Fumitaka Esaka

Efficient isotope ratio analysis of uranium particles in swipe samples by total-reflection X-ray fluorescence spectrometry and secondary ion mass spectrometry

A new particle recovery method and a sensitive screening method were developed for subsequent isotope ratio analysis of uranium particles in safeguards swipe samples. The particles in the swipe sample were recovered onto a carrier by means of vacuum suction-impact collection method. When grease coating was applied to the carrier, the recovery efficiency was improved to 48±9%, which is superior to that of conventionally-used ultrasoneration method. Prior to isotope ratio analysis with secondary ion mass spectrometry (SIMS), total reflection X-ray fluorescence spectrometry (TXRF) was applied to screen the sample for the presence of uranium particles. By the use of Si carriers in TXRF analysis, the detection limit of 22 pg was achieved for uranium. By combining these methods with SIMS, the isotope ratios of 235U/238U for individual uranium particles were efficiently determined.

Application of Fission Track Technique for the Analysis of Individual Particles Containing Uranium in Safeguard Swipe Samples

An effective method for isotope ratio analysis of individual particles containing uranium in safeguard swipe samples was developed by using a fission track (FT) technique combined with thermal ionization mass spectrometry (TIMS). The particles in the sample were directly recovered onto a polycarbonate membrane filter, which was set in a filtration system. After the particle recovery, the filter was dissolved to form a non coated FT detector film containing the particles. Individual particles containing uranium were then identified by the observation of fission tracks created by thermal neutron irradiation. By combining the FT technique with TIMS, isotope ratios of uranium for individual particles in the swipe sample prepared from a uranium standard reference material could be effectively determined.

Development of analytical techniques for ultra trace amounts of nuclear materials in environmental samples using ICP-MS for safeguards

The authors have begun to develop analytical techniques for ultra trace amounts of nuclear materials and to prepare a clean chemistry laboratory for environmental sample analyses. The analytical techniques include bulk and particle analyses. For the bulk analysis, concentrations and isotopic ratios of U and/or Pu are determined by inductively-coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS). In the particle analysis, isotopic ratios of U and/or Pu in each particle will be measured by secondary ion mass spectrometry (SIMS). This paper reports on the outline for the development of analytical techniques and the current situation of the development of the bulk analysis using ICP-MS is described.

The use of Si carriers for aerosol particle collection and subsequent elemental analysis by total-reflection X-ray fluorescence spectrometry

Abstract The adoption of polished Si carriers was studied for the sensitive elemental analysis of aerosol particles using total-reflection X-ray fluorescence (TXRF) spectrometry. The surface roughness of the Si carrier measured by atomic force microscopy was found to be smaller than those of glassy carbon and quartz glass carriers, which are commonly used for TXRF analysis. The detection limits of elements for the Si carrier were superior to those for the glassy carbon and the quartz glass carriers, presumably due to its smaller surface roughness. For example, the detection limit of Sr for the Si carrier was 9 pg, which was 100 times and 3 times lower than those for the glassy carbon and the quartz glass carriers, respectively. The Si carriers could be successfully applied to the direct aerosol particle collection by impaction and the subsequent elemental analysis by TXRF. From the results of the elemental analysis of aerosol particles, the variations in the concentrations of K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn Sr and Pb with time could be clarified.

Challenge to ultra-trace analytical techniques of nuclear materials in environmental samples for safeguards at JAERI: methodologies for physical and chemical form estimation

From a viewpoint of physical and chemical form estimation, ultra-trace analytical techniques of nuclear materials in environmental samples for safeguards have been investigated at Japan Atomic Energy Research Institute. This article deals with (1) an outline of the developed techniques for bulk and particle analyses of uranium and plutonium in the safeguards environmental samples; (2) current R&D on techniques relating to estimation of the physical and chemical form, such as SEM images and EDX spectra for fine particles of nuclear materials and fission track observation applicable to fissile materials; and (3) possible analytical methodologies, as future works, applicable to ultra-trace amounts of nuclear materials in environmental samples.

Isotope Ratio Measurement of Uranium in Safeguards Environmental Samples by Inductively-Coupled Plasma Mass Spectrometry (ICP-MS)

In order to measure isotope ratio of uranium in safeguards environmental samples with ICP-MS precisely, production of polyatomic ions of IrAr, PtAr and AuAr was measured and mass bias of ICP-MS is investigated by using isotopic standards of uranium and lead. The intensities of IrAr, PtAr and AuAr relative to the atomic ions were found to be 1.8×10-6, 1.6×10-5 and 4.1×10-5, respectively. The production of 193Ir40Ar is too small to interfere with the measurement of 233U, if the concentration of Ir is the same level as that of 233U. However, there is possibility that the presence of Pt and Au interferes with the measurement of minor isotopes of uranium and 237Np. On the other hand, the mass biases of 235U/238U and 208Pb/206Pb were measured with the parameter of 238U16O/238U. Since unexpected change of the mass bias during measurements causes frequently erroneous results, the monitoring of 238U16O/238U is effective for the precise isotope ratio measurement.

Application of Secondary Ion Mass Spectrometry to the Measurement of Lead Isotope Ratio in Individual Particles

Abstract The capability of secondary ion mass spectrometry (SIMS) for lead isotope ratio measurements of individual particles has been demonstrated by measuring lead‐containing particles in three kinds of environmental certified reference materials (CRMs): urban particulate matter, vehicle exhaust particulates, and coal fly ash. After mounting of the sample onto a glassy carbon carrier, the particles containing lead were identified and located by an electron probe micro‐analyzer equipped with wavelength dispersive x‐ray spectrometers. The isotope ratios of 207Pb/206Pb and 208Pb/206Pb for the individual particles on the carrier were determined by SIMS. The relative standard deviations of the lead isotope ratios were less than 1.6% for all particles measured. It was demonstrated that the results of the lead isotope ratios were clearly distinguished among the three samples. Moreover, the particles in the vehicle exhaust particulate sample were classified into two groups according to lead isotope ratios. The results indicated that the present SIMS technique can provide detailed information with regard to the origin and the transportation of individual particles, which is difficult to obtain by conventional bulk analysis techniques such as inductively coupled plasma mass spectrometry and thermal ionization mass spectrometry.

Establishment of a Clean Laboratory for ultra trace analysis of nuclear materials in safeguards environmental samples

The Japan Atomic Energy Research Institute has established a cleanroom facility with cleanliness of ISO Class 5: the Clean Laboratory for Environmental Analysis and Research (CLEAR). It was designed to be used for the analysis of nuclear materials in environmental samples mainly for the safeguards, in addition to the Comprehensive Nuclear-Test-Ban Treaty verification and research on environmental sciences. The CLEAR facility was designed to meet conflicting requirements of a cleanroom and for handling of nuclear materials according to Japanese regulations, i.e., to avoid contamination from outside and to contain nuclear materials inside the facility. This facility has been intended to be used for wet chemical treatment, instrumental analysis and particle handling. A fume-hood to provide a clean work surface for handling of nuclear materials was specially designed. Much attention was paid to the selection of construction materials for use of corrosive acids. The performance of the cleanroom and analytical background in the laboratory are discussed. This facility has satisfactory specification required for joining the International Atomic Energy Agency Network of Analytical Laboratories. It can be concluded that the CLEAR facility enables analysis of ultra trace amounts of nuclear materials at sub-picogram level in environmental samples.

SCREENING OF URANIUM PARTICLES BY TOTAL-REFLECTION X-RAY FLUORESCENCE SPECTROMETRY FOR SAFEGUARDS ENVIRONMENTAL SAMPLE ANALYSIS

The capability of total-reflection X-ray fluorescence spectrometry (TXRF) technique was studied to screen a swipe sample for uranium content, which was employed to decide on the further isotopic ratio measurements by secondary ion mass spectrometry (SIMS) for safeguards environmental sample analysis. A part of the measurement system of TXRF was modified to be able to use the same glassy carbon carrier for SIMS analysis. Particles in the swipe sample were recovered on the carbon carrier. The relative sensitivities of 11 elements including uranium were determined using selenium as an internal standard. The detection limit of uranium was 0.4 ng. The screening technique studied was applied to the practical swipe samples taken from the laboratories. The results confirm that TXRF can be a promising screening technique for uranium in swipe samples for safeguards environmental sample analysis.

Synthesis and Characterization of Copper Hydroxide Acetate With a Layered Discoid Crystal

Titration of copper acetate solution with a dilute NaOH solution to pH 6.5 and subsequent aging at 313 K yielded copper hydroxide acetate with an analytical composition of Cu2(OH)3.1(OCOCH3)0.9nH2O (n ∼ 0.7) and layered discoid crystals. The chemical composition, structure, and holistic trend in thermal behavior are similar to those of the previously known Cu2(OH)3(OCOCH3)H2O phase with layered rectangular crystals. The most obvious difference between the two compounds is morphology of the crystals. The other major differences are found in stability of bonding of the interlayer acetate ions to solid phase and behavior in anion-containing solutions. The interlayer acetate ions in the present compound begin to be dissociated from the solid phase at ∼343 K while those in the previous compound are not dissociated below 383 K. The reaction of the present compound is topotactic in Cl− and NO3− aqueous solutions but reconstructive in a SO42− aqueous solution while the reaction of the previous compound in those solutions is topotactic.