Rapid separation of zirconium using microvolume anion-exchange cartridge for 93Zr determination with isotope dilution ICP-MS.

Estimating the risks associated with radiation from long-lived fission products (LLFP) in radioactive waste is essential to ensure the long-term safety of potential disposal sites. In this study, the amount of 93Zr, a LLFP, was determined by ICP-MS after separating Zr from a spent nuclear fuel solution using a microvolume anion-exchange cartridge (TEDA cartridge). Zirconium in 9.4 M HCl was stably retained on the TEDA cartridge and readily eluted with 0.75 mL of a mixed solution of 9.4 M HCl and 0.01 M HF. The time taken to complete the Zr separation was 1.2 min. Almost all the other elements initially present in the spent nuclear fuel sample were removed, leading to accurate measurement of all six Zr isotopes (90Zr, 91Zr, 92Zr, 93Zr, 94Zr, and 96Zr). This demonstrated that the TEDA cartridge allowed highly selective separation of Zr regardless of its small bed volume of 0.08 cm3. The concentrations of these isotopes were determined by an isotope-dilution method using a natural Zr standard that has a different isotopic composition from that of the spent nuclear fuel sample. The amount of 93Zr in an initial spent nuclear fuel pellet was 1081 ±â€¯79 ng per mg of 238U. The measured concentrations of all Zr isotopes, as well as the isotopic composition, were consistent with values predicted using a burnup calculation code.

Analysis of plutonium isotope ratios including 238Pu/239Pu in individual U-Pu mixed oxide particles by means of a combination of alpha spectrometry and ICP-MS.

Isotope ratio analysis of individual uranium-plutonium (U-Pu) mixed oxide particles contained within environmental samples taken from nuclear facilities is proving to be increasingly important in the field of nuclear safeguards. However, isobaric interferences, such as 238U with 238Pu and 241Am with 241Pu, make it difficult to determine plutonium isotope ratios in mass spectrometric measurements. In the present study, the isotope ratios of 238Pu/239Pu, 240Pu/239Pu, 241Pu/239Pu, and 242Pu/239Pu were measured for individual Pu and U-Pu mixed oxide particles by a combination of alpha spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). As a consequence, we were able to determine the 240Pu/239Pu, 241Pu/239Pu, and 242Pu/239Pu isotope ratios with ICP-MS after particle dissolution and chemical separation of plutonium with UTEVA resins. Furthermore, 238Pu/239Pu isotope ratios were able to be calculated by using both the 238Pu/(239Pu+240Pu) activity ratios that had been measured through alpha spectrometry and the 240Pu/239Pu isotope ratios determined through ICP-MS. Therefore, the combined use of alpha spectrometry and ICP-MS is useful in determining plutonium isotope ratios, including 238Pu/239Pu, in individual U-Pu mixed oxide particles.

Preparation of Microvolume Anion-Exchange Cartridge for Inductively Coupled Plasma Mass Spectrometry-Based Determination of (237)Np Content in Spent Nuclear Fuel.

Microvolume anion-exchange porous polymer disk-packed cartridges were prepared for Am/Np separation, which is required prior to the measurement of Neptunium-237 ((237)Np) with inductively coupled plasma mass spectrometry (ICPMS). Disks with a volume of 0.08 cm(3) were cut out from porous sheets having anion-exchange-group-containing polymer chains densely attached on the pore surface. Four different amine-based groups, N,N-dimethylaminoethyl methacrylate, trimethylammonium, diethylamine, and triethylenediamine (TEDA), were selected as the anion-exchange groups to be introduced into the porous sheets. The separation performances of Am/Np were evaluated using a standard solution of (243)Am, which had the same activity as its daughter nuclide (239)Np in secular equilibrium. (239)Np recovery of close to 100% with practically no contamination of (243)Am was achieved using the TEDA-introduced disk-packed cartridge. The time to elute (239)Np from the cartridge was approximately 40 s. The TEDA-introduced disk-packed cartridge was applied to the separation of Np from a spent nuclear fuel sample to confirm its separation performance. A known amount of (243)Am ((239)Np) was added to the spent nuclear fuel sample solution to monitor the chemical yield of Np. The chemical yield of Np calculated from a measured concentration of (239)Np was 90.4%. Am leakage in the Np-eluted solution was less than 1 ppt, corresponding to 0.001% of the original Am concentration in the sample. This indicates that no additional (239)Np was produced by the decay of the (243)Am remaining in the Np-eluted solution, thus providing a reliable chemical yield. U, which can cause a serious spectral interference involving the peak tail from the mass spectrum of (238)U, was thoroughly removed with the TEDA cartridge, providing interference-free measurement of (237)Np. The concentration of (237)Np obtained by ICPMS was 718 ± 12 ng/mg-U, which agrees well with the theoretically calculated value. Compared with the conventional separation technique using commercially available anion-exchange resin columns, the time required to adsorb, wash, and elute Np using the TEDA- introduced disk-packed cartridge was reduced by 75%.

Accurate purification age determination of individual uranium-plutonium mixed particles.

Age of individual uranium-plutonium (U/Pu) mixed particles with various U/Pu atomic ratios (1-70) were determined by inductively coupled plasma mass spectrometry. Micron-sized particles were prepared from U and Pu certified reference materials. The Pu reference was stored for 4-6 years since the last purification (July 14, 2008). The Pu purification age was obtained from the (241)Am/(241)Pu ratio which was calculated from the product of three measured ratios of Pu and Am isotopes in the eluted fractions. These ratios were measured by a high-resolution inductively coupled plasma mass spectrometer equipped with a desolvation system. Femto-gram to pico-gram quantities of Am, U, and Pu in a sample solution were sequentially separated on a small anion-exchange column. The (241)Am/(241)Pu ratio was accurately determined by spiking pure (243)Am into the sample solution. The average determined age for the particles for the five independent U/Pu ratios was in good agreement with the expected age with high accuracy (difference age 0.27 years) and high precision (standard deviation 0.44 years). The described analytical technique can serve as an effective tool for nuclear safeguards and environmental radiochemistry. Figure Young (4-6 y) Pu purification age of individual U/Pu mixed micron-sized reference particles for the five independent U/Pu ratios (1-70) were determined with 0.27±0.44 y difference from the expected age. Sub pico-gram quantities of Am, U and Pu were sequentially separated a small column, and their isotope ratios were accurately measured using an ICP-MS by applying the (243)Am spiking technique to the analysis and correcting the impurity and the contaminations.

Correction: Sequential separation of ultra-trace U, Th, Pb, and lanthanides using a simple automatic system.

Correction for 'Sequential separation of ultra-trace U, Th, Pb, and lanthanides using a simple automatic system' by Yutaka Miyamoto, et al., Analyst, 2015, DOI: 10.1039/c5an00027k.

Sequential separation of ultra-trace U, Th, Pb, and lanthanides using a simple automatic system.

Uranium, thorium, lead, and the lanthanides were automatically and sequentially separated with a single anion-exchange column. This separation was achieved using eluents consisting of a simple and highly pure acid mixture of HCl, HNO3, acetic acid, and HF. The elements of interest were separated from the major constituents, which included alkaline metal elements, alkaline earth metal elements, and iron. This simple and automatic system is driven with pressurized nitrogen gas and controlled using a computer program. An optimized separation was accomplished under the following conditions: a 50 mm long and 2 mm diameter column, 11 µm diameter anion-exchange resin, and a 35 µL min(-1) flow rate. Using this system, 50 ng of varied elements in a 100 µL feed solution were perfectly separated within 5 h with >400 decontamination factors and >95% yield. In order to evaluate the performance of this system, a reference powdered rock sample was separated using this system. Abundances of objective elements, including 0.23 ng of lutetium, were accurately determined without corrections of chemical recovery yield or subtraction of the process blank. This separation technique saves time and effort for chemical processing, and is useful for ultra-trace quantitative and isotopic analyses of elements in small environmental samples.

Ultra-trace analysis of plutonium by thermal ionization mass spectrometry with a continuous heating technique without chemical separation.

Thermal ionization mass spectrometry (TIMS) with a continuous heating technique is known as an effective method for measuring the isotope ratio in trace amounts of uranium. In this study, the analytical performance of thermal ionization mass spectrometry with a continuous heating technique was investigated using a standard plutonium solution (SRM 947). The influence of the heating rate of the evaporation filament on the precision and accuracy of the isotope ratios was examined using a plutonium solution sample at the fg level. Changing the heating rate of the evaporation filament on samples ranging from 0.1fg to 1000fg revealed that the influence of the heating rate on the precision and accuracy of the isotope ratios was slight around the heating rate range of 100-250mA/min. All of the isotope ratios of plutonium (SRM 947), (238)Pu/(239)Pu, (240)Pu/(239)Pu, (241)Pu/(239)Pu and (242)Pu/(239)Pu, were measured down to sample amounts of 70fg. The ratio of (240)Pu/(239)Pu was measured down to a sample amount of 0.1fg, which corresponds to a PuO2 particle with a diameter of 0.2µm. Moreover, the signals of (239)Pu could be detected with a sample amount of 0.03fg, which corresponds to the detection limit of (239)Pu of 0.006fg as estimated by the 3-sigma criterion. (238)Pu and (238)U were clearly distinguished owing to the difference in the evaporation temperature between (238)Pu and (238)U. In addition, (241)Pu and (241)Am formed by the decay of (241)Pu can be discriminated owing to the difference in the evaporation temperature. As a result, the ratios of (238)Pu/(239)Pu and (241)Pu/(239)Pu as well as (240)Pu/(239)Pu and (242)Pu/(239)Pu in plutonium samples could be measured by TIMS with a continuous heating technique and without any chemical separation processes.

Identifying uranium particles using fission tracks and microsampling individual particles for analysis using thermal ionization mass spectrometry.

The analysis of isotope ratios in individual particles found in the environment is important to clarify the origins of the particles. In particular, the analysis of uranium particles in environmental samples from nuclear facilities is useful for detecting undeclared nuclear activities related to the production of nuclear weapons. Thermal ionization mass spectrometry (TIMS) combined with a fission track technique is an efficient method for determining the isotope ratios of individual uranium particles, but has a drawback called "particle-mixing". When some uranium particles are measured as a single particle and an average isotope ratio for the particles is obtained, it is called "particle mixing". This may lead to erroneous conclusions in terms of the particle sources that are identified. In the present study, microsampling using a scanning electron microscope was added to the fission track-TIMS procedure. The analysis of a mixture of SRM 950a and CRM U100 reference materials containing uranium particles indicated that particle mixing was almost completely avoided using the proposed technique. The performance of the proposed method was sufficient for obtaining reliable data for the sources of individual particles to be identified reliably.

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.

Size distribution of radioactive particles collected at Tokai, Japan 6 days after the nuclear accident.

Airborne radioactive particles released by the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident in 2011 were collected with a cascade low-pressure impactor at the Japan Atomic Energy Agency (JAEA) in Tokai, Japan, 114 km south of the FDNPP. Size-fractionated samples were collected twice, in the periods of March 17-April 1, 2011, and May 9-13, 2011. These size-fractionated samplings were carried out in the earliest days at a short distance from the FDNPP. Radioactivity of short-lived nuclides (several ten days of half-life) was determined as well as (134)Cs and (137)Cs. The elemental composition of size-fractionated samples was also measured. In the first collection, the activity median aerodynamic diameter (AMAD) of (129m)Te, (140)Ba, (134)Cs, (136)Cs and (137)Cs was 1.5-1.6 µm, while the diameter of (131)I was 0.45 µm. The diameters of (134)Cs and (137)Cs in the second collection were expressed as three peaks at <0.5 µm, 0.94 µm, and 7.8 µm. The (134)Cs/(137)Cs ratio of the first collection was 1.02 in total, but the ratio in the fine fractions was 0.91. A distribution map of (134)Cs/(137)Cs - (136)Cs/(137)Cs ratios was helpful in understanding the change of radioactive Cs composition. The Cs composition of size fractions <0.43 µm and the composition in the 1.1-2.1 µm range (including the AMAD of 1.5-1.6 µm) were similar to the calculated compositions of fuels in the reactors No. 1 and No. 3 at the FDNPP using the ORIGEN-II code. The Cs composition collected in May, 2011 was similar to the calculation results of reactor No. 2 fuel composition. The change of Cs composition implies that the radioactive Cs was released from the three reactors at the FDNPP via different processes.

Secondary ion mass spectrometry combined with alpha track detection for isotope abundance ratio analysis of individual uranium-bearing particles.

Secondary ion mass spectrometry (SIMS) was used in combination with alpha track detection for the efficient analysis of uranium-bearing particles with higher (235)U abundances in environmental samples. A polycarbonate film containing particles was prepared and placed in contact with a CR-39 plastic detector. After exposure for 28 days, the detector was etched in a NaOH solution and each uranium-bearing particle was identified through observation of the alpha tracks recorded in the detector. A portion of the film containing each uranium-bearing particle was cut out and put onto a glassy carbon planchet. The films on the planchet were decomposed through plasma ashing for subsequent uranium abundance ratio analysis with SIMS. The alpha track-SIMS analysis of 10 uranium-bearing particles in a sample taken from a nuclear facility enabled n((235)U)/n((238)U) abundance ratios in the range 0.0072-0.25 to be detected, which were significantly higher than those obtained by SIMS without alpha track detection. The duration of the whole analytical process for analysis of 10 particles was about 32 days. The detection efficiency was calculated to be 27.1±6.5%, based on the analysis of the particles in uranium reference materials. The detection limits, defined as the diameter of the particle which produces alpha tracks more than one for a 28-days exposure, were estimated to be 0.8, 0.9, 1.1, 2.1 and 3.0 µm for the particles having the same uranium abundance ratios with NBL CRM U850, U500, U350, U050 and U010 reference materials, respectively. The use of alpha track detection for subsequent SIMS analysis is an inexpensive and an efficient way to measure uranium-bearing particles with higher (235)U abundances.

Rapid collection of iron hydroxide for determination of Th isotopes in seawater.

This work introduces a novel method of recovery of iron hydroxide using a DIAION CR-20 chelating resin column to determine Th isotopes in seawater with a sector field (SF) inductively coupled plasma mass spectrometer (ICP-MS). Thorium isotopes in seawater were co-precipitated with iron hydroxide, and this precipitate was sent to chelating resin column. Ferric ions in the iron hydroxide were bonded to functional groups of the chelating resin directly, resulting in a pH increase of the effluent by release of hydroxide ion from the iron hydroxide. The co-precipitated thorium isotopes were quantitatively collected within the column, which indicated that thorium was retained on the iron hydroxide remaining on the chelating column. The chelating column quantitatively collected (232)Th with iron hydroxide in seawater at flow rates of 20-25 mL min(-1). Based on this flow rate, a 5 L sample was processed within 3-4 h. The >20 h aging of iron hydroxide tends to reduce the recovery of (232)Th. The rapid collection method was successfully applied to the determination of (230)Th and (232)Th in open-ocean seawater samples.

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.

Combined application of alpha-track and fission-track techniques for detection of plutonium particles in environmental samples prior to isotopic measurement using thermo-ionization mass spectrometry.

The fission track technique is a sensitive detection method for particles which contain radio-nuclides like (235)U or (239)Pu. However, when the sample is a mixture of plutonium and uranium, discrimination between uranium particles and plutonium particles is difficult using this technique. In this study, we developed a method for detecting plutonium particles in a sample mixture of plutonium and uranium particles using alpha track and fission track techniques. The specific radioactivity (Bq/g) for alpha decay of plutonium is several orders of magnitude higher than that of uranium, indicating that the formation of the alpha track due to alpha decay of uranium can be disregarded under suitable conditions. While alpha tracks in addition to fission tracks were detected in a plutonium particle, only fission tracks were detected in a uranium particle, thereby making the alpha tracks an indicator for detecting particles containing plutonium. In addition, it was confirmed that there is a linear relationship between the numbers of alpha tracks produced by plutonium particles made of plutonium certified standard material and the ion intensities of the various plutonium isotopes measured by thermo-ionization mass spectrometry. Using this correlation, the accuracy in isotope ratios, signal intensity and measurement errors is presumable from the number of alpha tracks prior to the isotope ratio measurements by thermal ionization mass spectrometry. It is expected that this method will become an effective tool for plutonium particle analysis. The particles used in this study had sizes between 0.3 and 2.0 µm.

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.