Masaaki Magara

Particle isolation for analysis of uranium minor isotopes in individual particles by secondary ion mass spectrometry

A new technique to measure (234)U/(238)U and (236)U/(238)U isotope ratios for individual particles in environmental samples was developed, which was a combination of particle isolation under scanning electron microscope (SEM) and secondary ion mass spectrometry (SIMS). The technique was verified by measuring (234)U/(238)U and (236)U/(238)U isotope ratios in individual particles in a simulated environmental sample containing uranium standard (NBL CRM U010) and Pb metal particles. When the uranium particles were not isolated, the relative deviations of the measured isotope ratios from the reference values increased with increasing the signal intensity ratio of (208)Pb to (238)U, which was due to the molecular ion interferences by the Pb particles co-existing in the sputtered area. By the isolation of individual uranium particles, the interferences were eliminated and the measured isotope ratios were in good agreement with the reference values. The maximum relative deviations among 20 particles were 8.9% for (234)U/(238)U and 13.1% for (236)U/(238)U isotope ratios, respectively. The technique was also successfully applied to the analysis of a real swipe sample containing various kinds of elements.

Comparison of ICP-MS and SIMS techniques for determining uranium isotope ratios in individual particles.

The determination of uranium isotope ratios in individual particles is of great importance for nuclear safeguards. In the present study, an analytical technique by inductively coupled plasma mass spectrometry (ICP-MS) with a desolvation sample introduction system was applied to isotope ratio analysis of individual uranium particles. In ICP-MS analysis of individual uranium particles with diameters ranging from 0.6 to 4.2 microm in a standard reference material (NBL CRM U050), the use of the desolvation system for sample introduction improved the precision of (234)U/(238)U and (236)U/(238)U isotope ratios. The performance of ICP-MS with desolvation was compared with that of a conventionally used method, i.e., secondary ion mass spectrometry (SIMS). The analysis of test swipe samples taken at nuclear facilities implied that the performance of ICP-MS with desolvation was superior to that of SIMS in a viewpoint of accuracy, because the problems of agglomeration of uranium particles and molecular ion interferences by other elements could be avoided. These results indicated that ICP-MS with desolvation has an enough ability to become an effective tool for nuclear safeguards.

Fission track–secondary ion mass spectrometry as a tool for detecting the isotopic signature of individual uranium containing particles

A fission track technique was used as a sample preparation method for subsequent isotope abundance ratio analysis of individual uranium containing particles with secondary ion mass spectrometry (SIMS) to measure the particles with higher enriched uranium efficiently. A polycarbonate film containing particles was irradiated with thermal neutrons and etched with 6M NaOH solution. Each uranium containing particle was then identified by observing fission tracks created and a portion of the film having a uranium containing particle was cut out and put onto a glassy carbon planchet. The polycarbonate film, which gave the increases of background signals on the uranium mass region in SIMS analysis, was removed by plasma ashing with 200 W for 20 min. In the analysis of swipe samples having particles containing natural (NBL CRM 950a) or low enriched uranium (NBL CRM U100) with the fission track-SIMS method, uranium isotope abundance ratios were successfully determined. This method was then applied to the analysis of a real inspection swipe sample taken at a nuclear facility. As a consequence, the range of (235)U/(238)U isotope abundance ratio between 0.0276 and 0.0438 was obtained, which was higher than that measured by SIMS without using a fission track technique (0.0225 and 0.0341). This indicates that the fission track-SIMS method is a powerful tool to identify the particle with higher enriched uranium in environmental samples efficiently.

Isomeric yield ratios of 134I and 136I in the proton-, 12C- and 19F-induced fission of 235U, 237Np and 238U

Short-lived nuclides of iodine produced in the proton-, 12C- and 19F-induced fission of 235U, 237Np and 238U were separated with a rapid chemical separation system SISAK. Relative yields of the nuclides were determined by γ -ray spectrometry to obtain the isomeric yield ratios of 134mI/134gI and 136mI/136gI. Angular momenta of the fission fragments, 134I and 136I, were derived from the measured isomeric yield ratios by the spin-dependent statistical model. In the light- and heavy-ion fission, variation of the observed angular momenta can be explained by the excitation energies of the fissioning nuclei and the spherical shell structure with N = 82.

Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles.

Improved Method of Fission Track Sample Preparation for Detecting Particles Containing Fissile Materials in Safeguards Environmental Samples

We have developed an effective method for fission track (FT) sample preparation to perform particle analysis of the safeguards environmental samples by the FT-thermal ionization mass spectrometry (TIMS) method. In this method, a FT detector and the layer containing particles are separated. The main feature of the developed FT sample is that the detection of a particle from the corresponding FT can be performed correctly and in a simple manner by fixing each one end of the detector and the particle layer and by using an etching tool. It is expected that this method will enhance the effectiveness of particle analysis.

Depositional records of plutonium and 137Cs 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.

Round-robin 230Th–234U age dating of bulk uranium for nuclear forensics

In an inter-laboratory measurement comparison study, four laboratories determined 230Th–234U model ages of uranium certified reference material NBL U050 using isotope dilution mass spectrometry. The model dates determined by the participating laboratories range from 9 March 1956 to 19 October 1957, and are indistinguishable given the associated measurement uncertainties. These model ages are concordant with to slightly older than the known production age of NBL U050.

Selective Detection of Particles Containing Highly Enriched Uranium for Nuclear Safeguards Environmental Samples

A method to selectively detect uranium particles with high 235U enrichment has been developed; this method can contribute to improving particle analysis on nuclear safeguards environmental samples. The newly developed method involves three key components: (1) a two-step filtration system for particle recovery from swipe samples, (2) a system for controlling the etching time of fission track (FT) detector, and (3) a system for comparing the FT morphologies and particle sizes. The method to screen uranium particles according to their enrichment is focused on detecting highly enriched uranium particles preferentially in various particles recovered from swipe sample; this is one of the most important tasks involved in nuclear safeguards. In order to verify the effectiveness of the screening method developed, a mixture sample containing uranium particles with natural composition and those with 10% enrichment is used. It was shown that enrichment-based screening of uranium particles is possible by comparing the FT morphologies and particle sizes, in addition to controlling the etching time. The developed method uses the etching behaviors of the FT detector mainly; thus, it can be applied to real swipe samples easily.

Direct isotope ratio analysis of individual uranium–plutonium mixed particles with various U/Pu ratios by thermal ionization mass spectrometry

Uranium and plutonium isotope ratios in individual uranium-plutonium (U-Pu) mixed particles with various U/Pu atomic ratios were analyzed without prior chemical separation by thermal ionization mass spectrometry (TIMS). Prior to measurement, micron-sized particles with U/Pu ratios of 1, 5, 10, 18, and 70 were produced from uranium and plutonium certified reference materials. In the TIMS analysis, the peaks of americium, plutonium, and uranium ion signals were successfully separated by continuously increasing the evaporation filament current. Consequently, the uranium and plutonium isotope ratios, except the (238)Pu/(239)Pu ratio, were successfully determined for the particles at all U/Pu ratios. This indicates that TIMS direct analysis allows for the measurement of individual U-Pu mixed particles without prior chemical separation.