Sequential radiochemical separations from Alpine Wetland soils (Boréon, France) with emphasis on 90Sr measurement

A radiochemical procedure to extract plutonium, americium and strontium from soils is presented. Strontium was separated from americium and plutonium fraction at the beginning of the method to increase the Sr recovery. The studied soils coming from an Alpine wetland site contain a big amount of iron which was eliminated by an oxalate precipitation before the column step. The hydroxide precipitation should be made by adding iron of known quantity to avoid interference. The procedure was validated by reference soils from IAEA. Plutonium-238, 239, 240, ²⁴¹Am, ⁹⁰Sr and ¹³⁷Cs activities are given and some isotopic ratios are calculated in order to know the origin of the radionuclides.     

Determination of difficult-to-measure actinides in evaporator concentrate

Radiochemical separation of americium, neptunium and plutonium was tested on model solution of evaporator concentrate sample for isolation of each of them for alpha-spectrometry analysis. A good chemical separation of radionuclides of interest from the matrix and interfering radionuclides is required, once the relatively small difference in alpha-particle energy makes it difficult to spectrometrically separate the peaks. This paper describes use of the molecular recognition technology product AnaLig^®Pu-01 gel from IBC Advanced Technologies, Inc. to effectively and selectively pre-concentrate, separate and recover americium, neptunium and plutonium from model solution of evaporator concentrate samples from Nuclear Power Plant which belong to the most difficult matrices to analyse. The method is suitable for analysing highly contaminated samples of radioactive waste in a relatively short time. For counting the alpha activity of ²⁴¹Am, ^239,240Pu, ²³⁸Pu and ²³⁷Np ORTEC 576A alpha-spectrometer equipped with ULTRA^TM ion implanted silicon detectors (600 mm² active area) was used. The spectra were processed by using the Alpha-vision^TM 32-bit emulation software from the EG&G ORTEC company.     

A new method for the determination of plutonium and americium using high pressure microwave digestion and alpha-spectrometry or ICP-SMS

Plutonium and americium are radionuclides particularly difficult to measure in environmental samples because they are α-emitters and therefore necessitate a careful separation before any measurement, either using radiometric methods or ICP-SMS. Recent developments in extraction chromatography resins such as Eichrom^® TRU and TEVA have resolved many of the analytical problems but drawbacks such as low recovery and spectral interferences still occasionally occur. Here, we report on the use of the new Eichrom^® DGA resin in association with TEVA resin and high pressure microwave acid leaching for the sequential determination of plutonium and americium in environmental samples. The method results in average recoveries of 83 ± 15% for plutonium and 73 ± 22% for americium (n = 60), and a less than 10% deviation from reference values of four IAEA reference materials and three samples from intercomparisons exercises. The method is also suitable for measuring ²³⁹Pu in water samples at the μBq/l level, if ICP-SMS is used for the measurement.     

Analysis of nuclear materials by energy dispersive X-ray fluorescence and spectral effects of alpha decay

Energy dispersive X-ray fluorescence (EDXRF) spectra collected from alpha emitters are complicated by artifacts inherent to the alpha decay process, particularly when using portable instruments. For example, ²³⁹Pu EDXRF spectra exhibit a prominent uranium L X-ray emission peak series due to sample alpha decay rather than source-induced X-ray fluorescence. A portable EDXRF instrument was used to collect qualitative spectra from plutonium and americium, and metal alloy identification was performed on a Pu-contaminated steel sample. Significant alpha decay-induced X-ray fluorescence peaks were observed in spectra obtained from the plutonium and americium samples due to the ²³⁵U and ²³⁷Np daughters, respectively. The plutonium sample was also analyzed by wavelength dispersive XRF (WDXRF) to demonstrate that alpha decay-induced X-ray emission has a negligible effect on WDXRF spectra.     

Determination of 238Pu, 239+240Pu and 241Am in air filters

The aim of this work is to present the method for sequential plutonium and americium activity determination in air filters using chromatographic radionuclide separation and alpha spectrometry measurement. The developed method may be employed for the purposes of workplace monitoring and as an indicator of the need of introducing the individual monitoring as well as a useful complementation of individual monitoring. Basic parameters describing the developed method such as values of chemical recoveries and minimum detectable activities for plutonium and americium isotopes have been determined. Applied counting efficiency was obtained using Monte Carlo calculation method.

     

Pre-concentration and separation of thorium, uranium, plutonium and americium in human soft tissues by extraction chromatography

An extraction chromatographic method is described for the pre-concentration and separation of thorium, uranium, plutonium and americium in human soft tissues. Tissues such as lung and liver are oven dried at 120°C, ashed at 450°C and the ashed sample is alternately wet (HNO₃/H₂O₂) and dry ashed, and then dissolved in 8M HCl. Because of the complex matrix and large sample samples (up to 1500 g), the actinides were preconcentrated from the tissue solution using the TRU^TM resin (EIChroM) prior to elemental separation by extraction chromatography and determination of americium, plutonium, uranium and thorium by alpha spectrometry. The actinides were eluted from the preconcentration column and each actinide was individually eluted on TEVA^TM and TRU^TM resin columns in a tandem configuration. Actinide activities were then determined by alpha spectrometry after electrodeposition from a sulfate medium. The method was validated by analyzing human tissue samples previously analyzed for americium, plutonium, uranium and thorium in the United States Transuranium and Uranium Registries (USTUR). Two National Institute of Standards and Technology (NIST) Standard Reference Materials, SRM 4351-Human Lung and SRM 4352-Human Liver were also analyzed. United States Transuranium and Uranium Registries, Washington State University, Pullman, WA, 99163, USA.     

Biochemical fractionation and cellular distribution of americium and plutonium in the biomass of freshwater macrophytes

Accumulation of americium (²⁴¹Am) and plutonium (^238,242Pu) and their distribution in cell compartments and biochemical components of the biomass of freshwater aquatic plants Elodea canadensis, Ceratophyllum demersum and Myrioplyllum spicatum and aquatic moss Fontinalis antipyretica have been investigated in laboratory experiments. Americium and plutonium taken up from water by Elodea canadensis apical shoots were mainly absorbed by structural components of plant cells (90% for ²⁴¹Am; 89% for ²³⁸Pu and 82–87% for ²⁴²Pu). About 10–18% of isotope activity was recorded in the cytosol fraction. The major concentration (76–92%) of americium was bound to cell wall cellulose-like polysaccharides of Elodea canadensis, Myriophyllum spicatum, Ceratophyllum demersum and Fontinalis antipyretica, 8–24% of americium activity was registered in the fraction of proteins and carbohydrates, and just a minor concentration (<1%) in the lipid fraction. The distribution of plutonium in the biomass fractions of Elodea was similar to that of americium. Hence, americium and plutonium had the highest affinity to cellulose-like polysaccharides of cell walls of freshwater submerged macrophytes.     

Sediment sample preparation for the determination of Pu and Am isotopes

Summary Sediment samples from the Romanian sector of the Danube River and the Black Sea coast were analyzed for Pu and Am. Three different ways of bringing the samples into solution were tested: acid attack, microwave digestion and alkaline fusion. A conventional anion-exchange resin was used to separate plutonium from other radionuclides and several variants were tried to improve the separation of americium. The preparation of thin sources for alpha-spectrometry was tested through electrodeposition and coprecipitation with Nd(III). Discussion and recommendations for the dissolution step, the americium separation and preparation of alpha sources are made.     

Effect of industrial pollution on the distribution of Pu and Am in soil and on soil-to-plant transfer of Pu and Am in a pine forest in SW Finland

The effect of industrial pollution on the behavior of plutonium and americium was evaluated in a pine forest in the vicinity of a Cu-Ni smelter in SW Finland. Soil and vegetation were sampled at distances of 0.5, 2, 4 and 8 km from the smelter. The vertical distribution of plutonium and americium was studied in litter, organic layer and mineral layers. The amount of Pu and Am in the litter layer increased and that in the organic layer decreased towards the smelter. Concentrations of plutonium and americium in different vegetation species decreased in the order mushrooms > lichens (Cladina spp., Cetraria islandica) > Empetrum nigrum > Vaccinium vitis-idaea.     

New fecal method for plutonium and americium

A new fecal analysis method that dissolves plutonium oxide was developedat the Westinghouse Savannah River Site. Diphonix Resin . (Eichrom Technologies),is used to pre-concentrate the actinides from digested fecal samples. A rapidmicrowave digestion technique is used to remove the actinides from the DiphonixResin ., which effectively extracts plutonium and americium from acidic solutionscontaining hydrofluoric acid. After resin digestion, the plutonium and americiumare recovered in a small volume of nitric acid that is loaded onto small extractionchromatography columns, TEVA Resin and TRU Resin (Eichrom Technologies). Themethod enables complete dissolution of plutonium oxide and provides high recoveryof plutonium and americium with good removal of thorium isotopes such as ²²⁸Th.     

Rapid determination of 239,240Pu, 238Pu, 241Am and 90Sr in radioactive waste using combined SPE sorbents AnaLig? Pu02, AnaLig? Sr01 and TRU? Resin

A rapid separation method has been developed which allows measurement of plutonium, americium and strontium isotopes in the radioactive sludge from Nuclear power plant A1 Jaslovske Bohunice (NPP A1) with high chemical recoveries and effective removal of matrix interferences. This method uses different commercial products stacked AnaLig^? Pu02, AnaLig^? Sr01 and TRU^? Resin cartridges from IBC Advanced Technologies and Eichrom Technologies. The method allows the rapid separation of plutonium, strontium and americium using a single multi-stage column in the vacuum box (cartridge technology) with rapid flow rates to minimize sample separation time. The ^239,240Pu, ²³⁸Pu and ²⁴¹Am were determined by alpha spectroscopy, ⁹⁰Sr was counted on TRICARB 2900 TR by Cerenkov counting of its progeny ⁹⁰Y.     

Separation of neptunium, plutonium, americium and curium from uranium with di-(2-ethylhexyl)-phosphoric acid (HDEHP) for radiometric and ICP-MS analysis

The possibility of using di-(2-ethylhexyl)-phosphoric acid (HDEHP) in solvent extraction for the separation of neptunium, plutonium, americium and curium from large amounts of uranium was studied. Neptunium, plutonium, americium and curium (as well as uranium) were extracted from HNO₃, whereafter americium and curium were back-extracted with 5M HNO₃. Thereafter was neptunium back-extracted in 1M HNO₃ containing hydroxylamine hydronitrate. Finally, plutonium was back-extracted in 3M HCl containing Ti(III). The method separates²³⁸Pu from²⁴¹Am for α-spectroscopy. For ICP-MS analysis, the interferences from²³⁸U are eliminated: tailing from²³⁸U, for analysis of²³⁷Np, and the interference of²³⁸UH⁺ for analysis of²³⁹Pu. The method has been used for the analysis of actinides in samples from a spent nuclear fuel leaching and radionuclide transport experiment.     

Sequential determination of Am, Cm, Pu, Np and U by extraction chromatography

Environmental contamination by artificial radionuclides and the evaluation of their sources require precise isotopic analysis and accurate determination of actinide elements above all plutonium and americium. These can be achieved by alpha spectrometry or by inductively coupled plasma mass spectrometry (ICP-MS) after chemical separation. In the present work, a simple, rapid method has been developed for the sequential separation of actinide elements from aqueous solutions and their determination by alpha spectrometry. Extraction chromatography was applied to the separation of ²⁴¹Am, ²⁴⁴Cm, ^{239 + 240,238}Pu, ²³⁷Np and ^238,235,234U using microporous polyethylene supporting tri-n-octylamine as the stationary phase and hydrochloric acid with and without reducing agents as the mobile phase. Actinide in 9 M HCl solution is introduced into the anion exchange column; Pu (IV), Np (IV) and U(VI) are retained on the column while Am (III) and Cm passed through. Pu is eluted first, reductively, after which, Np and then U are eluted. The method can be applied to all aqueous solutions which do not contain strong complexing or precipitation agents for the elements considered.     

Rapid determination of 239,240Pu, 238Pu, 241Am and 90Sr in high contaminated samples waste using combined SPE sorbents AnaLig® Pu-02, AnaLig® Sr-01 and DGA® Resin

A rapid separation method has been developed which allows measurement of plutonium, americium and strontium isotopes in the high active sample from CBRN Training and Testing Centre in Zemianske Kostolany (Slovakia) with high chemical recoveries and effective removal of matrix interferences. This method uses different commercial products stacked AnaLig^® Pu-02, AnaLig^® Sr-01 and DGA^® Resin cartridges from IBC Advanced Technologies and Eichrom Technologies. The method allows rapid separation of plutonium, strontium and americium using a single multi-stage column in the vacuum box (cartridge technology) with rapid flow rates to minimize sample separation time. The ^239,240Pu, ²³⁸Pu and ²⁴¹Am were determined by alpha spectroscopy, ⁹⁰Sr was counted on TRICARB 2900 TR by Cerenkov counting of its progeny ⁹⁰Y.     

Determination of plutonium isotopes in urine samples from radiation workers using <Superscript>236</Superscript>Pu tracer,anion exchange resin and alpha spectrometry

Bioassay technique is used for the estimation of actinides present in the body based on their excretion rate through body fluids. For occupational radiation workers urine assay is the preferred method for monitoring of chronic internal exposure. Determination of low concentrations of actinides such as plutonium, americium and uranium at low level of mBq in urine by alpha spectrometry requires pre-concentration of large volumes of urine. This paper deals with standardization of analytical method for the determination of Pu-isotopes in urine samples using anion exchange resin and ²³⁶Pu tracer for radiochemical recovery. The method involves oxidation of urine followed by co-precipitation of plutonium along with calcium phosphate. Separation of Pu was carried out by Amberlite, IRA-400, anion exchange resin. Pu-fraction was electrodeposited and activity estimated using tracer recovery by alpha spectrometer. Twenty routine urine samples of radiation workers were analyzed and consistent radiochemical tracer recovery was obtained in the range 74–96% with a mean and standard deviation of 85 and 6% respectively.     

Measurement of radionuclides using ion chromatography and on-line radiation detection

Summary A technique is presented for the relatively rapid measurement of actinide and beta-emitting radionuclides in waste streams and environmental samples. It uses ion chromatography for elemental selectivity and flow-through scintillation counting with dual parameter pulse-height and pulse-shape analysis for alpha/beta detection and discrimination. The system was tested for one surrogate sample (spiked groundwater from the southeastern U.S.) and two actual samples from the Savannah River Site (supernatant from a highactivity drain tank and sludge from a high level waste tank). For the spiked groundwater, recoveries were quantitative for all of the analytes (americium, curium, plutonium, and strontium) except uranium. For the actual samples, which contained americium, curium, plutonium, strontium, and cesium, the results using the system were within 20% of those obtained independently. Based on these tests, it is concluded that the system is capable of analyzing alpha- and beta-emitting radionuclides in samples that are representative of those encountered at contaminated former weapons sites.     

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 ²³⁵U or ²³⁹Pu. 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.     

Automated radiochemical procedure for plutonium and americium measurement

A radiochemical separation method for plutonium and americium from aqueous medium has been developed using a pre-packed resin column, a peristaltic pump, and the necessary tubing and valves for flow injection technique. All the radioanalytical operations were conducted in-line. Samples made of plutonium and americium tracers in water were analyzed by this technique and counted by alpha spectroscopy. The results show that plutonium and americium can be measured simultaneously using this technique.     

Characterization of purified <Superscript>241</Superscript>Am for common impurities by instrumental neutron activation analysis

Americium is an important actinide element having versatile applications based on its alpha and gamma emissions. Multi-element determination of radioactive samples using ICP-AES technique may be affected by the presence of americium due to its rich emission spectra. With a view to characterize plutonium based fuels containing americium for trace metals by ICP-AES technique accurately, a high purity ²⁴¹Am (using a separation procedure developed in our laboratory) was prepared. To ascertain its chemical purity it is essential to determine its impurity contents accurately. Instrumental neutron activation analysis (INAA), being a sensitive multi-elemental technique, was employed to determine the concentrations of impurities in purified ²⁴¹Am. Detection limits for the common elements and rare earth elements have also been determined. Comparison is made with the analytical data obtained by the ICP-AES method.     

Determination of plutonium,americium and curium in airborne effluents of nuclear power plants

A radiochemical method has been developed for the determination of²³⁸Pu,^{239, 240}Pu,²⁴¹Am,²⁴²Cm and²⁴⁴Cm in airborne effluents of nuclear power plants. The method involves conversion of transuranium elements to acid-soluble forms, dissolution, purification, electrodeposition and alpha spectrometric determination. Final recovery ranged from 69.0 to 75.4% for plutonium and from 26.8 to 68.3% for americium and curium.