IRMM-3100a: A new certified isotopic reference material with equal abundances of 233U, 235U, 236U and 238U

The new so-called Quad-IRM (“Quadruple Isotope Reference Material”) was prepared from highly enriched ²³³U, ²³⁵U, ²³⁶U and ²³⁸U isotopic materials using an optimized combination of gravimetrical mixing and mass spectrometry. Within the mixing process the isotope ratios were adjusted to about n(²³³U)/n(²³⁵U)/n(²³⁶U)/n(²³⁸U) = 1/1/1/1 and certified with expanded relative uncertainties of 0.0054% per mass unit (coverage factor k = 2). This new isotope reference material is ideal for verifying the inter-calibration of multi-detector systems in isotope mass spectrometry.The certified n(²³³U)/n(²³⁶U) ratio of IRMM-3100a was derived from the mass metrology data of the gravimetrical mixing of highly enriched ²³³U and ²³⁶U materials. It was verified by thermal ionization mass spectrometry (TIMS) measurements using the classical total evaporation (TE) and modified total evaporation (MTE) methods. The n(²³⁴U)/n(²³⁶U), n(²³⁵U)/n(²³⁶U) and n(²³⁸U)/n(²³⁶U) ratios were then determined by TIMS using the n(²³³U)/n(²³⁶U) ratio for internal normalization and using a multi-dynamic measurement procedure in order to circumvent any possible influence and uncertainties from Faraday cup efficiencies and amplifier gain factors. The certified n(²³⁵U)/n(²³⁶U) and n(²³⁸U)/n(²³⁶U) ratios were additionally verified using the classical and modified total evaporation methods using two TIMS instruments at IRMM and one TIMS instrument at IAEA-SGAS. The verification data can be regarded as results obtained at three independent instruments at two different nuclear safeguards laboratories.     

Plutonium Isotopes in Ground-Level Air in Northern Germany Since 1990

The activity concentrations, ratios and seasonal fluctuations of plutonium isotopes in ground-level air in Northern Germany are reported for the years 1990 to 1997. The ^239+240Pu activity concentrations (a) measured on quarterly samples lie in a range 0.4 nBq/m³<a<4 nBq/m³. The ²³⁸Pu activity concentrations are lesser by up to a factor of 0.1 (0.1 nBq/m³<a<0.8 nBq/m³). The total activity concentration shows a typical seasonal fluctuation in the time period under review. In a few quarterly samples the activity ratio of a(²³⁸Pu)/a(^239+240Pu) is significantly increased.     

Isotopic “fingerprints” for natural uranium ore samples

A set of six samples, collected worldwide from various uranium ore mining facilities, was analysed for uranium isotopic composition by high accuracy isotope mass spectrometry. The goal of this article was twofold: to measure isotopic variations between samples of different geographical origin and to produce calibrated isotope ratios with the smallest achievable uncertainty (as defined according to the ISO Guide to the Expression of Uncertainty in Measurement). In the first step, the molar ratio of the isotopes ²³⁵U and ²³⁸U, n(²³⁵U)/n(²³⁸U), was measured using a UF₆-gas-inlet isotope mass spectrometer (VARIAN MAT 511). This instrument was calibrated against gravimetrically prepared synthetic isotope mixtures thus allowing SI-traceable measurements to be made. The ratios of the “minor isotopes” to ²³⁸U [n(²³⁴U)/n(²³⁸U) and n(²³⁶U)/n(²³⁸U)] were determined in a second step using a thermal ionisation mass spectrometer with high abundance sensitivity (Finnigan MAT262-RPQ-PLUS). The mass-fractionation correction was done internally using the result of the n(²³⁵U)/n(²³⁸U) measurement. As a result, the complete measured uranium isotopic composition is traceable to the SI system. For all ratios n(²³⁴U)/n(²³⁸U), n(²³⁵U)/n(²³⁸U), and n(²³⁶U)/n(²³⁸U) significant differences for samples of different origin were found. Regarding the n(²³⁶U)/n(²³⁸U) results, only two samples, one of them from the Oklo reactor in Gabon, showed significant presence of ²³⁶U. For all other samples an upper limit for n(²³⁶U)/n(²³⁸U) of about 6 × 10⁻¹⁰, mainly dependent on the instrumentation, was found. As a result of this study we propose values for the isotope abundances of natural uranium for the “Best Measurement from a Single Terrestrial Source” and the “Range of Natural Variations” in the IUPAC-table of the “Isotopic Composition of the Elements.”     

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”.     

Reference material for radionuclides in sediment IAEA-384 (Fangataufa Lagoon sediment)

A reference material designed for the determination of anthropogenic and natural radionuclides in sediment, IAEA-384 (Fangataufa Lagoon sediment), is described and the results of certification are presented. The material has been certified for 8 radionuclides (⁴⁰K, ⁶⁰Co, ¹⁵⁵Eu, ²³⁰Th, ²³⁸U, ²³⁸Pu, ^239+240Pu and ²⁴¹Am). Information values are given for 12 radionuclides (⁹⁰Sr, ¹³⁷Cs, ²¹⁰Pb (²¹⁰Po), ²²⁶Ra, ²²⁸Ra, ²³²Th, ²³⁴U, ²³⁵U, ²³⁹Pu, ²⁴⁰Pu and ²⁴¹Pu). Less reported radionuclides include ²²⁸Th, ²³⁶U, ²³⁹Np and ²⁴²Pu. The reference material may be used for quality management of radioanalytical laboratories engaged in the analysis of radionuclides in the environment, as well as for the development and validation of analytical methods and for training purposes. The material is available from IAEA in 100 g units. Retired from IAEA in 2003.     

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.     

A certified reference material for radionuclides in the water sample from Irish Sea (IAEA-443)

A new certified reference material (CRM) for radionuclides in sea water from the Irish sea (IAEA-443) is described and the results of the certification process are presented. Ten radionuclides (³H, ⁴⁰K, ⁹⁰Sr, ¹³⁷Cs, ²³⁴U, ²³⁵U, ²³⁸U, ²³⁸Pu, ^239+240Pu and ²⁴¹Am) have been certified, and information values on massic activities with 95% confidence intervals are given for four radionuclides (²³⁰Th, ²³²Th, ²³⁹Pu and ²⁴⁰Pu). Results for less frequently reported radionuclides (⁹⁹Tc, ²²⁸Th, ²³⁷Np and ²⁴¹Pu) are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in water samples, for the development and validation of analytical methods and for training purposes. The material is available in 5 L units from IAEA (http://nucleus.iaea.org/rpst/index.htm).     

Determination of plutonium and its isotopic ratio in marine sediment samples using quadrupole ICP-MS with the shield torch system under normal plasma conditions

An analytical method for determining ²³⁹Pu and ²⁴⁰Pu in marine sediment samples, which uses quadrupole ICP-MS, was developed in this work. A simple anion-exchange chromatography system was employed for the separation and purification of Pu from the sample matrix. A sufficient decontamination factor of 1.4×10⁴ for U, which interferes with the determination of ²³⁹Pu, was achieved. High sensitivity Pu determination was obtained, which led to an extremely low concentration detection limit of ~8 fg/ml (0.019 mBq/ml for ²³⁹Pu; 0.071 mBq/ml for ²⁴⁰Pu) in a sample solution, or an absolute detection limit of 42 fg in a 5 ml sample solution, by using the shield torch technique. Analytical results for the determination of the ^239+240Pu and the ²⁴⁰Pu/²³⁹Pu ratio in IAEA 368 (ocean sediment) reference material indicated that the accuracy of the method was satisfactory. The method developed was successfully applied to a study of Pu behavior in the sediments from Sagami Bay, Japan. The observed high ²⁴⁰Pu/²³⁹Pu ratio in the sediment core indicated that there was additional Pu input derived from close-in fallout in addition to the global fallout.     

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.     

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.     

Identification of the contamination source of plutonium in environmental samples with isotopic ratios determined by inductively coupled plasma mass spectrometry and alpha-spectrometry

Concentrations of^239+249Pu in environmental samples were detemined by ICP-MS and spectrometry, showing consistent results, which suggests an applicability of ICP-MS to²³⁹Pu and²⁴⁰Pu measurement. The activity ratios of²³⁸Pu/^239+240Pu and²⁴⁰Pu/²³⁹Pu were significantly different in samples from the general environment and near Sellafield reprocessing plants, indicating the usefulness of these ratios for identification of the Pu contamination source.     

Evaluation of chronometers in plutonium age determination for nuclear forensics: What if the ‘Pu/U clocks’ do not match?

This article discusses the age dating results of plutonium/uranium chronometers with a focus on the consequences for age plutonium determination when the basic assumptions of the methodology are not fully met: Incomplete removal of the daughter nuclides at the production date and uranium contamination of plutonium samples. In addition to the ²³⁸Pu/²³⁴U, ²³⁹Pu/²³⁵U and ²⁴⁰Pu/²³⁶U, the ²⁴²Pu/²³⁸U chronometer is discussed. The ²⁴²Pu/²³⁸U radiochronometer has only scarcely been used, due to its high sensitivity to residual uranium. However, it can be a very useful indicator for uranium contamination of aged plutonium samples.     

Inflow of polonium, uranium and plutonium radionuclides in Odra River catchment area assessment by environmetric expertise

The study deals with the application of cluster analysis (CA) and non-parametric tests (Shapiro–Wilk, Kruskal–Wallis, Dunn, U Mann–Whitney) to classify and interpret of a monitoring data set for Odra River water quality assessment based on concentration values of radiochemical parameters. The data set represents results for 3 alpha emitters (²¹⁰Po, ²³⁸U and ^239+240Pu) measured in surface water samples collected at 13 different sampling locations (5 in major Odra stream while 8 in Odra tributaries) within four seasons: winter, spring, summer and autumn, in the framework of 1 year-term quality monitoring research. The correlation analysis of polonium, uranium and plutonium data indicates that significant values of Spearman’s correlation coefficient appears between ²¹⁰Po and ^239+240Pu (r = 0.55 in autumn and 0.77 in winter as well as 0.49 in all year), while statistical significant correlation between uranium and plutonium as well as uranium and polonium were not found. In the Odra drainage basin, the biggest differences were observed in the case of ²³⁸U. The hypothesis about possible geographic and seasonal differences between concentration of ²¹⁰Po, ²³⁸U and ^239+240Pu in the Odra River catchment area was verified by cluster analysis (CA). Finally, to asses if there are statistically significant differences in mean concentration value of ²¹⁰Po, ²³⁸U and ^239+240Pu for Vistula and Odra Rivers drainage basins were obtained by used of the non-parametric tests. Comparing to Vistula catchment area, statistically different concentration of ²¹⁰Po and ^239+240Pu in all year was observed for river samples collected on Odra drainage basin.     

A new reference material for radionuclides in the mussel sample from the Mediterranean Sea (IAEA-437)

A new Reference Material (RM) for radionuclides in mussel (Mytilus galloprovincialis) from the Mediterranean Sea (IAEA-437) is described and the results of the certification process are presented. Four radionuclides (⁴⁰K, ²³⁴U, ²³⁸U, and ^239+240Pu) have been certified, and information values on massic activities with 95% confidence intervals are given for nine radionuclides (¹³⁷Cs, ²¹⁰Pb(²¹⁰Po), ²²⁶Ra, ²²⁸Ra, ²²⁸Th, ²³⁰Th, ²³²Th, ²³⁵U, and ²⁴¹Am). Results for less frequently reported radionuclides (⁹⁰Sr, ¹²⁹I, ²³⁸Pu, ²³⁹Pu, and ²⁴⁰Pu) are also reported. The RM can be used for quality assurance/quality control of the analysis of radionuclides in mussel samples, for the development and validation of analytical methods and for training purposes. The material is available in 200 g units.     

Use of combined alpha-spectrometry and fission track analysis for the determination of240Pu/239Pu ratios in human tissue

Plutonium and other actinides were determined in human autopsy tissues of occupationally exposed workers who were registrants of the United States Transuranium and Uranium Registries (USTUR). In this study, Pu was purified and isolated from Am, U and Th, after drying and wet-ashing of the tissues, and the addition of²³⁸Pu as a radiotracer. After electrodeposition onto vanadium planchets the^239+240Pu activity was determined by alpha-spectrometry. A fission track method was developed to determine²³⁹Pu in the presence of²³⁸Pu and²⁴⁰Pu, using Lexan^TM polycarbonate detectors. Combining the two techniques allowed the determination of the²⁴⁰Pu/²³⁹Pu activity and atom ratios. Data from selected USTUR cases are presented.     

Sequential separation and determination of plutonium, americium-241 and strontium-90 in soils and sediments

A sensitive and reliable metbod for the sequential separation and determination of plutonium,²⁴¹Am and⁹⁰Sr in soil samples was developed. Plutonium was separated by a Microthene-TNOA column. Then⁹⁰Y (for⁹⁰Sr determination) was separated from americium by a HDEHP column after elimination of large amounts of interfering stable or radioactive nuclides (iron,²¹⁰Bi and²¹⁰Po etc.) by an oxalate precipitation and a Microthene-TNOA column. Finally americium was purified by another HDEHP column and a PMBP-TOPO extraction. A special attention was paid to the decontamination of Pu and Am from²¹⁰Po and of⁹⁰Y from²¹⁰Bi; the relevant decontamination factors resulted greater than 10⁵, 10⁶ and 10⁴ respectively. The detection limits were 1.2 mBq/kg for Pu and 1.7 mBq/kg for²⁴¹Am and 0.32 Bq/kg for⁹⁰Sr. The procedure was checked by analyzing three certified samples supplied by IAEA. Some Italian soil samples were also analyzed giving average yields of 84.9±7.2% for Pu, 57.8±3.2%for Am and 96.7±1.6% for Y; the^239+240Pu,²³⁸Pu,²⁴¹Am and⁹⁰Sr contents (Bq/kg) ranged from 0.347 to 1.53, from 0.013 to 0.048, from 0.126 to 0.556 and from 2.89 to 11.6 respectively and the average ratios were 0.037±0.017 for²³⁸Pu/^239+240Pu, 0.357±0.040 for²⁴¹Am/^239+240Pu and 7.0±1.2 for⁹⁰Sr/^239+240Pu.     

Certified reference material for radionuclides in seawater IAEA-381 (Irish Sea Water)

A certified reference material (CRM) for radionuclides in seawater, IAEA-381 (Irish Sea Water), is described and the results of certification are presented. The material has been certified for nine radionuclides (⁴⁰K, ⁹⁰Sr, ¹³⁷Cs, ²³⁷Np, ²³⁸Pu, ²³⁹Pu,²⁴⁰Pu, ^239,240Pu and ²⁴¹Am). Information on massic activities with the corresponding 95% confidence intervals are given for eight radionuclides (³H, ¹²⁵Sb, ²³⁴U, ²³⁵U, ²³⁶U, ²³⁸U, ²⁴¹Pu and ²⁴⁴Cm). Less reported radionuclides include ⁶⁰Co, ⁹⁹Tc, and ²⁴²Pu. The CRM may be used for quality assurance/quality control of the analysis of radionuclides in environmental water samples, for the development and validation of analytical methods and for training purposes. The material is available from the IAEA in 5 kg units.     

Determination of femtogram quantities of 239Pu and 240Pu in bioassay samples by thermal ionization mass spectrometry

Summary A thermal ionization mass spectrometry (TIMS) method is described for the determination of ultra-trace levels of plutonium isotopes in human urine samples. The method has been validated through the analysis of artificial urine samples spiked with known amounts of ²³⁹Pu ranging from 2.5 fg to 50 fg (6-115mBq). A slight positive bias of 1.7%-2.7% was determined, with a relative precision of 2.2% at 50 fg, increasing to 2.7% for 5-25 fg ²³⁹Pu. The detection limit of the method was 0.53 fg (1.2mBq) ²³⁹Pu, and the instrumental detection limit was at least 0.1 fg. The determination of the isotopic signature of the sample with ²³⁹Pu, ²⁴⁰Pu, and ²⁴¹Pu amounts of several femtograms is possible, and was demonstrated with the determination of the 240 to 239 ratio in an inter-laboratory sample comparison. The method is relatively free from interferences, 95% of sample preparations were acceptable both in terms of chemical recovery and lack of isobaric interference. The isotopic abundance of the ²⁴²Pu SRM 4334E of the National Institute of Standards and Technology (NIST) was also determined by TIMS and was found to be 99.99967 atom% ²⁴²Pu.     

Plutonium determination in bioassay samples using radiochemical thermal ionization mass spectrometry

Summary A new high-sensitivity plutonium bioassay program employing thermal ionization mass spectrometry (TIMS) has been developed to monitor Savannah River Site employees for intakes of PuO₂. The U.S. Department of Energy requires bioassay laboratories which have the ability to detect a 100 mRem, 50-year committed effective dose equivalent (CEDE) intake of radioactive material. For PuO₂, traditional alpha-spectrometry methods are not sensitive enough to meet this specification. To comply with this requirement, a radiochemical TIMS method was developed to determine Pu in urine bioassay samples. Four radiochemical separation steps were used to purify Pu from urine to ensure samples were free from matrix effects that interfere with TIMS analysis. These included precipitation, ion-extraction chromatography, electrodeposition, and ion-exchange chromatography. A batch of reagent blanks determined the detection limit for this method was 0.59 fg ²³⁹Pu/l (1.3 µBq ²³⁹Pu/l). The ²³⁹Pu concentration was also measured in 20 urine blank samples to determine the minimum ²³⁹Pu concentration that would indicate an occupational intake. A Probit plot was constructed for the results and the 99 th percentile of the urine blanks showed that the minimum ²³⁹Pu concentration that would indicate an uptake was 2.4 fg/l (5.5 µBq/l).     

Distribution of environmental radionuclides in sediment cores of the Jinheung catchment

Sediment core samples taken from the Jinheung catchment located in the middle of the Korean Peninsula were used to know environmental radionuclide distribution. The grain sizes of the sediment cores were found at depth of about 17 cm suggesting that it might have occurred during a dry period of 1969. The radionuclides, ¹³⁷Cs, ²³⁷Np, ²³⁹Pu, ²⁴⁰Pu, ²³⁴U, ²³⁸U, ²²⁸Th, ²³⁰Th, ²³²Th, were analyzed by sector type ICP-MS and gamma-spectrometry. The Cs and Pu distribution changed with the depth, in which the maximum ranged from 14 to 22 cm. This was due to the high activity of the results of nuclear bomb tests in the air from 1960s and showed different distribution pattern on the soil surface. The average activity ratio of ²⁴⁰Pu/²³⁹Pu and ²³⁷Np/²³⁹Pu was 0.173 and 0.45, respectively. These values were similar to the north hemisphere global fallout ratio of ²⁴⁰Pu/²³⁹Pu (0.18) and ²³⁷Np/²³⁹Pu (0.45). The ²³⁷Np/²³⁹Pu ratio showed a higher value than the global fallout ratio above 14 cm depth. The U, Th and their daughter radionuclides kept secular equilibrium in the sediment core because the average activity ratios were nearly 1.