A new68Ge/68Ga generator based on CeO2

A new⁶⁸Ge/⁶⁸Ga generator using CeO₂ as absorbent for⁶⁸Ge has been developed. Sharp elution curves were obtained by using 0.02 mol/l HCl as eluent. About 56% of⁶⁸Ga formed on the column was concentrated in 0.5 ml of eluate. Neither radioactive impurities, nor dissolved cerium were found in the eluate.     

Ion-Exchange Preconcentration and Separation of Trace mounts of Platinum and Palladium

ABSTRACT

The preconcentration and separation of platinum and palladium from weakly acidic solution (pH=4) were done on microcolumn packed with Cellex-T resin. Selective platinum elution from the column was performed with 0.01 mol/l glycine solution at pH=12, while for palladium elution 1.2 mol/l thiourea (pH=0.5) or 4.0 mol/l potassium thiocyanate (pH=1) may be used. As the detection technique was used either FAAS or GFAAS, depending on the concentration of studied metals in the eluate.     

Determination of cobalt in the presence of high concentrations of zinc by differential pulse polarography

Summary Cobalt(II) can be determined in 0.1 mol/l Na₃citrate + 0.1 mol/l NH₄Cl + 0.08% dimethylglyoxime as supporting electrolyte in the presence of a 50 000-fold excess of zinc by differential pulse polarography. The limit of determination is 4.2×10^–5 mol/l Co (2.5 mg/l). Linear calibration curves are obtained within the range of 1×10^–7 to 5×10^–6 mol/l cobalt without zinc and in the presence of 5×10^–3 mol/l Zn. The analytical method developed is suitable for the determination of cobalt in zinc plant solutions.

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Cobaltbestimmung in Gegenwart hoher Zinkkonzentrationen mit Hilfe der Differential-Puls-Polarographie

     

Determination of traces of molybdenum in sea water by combined anion-exchange — graphite furnace atomic absorption spectrometry

Summary Traces of molybdenum in sea water have been preconcentrated by anion-exchange from acidified samples in the presence of sodium azide. Molybdenum adsorbs strongly on a column of Bio-Rad AG 1 (Cl^–) and can be stripped easily by elution with 2 mol/l NH₄Cl — 2 mol/l NH₄OH solution. Molybdenum in the effluent is determined by graphite furnace atomic absorption spectrometry. The combined method allows to determine traces of molybdenum in sea water as well as non-saline water on a 100 ml sample basis. The method gives a relative standard deviation of better than 8% at a molybdenum level of 10 g 1^–1 of sea water.

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Bestimmung von Molybdänspuren in Meereswasser mit Hilfe einer Kombination von Anionenaustausch und elektrothermischer Atomabsorptionsspektrometrie

     

Determination of potassium in sea-water by capillary isotachophoresis

Summary A new analytical procedure for the determination of potassium in sea-water was developed using capillary isotachophoresis and ion-exchange. After the sea-water sample was passed through the column packed with an ammonium form cation-exchange resin, sodium ion was removed with 2×10^–2 mol/l ammonium chloride solution and then potassium ion was eluted with 3×10^–1 mol/l ammonium chloride solution. Simultaneous determination of potassium and sodium ions was performed with a newly developed electrolyte system; the leading electrolyte was 5 mmol/l cesium hydroxide containing 2 mmol/l 18-crown-6, 0.01% hydroxypropyl methylcellulose (HPMC) and 70% methanol; the terminating electrolyte was 5 mmol/l tetrabutylammonium bromide containing 0.01% HPMC and 70% methanol. A large amount of ammonium in the eluate did not interfere with the isotachophoretic measurement of potassium and sodium ions. A linear working curve was obtained for artificial sea-water samples containing up to 700 mg/l potassium ion. The proposed method was applied to the determination of potassium in surface and bottom sea-water samples.

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Kaliumbestimmung in Meereswasser durch Capillar-Isotachophorese

     

Determination of oxytetracycline in urine and human serum by differential pulse polarography

Summary A differential pulse polarographic method for the determination of oxytetracycline in urine and human serum in acid media (HClO₄ of pH 2) is proposed. The effects of the amount of sample taken and the concentration of HClO₄ present were investigated. The detection limit was 5.5×10^–6 mol/l. The standard deviation of the determination of 5.5×10^–5 mol/l of oxytetracycline in 2 ml of urine was 1.7×10^–6 mol/l and that of the determination of 5.5×10^–5 mol/l of oxytetracycline in 2 ml of human serum was 1.9×10^–6 mol/l.

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Bestimmung von Oxytetracyclin in Urin und Humanserum durch Differential-Pulspolarography

     

Radiotracer study of the behaviour of arsenic in the graphite furnace

Summary The behaviour of As(III) and As(V) in the graphite furnace during the individual steps of the temperature program was investigated by means of the radiotracer⁷⁶As. The investigated matrix systems include 1 mol/l HCl, 0.2 mol/l HNO₃, 0.2 mol/l NaCl, urine, human serum and a tetramethylammonium hydroxide solution of hair. Significant stabilization effects can be achieved in the preatomization steps by using Ni, W, Mo, Pd, H₂O₂ as well as the mixtures H₂O₂ + Pd, HNO₃ + Pd and H₂O₂ + Ni as matrix modifiers. In sample solutions containing chloride, stabilization of As(III) is possible only in presence of nitric acid. The experimental conditions for the determination of As in urine, human serum and hair have been optimized.

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Radiotracer-Untersuchung des Verhaltens von Arsen im Graphitofen

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Separation of uranium from uraniferous coaly clays using a selective ion-exchange two-step elution system

Summary An ion-exchange process for the selective separation and enrichment of uranium from the main elements Si, Al, Fe, Ca, Mg, Na, K as well as from Mo and V, which are present in uraniferous coaly clays, has been developed. After a selective carbonate leaching of the roasted ore, a 0.5 mol/l Na₂CO₃/0.5 mol/l NaHCO₃ solution was passed through the macroporous ion-exchanger AG MP-1, which at pH10 absorbed uranium quantitatively in form of a carbonato complex. Remaining absorbed amounts of Mo and V were eluted with 0.1 mol/l EDTA in 0.5 mol/l Na₂CO₃/0.5 mol/l NaHCO₃, while U was quantitatively separated by a second elution step with 0.5 mol/l HNO₃ and was afterwards precipitated with NH₄OH as a high-grade yellow cake. Differential pulse polarography (DPP), atomic absorption spectroscopy (AAS), X-ray fluorescence (XRF), instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS) had been used to determine the uranium content in the raw materials and to investigate the effectivity of the different steps of the developed process.     

Effect of chemical condition of technetium-99m sodium pertechnetate on the active kit components and radiolabeling yield of Tru-Scint® ADTM monoclonal antibody kit

The chemical condition of^99mTc eluate obtained from a⁹⁹Mo-^99mTc generator is a function of the source, time elapsed after elution and age of the eluate. The radiochemical purity and stability of^99mTc labeled MAb-170 (Tru-Scint^®AD^TM, photoactivated monoclonal antibody kit) preparations was evaluated comparing pertechnetate source of known age and elution history. The effect of H₂O₂, a radiolytic impurity in^99mTc eluates, on the active kit components stannous ion and photoactivated MAb and radiolabeling, yield has been investigated. The lyophilized Tru-Scint^® AD^TM kit has been labeled with 20 to 80 mCi in 0.5 to 4.0 ml of Sodium Pertechnetate^99mTc Injection, USP. The eluates were obtained from three brands of generators and used up to six hours after elution. The kits were reconstituted either with Sodium Pertechnetate^99mTc Injection, USP or Sodium Chloride Injection, USP, 0.9% containing known amounts of H₂O₂. The reconstituted kits were analyzed for radiolabeling yield and radiochemical impurities, stannous ion and protein sulfhydryl group. The results indicated that the radiolabeling yield is a function of both the chemical condition of^99mTc eluate, generator brand and the radiolabeling parameters like reconstitution volume and activity. The observed radiolabeling yield differences did not depend on the amount of chemical technetium in the eluate. The major radiochemical impurities at 15-minute post labeling have been identified as the^99mTc-buffer complex and column adsorbed reduced^99mTc (^99mTc-Ad) species and not the unreduced^99mTcO ₄ ^– .     

Kinetic resolution of both 1-phenylethanol enantiomers produced by hydrolysis of 1-phenylethyl acetate with <Emphasis Type="Italic">Candida antarctica</Emphasis> lipase B in different solvent systems

The enzymatic resolution of (R, S)-1-phenylethanol produced by hydrolysis of (R, S)-1-phenylethyl acetate catalyzed by immobilized Candida antarctica lipase B (CALB) was successfully carried out in different solvent systems. A systematic screening and optimization of the reaction parameters such as enzyme amount, the nature and the content of organic solvent, pressure and temperature in supercritical carbon dioxide (SC-CO₂) and phosphate buffer, with respect to the conversion rate, were performed. CALB exhibits high enantioselectivity in both tert-butanol with 0.025 mol/l phosphate buffer (pH 7.5) and SC-CO₂ with 0.025 mol/l phosphate buffer (pH 7.5) systems. The conversion rate was 41.2% higher in SC-CO₂ with 0.025 mol/l phosphate buffer (pH 7.5) then in tert-butanol with 0.025 mol/l phosphate buffer (pH 7.5) and the reaction time decreased from 8 h to 90 min.     

Separation of silver from waste waters by ion-exchange resins and concentration by microbial cells

Summary Waste waters of film processing plants are rich with silver. Part of the silver is regenerated electrochemically, but the rest (0.5 g) remains in waste waters and is sent to sewers. This is a bad politic from both the environmental (toxic waste waters) and the economical point of view (a waste of silver). In this work, the silver was isolated by ion-exchange resins and then concentrated by microorganisms. For exchange of silver, Ionenaustauscher I, II and IV were used. The batch method was used to obtain a static equilibrium. Silver elution from exchangers is based on silver transformation to a stable cation or anion complex. By varying the ligands, pH and eluent concentrations, optimum elution is found at 1 mol/l Na₂S₂O₃, 1 mol/l NH₃, 2 mol/l HNO₃ and 1 mol/l (NH₂)₂CO. The concentration of silver in the eluent is about 50 mg/l. The silver ion uptake from solutions after ion exchange by mixed bacterial culture isolated from photographic waste water drain and pure bacterial cultures Escherichia coli 3009 and Bacillus subtilis 3053. was studied. Experiments were carried out in submerse culture at pH 7 with different Ag⁺ concentrations (4, 8 and 40 mg/l) on a rotary shaker (100 rpm) at 37°C. At the lower Ag⁺ concentrations a good growth and simultaneous removal of Ag⁺ from the solutions was achieved. At Ag⁺ concentration of 40 mg/l growth and removal of Ag⁺ by mixed and pure culture differed significantly. Thus mixed bacterial culture grew well and at the same time removed efficiently Ag⁺ (approximately 90%) from medium. Pure bacterial cultures on the contrary were unable to grow at 40 mg/l Ag⁺, though their biomass showed to be an effective biosorbent for Ag⁺ (approximately 80% of Ag⁺ removal).     

Determination of inorganic salts in acid and direct dyes by chromatography on polyamide

Summary A method for the determination of the inorganic salts content (Na₂SO₄, NaCl) in acid and direct dyes has been developed. The solution of the dye is introduced into a column filled with a strong acid cation exchanger and elution is carried out with water. The dye is converted to its free acid and the eluate is allowed to pass through a second column filled with polyamide. The free dye acid is adsorbed and the whole content of chloride and sulphate appears in the first 150 ml of the eluate. The determination of both chloride and sulphate is carried out gravimetrically using common methods.With this procedure inorganic salt contents up to 60% can be determined with an accuracy of ±2.0% rel.

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Bestimmung von anorganischen Salzen in sauren und Direkt-Farbstoffen durch Chromatographie an Polyamid

Zusammenfassung 20 ml der wÄ\rigen Lösung mit 50 mg des Farbstoffes werden auf eine 120×8 mm SÄule eines stark sauren Kationenaustauschers (Ostion LG-KS) in H⁺-Form aufgetragen und mit Wasser eluiert. Das Eluat wird auf eine 120×8 mm SÄule von Polyamidpulver gegeben, wobei der Farbstoff adsorbiert wird. In 150 ml des Eluats sind dann die anorganischen Salze (Na₂SO₄, NaCl) enthalten. Sulfat sowie Chlorid werden am besten gravietrisch nach üblichen Methoden bestimmt.Auf diese Weise können die anorganischen Salze bei einem Gehalt bis zu 60 % mit einer Genauigkeit von ±2,0% rel. bestimmt werden.

     

Matrix solid‐phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high‐performance liquid chromatography

Matrix solid‐phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High‐performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid‐phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid‐phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion‐pairing agent (NH₄PF₆), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3–13.4 μg/kg.     

Cation-exchange isolation and ICP-AES determination of rare earth elements in geological silicate materials

An ion-exchange ICP-AES method for the determination of 14 rare earth elements (REEs) and Y in geological materials is described. The separation of REEs from Ba using a Dowex 50W-X8 cation resin is especially considered since Ba is an excellent internal standard for REE determination by this technique. Although total recovery with either HCl or HNO₃ may be achieved, it is advantageous to use both acids sequentially. Volume and concentration of the acids are optimized attaining a quantitative separation of REEs from Ba by the introduction of the sample solution in a 1.75 mol/l HCl medium, followed by elution with 2 mol/l HNO₃ to remove matrix elements and with 7 mol/l HNO₃ to elute the analytes. The total elution volume is significantly reduced without decreasing the efficiency. The behaviour of the matrix constituents under the selected conditions is also studied, evaluating their elution percentages in each step. The final solution obtained contains only the REEs and Y, with the bulk of Sc and minor amounts of Cr, Fe, Hf and Ta. Experimental data for 5 geological reference standards (NIM-G, GSP-1, AGV-1, NIM-L and NIM-S) are reported. Good agreement between the present results and previously accepted values by various analytical techniques is observed.     

Determination of tetramethrin (neo-pynamin) by differential pulse voltammetry with a carbon paste electrode modified with sepiolite

Summary A method is described for the determination of tetramethrin (neo-pynamin) by differential pulse voltammetry with a carbon paste electrode modified with 10% (w/w) sepiolite. Preconcentration was carried out under open circuit conditions in 0.01 mol/l acetic acid/potassium acetate medium at pH 5.3 over 10 min, recording the voltammogram in 0.01 mol/l of KH₂PO₄/K₃PO₄ at pH 12. This led to the appearance of a peak at –1.32 V against SCE at 40 mVs^–1 and a pulse amplitude of 100 mV. Under these conditions determination limits of 45 ng ml^–1 were achieved. The method was applied to the determination of tetramethrin in soil and water samples.

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Bestimmung von Tetramethrin (Neo-Pynamin) durch Differential-Puls-Voltammetrie unter Verwendung einer mit Sepiolit modifizierten Kohlepaste-Elektrode

     

Differential thermogravimetric analysis of the products of radiation-chemical telomerization of tetrafluoroethylene in acetone

Differential thermogravimetric (DTG) curves of the products of radiation-chemical telomerization of tetrafluoroethylene solutions in acetone with concentrations (c) of 0.06 to 2.0 mol/l were measured in the temperature range 20–600°C. The pattern of the DTG curves was determined by evaporation of telomers at c < 0.2 mol/l and their thermal degradation at c > 0.2 mol/l. Acetone-soluble telomers with an average chain length of less than 5 units prevail at c < 0.1 mol/l, whereas telomers with a chain length up to 15 units, which form colloid particles, dominate at higher c values. It was shown by means of atomic-force microscopy that such colloid solutions form coatings composed of submicron-sized particles.     

Cathodic stripping voltammetry of orotic acid (vitamin B13) at the hanging mercury drop electrode (HMDE)

Summary Controlled adsorptive accumulation of orotic acid (vitamin B₁₃) at the hanging mercury drop electrode (HMDE) provides the basis for the direct stripping measurement of that compound in nanomolar concentration. Differential pulse voltammetry applied to a sample at pH 11.20 fixed in NaOH has a detection limit of 5.0 × 10^–10 mol/l of orotic acid (with 3 min of preconcentration).The cathodic stripping response is evaluated with respect to experimental parameters such as preconcentration time, preconcentration potential, bulk concentration and other parameters. Cathodic stripping voltammetry can be proposed for the determination of the orotic acid, the reproducibility of this method was studied.

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Cathodic-Stripping Voltammetrie von Orotsäure (Vitamin B₁₃) an der hängenden Quecksilbertropfelektrode

     

Isothermal reduction of barite with hydrogen

The reduction of barite concentrate with hydrogen was studied by using a Shimadzu 31 H Thermoanalyser coupled with a gas-feeding system and a Uras 7 N infrared SO₂ gasanalyser made by Hartman Brown Co. The kinetic parameters were determined by means of a computer program on the basis of the thermogravimetric curves in the temperature range 1098–1223 K. The experimental data obey the contracting volume kinetic equationkt=1–(1–)^1/3.

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Zusammenfassung Mittels eines Shimadzu 31 H Thermoanalysators, ausgerüstet mit einem Gasspeisungssystem und einem von Hartman Brown Co hergestellten Uras 7 N Infrarot-SO₂-Gasanalysator, wurde die Reduktion von Bariumkonzentrat mit Wasserstoff untersucht. Auf der Basis der TG-Daten im Bereich 1098–1223 K wurden unter Zuhilfenahme eines Computerprogrammes die kinetischen Parameter ermittelt. Die experimentellen Daten folgen einer kinetischen Gleichung der Formkt=1–(1–)^1/3.

     

Radiochemical separation of 82Sr and the preparation of a sterile 82Sr/82Rb generator column

Summary Ion-exchange chromatography using the chelating resins Purolite S950 and Chelex 100 was investigated for the radiochemical separation of ⁸²Sr from a RbCl target. 0.25M NH₄Cl solution was employed for the retention of Sr and elution of Rb, and 2M HCl for the elution of Sr. Although both resins showed very similar results, the conditions for adsorption of Sr were different. The ammonium chloride solution was directly used with Purolite S950 while it was necessary to adjust the pH between 9 and 10 with Chelex 100. Purolite S950 was, therefore, selected for routine production of ⁸²Sr. A procedure has been introduced for the preparation of a hydrous tin dioxide as supporting material for the ⁸²Sr/⁸²Rb generator column. All components of the generator column were made up of stainless steel. The column was 4 cm long, 9.5 mm O.D. and 7.1 mm I.D. Using isotonic saline (0.9% NaCl) for elution of ⁸²Rb, elution curves with different flow rates ranging from 5 to 20 ml/min were obtained. Maximum available ⁸²Rb was eluted in the first 20 ml. The column generator provided a sterile ⁸²Rb in isotonic saline. The breakthrough of ⁸²Sr over 4 weeks of elution using 7 liter of saline was on average 4.5 ^. 10^-5% (based on the first 20 ml eluate).     

Electrical conductivity in alkali metal hydroxide-water systems

The specific electrical conductivity (EC) of the KOH-H₂O system was analyzed in the range 0–100°C. The maximal EC of KOH solutions for a given temperature and the concentration corresponding to the maximal specific EC were used as generalizing parameters. The values of normalized EC (the ratio of the EC to its maximal value for a given temperature) fall on one curve for temperatures over a range of 0–100°C and concentrations over a range of 0.01–12 mol/L if the normalized concentration (the ratio of the solution concentration to the concentration corresponding to the maximal specific EC) is used as the argument. The normalized EC values for NaOH-H₂O and LiOH-H₂O systems fall on the same curve. Analytical expressions fitting normalized EC as a function of concentration are given.