First measurements of (236)U concentrations and (236)U/(239)Pu isotopic ratios in a Southern Hemisphere soil far from nuclear test or reactor sites.

The variation of the (236)U and (239)Pu concentrations as a function of depth has been studied in a soil profile at a site in the Southern Hemisphere well removed from nuclear weapon test sites. Total inventories of (236)U and (239)Pu as well as the (236)U/(239)Pu isotopic ratio were derived. For this investigation a soil core from an undisturbed forest area in the Herbert River catchment (17°30' - 19°S) which is located in north-eastern Queensland (Australia) was chosen. The chemical separation of U and Pu was carried out with a double column which has the advantage of the extraction of both elements from a relatively large soil sample (∼20 g) within a day. The samples were measured by Accelerator Mass Spectrometry using the 14UD pelletron accelerator at the Australian National University. The highest atom concentrations of both (236)U and (239)Pu were found at a depth of 2-3 cm. The (236)U/(239)Pu isotopic ratio in fallout at this site, as deduced from the ratio of the (236)U and (239)Pu inventories, is 0.085 ± 0.003 which is clearly lower than the Northern Hemisphere value of ∼0.2. The (236)U inventory of (8.4 ± 0.3) × 10(11) at/m(2) was more than an order of magnitude lower than values reported for the Northern Hemisphere. The (239)Pu activity concentrations are in excellent agreement with a previous study and the (239+240)Pu inventory was (13.85 ± 0.29) Bq/m(2). The weighted mean (240)Pu/(239)Pu isotopic ratio of 0.142 ± 0.005 is slightly lower than the value for global fallout, but our results are consistent with the average ratio of 0.173 ± 0.027 for the southern equatorial region (0-30°S).

AMS of the Minor Plutonium Isotopes.

VERA, the Vienna Environmental Research Accelerator, is especially equipped for the measurement of actinides, and performs a growing number of measurements on environmental samples. While AMS is not the optimum method for each particular plutonium isotope, the possibility to measure 239Pu, 240Pu, 241Pu, 242Pu and 244Pu on the same AMS sputter target is a great simplification. We have obtained a first result on the global fallout value of 244Pu/239Pu = (5.7 ± 1.0) × 10-5 based on soil samples from Salzburg prefecture, Austria. Furthermore, we suggest using the 242Pu/240Pu ratio as an estimate of the initial 241Pu/239Pu ratio, which allows dating of the time of irradiation based solely on Pu isotopes. We have checked the validity of this estimate using literature data, simulations, and environmental samples from soil from the Salzburg prefecture (Austria), from the shut down Garigliano Nuclear Power Plant (Sessa Aurunca, Italy) and from the Irish Sea near the Sellafield nuclear facility. The maximum deviation of the estimated dates from the expected ages is 6 years, while relative dating of material from the same source seems to be possible with a precision of less than 2 years. Additional information carried by the minor plutonium isotopes may allow further improvements of the precision of the method.

236U/238U and 240Pu/239Pu isotopic ratios in small (2 L) sea and river water samples.

Accelerator Mass Spectrometry (AMS) and alpha spectrometry were used to determine uranium ((236)U, (238)U, (234)U) and plutonium isotopes ((239)Pu, (240)Pu) in sea and river water samples. Plutonium was separated by Dowex(®) 1 × 8 resin and UTEVA(®) resin was used for uranium purification. The measured (236)U/(238)U isotopic ratios for surface water from the Atlantic Ocean, the Pacific Ocean and the Black Sea were in the order of 10(-9), while values for river water were in the order of 10(-8). These contaminations may be attributed to global fallout. A sample of the reference material IAEA-443, collected from the Irish Sea, showed, in accordance to the reference value, a ratio that was 10(3) times higher due to effluents from the reprocessing plant at Sellafield. These results underline the good suitability of (236)U/(238)U as a tracer for hydrology and oceanography, and show that relatively small water samples are sufficient for the determination of (236)U by AMS, which is not the case for plutonium with present techniques. The plutonium concentrations in our water samples could only be measured with large uncertainties and were in the order of 10(-3) mBq/L (with the exception of the Irish Sea sample).

Depth profile of ²³6U/²³8U in soil samples in La Palma, Canary Islands.

The vertical distribution of the (236)U/(238)U isotopic ratio was investigated in soil samples from three different locations on La Palma (one of the seven Canary Islands, Spain). Additionally the (240)Pu/(239)Pu atomic ratio, as it is a well establish tool for the source identification, was determined. The radiochemical procedure consisted of a U separation step by extraction chromatography using UTEVA Resin (Eichrom Technologies, Inc.). Afterwards Pu was separated from Th and Np by anion exchange using Dowex 1 x 2 (Dow Chemical Co.). Furthermore a new chemical procedure with tandem columns to separate Pu and U from the matrix was tested. For the determination of the uranium and plutonium isotopes by alpha spectrometry thin sources were prepared by microprecipitation techniques. Additionally these fractions separated from the soil samples were measured by Accelerator Mass Spectrometry (AMS) to get information on the isotopic ratios (236)U/(238)U, (240)Pu/(239)Pu and (236)U/(239)Pu, respectively. The (236)U concentrations [atoms/g] in each surface layer (∼2 cm) were surprisingly high compared to deeper layers where values around two orders of magnitude smaller were found. Since the isotopic ratio (240)Pu/(239)Pu indicated a global fallout signature we assume the same origin as the probable source for (236)U. Our measured (236)U/(239)Pu value of around 0.2 is within the expected range for this contamination source.

Determination of U, Pu and Am isotopes in Irish Sea sediment by a combination of AMS and radiometric methods.

Samples from a marine sediment core from the Irish Sea (54.416 N, 3.563 W) were analyzed for the isotopic composition of uranium, plutonium and americium by a combination of radiometric methods and AMS. The radiochemical procedure consisted of a Pu separation step by anion exchange, subsequent U separation by extraction chromatography using UTEVA® and finally Am separation with TRU® Resin. Additionally to radiometric determination of these isotopes by alpha spectrometry, the separated samples were also used for the determination of (236)U/(238)U and plutonium isotope ratios by Accelerator Mass Spectrometry (AMS) at the VERA facility.

The first use of (236)U in the general environment and near a shutdown nuclear power plant.

We present a first effort to investigate (236)U in the environment near a shutdown nuclear power plant far away from highly contaminated sites, by using accelerator mass spectrometry. The detection limit of about 1pg (236)U allowed us to identify a minimal increase of the (236)U/(238)U isotopic ratio correlated to a peak of (137)Cs in river sediments downstream of the nuclear power plant, and to detect anthropogenic (236)U also upstream, where it is probably not related to the power plant but to global fallout. The (236)U content shoved variations of the (236)U/(238)U isotopic ratio in relation to the chemical-physical characteristics of the sediments. This demonstrates the potential of (236)U as an environmental tracer, and as an indicator for releases from nuclear facilities.

Uranium extraction from aqueous solutions by ionic liquids.

For determining natural levels of (236)U with its environmental abundance of 10(-16)% rather large sample volumes (approximately 30L) are necessary, therefore the conventional radiochemical uranium analysis (pre-concentration and column chromatography) is very time consuming. To speed up the procedure hydrophobic ionic liquids (ILs) were evaluated as a potential extraction agent for uranium from aqueous solutions. High selectivity and efficiency for uranium compared to calcium and magnesium in natural water was achieved with tricaprylmethylammonium thiosalicylate, [A336][TS]. Uranium was stripped successfully from the investigated ILs with 2M HNO(3).