Determination of <Superscript>238</Superscript>Pu in plutonium bearing fuels by thermal ionization mass spectrometry

Determination of ²³⁸Pu in plutonium bearing fuels is required as a part of the chemical quality assurance of nuclear fuels. In addition, the determination of ²³⁸Pu is required in nuclear technology for many other applications, e.g., for developing isotope correlations and while using ²³⁸Pu as a spike (tracer) in isotope dilution α-spectrometry (IDAS). This determination usually involves the use of α-spectrometry on purified Pu sample. In view of the random errors associated with the counting statistics and the systematic errors due to (1) in-growth of ²⁴¹Am in purified Pu sample and (2) tail contribution correction methodology in α-spectrometry, the precision and accuracy obtainable by α-spectrometry are limited. Thermal ionization mass spectrometry (TIMS) is generally used for the determination of different Pu isotopes other than ²³⁸Pu. This is due to the ubiquitous isobaric interference from ²³⁸U at ²³⁸Pu in TIMS. Recently, we have carried out studies on the formation of atomic and oxide ions of U and Pu by TIMS and developed a novel approach using interfering element correction methodology to account for the isobaric interference of ²³⁸U at ²³⁸Pu in TIMS. This methodology is based on the addition of ²³⁵U (enrichment >90 atom%) to Pu sample followed by the determination of ²³⁸U/²³⁵U atom ratio using UO⁺ ion and determination of Pu isotope ratios using Pu⁺ ion, from the same filament loading. The TIMS methodology was used for the determination of ²³⁸Pu in different Pu samples in U based nuclear fuels from PHWRs with ²³⁸Pu content about 0.2 atom%. The ²³⁸Pu determination was also carried out using α-spectrometry. This paper reports the results obtained by the two methods and presents the ments and shortcomings of the two approaches.     

A combined method of neutron activation analysis and radiometric measurements for <Superscript>234</Superscript>U and <Superscript>238</Superscript>U determination in soil samples of low uranium concentration

A method that combines the use of non-destructive neutron activation analysis and high-resolution α spectrometry has been developed for determination of the activities of ²³⁴U and ²³⁸U in geological samples of low uranium content. The ²³⁸U content is determined by k₀-based neutron activation analysis, whereas the ²³⁴U/²³⁸U relationship is measured by α spectrometry after isolation and electrodeposition of the uranium extracted from a lixiviation with 6 M HCl. The main advantage of the method is the simplicity of the chemical operations, including the fact that the steps destined to assure similar chemical state for the tracer and the uranium species present in the sample are not necessary. The method was applied to soil samples from sites of the North Peru Coast. Uranium concentration range 3–40 mg/kg and the isotopic composition correspond to natural uranium, with about 10% uncertainty.     

Comparison of analytical methods used to determine <Superscript>235</Superscript>U, <Superscript>238</Superscript>U and <Superscript>210</Superscript>Pb from sediment samples by alpha,beta and gamma spectrometry

An intercomparison of the methodology (alpha, beta and gamma spectrometry) used for ²³⁸U, ²³⁵U and ²¹⁰Pb determination was carried out based on 38 sediment samples. The activity range of the samples varied from 10–700 Bq/kg for ²¹⁰Pb, 1–35 Bq/kg for ²³⁵U and 10–800 Bq/kg for ²³⁸U. Results obtained using the three methods were not statistically different at high activity levels, but agreement between the results decreased at lower sample activity levels. For ²¹⁰Pb, the smallest difference was found between alpha and gamma spectrometry. A good correlation between results from alpha and gamma spectrometry was observed over the whole activity range. In beta spectrometry, the results were slightly higher than those obtained by alpha or gamma spectrometry due to the impurity of ²²⁸Ra. In ²³⁸U analysis, good correspondence was observed between ²³⁸U determined by gamma and alpha spectrometry, particularly at higher ²³⁸U activity concentrations over 100 Bq/kg. In ²³⁵U analysis, attention needs to be paid to interference from ²²⁶Ra and its reduction.     

Behavior and distribution of <Superscript>239+240</Superscript>Pu and <Superscript>241</Superscript>Am in the east coast of Peninsular Malaysia marine environment

The present distributions of ^239+240Pu, ²⁴¹Am and activity ratio of ²⁴¹Am/^239+240Pu in surface seawater of the Peninsular Malaysia east coast were studied. The surface seawater samples were collected at 30 identified stations during the expedition conducted in 2008. ^239+240Pu activity concentrations in surface seawater of the studied area were in the range of 2.33 ± 0.20–7.95 ± 0.68 mBq/m³, meanwhile ²⁴¹Am activity concentrations ranged from MDA to 1.90 ± 0.23 mBq/m³. The calculated activity ratios of ²⁴¹Am/^239+240Pu were varied and disperse distributed with the ranged of 0.12–0.53. The relationships between anthropogenic radionuclide and oceanographic parameters such as turbidity and salinity were examined. The linearly relationships between ^239+240Pu and oceanographic parameters are important for better understanding of its transport processes and behavior in the east coast of Peninsular Malaysia marine environment. Thus, the differ of distribution of ^239+240Pu, ²⁴¹Am and ²⁴¹Am/^239+240Pu in the studied area mainly due to high affinity of ^239+240Pu to associate with sinking particles, mobility nature of ²⁴¹Am, degree of particle reactive of both anthropogenic radionuclides, scavenging and removal process; and others.     

Large volume preconcentration and purification for determining the240Pu/<Superscript>239</Superscript>Pu isotopic ratio and <Superscript>238</Superscript>Pu/<Superscript>239+240</Superscript>Pu alpha-activity ratio in seawater

Summary The present paper describes a new analytical method for determining the ²⁴⁰Pu/²³⁹Pu isotopic ratio and ²³⁸Pu/^239+240Pu α -activity ratio in seawater, both of which are important parameters for determining Pu sources in the ocean. Plutonium isotopes were preconcentrated from a large volume of seawater (4700-10800 liter) by solid phase extraction using MnO₂-impregnated fibers and eluted into 3M HCl. After the elution, the Pu species of all oxidation states were converted to Pu(IV) using NaNO₂, purified by solvent extraction using thenoyltrifluoroacetone (TTA)-benzene, and concentrated in 5 ml of 0.2M HNO₂. The ²⁴⁰Pu/²³⁹Pu and ²³⁸Pu/^239+240Pu ratios in the 5-ml final solution were determined by inductively coupled plasma-mass spectrometry (ICP-MS) and α-spectrometry, respectively. A pg level of Pu, which was a sufficiently large amount for the determination, was obtained by the solid phase extraction. Through the redox conversion and solvent extraction, the Pu species, such as Pu(III), Pu(IV) and Pu(VI), were collected at a high recovery of 96±2% (n=3) despite the presence of large amounts of Mn, and interfering ²³⁸U (3.3 μg^. l^-1in seawater) was effectively removed with a decontamination factor of 1.7·10⁷. The accuracy of the method for the ²⁴⁰Pu/²³⁹Pu ratio was verified using reference materials of seawater and a terrestrial soil sample. The present technique was applied to the determination of the ²⁴⁰Pu/²³⁹Pu and ²³⁸Pu/^239+240Pu ratios in coastal and oceanic water.     

Distribution of <Superscript>137</Superscript>Cs, <Superscript>40</Superscript>K, <Superscript>232</Superscript>Th and <Superscript>238</Superscript>U in coastal marine sediments of Margarita Island,Venezuela

This work presents the results of ¹³⁷Cs, ⁴⁰K, ²³²Th and ²³⁸U concentration (Bq kg⁻¹) values in coastal marine sediments collected from 38 sites along the coastline of the island of Margarita, Venezuela. The purpose was to determine baseline values for these radionuclides in surface marine sediments and to detect if there were any anomalously high concentration values. Only three of the 38 sediments analyzed had measurable values above the detection limit of 0.9 Bq kg⁻¹ for ¹³⁷Cs and the highest only being 1.4 Bq kg⁻¹. While, the concentration (Bq kg⁻¹) ranges for the primordial radionuclides, ⁴⁰K, ²³²Th and ²³⁸U were as follows: 12.2–211.7, <1.5–9.8 and <4.4–20.7, respectively. These concentration ranges for the primordial radionuclides can be considered as baseline values for surface marine sediments for areas that are considered not polluted by man or contaminated by nature. Finally, the concentration range of ¹³⁷Cs can also be employed as baseline values, which only seem to have been the result of the atmospheric testing of nuclear weapons in the past.     

Adsorption and migration of <Superscript>241</Superscript>Am in aerated zone soil

As an important radioisotope in nuclear industry and other fields, ²⁴¹ Am is one of the most serious contamination concerns due to its high toxicity and long half-life. In order to supply useful reference for disposal of ²⁴¹Am waste with low-medium radioactivity, the adsorption and migration behavior of ²⁴¹Am on aerated zone soil were investigated by the static experimental method and column experiments. The results showed that more than 98% of the total ²⁴¹Am could be adsorbed from ²⁴¹Am solution of 0.32·10⁻⁷−1.1·10⁻⁷ mol/l by the soil at pH 4–9. The adsorption of ²⁴¹Am on the soil was a pH-dependent process at pH<4, but for pH>4, the adsorption rate of ²⁴¹Am on the soil changed minutely. The adsorption equilibrium was achieved within 24 hours and no significant effect on adsorption of ²⁴¹Am was observed at liquid-solid ratios of 50:1–500:1. The relationship between concentration of ²⁴¹Am and adsorption capacities of ²⁴¹Am can be described by the Freundlich adsorption equation. Adsorption of ²⁴¹Am on the soil can be inhibited by humic acid, ferric hydroxide colloid, or some anions, such as citric acid anion, saturated EDTA solution, C₂O₄ ²⁻ and CO₃ ²⁻. It was also noted that the adsorption rate of ²⁴¹Am drops in solutions containing Eu³⁺ or Nd³⁺, even 0.5 times above the ²⁴¹Am concentration. A migration distance of 8 mm for ²⁴¹Am(III) is observed only in the aerated zone soil containing ferric colloid, while a migration distance of less than 2 mm is noted in other soil samples after more than 250 days. All these results indicate that the aerated zone soil is an efficient sorbent for ²⁴¹Am and can inhibit the migration of ²⁴¹Am.     

ICP-MS analysis of plutonium activities and <Superscript>240</Superscript>Pu/<Superscript>239</Superscript>Pu ratio in alpha spectrometry planchet deposits

Plutonium isotopes were measured by alpha-spectrometry and ICP-MS in sediment samples from two European lakes: Blelham Tarn in U.K. and Stechlin lake in Germany. The ICP-MS measurements were made after alpha-spectrometry counting of the planchets. The planchets were prepared by traditional electrodeposition method after radiochemical extraction, separation and purification of the Pu fraction. A short radiochemical separation using plutonium selective resin, between the two spectrometry measures, is presented. The results show that these two complementary methods are in good agreement, the plutonium activity concentrations are the same. Alpha-spectrometry allows the ²³⁸Pu determination and ICP-MS individual measurement of ²³⁹Pu and ²⁴⁰Pu. ²³⁸Pu/^239+240Pu and ²⁴⁰Pu/²³⁹Pu ratios are calculated to determine the plutonium contamination source. With the results of these two techniques, it could be demonstrate that the plutonium is of global fallout origin.     

Radioactivity levels of <Superscript>238</Superscript>U and <Superscript>232</Superscript>Th,the α and β activities and associated dose rates from surface soil in Ulu Tiram,Malaysia

A survey was carried out to determine terrestrial gammaradiation dose rates, the concentration level of ²³⁸U and ²³²Th and α and β activities for the surface soil in Ulu Tiram, Malaysia A 125 measurements were performed using a NaI(T1) gamma-ray detector with crystal size of 1″ × 1″ on 15 soil samples collected from the site area about 102 km^{2 238}U and ²³²Th concentrations were determined in soils by using hyper pure germanium (HPGe) gamma-ray spectrometry. The activity of α and β from the surface soil was counted by using alpha beta counting system. The average value of ²³⁸U and ²³²Th concentrations in soil samples collected are 3.63±0.39 ppm within the range of 1.74±0.20 to 4.58±0.48 and 43.00±2.31 ppm within the range of 10.68±0.76 to 82 10±4.01 ppm, respectively. The average estimate of α and β activity in soil samples collected are 0.65±0.09 Bqg⁻¹ and 0.68±0.08 Bqg⁻¹, respectively. The average of terrestrial gamma-radiation dose rates measured in Ulu Tiram was found to be 200 nGy h⁻¹, within the range of 96 to 409 nGy h⁻¹. The population weighted outdoor annual effective dose was 1.2 mSv.     

<Superscript>237</Superscript>Np in peat and lichen in Finland

Activity concentrations of ²³⁷Np in peat and lichen samples in Finland were determined and contributions from nuclear weapons testing in 1950–1960s and the Chernobyl accident were estimated. ²³⁷Np was determined with ICP-MS using ²³⁵Np as a tracer. Activity concentrations of ²³⁷Np in peat samples varied between 1.98 ± 0.05 and 14.1 ± 0.3 mBq/m². The contribution from the Chernobyl accident to the total ²³⁷Np deposition in peat was 0.1–13%, the Chernobyl-derived fraction of total ²³⁷Np in peat being much lower than the previously determined corresponding Chernobyl-derived fractions of ^239+240Pu, ²⁴¹Pu, ²⁴¹Am and ²⁴⁴Cm.     

<Superscript>239, 240, 241</Superscript>Pu fingerprinting of plutonium in western US soils using ICPMS: solution and laser ablation measurements

Sector field inductively coupled plasma mass spectrometry (SF-ICPMS) has been used with analysis of solution samples and laser ablation (LA) of electrodeposited alpha sources to characterize plutonium activities and atom ratios prevalent in the western USA. A large set of surface soils and attic dusts were previously collected from many locations in the states of Nevada, Utah, Arizona, and Colorado; specific samples were analyzed herein to characterize the relative contributions of stratospheric fallout vs. Nevada Test Site (NTS) plutonium. This study illustrates two different ICPMS-based analytical strategies that are successful in fingerprinting Pu in environmental soils and dusts. Two specific datasets have been generated: (1) soils are leached with HNO₃-HCl, converted into electrodeposited alpha sources, counted by alpha spectrometry, then re-analyzed using laser ablation SF-ICPMS; (2) samples are completely dissolved by treatment with HNO₃-HF-H₃BO₃, Pu fractions are prepared by extraction chromatography, and analyzed by SF-ICPMS. Optimal laser ablation and ICPMS conditions were determined for the re-analysis of archived alpha spectrometry “planchette” sources. The best ablation results were obtained using a large spot size (200 μm), a defocused beam, full repetition rate (20 Hz) and scan rate (200 μm s⁻¹); LA-ICPMS data were collected with a rapid electrostatic sector scanning experiment. Less than 10% of the electroplated surface area is consumed in the LA-ICPMS analysis, which would allow for multiple re-analyses. Excellent agreement was found between ^239+240Pu activities determined by LA-ICPMS vs. activity results obtained by alpha spectrometry for the same samples ten years earlier. LA-ICPMS atom ratios for ²⁴⁰Pu/²³⁹Pu and ²⁴¹Pu/²³⁹Pu range from 0.038–0.132 and 0.00034–0.00168, respectively, and plot along a two-component mixing line (²⁴¹Pu/²³⁹Pu = 0.013 [²⁴⁰Pu/²³⁹Pu] – 0.0001; r ² = 0.971) with NTS and global fallout end-members. A rapid total dissolution procedure, followed by extraction chromatography and SF-ICPMS solution Pu analysis, generates excellent agreement with certified ^239+240Pu activities for standard reference materials NIST 4350b, NIST 4353, NIST 4357, and IAEA 385. ^239+240Pu activities and atom ratios determined by total dissolution reveal isotopic information in agreement with the LA-ICPMS dataset regarding the ubiquitous mixing of NTS and stratospheric fallout Pu sources in the regional environment. For several specific samples, the total dissolution method reveals that Pu is incompletely recovered by simpler HNO₃-HCl leaching procedures, since some of the Pu originating from the NTS is contained in refractory siliceous particles.     

Radioanalytical approach to determine 238Pu, 239+240Pu, 241Pu and 241Am in soils

The simultaneous determination of multiple actinide isotopes in samples where total quantity is limited can sometimes present a unique challenge for radioanalytical chemists. In this study, re-determination of ²³⁸Pu, ^239+240Pu, and ²⁴¹Am for soils collected and analyzed approximately three decades ago was the goal, along with direct determination of ²⁴¹Pu. The soils had been collected in the early 1970’s from a shallow land burial site for radioactive wastes called the Subsurface Disposal Area (SDA) at the Idaho National Lab (INL), analyzed for ²³⁸Pu, ^239+240Pu, and ²⁴¹Am, and any remaining soils after analysis had been archived and stored. We designed an approach to reanalyze the ²³⁸Pu, ^239+240Pu, and ²⁴¹Am and determine for the first time ²⁴¹Pu using a combination of traditional and new radioanalytical methodologies. The methods used are described, along with estimates of the limits of detection for gamma-and alpha-spectrometry, and liquid scintillation counting. Comparison of our results to the earlier work documents the ingrowth of ²⁴¹Am from ²⁴¹Pu, and demonstrates that the total amount of ²⁴¹Am activity in these soil samples is greater than would be expected due to ingrowth from ²⁴¹Pu decay.     

Low level Pu and Am estimation in liquid waste from nuclear reactor

Estimation of very low amount up to pico-gram of Am and Pu in the liquid waste of U–Pu fuel cycle of the irradiated U fuel from the nuclear reactor has been carried out using combined method of α- and γ-ray spectrometric techniques. ²⁴¹Am was estimated by γ-ray spectrometry from a plancheted source. In spite of the same α energy of 5.49 MeV for ²⁴¹Am and ²³⁸Pu, the amount ²³⁸Pu was estimated by α spectrometry from the same plancheted source after subtracting amount of the ²⁴¹Am obtained from γ-ray spectrometry. The amount of Am and Pu obtained by this technique is found to be superior compared to other techniques even in the presence of Th, U and fission products.     

Behavior of <Superscript>134</Superscript>Cs, <Superscript>90</Superscript>Sr,and <Superscript>238</Superscript>Pu in different Syrian soils

The experiment aimed to evaluate the vertical migration of ¹³⁴Cs, ⁹⁰Sr and ²³⁸Pu in the main types of Syrian soils; entisol, inceptisol, alluvial (rock outcrops) and gypsiferous soils, using soil columns through which the aqueous solution of the radionuclides percolated. The results show that the vertical migration of the studied radionuclides through the soil profile depend on the radionuclide and the soil type. More than 97% of ¹³⁴Cs and ²³⁸Pu concentrated in the upper 2 cm of the entisol, inceptisol, and alluvial soils, whereas only 46.2% to 68.6% of the ⁹⁰Sr was retained in the upper 2 cm of these soils. The vertical migration of the studied radionuclides in the gypsiferous soil was different from the other soils. The distribution of the radionuclides in the gypsiferous soil was irregular through the soil profile and reached the deeper layer of the soil. This may be due to its physical characteristics; poor structure stability, high permeability and low retention capacity.     

<Superscript>241</Superscript>Pu in the environment: insight into the understudied isotope of plutonium

Studies of plutonium in the environment have focused on the α-emitting isotopes ²³⁸Pu, ²³⁹Pu and ²⁴⁰Pu, often overlooking the β-emitting isotope ²⁴¹Pu  because of its relatively short half-life (14.4 years). Here, we summarize sources of  ²⁴¹Pu and discuss its distribution and behavior in the environment. In the short term, ²⁴¹Pu, the largest contributor to the total plutonium radioactivity whereas in the long term its decay products, ²⁴¹Am and ²³⁷Np, are the major contributors as some 46% of current total ²⁴¹Am is attributable to ²⁴¹Pu decay. In this context, understanding the fate and transport of ²⁴¹Pu is crucial to assessing long-term radiological dose.     

Refinement of Pu parent–daughter isotopic and concentration analysis for forensic (dating) purposes

Plutonium (Pu) metal samples from an interlaboratory exchange exercise and simulated swipe samples were dated using plutonium–uranium (Pu–U) and plutonium–americium (Pu–Am). Metal data were evaluated for consistency and the swipe data against its source material. Metal ages based on ²³⁹Pu versus ²³⁵U and ²⁴⁰Pu versus ²³⁶U agreed to within a few percent, while the ²³⁸Pu–²³⁴U and ²⁴¹Pu–²⁴¹Am measurements had larger uncertainties. Swipe ages compared favorably with the material’s known history. Neptunium (²³⁷Np) analyses were examined in the context of the ²⁴¹Pu–²⁴¹Am–²³⁷Np system to estimate whether Np can provide insights on material from which Am, Np, and U were removed.     

Attempt to reduce <Superscript>239</Superscript>Pu and <Superscript>241</Superscript>Am uptake by wheat plantlets by application of inorganic fertilizers

Inorganic fertilizers are applied to reduce plant uptake of anthropogenic radionuclides, but scarce data are available for ²³⁹Pu and ²⁴¹Am. Wheat plantlets were grown in laboratory on limited amount of soil with ²³⁹Pu, ²⁴¹Am and different application rates of NPK and diammonium phosphate (DAP). As rates increased, the uptake of ²³⁹Pu and ²⁴¹Am to the whole plantlet also increased. It was higher for DAP than for NPK, (higher supply of P₂O₅ and NH₄ ⁺). Root content was higher than shoots for all experiences, suggesting low mobility within the plantlet. Root content increased with fertilizer rate, but practically no effect in shoots.     

Combination of <Superscript>13</Superscript>C/<Superscript>113</Superscript>Cd NMR,potentiometry, and voltammetry in characterizing the interactions between Cd and two models of the main components of soil organic matter

This work allowed the characterization of the Cd-binding sites of two compounds taken as models for exudates, the main components of soil organic matter (SOM). The studied compounds were exopolysaccharides (EPS), specifically exudates of roots (polygalacturonic acid) and of soil bacteria (Phytagel). Potentiometric acid–base titrations were performed and fitting of the obtained results indicated the presence of two main classes of acidic sites, defined by their pK _a values, for both EPS but of a different nature when comparing the two compounds. The two studied exopolysaccharides presented different acidic/basic site ratios: 0.15 for Phytagel and 0.76 for polygalacturonic acid. Spectroscopic techniques (¹³C/¹¹³Cd NMR, FTIR) distinguished different Cd surroundings for each of the studied EPS, which is in agreement with the titration results. Furthermore, these analyses indicated the presence of –COOH and –OH groups in various proportions for each exopolysaccharide, which should be linked to their reactivity towards cadmium. Cadmium titrations (voltammetric measurements) also differentiated different binding sites for each compound and allowed the determination of the strength of the Cd-binding site of the EPS. Fitting of the results of such voltammetric measurements was performed using PROSECE (Programme d’Optimisation et de Speciation Chimique dans l’Environnement), a software coupling chemical speciation calculation and binding parameter optimization. The fitting, taking into account the Cd²⁺/H⁺ competition towards exopolysaccharides, confirmed the acid-base titrations and spectroscopic analyses by revealing two classes of binding sites: (i) one defined as a strong complexant regarding its Cd²⁺–EPS association (logK = 9–10.4) and with basic functionality regarding H⁺–EPS association (pK _a = 11.3–11.7), and (ii) one defined as a weak complexant (logK = 7.1–8.2) and with acidic functionality (pK _a = 3.7–4.0). Therefore the combination of spectroscopic analyses, voltammetry, and fitting allowed the precise characterization of the binding sites of the studied exopolysaccharides, mimicking the main SOM components. Furthermore, the binding parameters obtained by fitting can be used in biogeochemical models to better define the role of key SOM compounds like exudates of roots and of soil bacteria on trace metal transport or assimilation.     

Age determination of plutonium using inductively coupled plasma mass spectrometry

The age of plutonium is defined as the time since the last separation of the plutonium isotopes from their daughter nuclides. In this paper, a method for age determination based on analysis of ²⁴¹Pu/²⁴¹Am and ²⁴⁰Pu/²³⁶Pu using ICP-SFMS is described. Separation of Pu and Am was performed using a solid phase extraction procedure including UTEVA, TEVA, TRU and Ln-resins. The procedure provided separation factors adequate for this purpose. Age determinations were performed on two plutonium reference solutions from the Institute for Reference Materials and Measurements, IRMM081 (²³⁹Pu) and IRMM083 (²⁴⁰Pu), on sediment from the Marshall Islands (reference material IAEA367) and on soil from the Trinity test site (Trinitite). The measured ages based on the ²⁴¹Am/²⁴¹Pu ratio corresponded well with the time since the last parent-daughter separations of all the materials. The ages derived from the ²³⁶U/²⁴⁰Pu ratio were in agreement for the IRMM materials, but for IAEA367 the determination of ²³⁶U was interfered by tailing from ²³⁸U, and for Trinitite the determined age was biased due to formation of ²³⁶U in the detonation of the “Gadget”.