Determination of the origin of unknown irradiated nuclear fuel

An isotopic fingerprinting method is presented to determine the origin of unknown nuclear material with forensic importance. Spent nuclear fuel of known origin has been considered as the 'unknown' nuclear material in order to demonstrate the method and verify its prediction capabilities. The method compares, using factor analysis, the measured U, Pu isotopic compositions of the 'unknown' material with U, Pu isotopic compositions simulating well known spent fuels from a range of commercial nuclear power stations. Then, the 'unknown' fuel has the same origin as the commercial fuel with which it exhibits the highest similarity in U, Pu compositions.     

Fractionation of plutonium in environmental and bio-shielding concrete samples using dynamic sequential extraction

Fractionation of plutonium isotopes (²³⁸Pu, ^239,240Pu) in environmental samples (i.e. soil and sediment) and bio-shielding concrete from decommissioning of nuclear reactor were carried out by dynamic sequential extraction using an on-line sequential injection (SI) system combined with a specially designed extraction column. Plutonium in the fractions from the sequential extraction was separated by ion exchange chromatography and measured using alpha spectrometry. The analytical results show a higher mobility of plutonium in bio-shielding concrete, which means attention should be paid to the treatment and disposal of nuclear waste from decommissioning.     

Provenance of unknown plutonium material

The determination of the provenance of 'unknown' plutonium material is demonstrated through a simulation study based on an isotopic fingerprinting approach. Plutonium of known provenance was considered as the 'unknown' nuclear material in order to evaluate the potential of the approach and verify its predictive capabilities. Factor analysis was used to compare the Pu isotopic composition of the 'unknown' material with Pu isotopic compositions simulating well known spent fuels from a range of commercial nuclear power stations. The provenance of the 'unknown material' is assigned to the commercial fuel with which exhibits the highest degree of similarity with respect to the Pu composition. The approach appears promising since it accurately predicted the provenance of the one 'unknown' sample considered; nevertheless, the approach is still at the development stage. Important challenging issues related to the simulation uncertainties and its testing on real laboratory samples have to be explored prior to evaluating the potential of the approach.     

Radioactivity in trinitite six decades later

The first nuclear explosion test, named the Trinity test, was conducted on July 16, 1945 near Alamogordo, New Mexico. In the tremendous heat of the explosion, the radioactive debris fused with the local soil into a glassy material named Trinitite. Selected Trinitite samples from ground zero (GZ) of the test site were investigated in detail for radioactivity. The techniques used included alpha spectrometry, high-efficiency gamma-ray spectrometry, and low-background beta counting, following the radiochemistry for selected radionuclides. Specific activities were determined for fission products (90Sr, 137Cs), activation products (60Co, 133Ba, 152Eu, 154Eu, 238Pu, 241Pu), and the remnants of the nuclear fuel (239Pu, 240Pu). Additionally, specific activities of three natural radionuclides (40K, 232Th, 238U) and their progeny were measured. The determined specific activities of radionuclides and their relationships are interpreted in the context of the fission process, chemical behavior of the elements, as well as the nuclear explosion phenomenology.     

Isotopic composition and origin of uranium and plutonium in selected soil samples collected in Kosovo

Soil samples collected from locations in Kosovo where depleted uranium (DU) ammunition was expended during the 1999 Balkan conflict were analysed for uranium and plutonium isotopes content (234U, 235U, 236U, 238U, 238Pu, (239 + 240)Pu). The analyses were conducted using gamma spectrometry (235U, 238U), alpha spectrometry (238Pu, (239 + 240)Pu), inductively coupled plasma-mass spectrometry (ICP-MS) (234U, 235U, 236U, 238U) and accelerator mass spectrometry (AMS) (236U)). The results indicated that whenever the U concentration exceeded the normal environmental values (approximately 2 to 3 mg/kg) the increase was due to DU contamination. 236U was also present in the released DU at a constant ratio of 236U (mg/kg)/238U (mg/kg) = 2.6 x 10(-5), indicating that the DU used in the ammunition was from a batch that had been irradiated and then reprocessed. The plutonium concentration in the soil (undisturbed) was about 1 Bq/kg and, on the basis of the measured 238Pu/(239 + 240)Pu, could be entirely attributed to the fallout of the nuclear weapon tests of the 1960s (no appreciable contribution from DU).     

Plutonium isotopes concentration in seawater and bottom sediment off the Pacific coast of Aomori sea area during 1991-2005

A radioactivity survey was launched in 1991 to determine the background levels of ^239+240Pu in the marine environment off a commercial spent nuclear fuel reprocessing plant before full operation of the facility. Particular attention was focused on the ²⁴⁰Pu/²³⁹Pu atom ratio in seawater and bottom sediment to identify the origins of Pu isotopes. The concentration of ^239+240Pu was almost uniform in surface water, decreasing slowly over time. Conversely, the ^239+240Pu concentration varied markedly in the bottom water and was dependent upon the sampling point, with higher concentrations of ^239+240Pu observed in the bottom water sample at sampling points having greater depth. The ²⁴⁰Pu/²³⁹Pu atom ratio in the seawater and sediment samples was higher than that of global fallout Pu, and comparable with the data in the other sea area around Japan which has likely been affected by close-in fallout Pu originating from the Pacific Proving Grounds. The ²⁴⁰Pu/²³⁹Pu atom ratio in bottom sediment samples decreased with sea depth. The land-originated Pu is not considered as the reason of the increasing ^239+240Pu concentration and also decreasing the ²⁴⁰Pu/²³⁹Pu atom ratio with sea depth, and further study is required to clarify it.     

An assessment of the reported leakage of anthropogenic radionuclides from the underground nuclear test sites at Amchitka Island, Alaska, USA to the surface environment

Three underground nuclear tests representing approximately 15-16% of the total effective energy released during the United States underground nuclear testing program from 1951 to 1992 were conducted at Amchitka Island, Alaska. In 1996, Greenpeace reported that leakage of radionuclides, 241Am and 239+240Pu, from these underground tests to the terrestrial and freshwater environments had been detected. In response to this report, a federal, state, tribal and non-governmental team conducted a terrestrial and freshwater radiological sampling program in 1997. Additional radiological sampling was conducted in 1998. An assessment of the reported leakage to the freshwater environment was evaluated by assessing 3H values in surface waters and 240Pu/239Pu ratios in various sample media. Tritium values ranged from 0.41 Bq/l +/- 0.11 two sigma to 0.74 Bq/1 +/- 0.126 two sigma at the surface water sites sampled, including the reported leakage sites. Only at the Long Shot test site, where leakage of radioactive gases to the near-surface occurred in 1965. were higher 3H levels of 5.8 Bq/1 +/- 0.19 two sigma still observed in 1997, in mud pit #3. The mean 240Pu/239Pu for all of the Amchitka samples was 0.1991 +/- 0.0149 one standard deviation, with values ranging from 0.1824 +/- 1.43% one sigma to 0.2431 +/- 6.56% one sigma. The measured 3H levels and 240Pu/239Pu ratios in freshwater moss and sediments at Amchitka provide no evidence of leakage occurring at the sites reported by Buske and Miller (1998 Nuclear-Weapons-Free America and Alaska Community Action on Toxics, Anchorage, Ak, p.38) and Miller and Buske (1996 Nuclear Flashback: The Return to Anchitka, p.35). It was noted that the marine sample; 240Pu/239Pu ratios are statistically different than the global fallout ratios presented by Krey et al. (1976) and Kelley, Bond, and Beasley (1999). The additional non-fallout component 240Pu/239Pu ratio, assuming a single unique source, necessary to modify the global fallout 240Pu/239Pu ratio to that measured in the marine samples is on the order of 0.65 (Hameedi, Efurd, Harmon, Valette-Silver, & Robertson, 1999; Kelley et al., 1999). While this potentially suggests another plutonium source, such as high burn-up nuclear reactor fuel, rather than underground nuclear tests, the uncertainties in analyses and environmental processes need to be fully assessed before any conclusion can be reached. Further work is needed to evaluate these findings and to support any radiological assessment of the marine environment surrounding Amchitka. Based on geohydrological testing and modeling, leakage from the Amchitka Underground Nuclear Tests is projected to occur to the marine environment (Claassen, 1978; Fenske, 1972; Wheatcraft, 1995).     

Isotopic signature of atmospheric xenon released from light water reactors

A global monitoring system for atmospheric xenon radioactivity is being established as part of the International Monitoring System to verify compliance with the Comprehensive Nuclear-Test-Ban Treaty (CTBT). The isotopic activity ratios of (135)Xe, (133m)Xe, (133)Xe and (131m)Xe are of interest for distinguishing nuclear explosion sources from civilian releases. Simulations of light water reactor (LWR) fuel burn-up through three operational reactor power cycles are conducted to explore the possible xenon isotopic signature of nuclear reactor releases under different operational conditions. It is studied how ratio changes are related to various parameters including the neutron flux, uranium enrichment and fuel burn-up. Further, the impact of diffusion and mixing on the isotopic activity ratio variability are explored. The simulations are validated with reported reactor emissions. In addition, activity ratios are calculated for xenon isotopes released from nuclear explosions and these are compared to the reactor ratios in order to determine whether the discrimination of explosion releases from reactor effluents is possible based on isotopic activity ratios.     

Deposition and distribution of Chernobyl fallout fission products and actinides in a Russian soil profile

In this article the distribution of fission products and actinides in a soil profile from Novo Bobovicky in Russia, which was contaminated due to the Chernobyl nuclear power plant accident, is described. The ground deposition of long-lived fission products determined by gamma-spectrometry was (recalculated to 26 April 1986) 1600 kBq (137)Cs/m(2), 900 kBq (134)Cs/m(2) and 60 kBq (125)Sb/m(2). Of these radionuclides (137)Cs shows the dominating activity at the present time. After 6.5 years 90% of the Cs and Sb activity was contained in the upper 4 cm. A (239,240)Pu ground deposition of 77.4+/-8.0 Bq/m(2) was determined by alpha-spectrometry. The (238)Pu/(239,240)Pu activity ratio of 0.30+/-0.03 and (241)Pu/(239,240)Pu activity ratio of 115+/-14 (in 1986) measured in the soil profile, indicates that the analysed Pu originates mainly from the Chernobyl accident. The average (234)U/(238)U activity ratio of 1.06+/-0.29 indicates that the uranium in this soil is dominated by naturally occurring uranium.The alpha- and beta-autoradiography revealed that the activity is mainly present in particulate form. It could further be observed that the spots containing alpha- or beta-activity originated from different particles. A comparison of alpha-autoradiography with the bulk Pu and Am activity showed that 92% of the alpha-activity was present as clearly detectable alpha-spots.The beta-active particles, located by beta-autoradiography were correlated with gamma-spectrometric measurements and contained only (137)Cs. These hot spots ranged from 0.02 to 0.15 Bq.It could be concluded that the vertical transport of (137)Cs and fuel fragments occurs mainly by movement of particles through the soil. It could also be concluded that the fuel fragments found, in this soil were depleted in respect to Cs, Sb and Eu.Comparison of the analysed (238)Pu/(239,240)Pu, (241)Pu/(239,240)Pu and (241)Am/(239,240)Pu ratios with the ratios calculated with ORIGEN-S code gave an estimate of the average burn-up of the fuel particles to be in the range of 11-12 GWd/tU.The results presented in this article are valid for this single soil profile and should not be generalised unless validated in a more rigorous study of a larger number of soil profiles.     

Distribution of nuclear bomb Pu in Nishiyama area, Nagasaki, estimated by accurate and precise determination of 240Pu/239Pu ratio in soils

Plutonium isotopes in forest soils collected in Nishiyama area, Nagasaki, were successfully determined by high resolution inductively coupled plasma mass spectrometry after the treatment with a microwave decomposition system. The (240)Pu/(239)Pu atom ratios observed in the samples in the Nishiyama area were obviously lower than the range of the global fallout. The low ratios (minimum 0.032) observed in Nishiyama area indicated the influence of detonation of the Pu nuclear weapon in 1945. Since the area is contaminated also by global fallout, the (240)Pu/(239)Pu atom ratio can be more sensitive indicator of bomb-derived Pu than Pu activity concentration.     

Classification of hot particles from the Chernobyl accident and nuclear weapons detonations by non-destructive methods.

Both after the Chernobyl accident and nuclear weapon detonations, agglomerates of radioactive material, so-called hot particles, were released or formed which show a behaviour in the environment quite different from the activity released in gaseous or aerosol form. The differences in their characteristic properties, in the radionuclide composition and the uranium and actinide contents are described in detail for these particles. While nuclear bomb hot particles (both from fission and fusion bombs) incorporate well detectable trace amounts of 60Co and 152Eu, these radionuclides are absent in Chernobyl hot particles. In contrast, Chernobyl hot particles contain 125Sb and 144Ce which are absent in atomic bomb HPs. Obvious differences are also observable between fusion and fission bombs' hot particles (significant differences in 152Eu/l55Eu, 154Eu/155Eu and 238Pu/239Pu ratios) which facilitate the identification of HPs of unknown provensence. The ratio of 239Pu/240Pu in Chernobyl hot particles could be determined by a non-destructive method at 1:1.5. A non-destructive method to determine the content of non-radioactive elements by Kalpha-emission measurements was developed by which inactive Zr, Nb, Fe and Ni could be verified in the particles.     

Multi-technique characterization of a nuclear bomb particle from the Palomares accident

A January 1966 accident dispersed Pu and other nuclear bomb materials in the vicinity of Palomares, a village in southeastern Spain. Radioactive particles were identified in a soil sample collected in 1998 and analytical results obtained from one of the isolated particles are presented here. Isolation of the particle was performed using gamma-ray spectrometry and imaging plates. Scanning electron microscopy with X-ray microanalysis revealed the presence of U and Pu as well as Pb and Fe in the particle of approximately 10microm diameter. Radioisotopes of U, Pu, and Am were quantified using radiometric methods, inductively coupled plasma mass spectrometry and secondary ion mass spectrometry. The elevated (235)U/(238)U atom ratio indicates enriched U, and the Pu atom ratios are consistent with weapons-grade material. This work demonstrates that the analysis of individual particles provides information not available through bulk sample analysis.     

Radium geochemistry in Na-Cl type groundwater in Niigata Prefecture, Japan

Radium isotopes in 23 Na-Cl type groundwater sampled mainly from deep wells in Niigata Prefecture, which is the site of the largest oil- and gas-fields in Japan, were measured along with U isotopes, chemical components and hydrogen and oxygen isotope ratios to elucidate the distribution and behavior of Ra in a brackish environment underground. Also analyzed were U and Th isotopes in 38 rock samples collected from outcrops at 17 locations. Ra-226 concentrations (8.86-1637 mBq kg⁻¹) of groundwater samples roughly correlated with total dissolved solid (TDS) concentrations and other alkaline earth contents. Their ²²⁸Ra/²²⁶Ra activity ratios (0.32-5.2) were similar to or higher than the ²³²Th/²³⁸U activity ratios (0.6-1.7) in the rocks. The most likely transport mechanism of Ra isotopes into groundwater was due to their α-recoil from the solid phase, probably from the water-rock interface where Th isotopes had accumulated, and adsorption/desorption reaction based on the increase in ²²⁶Ra contents with TDS.     

Preliminary evaluation of (135)Cs/(137)Cs as a forensic tool for identifying source of radioactive contamination

Ratios of the fission products (135)Cs and (137)Cs were determined in soil and sediment samples contaminated from three different sources, to assess the use of (135)Cs/(137)Cs as an indicator of source of radioactive contamination. Soil samples from the Chernobyl exclusion zone were found to have to be heavily depleted in (135)Cs ((135)Cs/(137)Cs approximately 0.45), indicative of a high thermal neutron flux at the source. Sludge samples from a nuclear waste treatment pond were found to have a (135)Cs/(137)Cs ratio of approximately 1, whereas sediment collected downstream from a nuclear reactor was highly variable in both (137)Cs activity and (135)Cs/(137)Cs ratio. Comparison of these preliminary results of variability in radiocaesium isotope ratios with reports of Pu isotope ratios suggests (135)Cs/(137)Cs similarly varies with fuel and reactor conditions, and may be used to corroborate other methods of characterizing radioactive contamination.     

Determination of U, Pu and Am isotopes in Irish Sea sediment by a combination of AMS and radiometric methods

Samples from a marine sediment core from the Irish Sea (54.416 N, 3.563 W) were analyzed for the isotopic composition of uranium, plutonium and americium by a combination of radiometric methods and AMS. The radiochemical procedure consisted of a Pu separation step by anion exchange, subsequent U separation by extraction chromatography using UTEVA^® and finally Am separation with TRU^® Resin.Additionally to radiometric determination of these isotopes by alpha spectrometry, the separated samples were also used for the determination of ²³⁶U/²³⁸U and plutonium isotope ratios by Accelerator Mass Spectrometry (AMS) at the VERA facility.     

Radioisotope contaminations from releases of the Tomsk-Seversk nuclear facility (Siberia, Russia)

Soils have been sampled in the vicinity of the Tomsk-Seversk facility (Siberia, Russia) that allows us to measure radioactive contaminations due to atmospheric and aquatic releases. Indeed soils exhibit large inventories of man-made fission products including 137Cs (ranging from 33,000 to 68,500 Bq m(-2)) and actinides such as plutonium (i.e. 239+240Pu from 420 to 5900 Bq m(-2)) or 241Am (160-1220 Bq m(-2)). Among all sampling sites, the bank of the Romashka channel exhibits the highest radioisotope concentrations. At this site, some short half-life gamma emitters were detected as well indicating recent aquatic discharge in the channel. In comparison, soils that underwent atmospheric depositions like peat and forest soils exhibit lower activities of actinides and 137Cs. Soil activities are too high to be related solely to global fallout and thus the source of plutonium must be discharges from the Siberian Chemical Combine (SCC) plant. This is confirmed by plutonium isotopic ratios measured by ICP-MS; the low 241Pu/239Pu and 240Pu/239Pu atomic ratios with respect to global fallout ratio or civil nuclear fuel are consistent with weapons grade signatures. Up to now, the influence of Tomsk-Seversk plutonium discharges was speculated in the Ob River and its estuary. Isotopic data from the present study show that plutonium measured in SCC probably constitutes a significant source of plutonium in the aquatic environment, together with plutonium from global fallout and other contaminated sites including Tomsk, Mayak (Russia) and Semipalatinsk (Republic of Kazakhstan). It is estimated that the proportion of plutonium from SCC source can reach 45% for 239Pu and 60% for 241Pu in the sediments.     

Biogeochemical signatures in the lichen Hypogymnia physodes in the mid Urals

Multi-element content and uranium (U) isotopes were investigated in the lichen Hypogymnia physodes (native and transplants) sampled across a 60-km transect, centred on Karabash smelter town, from Turgoyak Lake (SW) to Kyshtym (NE) to investigate the origin of U. Kyshtym was the site of a major nuclear accident in 1957. (234)U/(238)U activity ratios in native thalli sampled during July 2001 were within the natural isotopic ratio in minerals. Uranium/thorium (U/Th) ratios were higher in native thalli towards the NE (average 0.73) than those in the SW (average 0.57). Element signatures in native thalli and transplants suggest U was derived from fossil fuel combustion from Karabash and sources lying further to the east. Systematic and significant U enrichment indicative of a nuclear fuel cycle source was not detected in any sample. Element signatures in epiphytic lichen transplants and native thalli provide a powerful method to evaluate U deposition.     

Some observations on the geochemistry and isotopic composition of uranium in relation to the reprocessing of nuclear fuels

In order to determine whether or not uranium depleted in ²³⁵U and derived from the British Nuclear Fuels Ltd (BNFL) nuclear fuel reprocessingg plant at Sellafield, Cumbria, UK can be detected in environmental samples, we have investigated the isotopic composition of uranium in ammonium carbonate leachates from marine and terrestial samples from near Sellafield. Some show a depletion in ²³⁵U and the presence of ²³⁶U which unequivocally identifies the presence of uranium derived from BNFL. The ²³⁴U/²³⁸U activity ratio and total uranium content of samples are not significantly different from those of natural uranium abundances. The highest concentrations of uranium are found in anaerobic organic-rich silts and the lowest in sandy silts and coarse-grained sands.     

Depth profile of ²³⁶U/²³⁸U in soil samples in La Palma, Canary Islands

The vertical distribution of the ²³⁶U/²³⁸U isotopic ratio was investigated in soil samples from three different locations on La Palma (one of the seven Canary Islands, Spain). Additionally the ²⁴⁰Pu/²³⁹Pu atomic ratio, as it is a well establish tool for the source identification, was determined. The radiochemical procedure consisted of a U separation step by extraction chromatography using UTEVA^® Resin (Eichrom Technologies, Inc.). Afterwards Pu was separated from Th and Np by anion exchange using Dowex 1x2 (Dow Chemical Co.). Furthermore a new chemical procedure with tandem columns to separate Pu and U from the matrix was tested. For the determination of the uranium and plutonium isotopes by alpha spectrometry thin sources were prepared by microprecipitation techniques. Additionally these fractions separated from the soil samples were measured by Accelerator Mass Spectrometry (AMS) to get information on the isotopic ratios ²³⁶U/²³⁸U, ²⁴⁰Pu/²³⁹Pu and ²³⁶U/²³⁹Pu, respectively. The ²³⁶U concentrations [atoms/g] in each surface layer (∼2 cm) were surprisingly high compared to deeper layers where values around two orders of magnitude smaller were found. Since the isotopic ratio ²⁴⁰Pu/²³⁹Pu indicated a global fallout signature we assume the same origin as the probable source for ²³⁶U. Our measured ²³⁶U/²³⁹Pu value of around 0.2 is within the expected range for this contamination source.     

Separation and measurement of thorium, plutonium, americium, uranium and strontium in environmental matrices

A technique for the isolation of thorium (Th), plutonium (Pu), americium (Am), uranium (U) and strontium (Sr) isotopes from various environmental matrices has been adapted from a previously published method specific to water samples (Maxwell, 2006). Separation and isolation of the various elemental fractions from a single sub-sample is possible, thereby eliminating the need for multiple analyses.The technique involves sample dissolution, concentration via calcium phosphate co-precipitation, rapid column extraction using TEVA™, TRU™ and Sr-Spec™ resin cartridges, alpha spectrometry for Th, Pu, U and Am and Cerenkov counting for Sr.Various standard reference materials were analysed and chemical yields are in the range of 70-80% for Th, Am, U and Sr and 50-60% for Pu. Sample sizes of up to 10 L for water, 5 g for dry soil and sediment and 10 g for dry vegetation and seaweed can be processed using this technique.