Chemical behavior of antimony and tellurium fission products in aqueous solutions

The oxidation states of antimony and tellurium fission products formed in the aqueous solutions of²³³U and²³⁵U irradiated in a reactor were studied by means of anion exchange method. Results were corrected for the thermal reactions such as radiation induced reactions using double tracers for each element. In hot reactions, the isotopes formed independently by fission take their reduced states almost completely, whereas the isotopes formed by β-decay of their precursors favor their oxidized states. The fractions of the tellurium isotopes in the oxidized state depend on the β-decay energy of their precursors, whereas those of the antimony isotopes are nearly constant irrespective of the β-decay energy. The different behaviors between those two elements would reflect the chemical properties of their precursors.     

Volatility of tellurium and various fission products in heated nitric acid solutions

The volatility of tellurium and some other fission products was radiochemically studied in heated nitric acid solutions. As tracers ¹²¹Te produced by bremsstrahlung of an electron LINAC and other fission products produced by neutron irradiation were used. The distribution rate of radionuclides between the mother solution and the condensate, was considered as volatility, and was determined. The volatility of tellurium was found to be small and close to that of cesium. Volatilization tests were also performed in the presence of large amounts of solutes.The authors wish to thank Mr. Roy Jacobus for his help in preparing this paper.     

Volatility of tellurium and various fission products in heated nitric acid solutions

The volatility of tellurium and some other fission products was radiochemically studied in heated nitric acid solutions. As tracers ¹²¹Te produced by bremsstrahlung of an electron LINAC and other fission products produced by neutron irradiation were used. The distribution rate of radionuclides between the mother solution and the condensate, was considered as volatility, and was determined. The volatility of tellurium was found to be small and close to that of cesium. Volatilization tests were also performed in the presence of large amounts of solutes.The authors wish to thank Mr. Roy Jacobus for his help in preparing this paper.     

Fission yields of molybdenum in the Oklo natural reactor

The isotopic compositions of molybdenum in six uranium-rich samples from the Oklo Zone 9 natural reactor were accurately measured by thermal ionization mass spectrometry. The samples were subjected to an ion exchange separation process that removed the isobaric elements zirconium and ruthenium, with high efficiency and a low blank. Molybdenum possesses seven isotopes of which ^92,94,96Mo are unaffected by the fission process, enabling the raw data to be corrected for isotope fractionation by normalising to ⁹²Mo/⁹⁶Mo, and to use ⁹⁴Mo to correct for the primordial component in each of the fission-produced isotopes. This enables the relative fission yields of Mo to be calculated from the isotopic composition measurements, to give cumulative fission yields of 1:0.941:0.936:1.025 for ^95,97,98,100Mo, respectively. These data demonstrate that the most important nuclear process involved in reactor Zone 9 was the thermal neutron fission of ²³⁵U. The consistency of the relative cumulative fission yields of all six samples from different locations in the reactor, implies that Mo is a mobile element in the uraninite comprising Zone 9, and that a significant fraction of molybdenum was mobilized within the reactor zone and probably escaped from Zone 9, a conclusion in agreement with earlier published work.     

Adsorption of fission products onto soils using a fission multitracer

The adsorption behavior of fission products to various soils was studied using a multitracer. The multitracer was prepared by neutron irradiation of ²³⁵U. Distribution coefficients of fission products were obtained for seventeen kinds of Japanese soils. It was found that zirconium, niobium, and rare earth elements show high distribution coefficients for all soil samples, however, elements like alkali metals show varied values.     

Bestimmung von Radiocerisotopen in bestrahlten Kernbrennstoffen

Zusammenfassung Eine Methode zur Abtrennung vpn Cer aus Spaltprodukten wurde beschrieben. Ihre chemischen Grundlagen wurden diskutiert und systematische Bestimmungen der Dekontaminationsfaktoren für einige Spaltelemente bei der Abtrennung von Cer durch Extraktion mit Methylisobutylketon und durch Oxalatfällung durchgeführt. Die Methode wurde überprüft durch die Abtrennung von Spaltcer aus bestrahltem Uranoxid.

---

Summary A method for the separation of cerium from fission products is described. The chemical principles of this method are discussed. Decontamination from a number of fission elements have been determined for two separation steps, solvent extraction with methylisobutyl ketone and precipitation of cerium(III)-oxalate. The method was tested by separating fission cerium from an irradiated sample of uranium oxide.

---

---

Fräulein Ch. Krückeberg danke ich für die Hilfe bei den Experimenten.     

Chemical analysis of heavy elements by identification of fission fragments through X-ray coincidence measurements

A two-parameter coincident (X-ray, X-ray) measurement was made using a Si(Li) X-ray detector and a Ge(Li) X-ray detector to study the X-ray production in the²⁵²Cf fission process.K X-ray peaks from adjacentZ fission products for elements Y through Rh and I through Pr are well resolved in both detectors. The measurement yields the result that there is a large number of coincident events with X-rays from the sameZ element as well as with X-rays from the complementary fission product (e.g. CsK X-rays are in coincidence with both the complementary TcK X-rays and the CsK X-rays). The various possibilities one may consider are: (1)K X-ray production by the primary fission process followed by internal conversion, (2) multipleK X-ray production in the stopping process of the fission products, (3)K shell ionization resulting from β-decay of the fission fragments followed by internal conversion in the same fragment, and (4) multiple internal conversion processes from cascading transitions. Each of these four possible causes for self-coincident X-ray production is explored. Further two-parameter measurements were made of low-energy γ-rays in coincidence with characteristicK X-rays from the individual elements formed in the fission. Combined with previous mass determinations, it was possible to identify many of the observed γ-rays with individual isotopes. However, a large number of low-energy transitions were observed and identified as to elemental charge, but which had not been seen previously so that no mass determination was possible.     

A fast separation for antimony produced in heavy-ion induced fission

Fission fragments from heavy ion induced fission were stopped in thin magnesium foils. A fast procedure based on evolution of stibine was developed to separate the antimony isotopes embedded in the foil. A separation system, and a glass pressure filtration system was constructed for this purpose. The chemical yield measured by three independent methods was 80–90%. The degree of decontamination from other fission products was >10². The whole separation took eight minutes.     

Charge degree of freedom as a sensitive probe for fission mechanism

The role of the charge degree of freedom in the heavy-ion-induced fission was investigated by carrying out a systematic analysis of radiochemically observed charge distribution in the fission of²³⁸U with¹²C ions of the incident energy between 85 and 140 MeV, particularly in connection with the energy given to the compound system. The charge distribution was found to follow essentially identical systematics as those which govern the light-ion fission except for the extremely weak energy dependence of the most probable chargeZ _p. That is, values of the derivative ofZ _p with respect to the energy were found to be quite small, or nearly zero, in the heavy-ion fission as compared to those of the light-ion fission. According to an analysis combining the derivatives ofZ _p and fission neutron data, it was deduced that the excess energy given to the fused system was spent completely in the form of pre-scission neutrons and hence the number of post-scission neutrons remained constant as in the case of light-ion fission. The observed charge distribution was reproduced under the conditions that the relaxation of the charge degree of freedom be very fast and that the separation between the two potential fragments at the moment when the charge degree of freedom has been frozen is determined by usingViola's systematics on the fragment kinetic energy.     

Plutonium-244 fission xenon and primordial xenon in lunar samples and meteorites

Xenon found in lunar samples is a binary mixture of²⁴⁴Pu fission xenon and a trapped xenon, whose isotopic composition often shows a striking resemblance to that ofTakaoka's¹ primitive xenon. The decay product of¹²⁹I is conspicuously absent in lunar samples and this may be attributed to the facts that (a) the half-life of¹²⁹I is much shorter than that of²⁴⁴Pu, and (b) the separation of xenon from plutonium may take place easily, since the former is a gaseous element, while the latter is a refractory element. The separation of xenon from iodine may not take place easily, however, since the former is a gaseous element, while the latter is a volatile element. The isotopic compositions of the trapped xenon released from ordinary chondrites and achondrites resemble that ofTakaoka's primitive xenon, which has been mass-fractionated in such a manner that the heavier isotopes are systematically enriched relative to the lighter isotopes.     

INAA of Zr,La, Ce and Nd in geological samples in the presence of different uranium concentratios

Rock samples which contain relatively high concentrations of uranium may create problems of interference produced by fission products, when instrumental neutron activation analysis is used. The isotopes⁹⁵Zr,¹⁴⁰La,¹⁴¹Ce, 143Ce and 147Nd, which are commonly used in the neutron activation analysis of the corresponding elements, are also produced as fission products of²³⁵U. For each of these radioisotopes, a contribution factor is calculated theoretically and meaured experimentally using geological samples with different uranium contents.     

Methodology for determination of <Superscript>89</Superscript>Sr and <Superscript>90</Superscript>Sr in radiological emergency: II. Method development and evaluation

In this work a method for the determination of both ⁸⁹Sr and ⁹⁰Sr is presented. The method can potentially be used in radiological emergency and deliver results shortly after an incident. The method development was based on theoretical calculations of potential interferences from other fission products and how these could be discriminated when applying different chemical separation schemes. Validation was done on reactor coolant water containing short-lived fission products, and on a reference material. The results indicate that correct results of ⁸⁹Sr and ⁹⁰Sr can be obtained 4 and 9 days, respectively, after an incident.     

Preliminary investigation into suitable techniques to measure the chemical yield of radionuclides in thermal neutron irradiated samples at AWE (Atomic Weapons Establishment)

Radiochemical separation methods are required for the accurate measurement of radionuclides in complex matrices. To be able to quantify the results after the separation of radionuclides, known amounts of either radioactive tracers or inactive carrier solutions are added at the start of the separation. The added isotopes/elements are then measured at the end of the analysis to calculate the chemical yield for the element or isotope. The chemical yield data is applied to the counting data of the analytes of interest to produce quantified results. Recently, changes have been made to the techniques used to measure chemical yields at the Atomic Weapons Establishment for samples containing fission products. Preliminary development work using wavelength dispersive X-ray fluorescence and inductively coupled plasma–atomic emission spectrometry is discussed, including a comparison of results and evaluation of measurement uncertainty. The use of the techniques to measure fission products in a thermal neutron irradiated uranium sample is described.     

The development of radioactive glass surrogates for fallout debris

The production of glass that emulates fallout is desired by the nuclear forensics community for training and measurement exercises. The composition of nuclear fallout is complex, with widely varying isotopic compositions (Fahey et al., Proc Natl Acad Sci USA 107(47):20207–20212, 2010; Bellucci et al., Anal Chem 85:7588–7593, 2013; Wallace et al., J Radioanal Nucl Chem, 2013; Belloni et al., J Environ Radioact 102:852–862, 2011; Freiling, Science 139:1058–1059, 1963; Science 133:1991–1999, 1961; Bunney and Sam Government Report: Naval Ordinance Laboratory, White Oak, 1971). As the gaseous cloud traverses from hotter to cooler regions of the atmosphere, the processes of condensation and nucleation entrain environmental materials, vaporized nuclear materials and fission products. The elemental and isotopic composition of the fission products is altered due to chemical fractionation (i.e. the fission product composition that would be expected from fission of the original nuclear material is altered by differences in condensation rates of the elements); the fallout may be enriched or depleted in volatile or refractory fission products. This paper describes preliminary work to synthesize, irradiate and fractionate the fission product content of irradiated particulate glass using a thermal distillation 2 h after irradiation. The glass was synthesized using a solution-based polymerization of tetraethyl orthosilicate. (Izrael, Radioactive fallout after nuclear explosions and accidents, 2002) Uranium was incorporated into the glass particulate at trace concentrations during polymerization. The particulate was subjected to a short thermal neutron irradiation then heated to 1,273 K approximately 2 h after the end of irradiation. Fission products of ^{133, 134, 135}I, ^{132, 134}Te, ¹³⁵Xe, ¹³⁸Cs and ^{91, 92}Sr were observed to be distilled from the particulate. The results of these preliminary studies are discussed.     

Dosimetric measurement of the disintegration rate of fission products

Investigations on the disintegration rate of fission products of²³⁸U and²³⁹Pu are presented. The intensity of the - and -radiation of fission products were measured continuously in an interval of 1–1300 hours following the fission, offering the possibility for determining the general and specific characteristics of the individual fission products. A universal measuring procedure was elaborated for the rapid in situ determination of the dosimetric features of fission products, which is suitable for the accurate evaluation and prediction of external absorbed dose even in case of fission products of various origin and unknown composition.     

Determination of radioisotopes of Ce,Eu, Pu,Am and Cm in low-level-wastes from power reactors

Long-lived isotopes of lanthanides and actinides are very important for the disposal of low-level radioactive wastes. These nuclides serve for risk calculations of accidents. Their determination requires radiochemical separation from high activity main nuclides. Supervision of waste vessels is done by direct non-destructive -spectrometry of the key nuclides:⁶⁰Co for corrosion products and¹³⁷Cs as for fission products as for transuranic elements. The activity ratios of the long-lived nuclides to the key nuclides are called scaling factors. They have to be determined radiochemically in the laboratory in representative samples of each waste type. They are used for activity calculations of long-lived nuclides in the waste vessels. The scaling factors determined are of the order of magnitude of 10^–6 and due to the fact that we have used low-level measurement techniques, we could performe the necessary chemical separations in a laboratory not exceeding the 10-fold free-level limit.     

Separation of95Zr and95Nb from each other and from other fission products by adsorption and desorption on silica gel using hydrochloric acid solutions

The silica gel adsorption behaviour of zirconium, niobium, ruthenium and cerium in hydrochloric acid has been investigated by batch and column techniques. A satisfactory radiochemical separation of zirconium and niobium from each other and from other fission products has been achieved by a two column technique. The recommended procedure consists of sorption of all the nuclides on a primary silica gel column. Fifteen per cent of⁹⁵Nb, all of the zirconium and all of the other fission products are eluted first by washing with 5.5 M HCl. A second elution with concentrated hydrochloric acid then recovers the⁹⁵Nb (free from other products). The solution from the first elution after evaporation to 1 ml is then passed through another silica gel column and successively washed with 0.5M HCl, 5.5M HCl and concentrated HCl to obtain three fractions—other fission products—⁹⁵Zr free from other products—⁹⁵Nb free from other products, respectively.     

Possible exit channel effect on isomer yield ratios

Isomer yield ratio measurements in fission are important in understanding the fission process. With the development of new instrumental techniques, a large number of yield data are now available. The experimental data on isomer yield ratios in the thermal neutron induced fission of²³⁵U are compared with those calculated from the simple statistical model byMadland andEngland. The method of calculation has been extended to the isotopes having more than one isomeric state. The results may be explained according to the multi-exit-channel model of fission.     

Determination of uranium fission interference factors for INAA

Instrumental neutron activation analysis (INAA) is a very suitable technique for the determination of several elements in different kinds of matrices. However, when the sample contains high uranium concentration this method presents interference problems of uranium fission products. The same radioisotopes used in INAA are formed in uranium fission. Among these radioisotopes are ¹⁴¹Ce, ¹⁴³Ce, ¹⁴⁰La, ⁹⁹Mo, ¹⁴⁷Nd, ¹⁵³Sm and ⁹⁵Zr. The purpose of this study was to evaluate uranium fission interference factors to be used in the INAA of environmental and geological samples containing high levels of U. The obtained interference factors agreed with literature reported values. The results point to the viability of using these experimentally determined interference factors for the correction of uranium fission products.     

Plutonium and uranium in Japanese human tissues

Plutonium and uranium in human tissues obtained from residents of the Tokyo area were determined by a-spectrometry and the fission track method, respectively. The distribution pattern of each element was estimated on the basis of mean concentration obtained. Plutonium is concentrated in some special organs, while uranium is distributed rather generally throughout the whole body. This difference of distribution tendency is considered to be due to the characteristics of stable chemical states of the elements in body fluid; Pu4+ for plutonium and UO2(2+) for uranium.