Determination of soft X-ray emitting isotopes in radioactive liquid wastes of nuclear power plants

The ⁵⁹Ni and ⁵⁵Fe radioisotopes were measured in radioactive wastes of some European nuclear power plants. A sample preparation method was developed that starts with the digestion in an oxygen atmosphere at an overpressure in a closed Berthelot calorimeter bomb. The detection limits for ⁵⁹Ni and ⁵⁵Fe were measured and calculated in the presence of high background activities from ⁶⁰Co, ¹³⁷Cs and ²⁴¹Am isotopes.     

Studies on a new solid–liquid Cs separation using the ionic liquid extraction system in comparison with the conventional adsorption

The process characteristics of a new solid–liquid Cs⁺ separation from the radioactive liquid waste using a crown ether dicyclohexano-18-crown-6 as an extractant and an ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide were studied. The physicochemical properties of the precipitate containing Cs⁺ which is an solid–liquid extraction product were investigated to identify the solid–liquid phase separability and Cs⁺ loading. The Cs⁺ separation process performances were compared experimentally with those of the conventional adsorption system for pretreatment requirement and the amount of Cs⁺ waste. It was observed that the solid–liquid separation method using ILs has high Cs⁺ separation performance especially in the low Cs⁺ concentration.

     

The rα-structure of thieno[2,3-b] thiophene. A 1H-NMR study in a nematic phase including 13C-satellites in natural abundance

The ¹H-NMR spectrum of thieno[2,3-b]thiophene in a nematic phase has been recorded and analysed. The ¹H,¹³C dipole—dipole couplings were obtained from ¹³C satellites in natural abundance. The indirect ¹H,¹H and ¹H,¹³C spin—spin coupling constants were determined from an isotropic sample. The dipole—dipole couplings were corrected for harmonic vibrational contribution. The corrected dipole—dipole couplings were used to evaluate the r_α-structure of the molecule.     

Determination of radionuclides in the environment using gamma-spectrometry

Summary Seventy nine samples, including soil and rock, were collected from the agrestic region of the State of Pernambuco, Brazil. The activity concentrations of ²³⁸U and ²²⁶Ra in the samples were determined by gamma-spectrometry using an HPGe detector. The concentrations of ²³⁸U were 22 Bq ^. kg^-1 to 22 kBq ^. kg^-1. The concentrations of ²²⁶Ra were 14 Bq ^. kg^-1 to 17 kBq ^. kg^-1. The ²³⁸U/²²⁶Ra ratios in the soil were 0.7 to 3.4 (arithmetic mean 1.7). The radiometric data were evaluated to explain ²³⁸U and ²²⁶Ra migration in the soil and the possible consequences to the environment.     

Migration of 99Tc in a Weak Loess Aquifer: A Field Column Experiment

The migration of ⁹⁹Tc in a weak loess aquifer was investigated in-situ with undisturbed aquifer medium columns. The columns were obtained horizontally at a depth of 3236 m in an Underground Research Facility (URF). Quartz containing ³H (HTO) and ⁹⁹Tc (in the form of ⁹⁹TcO₄ ^-) was introduced into one end of the columns and the columns were covered tightly. Aquifer water was introduced into the columns directly from an experimental shaft in the UFR. Effluents from the columns were collected and the activity of ³H and ⁹⁹Tc were determined with a liquid scintillation analyzer. The breakthrough curves of ³H and ⁹⁹Tc indicate that ⁹⁹Tc migrates a little faster than that ³H does in the aquifer.     

On the lowest electronic states of the C2F radical

The adiabatic energy surfaces of the lowest three electronic states [²(²A′ and ²A′)] and ²Σ⁺[²A′] of the C₂F radical were investigated by the Hartree-Fock multiconfiguration self-consistent field (HF—MCSCF) ab initio method using a large set of atomic natural orbitals (ANO) and an extended configuration space, and the results were shown to be in agreement with the predictions of valence theory for this radical. The electronic ground state was found to have a bent equilibrium structure, hence contradicting the Walsh rule which predicts for the isoelectronic molecules a ² linear state. The three states were found to be nearly degenerate and the potential energy surfaces of the two lowest electronic states exhibit an avoided crossing at an energy ∼2000 cm⁻¹ above the ground-state minimum, lower than the highest vibrational fundamental. The strong adiabatic interaction which is responsible for the ordering of the electronic states and their equilibrium geometry involves not only the bending coordinate as normally found for Renner-Teller pairs of states, but also the C—C stretching coordinate, due to the near degeneracy of the ²Σ⁺ and the ² lowest electronic states at linear geometries. © 1996 John Wiley & Sons, Inc.     

The calculation of the thermodynamic equilibrium in Fe3+/MoO 4 2− /H+(OH−)/H2O system and determination of reasonable conditions for iron molybdate deposition

The thermodynamic data on the Fe³⁺/MoO₄ ^2?/H⁺(OH^?)/H₂O system were analyzed. The iron(III) molybdate precipitates were studied by the X-ray phase analysis and electron probe microanalysis. It was shown that the content of the iron(III) oxide impurity in the precipitates depends on method and conditions of mixing of an iron precursor solution and an molybdenum precursor solution.     

Slipping of a histidine improved the peroxidase activity of a de novo designed polypeptide packing an iron porphyrin

Polypeptides with two histidines and an iron porphyrin (1H⁴⁰-7H⁴⁶) were synthesized with a variety of positions of a histidine. In 4H⁴³, histidine (H⁴³) was in the hydrophobic region of an α-helix. The other polypeptides were of slightly or substantially distorted conformation. In the pH 7.2 buffer solution, two histidines of the polypeptide coordinated the iron porphyrin regardless of their positions. Some polypeptides (1H⁴⁰, 3H⁴², and 5H⁴⁴) showed an enhanced catalytic activity in the peroxidase reaction using cumene hydroperoxide compared to that of 4H⁴³, whereas some polypeptides (2H⁴¹ and 6H⁴⁵) were ineffective catalysts. The distortion of the peptide conformation by the addition of MeOH was also effective for the peroxidase reaction.     

Inorganic composite membranes for electrodialytic desaltination

Application of inorganic composite membranes in electrodialytic desaltination of dilute solutions containing Na⁺, Ca²⁺, Mg²⁺, Cl^?, and SO ₄ ^2? ions was studied. The membranes are based on an oxide ceramic containing hydrated zirconium(IV) oxide as an ion-exchange component. The limiting currents were estimated theoretically.     

Measurement of <Superscript>228</Superscript>Ra in the Yellow Sea and East China Sea using the radon emanation method

²²⁸Ra levels in the Yellow Sea and East China Sea were determined using the emanation method. The seawater radium was concentrated using an Mn-fiber and the ²²⁴Ra ingrowth was measured after about half a year when the initial ²²⁴Ra in the sample would have decayed. The ²²⁴Ra activity in the sample was evaluated using the decay dynamics relationship between parent ²²⁸Ra and daughter ²²⁸Th. The concentration and distribution feature of ²²⁸Ra in the Yellow Sea and East China Sea were studied and the ²²⁸Ra concentrations in the surface seawater of the Yellow Sea and the East China Sea were in the range 0.09–15.0 Bq/m³ with an average of 6.84 Bq/m³ during the summer cruise, and in the range 0.09–16.9 Bq/m³ with an average of 6.37 Bq/m³ during the winter cruise. The ²²⁸Ra distribution in the northern Yellow Sea was different from the southern Yellow Sea and East China Sea. The highest ²²⁸Ra activity of surface water was located in the middle of the northern Yellow Sea, but for the southern Yellow Sea and East China Sea, it decreased with increasing distance from China continent.     

Kinetics and the Mechanism of Iron(II) Reduction of cis-α-halogeno(cetylamine) (triethylenetetramine)cobalt(III) Complex Ion in Aqueous Acid Medium

The kinetics and mechanism of iron(II) reduction of cis- α-chloro/bromo(cetylamine)(triethylenetetramine) cobalt(III) surfactant complex ions were studied spectrophotometrically in an aqueous acid medium by following the disappearance of Co^III using an excess of the reductant under pseudo-first-order conditions: [Fe^II = 0.25 mol dm⁻³, [H⁺ = 0.1 mol dm⁻³, [μ = 1.0 mol dm⁻³ ionic strength in a nitrogen atmosphere at 303, 308 and 313 K. The reaction was found to be second order and showed acid independence in the range [H⁺ = 0.05−0.25 mol dm⁻³. The second order rate constant increased with Co^III concentration and the presence of aggregation of the complex itself altered the reaction rate. The effects of [Fe^II], [H⁺] and [ μ] on the rate were determined. Activation and thermodynamic parameters were computed. It is suggested that the reaction of Fe²⁺(aq) with Co^III complex proceeds by an inner-sphere mechanism.     

Oxidative Splitting of a Pyrimidine Cyclobutane Dimer:A Pulse Radiolysis Study

The oxidative splitting process of cis-syn 1,3-dimethyluracil cyclobutane dimer(DMUD) in aqueous solution was investigated using pulse radiolysis technique.The results indicated that DMUD can be splitted into 1,3-dimethyluracil(DMU) by OH radicals(OH) and Br2 radical anions(Br2^-),but not by azide radicals(N3^).The oxidative mechanisms that an H-abstracted from DMUD for OH oxidative splitting and an electron transfer from DMUD to Br2-,were suggested.Related kinetic parameters were determined.     

The quantitative determination of the S0—T1 absorption in pyrene with the use of intracavity absorption spectroscopy

The spin-forbidden S₀—T₁ transition of pyrene was quantitatively investigated by applying intracavity absorption spectroscopy. The measurements were carried out in benzolic solutions. The molar decadic extinction coefficient of the 0—0 transition was determined to 6.0 × 10⁻⁴ dm³mol⁻¹ cm⁻¹. The integral absorptivity was calculated to 2.94 × 10⁻² dm³ mol⁻¹ cm⁻¹ and yielded an intrinsic phosphorescence lifetime of 55.4 s. The intracavity absorptions were measured in a cavity-dumped Rhodamine 6G dye laser. Absorbances were recorded in the range between 8 × 10⁻⁴ and 5 × 10⁻⁶.     

Calix[4]arene-based fluorescent probe and the adsorption capacity of its electrospun nanofibrous film for the cesium cation as an adsorbent

Calix[4]arene-based cation receptor 1 has been synthesised by following a multi-step synthetic procedure. The fluorescence properties of 1 upon the addition of various metal ions were investigated by fluorescence spectroscopy. As a result, it was revealed that 1 displayed dramatic quenching effect upon the exposure to Cs⁺. In contrast, no significant quenching effects were observed upon the addition of other metal ions such as Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ag⁺, Zn²⁺ and Ni²⁺. Compound 1 was also found by Job plot to form a 1:1 complex with Cs⁺. In addition, we also prepared 1-embedded electrospun nanofibrous film (NF-1) as an adsorbent for Cs⁺. NF-1 is proved to adsorb Cs⁺ effectively from an aqueous solution, indicating that it would be usefully utilised as an adsorbent to remove Cs⁺.     

Radioargon production through the irradiation of calcium oxide

The production of radioargon through the irradiation of CaO was performed in an in-core facility within the The University of Texas at Austin MARK II TRIGA reactor. The major radioargon isotope produced was ³⁷Ar via the ⁴⁰Ca(n,α)³⁷Ar reaction pathway. The CaO powder was vacuumed sealed in a quartz ampoule. The sample was irradiated in a Cd-lined Al alloy canister for 2 h at 500 kW. After the irradiation, the sample was counted using an HPGe detector five times with increasing count times. ⁴¹Ar, ⁴²K, ⁴³K, and ⁴⁷Ca were detected in the spectra. The induced activities of ³⁷Ar, ³⁹Ar, ⁴¹Ar, ⁴²K, ⁴³K, and ⁴⁷Ca were calculated using a 63-group energy-dependent neutron flux determined utilizing a neutron energy flux profile calculated from a MCNPX model of the TRIGA reactor core. The production ratios generated from the model allowed for the estimation of induced ³⁷Ar and ³⁹Ar activities through the measured induced activities of ⁴¹Ar, ⁴²K, ⁴³K, and ⁴⁷Ca.     

Use of zwitterionic micelles in the eluent II: a new approach to ion chromatographic analysis of inorganic cations in biological fluids with direct sample injection

A new ion chromatographic (IC) technique has been developed for the determination of inorganic cations in biological fluids with direct sample injection. This involved the use of a mixed zwitterionic-micelle/electrolyte solution as an eluent. The proteins in the sample became bound to the zwitterionic micelles in the eluent and were thus eliminated from the column. The cations were separated by cation exchange. This method is ideal for the on-line, simultaneous determination of common inorganic cations (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, and Ca²⁺) in urine and serum samples. Such an application was demonstrated experimentally. Non-suppressed conductivity was used for analyte detection. The detection limits obtained using this IC system were 2.94, 5.22, 34.9, 32.6, and 56.7 μg/L for Na⁺, NH₄ ⁺, K⁺, Mg²⁺, and Ca²⁺, respectively.     

Determination of the k 0-values for 75Se, 110mAg, 115Cd–115mIn, 131Ba, and 153Sm by irradiation in highly thermalized neutron flux

The k ₀-values were determined for five high Q ₀(n,γ) reactions, including ⁷⁴Se(n,γ) ⁷⁵Se, ¹⁰⁹Ag(n,γ) ^110mAg, ¹¹⁴Cd(n,γ) ¹¹⁵Cd–^115mIn, ¹³⁰Ba(n,γ) ¹³¹Ba, and ¹⁵²Sm(n,γ) ¹⁵³Sm. These determinations were carried out under favorable experiment conditions: the irradiations were performed in a highly thermalized neutron flux, the irradiated target samples were counted at a far distance from HPGe detector with an efficiency carefully calibrated, and the k ₀-values were calculated against an internal comparator. When compared to the new values from this work, the 2003 recommended ^110mAg k ₀-values are confirmed. The other confirmed recommended k ₀-value is that of ⁷⁵Se 400.7 keV line. However, for the other ⁷⁵Se γ-lines, the new k ₀-values are 4–10 % higher. It is assumed that an inaccurate efficiency calibration was used when the recommended k ₀-values were measured. For the other three nuclides, the new k ₀-values are higher by 4 % for the ¹¹⁵Cd–^115mIn γ-lines, lower by 6–8 % for the ¹³¹Ba γ-lines, and lower by 8.8 % for the ¹⁵³Sm 103.2 keV γ-line.     

Determining coastal mixing rates of western Taiwan Strait using 224Ra

²²⁴Ra concentrations in the coastal sea water of western Taiwan Strait in winter were measured using Mn-fiber adsorption—successive emanation scintillation method. ²²⁴Ra activities in the seawater of the western Taiwan Strait varied from 0.90 to 16.25 Bq/m³ with an average of 4.60 Bq/m³. The horizontal and vertical distributions of ²²⁴Ra were studied. The distributions of ²²⁴Ra in the surface water decreased gradually with increasing distance offshore. The apparent horizontal and vertical eddy diffusion coefficients estimated from the one dimensional steady state model of ²²⁴Ra were (5.0–55.4) × 10⁶cm²/s and (4.0–51.7) cm²/s, respectively.     

Ab-initio calculations of excited rare gas alkali ions

The excimer-like ions formed by combining a rare gas ion with an alkali atom were investigated by an ab initio HF-CI calculation. The resulting four bound excited states¹Σ⁺,¹Π,³Σ⁺ and³Π were subjected to a semiempirical spin orbit (SO)-coupling yielding eight fine structure levels with angular momenta Ω=2, 1(3) and 0(4). For (NeLi)⁺, (NeNa)⁺, (ArLi)⁺, (ArNa)⁺, (ArK)⁺ and (KrLi)⁺ the wavelengths for the five allowed transitions to the ground state were calculated. The results are in close agreement with the experimental results. Also other spectroscopic properties as binding energies, transition moments and vibrational quanta are given.     

Determination of Cd,Hg, Pb and Se in sediments slurries by isotopic dilution calibration ICP-MS after chemical vapor generation using an on-line system or retention in an electrothermal vaporizer treated with iridium

A method for the determination of Cd, Hg, Pb and Se in sediments reference materials by slurry sampling chemical vapor generation (CVG) using isotopic dilution (ID) calibration and detection by inductively coupled plasma mass spectrometry (ICP-MS) is proposed. Two different systems were used for the investigation: an on-line flow injection system (FI-CVG-ICP-MS) and an off-line system with in situ trapping electrothermal vaporization (CVG-ETV-ICP-MS). About 100 mg of the reference material, ground to a particle size ≤50 μm, was mixed with acid solutions (aqua regia, HF and HCl) in an ultrasonic bath. The enriched isotopes ¹¹¹Cd, ¹⁹⁸Hg, ²⁰⁶Pb and ⁷⁷Se were then added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. For the on-line system, a standing time for the slurry of 12 h before measurement was required, while for the batch system, no standing time is needed to obtain accurate results. The conditions for the formation of the analyte vapor were optimized for the evaluated systems. The following altered isotope ratios were measured: ¹¹¹Cd/¹¹⁴Cd, ¹⁹⁸Hg/¹⁹⁹Hg, ²⁰⁶Pb/²⁰⁸Pb e ⁷⁷Se/⁸²Se. The obtained detection limits in the on-line system, in μg g⁻¹, were: Cd: 0.15; Hg: 0.09; Pb: 6.0 and Se: 0.03. Similar detection limits were obtained with the system that uses the ETV: 0.21 for Hg, 6.0 for Pb and 0.06 μg g⁻¹ for Se. No signal for Cd was obtained in this system. One estuarine, two marine and two river certified sediments were analyzed to check the accuracy. The obtained values by both systems were generally in agreement with the certified concentrations, according to the t-test for a confidence level of 95%, demonstrating that isotope equilibration was attained in the slurries submitted to a chemical vapor generation procedure and detection by ICP-MS. The relative standard deviations were lower than 10%, adequate for slurry analysis. The almost quantitative analytes extractions to the aqueous phase of the slurry must favor equilibration of the added enriched isotope with the isotope in the sample, allowing the use of isotopic dilution calibration for slurry analysis.