Improvements of neutron activation techniques for the determination of fissile material concentrations

Certain experimental improvements, as variable sample size and irradiation position, automation and flexibility in radiation detection, broaden the measurable concentration range, increase the possible rate and accuracy of analysis and enlarge the application range of the home-made nuclear analyzer for fissile material analysis by delayed fission neutron counting and for short-lived multielement analysis by neutron activation gamma-ray spectrometry. Intercomparisons of results by various methods and laboratories show the need for regular checks of techniques to ensure reliable measurements.     

Spontaneous-fission decay constant of 238U measured by nuclear track techniques without neutron irradiation

A value of the decay constant for spontaneous fission of ²³⁸U, l_f, determined by particle-track detector techniques, is presented. The main source of systematic error in fission-track measurements of l_f, the so called neutron dosimetry, has been avoided. Instead of calibrating the neutron source and the usual mica detector through tracks of ²³⁵U fission induced by thermal neutrons, spontaneous-fission tracks and alpha-particle tracks of ²³⁸U and ²⁴²Pu were used. A value of l_f = (8.66±0.38)·10^-17 y^-1 has been obtained.     

Decomposition of nuclear magnetic resonance spin-spin coupling constants into active and passive orbital contributions

The theory of the J-OC-PSP (decomposition of J into orbital contributions using orbital currents and partial spin polarization) method is derived to distinguish between the role of active, passive, and frozen orbitals on the nuclear magnetic resonance (NMR) spin-spin coupling mechanism. Application of J-OC-PSP to the NMR spin-spin coupling constants of ethylene, which are calculated using coupled perturbed density functional theory in connection with the B3LYP hybrid functional and a [7s,6p,2d/4s,2p] basis set, reveal that the well-known pi mechanism for Fermi contact (FC) spin coupling is based on passive pi orbital contributions. The pi orbitals contribute to the spin polarization of the sigma orbitals at the coupling nuclei by mediating spin information between sigma orbitals (spin-transport mechanism) or by increasing the spin information of a sigma orbital by an echo effect. The calculated FC(pi) value of the SSCC (1)J(CC) of ethylene is 4.5 Hz and by this clearly smaller than previously assumed.     

Simultaneous estimation of copper, zinc, cadmium and mercury in biological material by neutron activation analysis

Simultaneous determination of copper, zinc, cadmium and mercury with high sensitivity is possible by neutron activation analysis. After irradiation, the samples are digested and an initial separation of the four elements made by means of an ion-exchange resin. The elements in the separated fractions are then treated to give radio-chemical purity, precipitated, and their activities measured. A purely instrumental technique for the analysis of zinc in samples of biological material is also described. The samples are irradiated for a week and after the activity has decayed for about three months it is measured on a gamma-spectrometer.     

Determination of sulfur in steels by radiochemical neutron activation analysis with liquid scintillation counting

A method has been developed for the determination of low-level sulfur in steels by radiochemical neutron activation analysis. During sample irradiation, ³⁵S is produced by the ³⁴S(n,γ)³⁵S reaction. Irradiated steels are mixed with sulfur carrier and dissolved in HCl/HNO₃. Sulfur is reduced to H₂S by reaction with HI/H₃PO₂/HCl. The evolved H₂S is absorbed in dilute NaOH, which is mixed with scintillation cocktail for the measurement of ³⁵S by liquid scintillation counting. Sulfur carrier yield is determined by iodometric titration. Chlorine is also determined by RNAA in order to correct for ³⁵S produced via the ³⁵Cl(n,p)³⁵S reaction. Sulfur has been determined at mass fractions as low as ≈5 mg/kg in ultra-high-purity iron using this method.     

A simple method for the determination of uranium and thorium by delayed neutron counting

A simple method for the determination of uranium and thorium by delayed neutron counting is described. One portion of the sample is irradiated in a reactor and the delayed neutrons are counted. Another portion of the sample is mixed with B₄ C powder absorbing the thermal neutrons, and irradiated in the same position. From those data, both uranium and thorium can be calculated when a quantitative calibration has been made beforehand. The detection limits for the pure elements are 0.07 ppm for uranium and 2 ppm for thorium with the minimum analyzing time being 2 min. The accuracy of the method is investigated by comparing results obtained by the method described here with results obtained by epithermal activation analysis.     

Nitrogen distribution in polymers determined by proton track counting and 14 MeV neutron activation analysis

Bulk and surface nitrogen levels of compression-molded samples of polyacrylonitrile, poly (styrene-co-acrylonitrile), poly(methacrylonitrile), polycaprolactam, polyimide, and a cured epoxy resin (EPON 828 — JEFFAMINE T-403, 100:50) were determined, respectively, by 14 MeV NAA (¹⁴N(n,2n)¹³N) and by analysis of proton tracks registered in cellulose nitrate detectors (CN85) as a result of their exposure to protons from the termal neutron induced reaction,¹⁴N(n,p)¹⁴C. Except for a few polymers, agreement of results obtained for nitrogen levels in the bulk and surface regions is within expected limits. Intrinsic limitations of the method for practical determinations of nitrogen are covered. The spatial homogeneity of materials consisting of nitrogen and non-nitrogen containing segments is easily determined by image analysis of proton track densities. These data are then used to construct nitrogen distribution plots and topographical maps. The potential ability of the proton track image analysis technique for distinguishing phase separation or immiscibility of nitrogen containing polymers is discussed.     

Assay of platinum and gold in biological material by neutron activation analysis

Compounds of both gold and platinum are used in medicine, the former as salts to treat arthritides and the latter as the metal complex cisplatin to treat cancer. We have investigated neutron activation analysis with the Slowpoke II reactor as an assay method for both elements using human blood plasma as a matrix. Neutron activation of platinum gives rise to 3.15 day¹⁹⁹Au while that of gold produces 2.7 day¹⁹⁸Au. Activated samples are dissolved during heating in test tubes and the gold extracted by adding dibutyl sulphide to the same tube. The latter is formed to able to quantitate Pt down to 60 ng and Au down to 60 pg. The dissolution technique and possible interferences in the assay are discussed.     

Adsorption of supercritical CO2 in aerogels as studied by small-angle neutron scattering and neutron transmission techniques

Small-angle neutron scattering (SANS) has been used to study the adsorption behavior of supercritical carbon dioxide (CO2) in porous Vycor glass and silica aerogels. Measurements were performed along two isotherms (T=35 and 80 degrees C) as a function of pressure (P) ranging from atmospheric up to 25 MPa, which corresponds to the bulk fluid densities ranging from rho(CO2) approximately 0 to 0.9 gcm3. The intensity of scattering from CO2-saturated Vycor porous glass can be described by a two-phase model which suggests that CO2 does not adsorb on the pore walls and fills the pore space uniformly. In CO2-saturated aerogels an adsorbed phase is formed with a density substantially higher that of the bulk fluid, and neutron transmission data were used to monitor the excess adsorption at different pressures. The results indicate that adsorption of CO2 is significantly stronger in aerogels than in activated carbons, zeolites, and xerogels due to the extremely high porosity and optimum pore size of these materials. SANS data revealed the existence of a compressed adsorbed phase with the average density approximately 1.07 gcm3, close to the density corresponding to closely packed van der Waals volume of CO2. A three-phase model [W. L. Wu, Polymer 23, 1907 (1982)] was used to estimate the volume fraction phi3 of the adsorbed phase as a function of the fluid density, and gave phi3 approximately 0.78 in the maximum adsorption regime around rho(CO2) approximately 0.374 gcm3. The results presented in this work demonstrate the utility of SANS combined with the transmission measurements to study the adsorption of supercritical fluids in porous materials.     

Optimum timing parameters in 14 MeV neutron activation analysis of thorium and uranium using delayed neutron counting

A detailed theoretical treatment of cyclic activation analysis of thorium and uranium using a 14 MeV neutron generator and delayed neutron counting is presented. Variations of the detector response with sample transfer and total experiment times are examined in order to obtain the optimum cycle periods for the maximum detector response. Cycle optimization for 95% and 90% of the maximum detector response is investigated. Furthermore, elimination of the delayed neutrons produced by the reaction¹⁷O(n,p)¹⁷N is also considered in optimum cycle timing. Finally, calculations are carried out to estimate detection limits for thorium and uranium. Experimental results will be reported in a subsequent paper.     

Bulk and localized oxygen concentration measurements of steam-oxidized zircaloy-4 using nuclear analysis techniques

Quantitative measurement of both bulk and localized oxygen concentrations is of importance in the study of oxidation kinetics. We describe the combined application of two nuclear techniques, fast neutron activation analysis and (d, p) nuclear microprobe, to the determination of oxygen concentrations and surface profiles for steam-oxidized Zircaloy-4 cladding specimens. Results of measurements using these techniques are presented. Work partially supported by Electric Power Research Institute Contract T.S.A. No. 20.     

Separation and analysis of radioiodine in nuclear reprocessing solutions of high ionic strength

Ion chromatography (IC) can be used to separate radioiodine from fission products and other ionic species in complex reprocessing solution matrices. A preliminary concentration and separation of the radioiodine is performed using a column filled with a platinum-coated copper bed which converts all forms of iodine to iodide and selectively adsorbs the iodide. The separation is completed by employing an anion chromatographic system. The iodide peak aliquot is collected for subsequent radioanalysis by low energy photon spectroscopy. Results indicate quantitative separation and recovery of iodine. The entire system is automated under computer control and is able to handle small (l) and large (500 ml) sample sizes.     

The estimation of barium in biological material by neutron activation analysis

Barium is estimated in biological material by thermal neutron activation analysis and measurement of¹³⁹Ba by γ-counting. The biological material is digested with nitric acid and scavenged with ferric hydroxide. A special fluoride precipitation removes calcium and strontium and the barium is recovered as the chromate. The method allows the analysis of up to 40 samples per day and the sensitivity is 0.1 μg after irradiation for 85 mins at 4·10¹²n·cm⁻²·sec⁻¹.     

Determination of trace elements in biological material by neutron activation analysis

Eighteen trace elements in biological material [grass /Imperata cylindrica/, mimosa plant /Mimosa pudica/, rice] by neutron activation method were determined. In the comparative analysis, we found the content of the same elements was different in the each material, although they were collected at the same place and the same sampling method was applied.     

Characterization of zirconium complexes of interest in spent nuclear fuel reprocessing by electrospray ionization mass spectrometry

Liquid-liquid extraction of zirconium, one of the most important fission products, was followed using electrospray ionization mass spectrometry under conditions simulating reprocessing of nuclear spent fuel. Zr(IV) can precipitate from the organic phase after extraction by dibutylphosphoric acid (HDBP), the most common degradation product of tributylphosphate (TBP) radiolysis. Different complexes were detected with electrospray used in positive or negative ion modes, according to the extraction conditions such as the ligand/metal ratio. Stoichiometry of the Zr(IV) complexes was determined by combining isotopic labeling [H(15)NO(3)] of the aqueous phase in the extraction system and tandem mass spectrometry experiments. These results were compared with the species observed using other techniques reported in the literature. The mechanisms of ionization/desorption of these complexes are proposed depending on the organic ligand character (neutral (L) such as TBP, or acidic (HL') such as HDBP), and the ionization mode used. Copyright 2000 John Wiley & Sons, Ltd.     

Characterization of protein-bound metal species by bioanalytical and neutron activation techniques

Several bioanalytical techniques have been employed in conjunction with instrumental neutron activation analysis (INAA) to study metalloproteins and protein-bound trace elements in bovine kidneys. The accuracy of the INAA method developed has been evaluated by analyzing certified reference materials. Up to 29 elements can be reliably determined in biological tissue samples by INAA. Dialysis of the bovine kidney homogenate shows that more than 90% of Ca, Cd, Cu, Fe, Mg, Mn, Mo, Se, V and Zn, and about 20% of Br are bound to macromolecules, mainly proteins. A combination of gel filtration and ion exchange chromatography, chromatofocusing, electrofocusing, ammonium sulphate precipitation and INAA of the bovine kidney microsomecytosol subcellular fraction further indicates that much of the copper is associated with a single protein of an isoelectric point around 5 and a molecular weight of about 30 000 daltons. Some results on manganese proteins are also reported.     

Determination of copper in geological material by neutron activation and gamma-gamma coincidence spectrometry

The copper content of some geological samples has been determined by thermal neutron activation and subsequent coincidence gamma-spectrometry, taking advantage of the 180 degrees annihilation quanta of (64)Cu. By this means the interference of (24)Na, which is often the major gamma-activity induced in geological materials, is greatly reduced. The method is precise to about +/- 5 %, and the error is of the same order. The method should be especially attractive for application to samples with a copper content of 100-1000 ppm.     

Simple and direct determination of active ingredients in drugs by neutron activation analysis

The increasing number of drugs in the market and the need for their control requires new, simple, fast and accurate methods of analysis. The elements iodine, iron, manganese, silver and sodium were determined by Instrumental Neutron Activation Analysis in various pharmaceutical formulations, representing capsules, injectables, powders for injection, solutions and tablets. From the results it appears that Neutron Activation Analysis could be used as an official method for the determination of the elements iron, manganese and silver in pharmaceutical products, in which these elements are present as active ingredients, as well as for the control of the concentration limits for iodine and sodium.