Determination of total content and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes by ICP-QMS

The aim of this work was to determine the concentrations and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes. An analytical method was developed with a plutonium and uranium separation procedure based on extraction chromatography (using 2 mL TEVA and UTEVA columns) and detection with a quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with a membrane desolvation system. Starting from blank swipes, the background equivalent concentration (BEC) was 8 fg for ²³⁹Pu and 1 ng ²³⁸U. The method was successfully applied to certified reference materials as well as to round robin samples obtained in the framework of the inter-laboratory exercise program, promoted by the Brazilian–Argentine Agency for Accounting and Control of Nuclear Materials (ABACC), together with the US Department of Energy (USDOE). After the introduction of an additional ion-exchange separation step, the methodology was applied to the IAEA-384 sediment reference sample with precise and accurate total plutonium and uranium, ²⁴⁰Pu/²³⁹Pu, ²⁴¹Pu/²³⁹Pu, ²³⁴U/²³⁸U and ²³⁵U/²³⁸U atomic ratio results.     

Plutonium contamination from accidental release or simply fallout: study of soils at Palomares (Spain)

The activity concentration of plutonium in an environmental sample does not usually constitute sufficient information to determine if it is due only to fallout. Alpha and gamma spectrometry are used here conjointly in the study of environmental soil samples to distinguish between samples showing plutonium contamination due to fallout exclusively, and samples contaminated with plutonium from another source. The method was applied to soil samples collected in Palomares (Spain), where an accidental release of aerosols contaminated with plutonium occurred. The two contributions (fallout and accidentally released plutonium) were separated by means of the activity ratios between various radionuclides present in the samples analyzed. The fallout level was estimated from the 239 + 240Pu/137Cs activity ratio. For samples showing contamination due to the accident, the 238Pu/239 + 240Pu and 239Pu/240Pu activity ratios were also calculated to determine the grade of plutonium of this contamination.     

Depositional records of plutonium and (137)Cs released from Nagasaki atomic bomb in sediment of Nishiyama reservoir at Nagasaki

In a sediment core of Nishiyama reservoir at Nagasaki city, depth profiles of (240)Pu/(239)Pu isotopic ratio, (239+240)Pu and (137)Cs activities were determined. Sediments containing plutonium and (137)Cs, which were deposited immediately after a detonation of Nagasaki atomic bomb, were identified in the core. Observed below the sediments were macroscopic charcoals, providing evidence for initial deposit of the fallout of the Nagasaki atomic bomb. This is the first entire depositional records of plutonium and (137)Cs released from the Nagasaki atomic bomb together with those from atmospheric nuclear tests.     

Artificial radionuclides in the atmosphere over Lithuania

Measurements of airborne radioactive aerosol concentration were carried out on the basis of 1-3 days samples after the Chernobyl disaster and during the period of 1992-2003. Transport of "hot" particles of different composition resulted in the high activity concentrations of (137)Cs, (238)Pu, (239,240)Pu and (241)Am in the atmosphere in Vilnius at the end of April 1986. The (240)Pu/(239)Pu atom ratio showed clear evidence of non-global plutonium originating from the Chernobyl accident in the atmosphere over Lithuania. The (240)Pu/(239)Pu atom ratio ranged from 0.14 to 0.40 in monthly samples in Vilnius in 1995-2003. An increase in activity concentration of (137)Cs by a factor of 100 (up to 300 microBq/m(3)) was found following forest fires in the Ukraine and Belarus. However, no transport of the Chernobyl plutonium was observed and the (240)Pu/(239)Pu atom ratio in samples collected during the forest fires was found to be 0.229 and 0.185, respectively. The exponential decrease in the (240)Pu/(239)Pu atom ratio from 0.30 to 0.19 (mean values) was observed in 1995-2003.     

240Pu/239Pu atom ratios in seawater from Sagami Bay, western Northwest Pacific Ocean: sources and scavenging

Seawater samples were collected in Sagami Bay, western Northwest Pacific Ocean, and their (239+240)Pu activities and (240)Pu/(239)Pu atom ratios were determined by alpha-spectrometry and sector field high-resolution ICP-MS. A few samples also were analyzed for (137)Cs activities. The (239+240)Pu inventory of 41.1 Bq m(-2) was equivalent to the expected cumulative deposition density of atmospheric global fallout at the same latitude and this inventory was considerably lower than inventories in the underlying sediment columns. This result indicated that a significant amount of (239+240)Pu has been removed into the underlying sediments through enhanced scavenging from the water column by the high fluxes of particles in this region. The atom ratio of (240)Pu/(239)Pu showed no notable variation from the surface to the bottom; the average value was 0.234+/-0.004. This atom ratio was significantly higher than the mean global fallout ratio of 0.18, proving the existence of close-in fallout plutonium originating from the Pacific Proving Grounds (PPG). The relative contributions of the global stratospheric fallout and the PPG close-in fallout were evaluated by using the two end-member mixing model. The contribution of the PPG close-in fallout was estimated to be 15.2 Bq m(-2), which corresponded to 37% of the (239+240)Pu inventory in the water column. Thus (239)Pu and (240)Pu from the two sources of global fallout and close-in fallout have been homogenized in the water masses in the western Northwest Pacific margin during the past three decades.     

Radioactivity concentrations of 40K, 134Cs, 137Cs, 90Sr, 241Am, 238Pu and 239+240Pu radionuclides in Jordanian soil samples

In November 2000, surface and core soil samples were collected from different regions of Jordan. The samples were analyzed by direct gamma spectrometry and combined radiochemical separation procedure to quantify (40)K, (134)Cs, (137)Cs, (90)Sr, (241)Am, (238)Pu and (239+240)Pu radioactivity. Concentrations (Bq.kg(-1) dry weight) have been observed to vary in the range 1.5-2.6 for (134)Cs, 2.8-11.4 for (90)Sr, and 0.13-0.48 for (241)Am, 0.016-0.062 for (238)Pu, 0.28-1.01 for (239+240)Pu and 155-543 for (40)K. The typical concentration of (137)Cs found in topsoils (0-2 cm) ranged in 7.5-576 Bq.kg(-1), dry weight. These values were greater than those observed in samples taken at greater depths (up to 32 cm). Activity ratios of (134)Cs/(137)Cs, (90)Sr/(137)Cs, (239+240)Pu/(137)Cs, (238)Pu/(137)Cs, (241)Am/(137)Cs, (239+240)Pu/(238)Pu and (241)Am /(238)Pu have mean values of 0.0049 (R=1), 0.29 (R=0.76), 0.41 (R=0.90), 0.39 (R=0.85), 0.41 (R=0.88), 7.72 (R=0.97) and 16.66 (R=0.98), respectively. The underlying concentrations were correlated and relatively higher than those reported in neighboring countries. One moss sample, as a biomonitor indicator, was measured and evaluated along with the soil samples. Its data showed higher concentrations of all measured radionuclides due to accumulations over years. The depth distribution of the fission product (137)Cs and the total deposition (Bq.m(-2)) were also studied in selected samples. Estimations of the annual effective dose equivalent due to (137)Cs-soil contamination showed values up to more than 200 microSv.     

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.     

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.     

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).     

Comparison of Pu and (137)Cs as tracers of soil and sediment transport in a terrestrial environment

Following atmospheric nuclear weapons testing in the 1950s and 1960s significant quantities of (137)Cs and (239+240)Pu were deposited worldwide. In recent decades, (137)Cs has been commonly used as a tracer of soil erosion and sedimentation, particularly in the Northern Hemisphere where atomic deposition was three times as great as in the Southern Hemisphere. The relatively short 30-year half-life of this isotope means that its sensitivity as a tracer is rapidly decreasing. In contrast, with half-lives of 24,110 and 6561 years, the sensitivity of the two plutonium isotopes remains essentially the same as when it was deposited. Here we use the technique of Accelerator Mass Spectrometry to demonstrate the potential of anthropogenic Pu as an alternative to (137)Cs as a tracer of soil transport in Australia. We measure an average (137)Cs/(239+240)Pu activity ratio of 27.3+/-1.5 and an average (240)Pu/(239)Pu atom ratio of 0.149+/-0.003, both slightly lower than the global average.     

Estimates of (239+240)Pu inventories in Gdańsk Bay and Gdańsk basin

This paper presents and discusses the results of (239+240)Pu determinations in different components of Gdańsk bay and Gdańsk basin ecosystem, as well as estimated sources and inventories of plutonium in these basins. The total plutonium (239+240)Pu activities deposited in Gdańsk bay and Gdańsk basin sediments are 1.18 TBq and 3.77 TBq, respectively. Two rivers, the Vistula and Neman rivers, and atmospheric fallout were distinguished as the main sources of plutonium in these basins. In seawater (with suspended matter included) there is about 2.33 GBq (239+240)Pu (0.2% of total activity) in Gdańsk bay and 9.92 GBq (239+240)Pu (0.3% of total activity) in Gdańsk basin. In both cases, 56% of (239+240)Pu is associated with suspended matter. Organisms contain 3.81 MBq in Gdańsk bay and 7.45 MBq (239+240)Pu in Gdańsk basin. From this value in Gdańsk bay 82.1% of plutonium is associated with zoobenthos, 13.6% with phytobenthos, 1.6% with phytoplankton, 1.5% with zooplankton and 1.2% with fish. In Gdańsk basin, 83.2% is associated with zoobenthos, 7.5% with phytobenthos, 3.6% with phytoplankton, 3.2% with zooplankton and 2.5% with fish.     

Distribution of Np and Pu in Swedish lichen samples (Cladonia stellaris) contaminated by atmospheric fallout

The activity concentrations of (237)Np and the two Pu isotopes, (239)Pu and (240)Pu, were determined in lichen samples (Cladonia stellaris) contaminated by fallout from atmospheric nuclear test explosions and the Chernobyl accident. The samples were collected at 18 locations in Sweden, from north to south, between 1986 and 1988 and analysed with high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and alpha spectrometry. Data on the activity ratios (238)Pu/(239+240)Pu and (134)Cs/(137)Cs measured previously were also included in this study for comparison. The (237)Np activity concentration ranged from 0.08 +/- 0.01 to 2.08 +/- 0.17 MBq kg(-1), depending on the location of the sampling site and time of collection. The (239+240)Pu activity concentration ranged from 0.09 +/- 0.01 to 4.09 +/- 0.15 Bq kg(-1), with the (240)Pu/(239)Pu atomic ratio ranging between 0.16 +/- 0.01 and 0.44 +/- 0.03, the higher ratios indicating a combination of weapons test fallout and Chernobyl fallout. The (237)Np/(239)Pu atomic ratios ranged between 0.06 +/- 0.01 and 0.42 +/- 0.04, the lower ratios indicating combination of weapons test fallout and Chernobyl fallout. At a well-defined sampling site at Lake Rogen (62.32 degrees N, 12.38 degrees E), additional lichen samples were collected between 1987 and 1998 to study the distribution of Np and Pu in different layers. The concentrations of the two elements follow each other quite well in the profile.     

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.     

Modelling the distribution of plutonium in the Pacific Ocean

An Oceanic General Circulation Model (OGCM) including a plutonium scavenging model as well as an advection-diffusion model has been developed for modelling the distribution of plutonium in the Pacific Ocean. Calculated 239, 240Pu water profile concentrations and 239, 240Pu inventories in water and sediment of the Pacific Ocean have showed a reasonable agreement with the experimental results. The presence of local fallout plutonium in central North Pacific waters has been confirmed. The observed 240Pu/239Pu mass ratios confirm that plutonium originating from local fallout from nuclear weapons tests carried out at Bikini and Enewetak Atolls is more rapidly removed from surface waters to deeper waters than plutonium originating from global fallout. The developed OGCM can be used for modelling the dispersion of other non-conservative tracers in the ocean as well.     

Size-fractionated plutonium isotopes in a coastal environment

We have examined the distribution of individual Pu isotopes (239Pu, 240Pu, and 241Pu) in seawater from the Gulf of Maine (GOM). Samples were size-fractionated with a 1 kD cross-flow ultrafiltration (CFF) membrane. Subfractioned samples were radiochemically purified and Pu isotopes were analyzed using a three-stage thermal ionization mass spectrometer (TIMS). To our knowledge, this is the first time that both size class and Pu isotopic data have been obtained for seawater samples. Within measurement uncertainties a single 240Pu/239Pu atom ratio of 0.18 was found for all sample collection depths and sample size fractions. This signifies a current, single Pu source in GOM waters, namely global fallout, and suggests that no measurable isotopic fractionation occurred during CFF processing. The majority of Pu was found in the low molecular weight fraction (< 1 kD). Colloidal Pu varied from 8% of the total in surface waters to < 1% in the deepest (250 m) seawater sample. Evidence suggests that the vertical distribution of Pu in GOM is primarily controlled by conservative mixing processes. The high Pu fraction found in the low molecular size fraction implies that most of the Pu is in the non-particle-reactive oxidized fraction, and is consistent with the conservative Pu behavior. The activity levels are in agreement with other studies which show a slow decrease in Pu with time due to continued mixing and relatively slow particle removal.     

Plutonium concentrations in waters from the southern Baltic Sea and their distribution in cod (Gadus morhua) skin and gills

The concentrations of (238)Pu and (239+240)Pu in water samples and suspended particulate fractions, as well as in colloidal fraction from the southern Baltic Sea are presented. The (239+240)Pu concentration in surface seawater samples fall within range from 5.2 mBq.m(-3) for Gdańsk Bay to 150 mBq.m(-3) for Pomeranian Bay, most of which (from 52 to 96%) constituted filterable forms (相似文献   

Plutonium isotopes in the lower reaches of the River Rhône over the period 1945-2000: fluxes towards the Mediterranean Sea and sedimentary inventories

Plutonium isotopes in the Rh?ne River originate from both the weathering of the catchment basin contaminated by global atmospheric fallout, and the liquid effluents released from the Marcoule reprocessing plant since 1961. Due to a new treatment process applied to the liquid effluents, a decrease of two orders of magnitude in the industrial plutonium discharged into the River Rh?ne has been registered from 1991. Today, 238Pu industrial inputs to the River Rh?ne are still about 10 times higher than those derived from global fallout, while 239+240Pu inputs from industrial and global fallout sources are of similar importance, i.e. 1 GBq y(-1). Our results indicate that the river sedimentary compartment act either as a sink or a delayed-source term of plutonium for the freshwaters depending on the hydraulic regime and flood events. This compartment may then represent an important industrial delayed-source term for the River Rh?ne freshwaters in the coming years as the Marcoule reprocessing plant is being dismantled. These results were obtained from samples collected from the lower course of the River Rh?ne over the 1987-1998 period and analysed for 238Pu and 239+240Pu activities. Both river sedimentary inventories of plutonium isotopes and effective outputs from the River Rh?ne towards the Gulf of Lions have been estimated for each year over the 1945-2000 period. Regarding 239+240Pu, the sedimentary inventory accumulated since 1945 is estimated to be 172+/-35 GBq. If mobile, this amount represents a significant delayed-source term of plutonium on the scale of the Rh?ne watershed.     

Bioaccumulation and distribution of plutonium in fish from Gdansk Bay

In this paper, the results of 238Pu and 239 + 240Pu determinations in four representative species of Baltic fish collected in Gdansk Bay; flounder, herring, cod and sprat, are presented and discussed. The plutonium isotopes are amongst the more radiotoxic nuclides. In the marine environment, the highest concentrations of plutonium are found in the sediments, but the complex biogeochemical cycle of the element means that it is also found in all other compartments. The activities of the fish samples were measured using alpha spectrometry and the concentrations of plutonium 238Pu and 239 + 240Pu were estimated for particular organs and tissues and the whole body. The 239 + 240Pu concentrations for fish species were: flounder 0.94 mBq kg-1 w.w., herring 2.22 mBq kg-1 w.w., cod 2.35 mBq kg-1 w.w. and sprat 0.33 mBq kg-1 w.w. On the basis of the 238Pu/239 + 240Pu activity ratio in the organs and tissues, the proportion of Chernobyl-derived plutonium in the Baltic Sea was calculated. The lowest values of Chernobyl plutonium were accumulated in flounder stomach, herring skin, cod intestine, the highest in cod gills and skin.     

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.     

Sector field inductively coupled plasma mass spectrometry, another tool for plutonium isotopes and plutonium isotope ratios determination in environmental matrices

The transfer of radio nuclides into the different compartments of the environment are widely studied and leads to the elaboration of transfer models in order to evaluate potential impact onto the environment and humans. Accurate experimental data are needed to validate these models for all types of matrices (air, water, sediments, soils, biota and food...). Among these radionuclides, 238Pu, 239Pu, 240Pu and 241Pu, are often mentioned. They have been released into the environment by nuclear weapon tests, nuclear facilities, reactors or satellite accidents. These different sources have different 240Pu/239Pu ratios and therefore this ratio is used to provide information on the source of contamination into the environment. The most conventional analytical tools used for plutonium isotope determination are liquid scintillation and alpha spectrometry, and thermal ionisation mass spectrometry (TIMS) is still considered as the primary method for determination of plutonium isotope ratios. During the last decade, mass spectrometers equipped with plasma ion sources and sector field analysers were developed and can offer now another alternative method for the accurate determination of isotope content and ratios of long-lived radionuclides in environmental samples. This paper presents and discusses the results obtained for 239Pu, 240Pu and 241Pu content and isotope ratios by sector field ICP-MS in different environmental matrices.