Polarographic analysis. I

Summary Reduction of Cu^II in 0.5 M NaOH containing triethanolamine proceeds irreversibly. A similar behaviour is observed in acetate buffer of p_H 6. A reversible wave is obtained in (NH₄)₂CO₃ containing EDTA. The diffusion current measured at the proper voltage is proportional to the Cu^II concentration within a wide range. The waves in 0.5 M NaOH are not well developed being better in acetate buffer and in the presence of EDTA. Ammoniacal solutions containing EDTA can be utilised for the simultaneous estimation of Fe^III and Cu^II. A mixture of Fe^III, Cu^II and U^VI can be fairly well analysed in a medium of (NH₄)₂CO₃ containing EDTA.     

Polarographic analysis. II

Summary The polarography of hexavalent uranium in sulphuric acid solutions of different concentrations and solutions containing sodium sulphate is studied. In 0.01 M H₂SO₄ three waves are obtained corresponding to the successive reduction of U^VI to U^V, U^V to U^IV and U^IV to U^III. The second and third waves intermingle by increasing the H₂SO₄ concentration up to 0.055 M or by adding Na₂SO₄ or sulphosalicylic acid. In 0.25 M H₂SO₄ or in the presence of EDTA the second wave shifts to less negative potentials and intermingles with the first wave, forming a single wave along which reduction of U^VI gives a mixture of U^V and U^IV. The diffusion current of this wave increases up to 1 M H₂SO₄ and then decreases above this acidity. The diffusion current measured at –0.6 V is proportional to the U^VI concentration in the presence of 0.25–0.6 M H₂SO₄. This is not the case in the presence of EDTA. The proportionality is better at lower than at higher acidity.Part I: See Z. analyt. Chem.174, 4 (1960).     

Rare-earth elemental analysis of banded iron-formations by instrumental neutron activation analysis

Representative banded iron-formations (BIFs) from various locations of the eastern Indian geological belt were investigated by instrumental neutron activation analysis (INAA). After pre-concentration, irradiation was carried out using a neutron flux of 5.1·10¹⁶ m⁻²·s⁻¹, 1.0·10¹⁵ m⁻²·s⁻¹ and 3.7·10¹⁵ m⁻²s⁻¹, with thermal, epi-thermal and fast neutrons, respectively. The activities in these samples were measured by a HPGe detector. Ten rare-earth elements, such as La, Ce, Nd, Sm, Eu, Tb, Ho, Tm, Yb and Lu, have been qualitatively identified and quantitatively estimated in these samples. The present investigation is an example of employing a pre-concentration method for high iron-containing ores prior to neutron activation analysis.     

Organic azo-dyes in quantitative analysis

Summary Eliamina blue FFL is used as indicator in the complexometric titration of thorium in the p_H range 2.5–3.5. The end-point is sensitive, sharp and obvious. Solutions containing from 20 g to 20 mg thorium — in the nitrate form — per 10 ml aliquot can be easily titrated. Fe³⁺, Zr, Cu²⁺, Ni and Al interfere while Sb⁵⁺, Sn⁴⁺, As⁵⁺, Ce⁴⁺, U⁶⁺, Ca, Pb, Cd Na, K, Co, Mn²⁺ and Cr⁶⁺ do not.     

HPLC analysis of radiolabeled octreotide

Radiolabeled somatostatin analogue is a useful ligand for scintigraphic imaging of somatostatin receptor-bearing tumors. In this study, we investigated the effects of different radiolabeling conditions on labeling yield and ratio between mono-iodinated and di-iodinated¹²⁵I-Tyr³-octreotide by HPLC analysis. In vitro and in vivo stabilities of¹²⁵I-Tyr³-octreotide and¹¹¹In-DTPA-D-Phe¹-octreotide were also determined. Both radiolabeled compounds were relatively stable in vitro, but were decomposed to free¹²⁵I− and¹¹¹In-DTPA in vivo, respectively.     

Alpha-spectrometry in nuclear fuel analysis

A survey is given of the analysis of actinide nuclides by means ofa-spectrometry in high-level radioactivity process solutions resulting from reprocessing of spent U-Th fuel. Separation of fission products and isolation of the nuclides²²⁸Th,²³¹Pa,²³²U,²³⁷Np and²³⁸Pu are performed by adsorption, ion-exchange, extraction chromatography and extraction techniques. After separation, samples for quantitative determination are prepared by electrodeposition and measured using a silicon-surface barrier detector combined with a multichannel analyzer. An error estimation is given.     

Studies in heavy ion activation analysis

¹⁸O induced radioactivation may be used for the trace detection of¹H via¹H (¹⁸O, n)¹⁸F. Matrices in which this reaction is interference-free include: Al, Si, S, K, Ti, V, Ni, Cu and Zn. However, due to numerous radioisotopes created at the bombarding energies used (E≥51 MeV), a post-irradiation chemical separation of¹⁸F is required.¹⁸O activation also appears as a promising means for the trace determination of S[S(¹⁸O, x)⁴⁷V], Si[Si(¹⁸O, x)^43–44Sc] and B[B(¹⁸O, x)³⁷Mg]. Part I: in Journal of Radioanalytical Chemistry, 53 (1979) 181.     

Polarographic analysis. III

Summary Reduction of U^VI in H₃PO₄ solution passes to U^IV, the behaviour of the polarogram depends upon the acidity of the medium. In 0.1 M H₃PO₄ solution, a single wave is obtained which is characterised by a minimum due to the formation of an insoluble U^III phosphate. In 0.6 M H₃PO₄ and 1 M H₃PO₄ solutions two waves appear. The two waves join together to form a single wave representing the reduction of U^VI to the U^IV, by increasing the acidity of the medium or by the addition of gelatin. The diffusion coefficient of the phosphate complex varies with the concentration of H₃PO₄. It possesses a maximum value of 6.25×10^–6 cn²/sec in 0.5 M H₃PO₄ solution in absence of gelatin and of 5.59×10^–6 cm²/sec in presence of 0.005% gelatin.Part II: See Z. analyt. Chem. 176, 250 (1960).     

Mercury analysis: a special example of species analysis

Summary Mercury species analysis requires the determination of numerous different compounds with very different behaviour regarding environment and toxicity. For these differing species several new and more sensitive analytical methods have been developed and tested. Mercury species cannot be detected directly in most cases, and are normally derivatized by different agents and determined by different detector systems. In a new HPLC method with photometric detection more than 10 different organomercurials could be analysed as their thio-ethanol complexes. By alkylation of mercury compounds they can be separated by GC and analysed with an AAS or AFS as detector. Volatile organic species of Hg can be separated on Carbotrap^®, where Hg⁰ is not adsorbed, and analysed thereafter. With atomic fluorescence the detection limit for Hg⁰ measurement is improved significantly when compared with the widely used atomic absorption method. Results obtained with this new method are shown and discussed. Future developments for species analysis are outlined; not only to analyse the covalent metal — carbon/oxygen compounds — primary species-analysis — but also compounds with ionic or complex bonding: secondary species-analysis. With these developments, prediction of species behaviour in the environment, including toxicity assessment and decontamination proposals, should be made possible.     

Potentiometric stripping analysis for mercury

In potentiometric stripping analysis for mercury, elemental mercury is deposited on a glassy carbon electrode surface by means of potentiostatic reduction. It is then oxidized by potassium permanganate added to the sample prior to analysis and the “redox titration curve” thus obtained is recorded on a high-input impedance recorder. Deaeration of the sample is unnecessary. The analytical range is 5 × 10^-9–10^-3 M mercury(II), the times needed for potentiostatic accumulation ranging from 64 min at 10^-8 M to 1 min at concentrations above 10^-6 M. The chemistry of the stripping process is discussed and an automatic instrument for potentiometric stripping analysis is described.     

Neutron activation analysis of scandium

A neutron activation method is proposed for the determination of trace quantities of scandium, down to submicrogram level, in rocks, ores and meteorites. The sample and standard are irradiated intermittently for a total of 30 h, at a neutron flux of 5·10¹¹ n/cm²/sec; the radiochemical separation consists essentially of a one-step anion exchange. The induced γ-activity of ⁴⁰Sc, 85 days, isolated from the sample is measured and compared with that of a standard. The chemical yield averages 85% and there is a considerable saving of time in the radiochemical work. Results are quoted for the scandium contents of 2 standard rocks, cassiterite and several stony meteorites. Details of conflicting nuclear reactions are also given.     

Studies in heavy ion activation analysis

⁷Li induced radioactivation was used for the trace determination of hydrogen via the¹H(⁷Li, n)⁷ Be reaction. At 21 MeV⁷Li, only boron and magnesium present small nuclear interferences. An activation curve has been established by bombarding a stack of thin mylar foils. The comparison of this curve with the excitation function for the forward reaction, namely⁷Li(p, n)⁷ Be, shows that the recoil range from the superficial hydrogen atoms is only 1.7 mg·cm^–2, allowing post-irradiation etching. Hydrogen has been determined in titanium and lead bronze at the 100 ppm level with a relative precision of 6 to 10%. Studies of 32 potential interfering elements suggest the extension of Li activation to the trace determination of Na[²³Na(⁷Li,⁶Li)²⁴Na] and K[³⁹K(⁷Li, d)^44m,⁴⁴Sc].     

Fractionation analysis of iodine in bovine milk by preconcentration neutron activation analysis

Iodine is an essential trace element for human beings. The main source of iodine is generally food items such as fish and milk. Either the lack or the excess of iodine can cause health problems. There exists an increasing interest in the determination of total iodine as well as various species of iodine in milk. We have developed an epithermal neutron activation analysis method with a Compton suppression (ENAA-CS) counting system for the determination of ng mL⁻¹ levels of iodine. We have also employed chemical separation methods prior to ENAA-CS to measure the fraction-specific concentrations of iodine in bovine milk. We have measured the following iodine concentrations in homogenized milk (3.25%milk fat): 0.48 ± 0.02 μg mL⁻¹ of total iodine, 0.020 ± 0.003 μg mL⁻¹ of lipid-bound iodine, 0.039 ± 0.002, 0.019 ± 0.002 and 0.021 ± 0.004 μg mL⁻¹ of protein-bound iodine depending on the protein separation method and 0.45 ± 0.02 μg mL⁻¹ of inorganic species.     

Automatic activation analysis

Automatic activation analysis (AAA) is rendered possible by a unique neutron activation analysis facility for short-lived isomeric transitions based on a fast rabbit system with sample changer and sample separation, and an adaptive digital gamma-spectrometer for very high counting rates of up to 10⁶ cps. The system is controlled by a computer program performing irradiation control, neutron flux monitoring, and gamma-spectrometry with real-time correction of counting losses, spectra evaluation, nuclide identification and calculation of concentrations in a fully automatic procedure. As spectrometry is done by means of hundreds of sequentially measured pairs of concurrently recorded loss-corrected and non-corrected spectra, concentrations are derived from an optimally weighted average of all individual occurrences in this sequence of spectra which also enable the separation of isomeric transitions with coinciding energies but different half-lives such as ^116m2In (162.4 keV, T _1/2 = 2.2 s) and ^77mSe (162.2 keV, T _1/2 = 17.4 s). To clear up repeatedly voiced misconceptions concerning the errors of loss-free counting our findings of 1978 and 1981 are reiterated, namely that the counting error of a peak in a corrected spectrum may be derived consistently from the error of the same peak in the respective non-corrected spectrum and from the error of weighting factors in the corresponding region of interest, according to the principle of propagation of errors. Experimental proof is provided for conditions of stationary as well as rapidly varying counting rates and spectral shapes. To the memory of Vincent P. Guinn.     

Resonance activation analysis of iodine

Resonance neutron activation and gamma-ray spectrometry were used to determine traces of iodine in biological materials. The method developed is purely instrumental and fairly rapid. The major interfering activities of²⁴Na,³⁸Cl,³⁶Mn and⁸²Br were significantly reduced by irradiating the samples inside a shield of Cd, NaCl, MnBr₂ and MnO₂. Neutrons with energies close to the resonances of Na, Cl, Mn and Br were absorbed in the shield and did not activate the sample while neutrons with energies close to the resonances of iodine were not absorbed appreciably. Thus the activity of¹²⁸I was enhanced relative to the interfering activities. The 442 keV gamma of¹²⁸I (T=25 min) was measured using a high-resolution Ge(Li) detector and a multichannel analyzer. Sensitivity of 0.05 ppm was obtained.     

Precise trace rare earth analysis by radiochemical neutron activation

A rare earth group separation scheme followed by normal Ge(Li), low energy photon detector (LEPD), and Ge(Li)−NaI(Tl) coincidence-noncoincidence spectrometry significantly enhances the detection sensitivity of individual rare earth elements (REE) at or below the ppb level. Based on the selected γ-ray energies, normal Ge(Li) counting is favored for¹⁴⁰La,¹⁷⁰Tb and¹⁶⁹Yb; LEPD is favored for low γ-ray energies of¹⁴⁷Nd,¹⁵³Sm,¹⁶⁶Ho and¹⁶⁹Yb; and noncoincidence counting is favored for¹⁴¹Ce,¹⁴³Ce,¹⁴²Pr,¹⁵³Sm,¹⁷¹Er and¹⁷⁵Yb. The detection of radionuclides^152mEu,¹⁵⁹Gd and¹⁷⁷Lu is equally sensitive by normal Ge(Li) and noncoincidence counting;¹⁵²Eu is equally sensitive by LEPD and normal Ge(Li); and¹⁵³Gd and¹⁷⁰Tm is equally favored by all the counting modes. Overall, noncoincidence counting is favored for most of the REE. Precise measurements of the REE were made in geological and biological standards. Prepared for the U.S. Department of Energy under Contract DE-AC06-76RLO 1830.     

Neutron activation analysis of zeolite catalysts

A new method for the determination of aluminum and silicon has been developed for zeolite catalysts. In contrast to previous methods, thermal neutrons are used for the analysis of both elements, and cadmium absorbers are not needed. The silicon determination utilizes a one-hour irradiation to observe the³¹Si produced by the (n, ) reaction of³⁰Si. A 15-second irradiation is used for the²⁷Al(n, )²⁸Al reaction. The²⁸Al activity is corrected for the contribution from the²⁸Si(n,p)²⁸Al reaction by using the analyzed weight of silicon in the sample and the data for a silicon standard irradiated simultaneously with the zeolite and the aluminum standard. The quantitation limits are 0.012 g for silicon and 3.3×10^–5 g for aluminum. Sodium presents a significant interference, but this element can be removed by taking advantage of the ion exchange properties of these materials.     

Kinetic energy analysis of atomic multiplets

Summary A kinetic energy analysis of total energy differences in atomic multiplets arising fromf ^m (m=2–12) electronic configurations is performed within the nonrelativistic restricted Hartree-Fock framework. For these 1290 multiplets of 22 lanthanoid (Ce to Er) and actinoid (Th to Fm) atoms, a very good linear correlation between the total energy difference and the kinetic energy difference of the outermostf-electrons is found. The present results, together with our previous ones for the multiplets arising froms ^mpⁿ (m=1,2;n=2–4) ands ^mdⁿ (m=0–2;n=2–8) electronic configurations, demonstrate that the kinetic energy difference of electrons in open subshells is an excellent predictor of total energy differences among atomic multiplet states.     

The vibrational analysis of some oxamide complexes

Summary The vibrational spectra of the oxamide and deuteriooxamide complexes with Ni^II, Pd^II, Cu^II, Zn^II and Co^III are presented. The vibrational analysis is given for a planarD _2h structure for the Ni^II, Cu^II and Pd^II compounds; the Zn^II and Co^III complexes have a tetrahedral and octahedral structure respectively.Presented in part at the XIX I.C.C.C. Prague 1978.     

Neutron resonance capture analysis and applications

This paper addresses the development of two new radiopharmaceuticals for infection imaging. The optimization of the labeling yield of ciprofloxacin analogous, lomefloxacin and ofloxacin, with ^99mTc is described. ^99mTc-lomefloxacin was obtained with a radiochemical yield of 93.6% by adding ^99mTc to 2.5 mg lomefloxacin in the presence of 50 μg SnCl₂ while ^99mTc-ofloxacin was obtained (96.6%) by adding ^99mTc to 2 mg ofloxacin in the presence of 50 μg SnCl₂. Biodistribution studies in rats were carried out in experimentally induced infection in the left thigh using Staphylococcus aureus. Both thighs of the rats were dissected and counted and the ratio of bacterial infected thigh/contralateral thigh was then evaluated. ^99mTc-lomefloxacin showed higher uptake (T/NT = 6.5±0.5) in the infectious lesion than ^99mTc-ofloxacin (T/NT = 4.3±0.6) and abscess-to-muscle ratios for both preparations were higher than that of ^99mTc-ciprofloxacin (T/NT = 3.8±0.8), indicating that ^99mTc-lomefloxacin could be used for infection imaging.