A very sensitive LSC procedure to determine Ni-63 in environmental samples,steel and concrete

This procedure to determine Ni-63 contributes to a safe and economically resonable decommissioning of nuclear power plants. Co-60, Fe-55 and Ni-63 are the most abundant long-lived radionuclides associated with contaminated piping, hardware and concrete for a period of several decades of years after shutdown, Samples are carefully ashed, leached, or dissolved by suitable mixtures of acids. The analysis starts with the absorption of Ni²⁺ on the chelating resin CHELEX 100. The next purification steps include an anionic exchange column and a precipitation as Ni-dimethyl-glyoxime, which is extracted into chloroform. After reextraction with sulfuric acid the solution containing Ni²⁺ is mixed with a scintillation cocktail and counted in an anticoincidence shielded LSC. The decontamination factors are determined for all important artificially and naturally occurring radionuclides ranging from above 10⁴ to 10⁹. The chemical yield adopts a value of (95±5)%. up to maximum sample amounts of 0,4 g steel, 5 g concrete and about 100 g of environmental samples the detection limits are about 5 mBq per sample or 12 mBq/g steel, 1 mBq/g concrete and 0,05 mBq/g environmental sample at a counting time of 1000 minutes.     

Measurements of210Pb and210Po in Japanese human hair

²¹⁰Pb and²¹⁰Po in human hair have been measured to serve as an aid in order to estimate the dietary intake and body burden of these radionuclides of Japanese. The²¹⁰Po concentrations found in 83 hair samples were ranging from 4.0 to 59.3 mBq/g with a mean (median) value of 18.2±12.2 (14.9) mBq/g as compared to the²¹⁰Pb concentrations from 0.7 to 6.5 mBq/g with a mean (median) value of 2.3±1.1 (2.0) mBq/g. The²¹⁰Po/²¹⁰Pb activity ratios (mean: 8.7±5.1, median: 7.1) were surprisingly higher compared with the available literature value of about 2. The high concentration of²¹⁰Po in human hair of Japanese may be due to the ingestion of animal protein mainly in the form of seafood.     

Non-destructive gamma-spectrometry analysis of cosmogenic radionuclides in fragments of the Ko?ice meteorite

Results of analysis of cosmogenic radionuclides (^57,58,60Co, ⁵⁴Mn, ⁴⁶Sc, ²²Na, ⁴⁸V and ²⁶Al) in fragments of the Ko?ice meteorite are presented and discussed. Analyses were carried out using a low-level HPGe-spectrometer placed in a lead-iron-copper shield. Twelve meteorite fragments were available for the analysis with masses from 27 to 2,163?g. The lowest massic activities were observed for ⁴⁶Sc (down to 0.1?mBq/g), and the highest for ²²Na (up to 2?mBq/g). The measured radionuclide activities showed differences between fragments, as indicated mainly by the ⁶⁰Co data, which were caused by different positions of meteorite fragments from the center of the meteorite body.     

210Pb and 210Po radionuclides in the urban air of Lodz, Poland

The concentration of two important radionuclides: ²¹⁰Pb and its decay product ²¹⁰Po in the urban air in the center of the Polish city of Lodz were measured during the winter and spring seasons of 2008–2009. Urban airborne particulate matter was collected using two methods: an Anderson 9-stage impactor, and a high-volume aerosol sampler type ASS500 working in the frames of the aerosol sampling network in Poland, established for radionuclide monitoring. Average concentrations for 10 months sampling period for ²¹⁰Pb and ²¹⁰Po were 0.556 and 0.067 mBq/m³, respectively. However remarkable fluctuations due to meteorological condition were observed: from 0.010 to 0.431 mBq/m³ for ²¹⁰Po and from 0.167 to 1.847 mBq/m³ for ²¹⁰Pb. The highest concentrations, almost 60% of the total activities, of both radionuclides were found in the first two fine aerosol fractions with particle diameters below 0.36 μm. The aerosol residence times calculated from the ²¹⁰Po/²¹⁰Pb ratio ranged from 7 to 120 days.     

Laboratory standard for radionuclides in nuclear waste

A laboratory standard for the determination of long-lived radionuclides in nuclear waste has been prepared using concrete as matrix. It will be used to check sample preparation procedures, chemical separations and methods for the determination of nuclides, e.g., nuclear counting techniques or mass spectrometry. The material chosen was a fine-grained ready-to-use cement mixture, to which the following radionuclides were added:⁶⁰Co and¹³⁷Cs as -ray-emitting nuclides,⁹⁹Tc,⁹⁰Sr and⁵⁵Fe as radionuclides emitting pure -radiation or low-energy electrons, and²³³U,²³⁷Np,²³⁸Pu and²⁴¹Am as -emitters. Care was taken to attain a homogeneous distribution of the nuclides in the standard material. Pieces of about 1 g were formed as suitable and representative samples. Repeated analyses were carried out with the standard to check its homogeneity. The analytical procedures are described in brief. The pieces of the standard material have the same content of nuclides within ±5% at a 95% level of confidence.     

A comparative study using liquid scintillation counting and X-ray spectrometry to determine 55Fe in radioactive wastes

The radionuclide ⁵⁵Fe was determined in samples of radioactive wastes from the water cleanup system of the IEA-R1 nuclear research reactor. In order to validate the results, the ⁵⁵Fe activity concentration was measured in eight waste samples and in six simulated samples containing the most important interfering radionuclides. A simple method was employed to separate and purify ⁵⁵Fe from other radionuclides present in these samples, combining co-precipitation with ammonium hydroxide and purification with anionic ion-exchange resin, which enables ⁵⁵Fe to be quantified either by liquid scintillation counting (LSC) or by X-ray spectrometry using a low-energy germanium spectrometer (LEGe). Both measurement methods were used so that the separation and purification process could be confirmed by comparison of spectra with and without the utilization of anionic ion-exchange resin. Activity and interferences were compared in the results obtained from LSC and LEGe measurement methods.     

Preparation of <Superscript>26</Superscript>Al, <Superscript>59</Superscript>Ni, <Superscript>44</Superscript>Ti, <Superscript>53</Superscript>Mn and <Superscript>60</Superscript>Fe from a proton irradiated copper beam dump

The station for pions cancer therapy was operated at PSI from 1980 to 1992. After a cooling time of 12 years it’s made of copper beam dump was cut and samples were taken for analytical purposes. The sampling collected about 500 g of high active copper chips that can be used for separation of exotic radionuclides. The analyses by gamma spectrometry, LSC and AMS showed main nuclides present to be ⁶⁰Co, ⁵⁴Mn, ²²Na, ⁶⁵Zn, ²⁶Al, ⁵³Mn, ⁵⁹Ni, ⁶³Ni, ⁵⁵Fe and ⁶⁰Fe and ⁴⁴Ti with a daughter nuclide ⁴⁴Sc. In the frame of ERAWAST project a procedure combining selective precipitation and ion exchange for the separation of the rare radionuclides from the copper beam dump was developed. The proposed separation procedure is easy for remote controlled implementation in a hot cell. The ion exchange separation of Ni, Al, Mg, Ti and Fe was complete and high decontamination factors for copper and cobalt were achieved. Based on the developed procedure a remotely controlled system for separation of exotic radionuclides from the copper chips was set up. The full scale system was installed in a hot cell where high activity levels can be handled. In order to evaluate the reliability and functionality of the system extensive tests have been done. During the test period 13.86 g in total of the proton irradiated copper beam dump were processed for separation of ²⁶Al, ⁵⁹Ni, ⁵³Mn, ⁴⁴Ti and ⁶⁰Fe. The results showed that the system was operational and the radionuclide separation was selective with high chemical yield. The procedure manages as well the generated liquid wastes containing high level of ⁶⁰Co activity.     

A new very sensitive LSC procedure for determination of Tc-99 in environmental samples

A new method for the determination of Tc-99 in different environmental samples has been developed. The sample is carefully ashed in a muffle furnace and then fused with Na₂CO₃ and K₂CO₃. The first step is an enrichment and purification of TcO ₄ ^– on an anion exchange resin. The Tc is desorbed as a cationic thiourea complex, which is held on a cation exchange resin. The complex is destroyed by oxidation to TcO ₄ ^– with (NH₄)₂S₂O₈ in sulfuric acid. From this solution TcO ₄ ^– is extracted into TBP/toluene and the organic phase is mixed with a scintillation cocktail and counted in an anticoincidence shielded LSC. Tc-99m is used as a chemical yield tracer. The decontamination factors for all important fission and activation products and naturally occurring radionuclides are in the range between > 10⁵ and > 10⁸. The detection limit is about 5 mBq per sample at a counting time of 1000 minutes. The maximum sample amount of plants is 500 g dry weight and therefore the lowest detection limit achievable is 10 mBq/kg. Ashing and dissolution of the samples takes 24 h and 4 analyses are performed by one technician in 8 hours. The chemical yield ranges from 50 to 80%.     

Determination of alpha,beta, X-ray and gamma emitting radionuclides in reactor components and fuel assemblies from NPP V1 Jaslovske Bohunice

The radionuclides in reactor and fuel construction parts of the V1 Jaslovske Bohunice nuclear power plant (NPP V1) were identified and their activity was measured. Samples from reactor and fuel assemblies such as control rod connection rod, shielding/absorber parts of fuel rod, neutron in-core measurement channels, pressure vessel basic construction material and internal cladding, core barrel and protective tube unit were analyzed. Activity concentrations of ⁶⁰Co, ⁵⁵Fe, ^63,59Ni, ⁹⁰Sr, ⁹⁹Tc, ⁹³Mo, ⁹⁴Nb, transuranic elements were determined. Analytical and sampling methods are briefly described for the measured radionuclides. The presented results were used for characterization of the waste during the decommissioning of NPP V1 nuclear reactors.     

New method for simultaneous determination of55Fe and59Fe in blood samples

A new simple method for the simultaneous determination of⁵⁹Fe and⁵⁵Fe concentration in 5 ml samples of blood is described and carefully evaluated. Before the measurement of the activity of the radionuclides, organic matter was eliminated by HNO₃?HClO₄ wet ashing. Iron was electroplated onto a copper plate. The accuracy of results was studied by assessing samples, which contained known amounts of radioactivity and determining the counts per nanocurie in each case. The accuracy of the results of⁵⁹Fe and⁵⁵Fe determinations was found to be about 5%.     

Decontamination of radionuclides on construction materials

A wide variety of materials can become contaminated by radionuclides, either from a terrorist attack or an industrial or nuclear accident. The final disposition of these materials depends, in large part, on the effectiveness of decontamination measures. This study reports on investigations into the decontamination of a selection of building materials. The aim has been to find an effective, easy-to-use and inexpensive decontamination system for radionuclides of cesium and cobalt, considering both the chemical and physical nature of these potential contaminants. The basic method investigated was surface washing, due to its ease and simplicity. In the present study, a basic decontamination formulation was modified by adding isotope-specific sequestering agents, to enhance the removal of cesium(I) and cobalt(II) from such construction materials as concrete, marble, aluminum and painted steel. Spiking solutions contained ¹³⁴Cs or ⁶⁰Co, which were prepared by neutron activation in the SLOWPOKE-2 nuclear reactor facility at the Royal Military College of Canada. Gamma spectroscopy was used to determine the decontamination efficiency. The results showed that the addition of sequestering agents generally improved the radiological decontamination. Although the washing of both cesium and cobalt from non-porous materials, such as aluminum and painted steel, achieved a 90–95 % removal, the decontamination of concrete and marble was more challenging, due to the porous nature of the materials. Nevertheless, the removal efficiency from 6-year-old concrete increased from 10 % to approximately 50 % for cobalt(II), and from 18 to 55 % for cesium(I), with the use of isotope binding agents, as opposed to a simple water wash.     

Alpha spectroscopic analysis of actinides (Th,U and Pu) after separation from aqueous solutions by cation-exchange and liquid extraction

The radioactivity concentration of ²³⁶Pu, ²³²U and ²²⁸Th in aqueous samples has been determined by means of alpha spectroscopy after chemical separation and pre-concentration of the radionuclides by cation exchange and liquid–liquid extraction using the Chelex-100 resin and 30% TBP/dodecan, respectively. Method calibration using a ²³⁶Pu standard solution containing the daughter radionuclides results in a detector efficiency of 18% and in a chemical recovery for cation-exchange which is (30 ± 7)%, (90 ± 5)% and (20 ± 5)% for plutonium, uranium and thorium, respectively. The chemical recovery for liquid–liquid extraction is found to be (60 ± 7)%, (50 ± 5)% and (70 ± 5)%, for plutonium, uranium and thorium, respectively. The differences in the efficiencies can be ascribed to the oxidation states, the different actinides present in solution. Taking into account that the electrodeposition of the radionuclides under study is quantitative, the total method efficiency is calculated to be (18 ± 15)%, (46 ± 7)% and (15 ± 5)%, for plutonium, uranium and thorium, respectively, at the mBq concentration range. The detection limit of the alpha spectrometric system has been found to be 0.2 mBq/L, suggesting that the method could be successfully applied for the radiometric analysis of the studied radionuclides and particularly uranium in aqueous samples.     

A simple radiochemical method for determining bone-seeking radionuclides in bone and teeth: 90Sr in teeth of children from Ukraine and Germany

Bone is a critical organ for the accumulation of ⁹⁰Sr but also of other “bone-seeking” radionuclides such as Ra, Pb, Th, U and Pu. That's why a simple radiochemical procedure to separate ⁹⁰Sr, ²¹⁰Pb, ²²⁶Ra, Th_nat. U_nat., ²³⁸Pu and ^239/240Pu from bone and teeth was developed. The separation scheme is based on extraction chromatography. Deciduous teeth, extracted from children born in 1982-1991 were collected in various regions of Germany and in Northwest Ukraine and analyzed for ⁹⁰Sr concentrations with regard to the Chernobyl accident in 1986. The teeth were grouped into samples according to the year of birth and the residence of the donors. The ⁹⁰Sr content in teeth from the Ukraine (mean = 63.8 mBq/g Ca) averaged more than twice as much as that found in teeth from Germany (mean = 28.4 mBq/g Ca). The obvious explanation for this effect is that the concentration of ⁹⁰Sr decreased with increasing distance from the damaged Chernobyl nuclear power plant. The measured levels of ⁹⁰Sr concentrations, however, were much lower than ⁹⁰Sr concentrations determined in the mid-60s and mid-70s. This revised version was published online in July 2006 with corrections to the Cover Date.     

Simultaneous determination of lead-210, gross beta and gross alpha activities of air filters by pulse shape discrimination liquid scintillation counting

A chemical procedure for transferring deposited solid matter from a cellulose filter into the liquid scintillation cocktail has been described. The influence of chemical and color quenching on alpha and beta detection efficiency, as well as on misclassification of beta and alpha pulses was corrected by an external standard method. Under the chosen pulse shape discrimination level (PSD), the alpha and beta detection efficiencies were above 85% and spillovers of alpha and beta pulses were below 10% and 2% respectively. Determination limits for samples containing up to 200 mg of mineral matter were 0.015 mBq m^–3 for alpha, 0.055 mBq.m^–3 for²¹⁰Pb and 0.055 mBq.m^–3 for beta activity (counting time 12000 s and volume of filtered air 1000 m³). The method has been applied for routine monitoring of²¹⁰Pb as well as for gross alpha and beta activities of longer-living radionuclides (T_1/2.>11 hrs) in suspended air matter.     

Effects of Fe(III) ions on the electrodeposition of trace amounts of plutonium and americium

The electrodeposition of Pu and Am onto stainless steel discs from 3.2M ammonium chloride solution is strongly affected by the iron concentration of the electrolyte. At Fe(III) concentrations of more than 0.1mM (30 g Fe in 5 ml) only 30–40% of²³⁶Pu and 6% of²⁴¹Am can be deposited. Tracer experiments with⁵⁹Fe suggest that exchange processes take place between Fe from the surface layer of the cathode and from the electrolyte. Double tracer studies show increasing²³⁶Pu/⁵⁹Fe- and decreasing²⁴¹Am/⁵⁹Fe-ratios with increasing iron content of the electrolyte, which may be due to different sorption properties on colloidal iron hydroxides formed at pH<3.6.     

Extraction-chromatographic method for the determination of plutonium-239,240 and plutonium-238 in soils with high natural radioactivity

A highly selective method is described for the determination of ^239,240Pu and ²³⁸Pu in soils by extraction chromatography with Microthene-710/tri-n-octylamine. The method is especially suitable for volcanic soils containing high concentrations of natural alpha radionuclides (Th, Po, U, etc.). The detection limit by α-spectrometry is 2.2 mBq kg^?1 for 50-g soil samples. The average chemical yield, obtained by adding ²⁴²Pu as the internal standard, is 69.5 ± 17.1%. An IAEA reference soil was analyzed, with a relative error of 6.7% for ²³⁹Pu. The concentration of ^2239,240Pu in thirteen analyzed soils and sediments ranged from 26.6 to 429 mBq kg^?1.     

Gamma-emitters 90Sr, 238,239+240Pu and 241Am in bones and liver of eagles from Poland

Summary The present study focused on analyzing samples of bones, livers and kidneys of European white-tailed eagles (Halia?tus albicilla) and lesser-spotted eagle (Aquila pomarina). Bone samples were collected for both species, from 7 and 2 individuals, respectively, whereas liver and kidney samples for white-tailed eagle species only, 2 and 1 individuals, respectively. The samples were analyzed for the presence of gamma-emitters and then for ⁹⁰Sr, ²³⁸Pu, ^239+240Pu and ²⁴¹Am. The applied radiochemical method is presented. Activity concentration in ashen bones (600 °C) for ⁹⁰Sr ranged from 4.6±1.2 to 31.0±2.5 Bq/kg, for ^239+240Pu from <1.7 to 21±4 mBq/kg, for ²³⁸Pu from <2.7 to 6.5±1.3 mBq/kg and for ²⁴¹Am from <1.2 to 6.5±4.4 mBq/kg. Relatively high ^239+240Pu activity concentration of 78±9 mBq/kg (for fresh weight) was recorded in a single kidney sample. The liver samples showed activities of magnitude at least one order lower. No clear correlations were found between the activities of different radionuclides.     

Activity concentrations of selected artificial and natural radionuclides in water and sediment samples from the North Western Black Sea, 1999

Radioactive concentrations of several artificial and natural radionuclides were determined in water and sediment samples collected from various locations in the NW Black Sea in December 1999. For water samples, ⁹⁰Sr and ¹³⁷Cs activity concentrations were of approximately 11 mBq/l and 26.3-41.2 mBq/l, respectively. The concentration of tritium ranged from 7 to 24 T.U. In sediment samples, maximum concentrations of ¹³⁷Cs, ^239+240Pu and ²⁴¹Am were found of 128±6 Bq·kg^-1, 1.8±0.1 Bq·kg^-1 and 0.05±0.04 Bq·kg^-1, respectively. For U and Th radionuclides, the concentrations ranged from 20-80 Bq·kg^-1 and 30-50 Bq·kg^-1, respectively. The results were consistent with those reported in earlier research for the Black Sea. This revised version was published online in July 2006 with corrections to the Cover Date.     

Improved sample preparation method for environmental plutonium analysis by ICP-SFMS and alpha-spectrometry

A rapid and simple sample preparation method for plutonium determination in environmental samples by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) and alpha-spectrometry is described. The developed procedure involves a selective CaF₂ co-precipitation for preconcentration followed by extraction chromatographic separation. The proposed method effectively eliminates the possible interferences in mass spectrometric analysis and also removes interfering radionuclides that may disturb alpha-spectrometric measurement. For ²³⁹Pu, ²⁴⁰Pu and ²⁴¹Pu limits of detection of 9.0 fg·g⁻¹ (0.021 mBq), 1.7 fg·g⁻¹ (0.014 mBq) and 3.1 fg·g⁻¹ (11.9 mBq) were achieved by ICP-SFMS, respectively, and 0.02 mBq by alpha-spectrometry. Results of certified reference materials agreed well with the recommended values.     

Isolation and quantification of Fe and Ni in reactor effluents using extraction chromatography and liquid scintillation analysis

A novel extraction chromatographic resin based on diisobutyl ketone has been developed for the isolation of ⁵⁵Fe. This material has been used in conjunction with a dimethylglyoxime-based resin for the sequential separation of ⁵⁵Fe and ⁶³Ni and isolation of these radionuclides from associated contaminants. The preparation and characterisation of these resins is described along with an assessment of their performance for the isolation of ⁵⁵Fe and ⁶³Ni from a mixture of nuclear activation products. In addition, a refined approach for the measurement of these nuclides by liquid scintillation counting is discussed. The findings of these studies have been combined to develop a robust procedure for the analysis of ⁵⁵Fe and ⁶³Ni in reactor effluents which is now the preferred method for a number of UK analytical laboratories.