Characterization of the Aerosol-Based Synthesis of Uranium Particles as a Potential Reference Material for Microanalytical Methods.

A process for production of micrometer-sized particles composed of uranium oxide using aerosol spray pyrolysis is characterized with respect to the various production parameters. The aerosol is generated using a vibrating orifice aerosol generator providing monodisperse droplets, which are oxidized in a subsequent heat treatment. The final particles are characterized with microanalytical methods to determine size, shape, internal morphology, and chemical and structural properties in order to assess the suitability of the produced particles as a reference material for microanalytical methods, in particular, for mass spectrometry. It is demonstrated that physicochemical processes during particle formation and the heat treatment to chemically transform particles into an oxide strongly influence the particle shape and the internal morphology. Synchrotron µ-X-ray based techniques combined with µ-Raman spectroscopy have been applied to demonstrate that the obtained microparticles consist of a triuranium octoxide phase. Our studies demonstrate that the process is capable of delivering spherical particles with determined uniform size and elemental as well as chemical composition. The particles therefore represent a suitable base material to fulfill the homogeneity and stability requirements of a reference material for microanalytical methods applied in, for example, international safeguards or nuclear forensics.

Validation of reference materials for uranium radiochronometry in the frame of nuclear forensic investigations.

The results of a joint effort by expert nuclear forensic laboratories in the area of age dating of uranium, i.e. the elapsed time since the last chemical purification of the material are presented and discussed. Completely separated uranium materials of known production date were distributed among the laboratories, and the samples were dated according to routine laboratory procedures by the measurement of the (230)Th/(234)U ratio. The measurement results were in good agreement with the known production date showing that the concept for preparing uranium age dating reference material based on complete separation is valid. Detailed knowledge of the laboratory procedures used for uranium age dating allows the identification of possible improvements in the current protocols and the development of improved practice in the future. The availability of age dating reference materials as well as the evolvement of the age dating best-practice protocol will increase the relevance and applicability of age dating as part of the tool-kit available for nuclear forensic investigations.

Isotopic investigation of the colloidal mobility of depleted uranium in a podzolic soil.

The mobility and colloidal migration of uranium were investigated in a soil where limited amounts of anthropogenic uranium (depleted in the 235U isotope) were deposited, adding to the naturally occurring uranium. The colloidal fraction was assumed to correspond to the operational fraction between 10 kDa and 1.2 µm after (ultra)filtration. Experimental leaching tests indicate that approximately 8-15% of uranium is desorbed from the soil. Significant enrichment of the leachate in the depleted uranium (DU) content indicates that uranium from recent anthropogenic DU deposit is weakly bound to soil aggregates and more mobile than geologically occurring natural uranium (NU). Moreover, 80% of uranium in leachates was located in the colloidal fractions. Nevertheless, the percentage of DU in the colloidal and dissolved fractions suggests that NU is mainly associated with the non-mobile coarser fractions of the soil. A field investigation revealed that the calculated percentages of DU in soil and groundwater samples result in the enhanced mobility of uranium downstream from the deposit area. Colloidal uranium represents between 10% and 32% of uranium in surface water and between 68% and 90% of uranium in groundwater where physicochemical parameters are similar to those of the leachates. Finally, as observed in batch leaching tests, the colloidal fractions of groundwater contain slightly less DU than the dissolved fraction, indicating that DU is primarily associated with macromolecules in dissolved fraction.

Determination of weight distribution ratios of Pa(V) and Np(V) with some extraction chromatography resins and the AG1-X8 resin.

Literature data on distribution ratios (Dw) of Np(V) and Pa(V) for the AG1-X8 resin are scarce whereas those related on resin capacity factors (k') values for TEVA, TRU and U/TEVA resins are absent. Therefore, batch extraction experiments for Pa(V) and Np(V) from HCl and HNO3 media were realized, at tracer scale, with AG1-X8 and EIChroM resins (TEVA, TRU and U/TEVA). Based on the new Dw and k' values obtained in this study, a new protocol for Pa/Np separation has been developed leading to a better separation factor of 10(5) and a chemical yield of 97±3% and 99±1% for Pa and Np, respectively. A separation of (231)Pa from uranium matrix was successfully tested.

A follow up of the decrease of non exchangeable organically bound tritium levels in the surroundings of a nuclear research center.

In the past decades limited amounts of tritium were handled on the CEA site of Bruyères le Châtel with authorised atmospheric releases. A small fraction of the tritium released entered into environmental samples under three forms: (i) as part of free water (TFWT - Tissue Free Water Tritium), or associated with organic matter in two ways; either (ii) bound to the oxygen and nitrogen atoms of the material as exchangeable organically bound tritium (E-OBT), or (iii) bound to carbon atoms as non exchangeable organically bound tritium (NE-OBT). The first two components provide only a picture of atmospheric tritium concentrations at the sampling time as they are in equilibrium with atmospheric moisture and soil humidity. Unlike these exchangeable forms, however, NE-OBT is tightly bound to the organic matter and provides an integrated record of atmospheric tritium during the growing phase of the vegetation. We mapped NE-OBT in tree leaf samples in an area of about 25×30km(2) around the centre of the CEA site and compared the results with those obtained during a previous sampling exercise in 1989. At this time, the activity levels were almost ten times higher than those observed presently in a similar area almost 20 years later which is consistent with the decrease of atmospheric releases issued from the centre. As the activity levels are now close to environmental background specific attention was also paid to the analytical procedure to ensure reliable low level NE-OBT detection.

A method for the determination of low-level organic-bound tritium activities in environmental samples.

The authors discuss some of the difficulties encountered when analyzing organically bound tritium (OBT) and describe a sensitive method for low-level OBT determination in biological samples. The methodology, which combines suitable sample treatment, a combustion apparatus for large-sized samples and low-background liquid scintillation counting, provides exclusively carbon-bound tritium measurement. Two key points of this methodology are described and illustrated. The first one is the stage of removal of the exchangeable organic tritium. The efficiency of this stage, carried out by mixing powdered dry samples with tritium-free water, is evaluated. The second key point is the set of precautions taken at any stage of the treatment to avoid contamination of the samples by ambient atmospheric moisture. The detection limit of the method is about 0.5 Bq kg(-1) of dry material. Low-level applications of this methodology are given with estimation of the OBT/HTO ratios.

Atmospheric xenon radioactive isotope monitoring.

The Comprehensive Nuclear Test Ban Treaty (CTBT) organisation is implementing a world-wide monitoring network in order to check that the State Signatories comply with the treaty. One of the monitoring facilities consists of an atmospheric noble gas monitoring equipment. According to the requirements annexed in the treaty, the French Atomic Energy Commission (CEA) developed a device, called SPALAX, which automatically extracts xenon from ambient air and makes in situ measurements of the activities of four xenon radioisotopes (131mXe, 133mXe, 133Xe, 135Xe). The originality of this device is noticeable essentially in the gas sample processing method: thanks to the coupling of a gas permeator and of a noble gas specific adsorbent, it can selectively extract and concentrate xenon to more than 3 x 10 E6. This process is carried out continuously without cryogenic cooling, without any regeneration time. The detection of the xenon radioactive isotopes is done automatically by high spectral resolution gamma spectrometry, a robust technology well-suited for on-field instrumentation. In the year 2000, a prototype was involved in an international evaluation exercise directed by the CTBT organisation (CTBTO). This exercise demonstrated that the SPALAX equipment perfectly met the requirements of the CTBTO for such systems. On the basis of the continuous 24-h resolution record of the atmospheric xenon radioactive isotopes concentrations, the SPALAX system also demonstrated that ambient levels of 133Xe can fluctuate quickly from less than the detection limit to over 40 x 10(-3) Bq m(-3). In order to build an industrial version of this equipment, the CEA entered into a partnership with a French engineering company (S.F.I., Marseille, France), which is now able to produce an industrial version of SPALAX, i.e. more compact and more efficient than the prototypes. The 133Xe minimum detectable concentration is 0.15 x 10(-3) Bq m(-3) air per 24 h sampling cycle.

Ultra low-level measurements of actinides by sector field ICP-MS.

In the present work, a double-focusing sector field inductively coupled plasma-mass spectrometer was optimised for ultra trace and isotopic analyses of actinide long-lived isotopes in low concentration solutions of the fgml(-1) to the ngml(-1) range. Sensitivities of about 3GHz/(microgml(-1)), with as low a background as 0.1cps, were obtained for U using a conventional concentric pneumatic nebuliser. Detection limits are below the fg range for 239Pu and 240Pu. With natural U, a precision lower than 0.5% RSD is currently obtained for 235U/238U isotopic ratio at the 200pgml(-1) level.

Determination of organically bound tritium background level in biological samples from a wide area in the south-west of France.

In this paper, the authors describe a sensitive method for low-level non-exchangeable OBT determination. This methodology combines suitable sample treatment, a combustion apparatus for large-sized samples and low-background liquid scintillation spectrometry, along with precautions that substantially reduce the risks of sample contamination. Great care must be taken in the measurement of non-exchangeable OBT at environmental levels. Many authors have discussed the opportunities for cross-contamination between samples and contamination by exchange with the laboratory atmosphere. The authors also describe an application of the methodology to a large-scale sampling and measurement campaign, aimed at the determination of the environmental non-exchangeable OBT background level in tree leaves and ferns collected on the site and in the vicinity of a research centre located in the south-west of France, not far from Bordeaux. This study constitutes a "zero level" for the non-exchangeable OBT activity, as, to our knowledge, there is no tritium source within or in the surroundings of the sampled area capable of producing non-exchangeable OBT activities above the natural levels. Our analyses showed that non-exchangeable OBT activities in the collected samples were very low, ranging from below the detection limit (ca 0.7 Bq kg(-1) of dry material) to ca 2 Bq kg(-1) of dry material. These values are similar to the natural tritium background measured in water samples. No discrepancies can be shown between fern samples and oak tree leaf samples or between samples collected inside and outside the research site.

240Pu/239Pu isotopic ratios and 239 + 240Pu total measurements in surface and deep waters around Mururoa and Fangataufa atolls compared with Rangiroa atoll (French Polynesia).

The average values of 240Pu/239Pu mass isotopic ratios of plutonium deposited in Mururoa and Fangataufa atoll sediments by French atmospheric nuclear tests range from 3.5 to 5%. In order to assess the near field and far field influence of those deposits in the open ocean, two water profiles were measured for 239 + 240Pu and 240Pu/239Pu using, for the first time, an Inductively Coupled Plasma Mass Spectrometer which was developed to achieve femtogram detection limits. One site was located at the limit of the French territorial waters, which is 22 km distant from Mururoa. The second site was located close to Rangiroa atoll, at a distance of approximately 1200-km from French nuclear test sites. The sample volumes were approximately 500 litres and plutonium was purified prior to mass spectrometry and alpha spectrometry measurements. In Rangiroa, the 239 + 240Pu profile is comparable with those already determined in world open oceans but the maximum detected activity, 9 mBq/m3 at 500-600 m is a lot lower than those measured in the northern hemisphere. 240Pu/239Pu ratios were measured between 500 and 1000 m and were not statistically different from the typical 0.18 +/- 0.01 ratio which characterises the global fallout. Consequently, any influence of plutonium from the tests in Mururoa and Fangataufa is not apparent at Rangiroa. The vertical distribution of 239 + 240Pu near Mururoa shows similar changes with depth but with a slight increase in concentration. 240Pu/239Pu mass ratios vary with depth, from 7 to 10% in the upper 500 m and in the deep waters (below 1000 m) to 15-16% between 600 and 1000 m. A contribution from plutonium deposited in the sediments at Mururoa and Fangataufa is observed at the limit of territorial waters, especially in surface and deep waters.