as an adsorbent

In this work, a synthetic hydroxyapatite, Bio-gel HTP, marketed by BIO-RAD®, has been studied in order to propose a method to remove the excess fluoride present in drinking water. The removal of fluoride ions by this adsorbent has been studied as a function of solution pH, and fluoride ion concentration. Experiments of fluoride ions sorption have been carried out with the use of ¹⁸F radiotracer in solutions of NaF at several concentrations with an ion selective electrode used for fluoride analysis. The adsorption isotherms show that the best fluoride adsorption on hydroxyapatite occurs at a pH range of 7.0–7.5. At this pH value the solid presents an important capacity of subtraction of fluoride, of around of 100 mmol/100 g.