Gamma-ray spectrometry combined with acceptable knowledge (GSAK): A technique for characterization of certain remote-handled transuranic (RH-TRU) wastes

Gamma-ray spectrometry combined with acceptable knowledge (GSAK) is a technique for the characterization of certain remote-handled transuranic (RH-TRU) wastes. GSAK uses gamma-ray spectrometry to quantify a portion of the fission product inventory of RH-TRU wastes. These fission product results are then coupled with calculated inventories derived from acceptable process knowledge to characterize the radionuclide content of the assayed wastes. GSAK has been evaluated and tested through several test exercises. This paper describes the GSAK approach, while Part II presents the test results.     

Determination of fission products in nuclear samples by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS)

Determination of fission products and of their isotopic composition is of high importance for the characterisation and complete inventory of nuclear fuels. Radiometric and mass spectrometric methods, which are currently used, enable only an incomplete determination of the fission products. Radiometric methods cannot be applied to all fission products and mass spectrometric methods are hindered by the existence of isobaric interferences, therefore a previous chemical separation is required before mass spectrometric analysis. Capillary electrophoresis (CE) has been coupled with inductively coupled plasma mass spectrometry (both ICP-QMS and ICP-SFMS). Typical detection limits of 6 ng/mL and 4 pg/mL for caesium as well as 8 ng/mL and 7 pg/mL for lanthanides have been obtained by CE-ICP-QMS and CE-ICP-SFMS, respectively. In addition to these very low detection limits, the procedures present the advantages to be fast (6 min for caesium and 13 min for lanthanides, respectively), to require a low microliter range sample volume and a nanoliter range injection volume. The radiation dose for the personnel as well as the volume of nuclear liquid wastes generated during the measurements are consequently reduced.The procedures have been applied to nuclear samples from PUREX process and leachates from MOX fuels.     

Mass yields in 229Th(n,f)

Cumulative yields of 27 fission products have been determined in ²²⁹Th(n,f) by recoil catcher technique followed by gamma-ray spectrometry. Absolute fission yields were arrived at from the fission rate measured by track etch counting method. Mass yields were obtained from the cumulative yields using the charge distribution parameters reported in the literature. The values agree well with the reported values obtained both by physical and radiochemical methods. The resulting asymmetric mass distribution shows strong fluctuation in the yields in the light and heavy wings with a periodicity of five mass units.     

Toughening of Poly(ethylene terephtalate) (PET) Bottle Wastes by Modified Styrene-Butadiene Rubber (SBR) Elastomer

Summary: Modified SBR was blended with dried PET bottle wastes in an internal mixer. During the process mechanical and morphological properties were studied. When PET bottle wastes were blended with unmodified SBR, the final blend had a rough morphology and low impact strength. In contrary, blending of PET with modified SBR lead to smooth and fine morphology. Utilizing grafted SBR in PET blends creates an enormous difference in particle size and morphology, which is a result of powerful interactions and effective chemical bonding between the components of the blend. The final product had high impact strength in comparison with PET and unmodified SBR blend. These results are mainly related to formation in situ of PET/SBR graft copolymer in interface, which is produced by chemical reaction among active maleic anhydride groups and active PET groups.     

Evaluation of Ge(Li) Compton suppression spectrometers for non-destructive radiochemical analysis

Ge(Li) Compton suppression spectrometers are evaluated relative to the specific needs of the analytical radiochemist. Their application to the analysis of radionuclides found in neutron activation, fission product, and environmental radionuclide analyses is discussed. This paper is based on work performed under United States Atomic Energy Commission Contract AT(45-1)-1830.     

Effective threshold energies for (n, 2n) reactions induced in a fission neutron spectrum

The table presents computed values of effective threshold energies, E_eff, for (n, 2n) reactions induced in a fission neutron spectrum. E_eff-values are given for the (n, 2n) reactions for which the charge of the target nucleus is greater than 11 and for which the reaction product cannot be formed by (n, γ) reaction on another stable isotope. A closed expression is given for the integral of a fission neutron distribution of the Cranberg type, N(E), and for the mean energy of the fission neutrons with spectral distribution N(E).     

Solvent extraction of uranium(VI) with benzyloctadecyldimethylammonium chloride (BODMAC) from highly concentrated chloride solution

The ²²²Rn emanation fraction (EF) released from the technically enhanced naturally occurring radioactive material (TE-NORM) wastes at certain sites of petroleum and gas production was determined. The samples were analyzed by γ-ray spectrometry to determine the activity concentration of the ²²⁶Ra content, of which the ²²²Rn emanation fraction was calculated. The results showed that the ²²²Rn emanation fraction differs in the oil and gas production sites and it is independent of the activity concentration of ²²⁶Ra. This revised version was published online in August 2006 with corrections to the Cover Date.     

Formation of diagnostic product ions from cyanobacterial cyclic peptides by the two-bond fission mechanism using ion trap liquid chromatography/multi-stage mass spectrometry

Product ions obtained by tandem mass spectrometry (MS/MS) are quite effective for the amino acid sequencing of linear peptides. However, in the case of cyclic peptides, the fragmentation pattern is complicated because the cleavages occur randomly and product ions are generated as a(n), b(n), c(n), x(n), y(n) and z(n) series ions; therefore, the authors have never obtained sufficient sequence information. In order to overcome this problem, we applied ion trap liquid chromatography/multi-stage mass spectrometry (LC/MS(n)) and characterized the product ions obtained from anabaenopeptins and aeruginopeptins as the cyclic peptides. For the anabaenopeptins, MS(2) analysis did not provide sufficient sequence information on the cyclic structure, and MS(3) analysis was applied to sequence the constituent amino acids. Diagnostic product ions were obtained by the MS(3) analysis and were quite effective for obtaining the sequence information of the constituent amino acids. MS(2) analysis was, however, sufficient to obtain the sequence information of the aeruginopeptins. In both cases, the resulting product ions obtained from the cyclic structures were formed by the two-bond fission mechanism of the precursor ion, in which an initial fission of the cyclic structure to a linear one and subsequent fission(s) at the peptide bonds are included. The fragmentations were similar for the structurally related compounds, indicating that the cleavages occurred at definite peptide bonds. In addition, the resulting product ions are generated as b(n) series ions and the mass difference facilitates the amino acid sequencing. Thus, ion trap LC/MS(n) provides sequence information, and the resulting product ions are reproducible among the structurally related compounds and reliable for the sequencing of the constituent amino acids of the cyclic structure.     

The role of NAA in nuclear chemistry education

One of the missions of our Institute is the promotion of basic nuclear teaching for students as well as professional teaching for workers in nuclear industry and research. For nuclear chemistry education, we present here a one day teaching course on radioactive decay and nuclear reactions, and a two or three days course based on reactor irradiation of uranium oxide, instrumental and radiochemical analysis of fission products. In the first experiment, the neutron capture is presented as an example of nuclear reaction; the neutron activation of a silver coin with a Am-Be neutron source, followed by γ-ray spectrometry, is used to identify three radionuclides of silver and to calculate their half-lives. In the second experiment, our teaching reactor is used as a neutron source with a flux about 10¹⁰ n·cm⁻²·s⁻¹ at a low thermal power (10 kW). This low flux allows us to irradiate a small uranium sample which is usable for spectrometry after a short cooling time of about two hours. The first day is reserved for instrumental analysis of the fission products and a second day for the radiochemical separation of a fission radionuclides. With these experimental results, the students have to calculate the number of fissions in the irradiated sample. On optional third day for postgraduate students is devoted to the presentation of NAA and some applications as uranium determination by the fission product spectrometry.     

Isotopic study of natural fission reactors at Oklo and Bangombé, Gabon

The Oklo and Bangombé uranium ores in the Republic of Gabon are fossils of natural fission reactors. Many elements in these natural fission reactors show isotopic anomalies derived from fission and neutron capture reactions. Isotopic analyses of uraninites and some other minerals provide useful information on the geochemical behavior of fission products and nuclear chemical characterization of the reactors. Integrated isotopic measurements by whole rock analysis with inductively coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS) and by in-situ analysis with secondary ion mass spectrometry (SIMS) make it possible to clarify the migration processes of fissiogenic nuclides over a range of scales from micro meters to meters.     

Determination of radiocerium in fission products by extraction chromatography using di-(2-ethylhexyl)phosphoric acid

An extraction chromatographic method is described for the determination of cerium in a fission product mixture. Cerium(IV) is separated on a column of siliconized kieselguhr saturated with di-(2-ethylhexyl)phosphoric acid (HDEHPA). After washing the column with a mixture of sodium bromate and nitric acid, cerium is eluted by a mixture of 5M HNO₃ and 0.1M ascorbic acid. The optimum conditions for the quantitative sorption and elution of cerium were found, and the reproducibility of the yield was verified. The influence of other fission and corrosion products (Mg, Fe, Al, U) on the sorption and elution of cerium was studied. The method has been successfully applied for the determination of cerium in artificial and natural mixtures of fission products.     

Distribution of uranium at Mumbai Harbour Bay (MHB)

Mumbai Harbour Bay (MHB) is a recipient of low level treated effluents from BARC, Trombay. In addition, the Bay is also a recipient of domestic and industrial wastes from the city of Mumbai and adjoining areas. The average value of uranium concentration reported for Indian Bay water at Tarapur and Mumbai is ~3.0 ppb which is comparable with the reported value for Arabian sea. As such the global average is reported to be ~3.3 ppb by Oceanologists. The present study deals with the distribution of uranium in seawater of MHB. The uranium activity in MHB by alpha spectrometry was found to be between 1.0 and 4.4 ppb with an average concentration of 2.5 ppb which is comparable with the earlier reported average activity of 2.6 ppb in the MHB as well as those reported globally. To compare the results obtained by alpha spectrometry, uranium estimation was also carried out using Laser fluorimeter and the levels of uranium concentration have ranged between 0.8 and 4.9 ppb with an average concentration of 2.7 ppb.     

Determination of70Ge(n,p)70Ga and74Ge(n,p)74Ga reaction cross sections for a fission neutron spectrum

The fission neutron spectrum averaged cross-sections for the reactions⁷⁰Ge(n,p)⁷⁰Ga and⁷⁴Ge(n,p)⁷⁴Ga have been determined. The averages of four determinations are, respectively, (3.10±0.30) mb and (0.00938±0.00059) mb. The present values are, to the authors' knowledge, the first experimental data on the fission averaged cross-section for these reactions.     

Extraction chromatographic separation of uranium and fission products in the system di-(2-ethylhexyl)phosphoric acid-hydrochloric acid

An elution scheme has been developed for obtaining separate fission product and uranium fractions using extraction chromatographic techniques with di-(2-ethylhexyl)phosphoric acid as a stationary phase and HCl of varying concentration as eluting agent. The investigations have been concentrated on the fission products cerium, europium, molybdenum and zirconium. The elution of zirconium by oxalic acid is characterized by a peak broadening and has been explained by considering extraction kinetics. Experiments on column performance with different support materials have proved Ftoroplast-4 and Celite Hyflo Super Cel to be capable of giving column fillings with equal separation ability.     

Fission in the reaction of12C with209Bi at 73.4 and 84.2 MeV

Fission product yield studies in the reaction of 73,4 and 84.2 MeV¹²C with²⁰⁹Bi have been carried out using gamma-ray spectrometry. The cross sections for the production of fission products have been determined. The yield distribution of fission products is found to be symmetric and broad with FWHM around 25 mass units and peak near mass 107.7 and 107.0. The average number of neutrons emitted per fission have been found to be around 5.5 at 73.4 MeV and 7.1 at 84.2 MeV, respectively.     

(E)-2-(2-(1-(4-氯苯基)-3,5-二甲基-吡唑-4-基)乙烯基)-8-羟基喹啉的合成及光学性质

利用缩合反应合成了(E)-2-(2-(1-(4-氯苯基)-3,5-二甲基-吡唑-4-基)乙烯基)-8-羟基喹啉,利用质谱仪、核磁共振谱仪及红外光谱仪表征了其结构;并测定了其紫外光谱和荧光光谱.结果表明,所合成的8-羟基喹啉化合物在253.5 nm、303 nm和338.5 nm处出现紫外吸收峰;当激发光波长为225 n...     

Transformations of DI(phosphinylsulfide) complexes of Pd(II) during bombardment with fission products of252Cf

Transformations of chelate complexes of Pd(II) with di(phosphinylsulfide) during bombardment with fission products of²⁵²Cf have been investigated for the first time using plasma desorption mass spectrometry. Disproportionation of Pd(II) to Pd(I) and Pd(III) was observed for a number of the complexes studied. Formation of polynuclear complexes in the gas phase was observed.L. V. Pisarzhevskii Institute of Physical Chemistry, Ukraine Academy of Sciences, Ukraine, 252039 Kiev, Prospekt Nauki, 31. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 3, pp. 172–176, May–June, 1996. Original article submitted July 13, 1995.     

Study of thermodynamic properties of SrThF6(s) in SrF2-ThF4 system using solid state electrochemical cell method

Journal of Solid State Electrochemistry - The fission product strontium (Sr), after generation in the reactor due to fission of 233U, might exist as SrF2 in the molten fluoride medium of molten...     

Exciton fission and fusion in bis(tetracene) molecules with different covalent linker structures

Bichromophoric molecules can support two spatially separated excited states simultaneously and thus provide novel pathways for electronic state relaxation. Exciton fission, where absorption of a single photon leads to two triplet states, is a potentially useful example of such a pathway. In this paper, a detailed study of exciton fission in three novel phenylene-linked bis(tetracene) molecules is presented. Their spectroscopy is analyzed in terms of a three-state kinetic model in which the singlet excited state can fission into a triplet pair state, which in turn undergoes recombination on a time scale longer than the molecule's radiative lifetime. This model allows us to fit both the prompt and delayed fluorescence decay data quantitatively. The para-phenylene linked bis(tetracene) molecules 1,4-bis(tetracen-5-yl)benzene (1) and 4,4'-bis(tetracen-5-yl)biphenylene (2) show intramolecular exciton fission with yields of approximately 3%, whereas no delayed fluorescence is observed for tetracene or the meta-linked molecule 1,3-bis(tetracen-5-yl)benzene 3. Analysis of the temperature-dependent fluorescence dynamics yields activation energies for fission of (10.0 +/- 0.6) kJ/mol for 1 and (4.1 +/- 0.5) kJ/mol for 2, with Arrhenius prefactors of (1.48 +/- 0.04) x 10(8) s(-1) for 1 and (1.72 +/- 0.02) x 10(7) s(-1) for 2. The observed trends in activation energies are reproduced by ab initio calculations of the independently optimized singlet and triplet energies. The calculations indicate that electronic coupling between the two tetracene units is primarily through-bond, allowing differences in fission rates to be qualitatively explained in terms of the linker structure as well. Our results show that it is important to consider the effects of the linker structure on both energy relaxation and electronic coupling in bichromophoric molecules. This study provides insight into the structural and energetic factors that should be taken into account in the design of exciton fission molecules for possible solar cell applications.     

Ultra-sensitive Mass Spectrometric and Other Advanced Methods Applied to Biological Samples; Second interlaboratory comparison study for the analysis of 239Pu in synthetic urine at the µBq (~100 aCi) level by mass spectrometry

Summary As a follow up to the initial 1998 intercomparison study, a second study was initiated in 2001 as part of the ongoing evaluation of the capabilities of various ultra-sensitive methods to analyze ²³⁹Pu in urine samples. The initial study¹ was sponsored by the Department of Energy, Office of International Health Programs to evaluate and validate new technologies that may supersede the existing fission tract analysis (FTA) method for the analysis of ²³⁹Pu in urine at the µBq/l level. The ultra-sensitive techniques evaluated in the second study included accelerator mass spectrometry (AMS) by LLNL, thermal ionization mass spectrometry (TIMS) by LANL and FTA by the University of Utah. Only the results for the mass spectrometric methods will be presented. For the second study, the testing levels were approximately 4, 9, 29 and 56 µBq of ²³⁹Pu per liter of synthetic urine. Each test sample also contained ²⁴⁰Pu at a ²⁴⁰Pu/²³⁹Pu atom ratio of ~0.15 and natural uranium at a concentration of 50 µBq/ml. From the results of the two studies, it can be inferred that the best performance at the µBq level is more laboratory specific than method specific. The second study demonstrated that LANL-TIMS and LLNL-AMS had essentially the same quantification level for both isotopes. Study results for bias and precision and acceptable performance compared to ANSI N13.30 and ANSI N42.22 have been compiled.