Systematic radiochemical separation for the determination of <Superscript>99</Superscript>Tc, <Superscript>90</Superscript>Sr, <Superscript>94</Superscript>Nb, <Superscript>55</Superscript>Fe and <Superscript>59,63</Superscript>Ni in low and intermediate radioactive waste samples

A simple and rapid separation procedure was systemized for the determination of ⁹⁹Tc, ⁹⁰Sr, ⁹⁴Nb, ⁵⁵Fe and ^59,63Ni in low and intermediate level radioactive wastes. The integrated procedure involves precipitation, anion exchange and extraction chromatography for the separation and purification of individual radionuclide from sample matrix elements and from other radionuclides. After separating Re (as a surrogate of ⁹⁹Tc) on an anion change resin column, Sr, Nb, Fe and Ni were sequentially separated as follows; Sr was separated as Sr (Ca-oxalate) co-precipitates from Nb, Fe and Ni followed by purification using Sr-Spec extraction chromatographic resin. Nb was separated from Fe and Ni by anion exchange chromatography. Fe was separated from Ni by anion exchange chromatography. Ni was separated as Ni-dimethylglyoxime precipitates after the removal of ^134,137Cs and ^110mAg by Cs-phosphotungstate and AgCl precipitation, respectively. Finally, the radionuclide sources were prepared by precipitation for their radioactivity measurements. The reliability of the procedure was evaluated by measuring the recovery of chemical carriers added to a synthetic radioactive waste solution.     

Determination of radionuclidic impurities in <Superscript>99m</Superscript>Tc eluate from <Superscript>99</Superscript>Mo/<Superscript>99m</Superscript>Tc generator for quality control

Technetium-99m is the principal radioisotope used in medical diagnostics; radionuclidic impurity is the major concern of its quality. This work presents a analytical method for sequential determination of all radionuclidic impurities listed in pharmacopoeia including gamma emitters, alpha emitters, ⁸⁹Sr and ⁹⁰Sr. Radioactive decay for removal of ^99mTc, ion exchange and extraction chromatography for removal of ⁹⁹Mo and ⁹⁹Tc are effective for separation of interferences. Gamma spectrometry, LSC with alpha/beta discrimination, and Cherenkov counting using LSC are sensitive methods for measurement of the impurity radionuclides. The detection limits of this method are well meet the requirement of the quality control according to the limitation of the pharmacopoeia.     

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.     

Combined determination of <Superscript>99</Superscript>Tc and <Superscript>108m</Superscript>Ag in L/ILW liquid wastes

The low- and intermediate-activity level liquid wastes produced by the Paks Nuclear Power Plant (NPP) contain routinely measureable gamma-emitting (e.g., ⁵⁴Mn, ⁶⁰Co, ^110mAg, and ¹³⁷Cs) as well as many so-called “difficult-to-measure” radionuclides. Despite of their low specific activity compared to the total, the reliable determination of these radionuclides is an important issue of nuclear waste management. The increasing amount of waste samples to be qualified yearly by our laboratory put a pressure on revising the existing procedure of ⁹⁹Tc separation applied. We have managed to halve the initial amount of the sample required to achieve the same level of detection of technetium. Furthermore, one of the new purifying steps introduced have proved to be able to separate ^108mAg (and ^110mAg) better than 99% keeping the ⁹⁹Tc content of the product almost intact. Means of separation of ⁹⁹Tc from ¹⁰⁶Ru and ^124+125Sb have also been successfully investigated. As intended, this new procedure has a major impact on the chemical reagent as well as the electricity requirement of the separation making it more cost-effective.     

Separation of no-carrier-added <Superscript>90</Superscript>Nb from proton induced natural zirconium target

Amongst various radionuclides of molybdenum, ⁹⁰Mo and ⁹⁹Mo have suitable β energy for clinical uses. In this paper we report separation of ⁹⁹Mo from ⁹⁹Mo-^99mTc equilibrium mixture. The liquid–liquid extraction technique has been employed using trioctylamine (TOA) diluted in cyclohexane as organic phase and HCl as aqueous phase. At 10⁻⁵ M HCl and 0.5 M TOA concentration ^99mTc quantitatively transferred to the organic phase leaving ⁹⁹Mo in the aqueous phase. The developed separation method is efficient and provides very high separation factor.     

An ion chromatographic separation method for the sequential determination of <Superscript>90</Superscript>Sr, <Superscript>241</Superscript>Am and Pu isotopes in a urine sample

A radiobioassay method has been developed for the sequential determination of ⁹⁰Sr, ²⁴¹Am and Pu isotopes in a urine sample. Unlike the existing methods using multiple extraction chromatographic cartridges, this work demonstrates an application of an automated ion chromatographic (IC) system for the separation of these radionuclides on a single IC column. The method meets the bioassay performance criteria for relative bias and relative precision as recommended by ANSI/HPS N13.30-2011. The detection limits for the radionuclides are found to be satisfactory for medical intervention in case of an accidental exposure scenario. Sample preparation time is less than 11 h.     

A novel electrochemical <Superscript>99</Superscript>Mo/<Superscript>99m</Superscript>Tc generator

A novel electrochemical process to avail clinical grade ^99mTc from (n,γ)⁹⁹Mo has been demonstrated. The electrochemical parameters were optimized to maximize the ^99mTc yield with minimal ⁹⁹Mo contamination. ⁹⁹Mo/^99mTc generators containing up to 29.6 GBq (800 mCi) ⁹⁹Mo were developed and their performance were extensively evaluated for 10 days without changing the operating conditions. Very high radioactive concentration of ^99mTcO₄ ⁻ of acceptable quality, commensurate with hospital radiopharmacy requirements could be availed from the system with >90% yield. The compatibility of the product for the formulation of ^99mTc labeled radiopharmaceuticals such as ^99mTc-DMSA and ^99mTc-EC was found to be satisfactory in terms of high labeling yields. The proposed route represents an important step for enhancing the scope of accessing clinical grade ^99mTc from low specific activity (n, γ)⁹⁹Mo.     

Leaching kinetics of <Superscript>54</Superscript>Mn and <Superscript>89</Superscript>Sr radionuclides fixed in cement­vermiculite composition

Summary Leach characteristics of ⁵⁴Mn and ⁸⁵Sr radionuclides from ordinary Portland cement have been studied using International Atomic Energy’s (IAEA) standard leach method. The retardation factors, K_F, and coefficients of distribution, k_d, have been determined using a simplified mathematical model for analyzing the migration of radionuclides. The lowest leaching values after 60 days were achieved in samples with 5% of vermiculite. Results presented in this paper are the examples of results obtained in a 10 year mortar and concrete testing project, which will influence the design of the engineered trench system for a future central Serbian radioactive waste storage center.     

Separation and determination of <Superscript>90</Superscript>Sr in low- and intermediate-level radioactive wastes using extraction chromatography and LSC

A methodology for the determination of ⁹⁰Sr in low- and intermediate-level radioactive wastes from nuclear power plants is presented in this work. It is a part of a methodology developed for the sequential radiochemical separation of radionuclides difficult-to-measure directly by gamma spectrometry in these radioactive wastes. The separation procedure was carried out using precipitation and extraction chromatography with Sr Resin, from Eichrom and the ⁹⁰Sr was measured by liquid scintillation counting (LSC). Optimum conditions for the pretreatment, separation and LSC measurements were determined using simulated samples, which were prepared using standard solutions and carriers. The procedure showed to be rapid and achieved a good chemical yield, in the range 60–90%, and a detection limit of 6.0 × 10⁻⁴ Bq g⁻¹. The method was also tested by participation in a national intercomparison program, with aqueous samples, with good agreement of results.     

Behavior of <Superscript>134</Superscript>Cs, <Superscript>90</Superscript>Sr,and <Superscript>238</Superscript>Pu in different Syrian soils

The experiment aimed to evaluate the vertical migration of ¹³⁴Cs, ⁹⁰Sr and ²³⁸Pu in the main types of Syrian soils; entisol, inceptisol, alluvial (rock outcrops) and gypsiferous soils, using soil columns through which the aqueous solution of the radionuclides percolated. The results show that the vertical migration of the studied radionuclides through the soil profile depend on the radionuclide and the soil type. More than 97% of ¹³⁴Cs and ²³⁸Pu concentrated in the upper 2 cm of the entisol, inceptisol, and alluvial soils, whereas only 46.2% to 68.6% of the ⁹⁰Sr was retained in the upper 2 cm of these soils. The vertical migration of the studied radionuclides in the gypsiferous soil was different from the other soils. The distribution of the radionuclides in the gypsiferous soil was irregular through the soil profile and reached the deeper layer of the soil. This may be due to its physical characteristics; poor structure stability, high permeability and low retention capacity.     

Characterisation of a Cu selective resin and its application to the production of <Superscript>64</Superscript>Cu

Cu isotopes (e.g. ⁶⁴Cu) increasingly find use in radiopharmaceutical applications, accordingly fast and reliable methods for the production of these isotopes are needed. The aim of the presented project is the characterization of a Cu selective extraction chromatographic resin for the fast and selective separation of Cu radionuclides, e.g. from irradiated targets. The characterisation of the resin includes the determination of weight distribution factors D _w of Cu, Ni, Zn and other potentially interfering elements and impurities for varying acids and pH values, the influence of macro amounts of Ni and Zn on the extraction of Cu as well as the influence of other potential interferents. Based on the obtained results, a method for the separation of Cu and its purification from irradiated Ni or Zn targets was developed and tested on simulated Ni and Zn targets.     

Determination of <Superscript>237</Superscript>Np, <Superscript>93</Superscript>Zr and other long-lived radionuclides in medium and low level radioactive waste samples

The majority of long-lived radionuclides produced in the nuclear fuel cycle can be regarded as “difficult-to-measure” nuclides, hence chemical separation is needed before the nuclear measurement of them. A combined radiochemical procedure that enables the simultaneous determination of some “difficult-to-measure” nuclides in medium and low level radioactive wastes has been developed in our laboratory. Recently, this method has been extended for determination of ²³⁷Np and ⁹³Zr. ²³⁷Np and ⁹³Zr are pre-concentrated by co-precipitation on iron(II) hydroxide and zirconium oxide, separated by extraction chromatography using UTEVA, and measured by inductively coupled plasma mass spectrometry (ICP-MS). As even traces of polyatomic ions and isotopes at m/z 237 or 93 cause considerable interferences during ICP-MS detection, a purification step by extraction chromatography was needed. Analyzing real samples (evaporation concentrates of a nuclear power plant) 66–99% and 31–99% chemical yields were achieved for Np and Zr, respectively.     

Determination of calibration curves for <Superscript>131</Superscript>I in thyroid tumour metabolic radiotherapy and other radionuclides used in SPECT imaging

Large columns containing aluminum oxide (Al₂O₃) or gel (e.g. zirconium molybdate) are needed to prepare ⁹⁸Mo(n,γ)⁹⁹Mo→^99mTc column chromatographic generators that results in large elution volumes containing relatively high ⁹⁹Mo impurity and low concentrations of ^99mTc. The decrease in radioactive concentration or specific volume concentration of ^99mTc places a limitation on some pharmaceutical kits (DTPA, MIBI, ECD, etc.) or clinical procedures. We report on the post elution concentration of ^99mTc using in house prepared lead cation-exchange and alumina columns. Using these columns high bolus volumes (10–60 mL 0.02M sodium sulfate) of ^99mTc can conveniently be concentrated in 1 mL of physiological saline. This approach also works very effectively to prepare high specific volume solutions of ^99mTc-pertechnetate from a fission based ⁹⁹Mo/^99mTc generator in the second week of its normal working life.     

Atmospheric depositional fluxes of cosmogenic <Superscript>32</Superscript>P, <Superscript>33</Superscript>P and <Superscript>7</Superscript>Be in the Sevastopol region

⁹⁰Y was separated from ⁹⁰Sr using an extraction chromatographic resin consisting of 4, 4′(5′)-bis-t-butylcyclohexano-18-crown-6 (DtBuCH₁₈C₆), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide (C₂mimNTf₂), and a polymer (Amberlite XAD-7). Ionic liquid was introduced into the column to improve the separation efficiency. The column showed an excellent performance for the separation of Y from Sr. After the separation, the ratio of ⁹⁰Sr/⁹⁰Y was <2.0 × 10^?5; the column was recycled for >18 times. This study provides preliminary results on columns to produce ⁹⁰Y with a high purity in radiopharmaceuticals.     

Application of an experimental design to optimize a segregation method of <Superscript>129</Superscript>I and <Superscript>14</Superscript>C

In this work, the optimization of a segregation method of ¹²⁹I and ¹⁴C, two long-living radionuclides, main constituents of nuclear radioactive waste, has been developed. To be able to carry out this project, a fractional factorial experimental design was applied using 5 factors and 2 levels by factor (2^5–2). Only 8 experiments were necessary to identify the variables affecting the process, and very good recoveries of both radionuclides were obtained: (94?±?2)% for ¹²⁹I, and (99?±?1)% for ¹⁴C. The segregation of ¹²⁹I was influenced by flow (Q), volume of H₂SO₄ (V_H+), and carriers (CR), while V_H+ and time (t) played a major role in the segregation of ¹⁴C.     

Validation of <Superscript>90</Superscript>Sr separation method using molecular recognition product AnaLig<Superscript>®</Superscript> Sr01 gel and extraction chromatography Sr<Superscript>®</Superscript> resin

Two separation techniques for strontium determination using AnaLig^® Sr01 molecular recognition technology and extraction chromatography Sr^®  resin were tested. The methods performance was investigated by analysis of NPL (High Alpha–Beta 2003) intercomparison sample. The results obtained for both procedures were compared in terms of activities and recoveries. Data analysis proved a good agreement with the reference values. The AnaLig^® Sr01 separation method for ⁹⁰Sr determination was successfully validated with the same performance as the Sr^® resin method.     

Study on the method of preparation <Superscript>97</Superscript>Tc

Technetium-99 is one of several long-lived fission products which, when detected in the environment can give an indication of a specific nuclear activity. The most sensitive analytical technique for ⁹⁹Tc yet reported is by isotopic dilution mass spectrometry with technetium-97 as the yield tracer. A method for the preparation of ⁹⁷Tc is reported in this paper. ⁹⁷Tc was obtained by irradiation of a sample of natural ruthenium metal in a high flux reactor. After cooling for 2 years, the technetium was isolated from the sample by technique combining; deposition, solvent extraction, and ion-exchange chromatography techniques. ^99mTc and ¹⁰³Ru were used as radio-tracers for the process. The results showed that more than 70% of the Tc was recovered the decontamination factor is more than 2.3 × 10⁷. The ⁹⁷Tc was calibrated by isotope dilution mass spectrometry with ⁹⁹Tc as the yield tracer. The final yield was 29.56 μg of ⁹⁷Tc suitable for use as a mass spectrometric spike (weight % ⁹⁷Tc spike: ⁹⁷Tc, 84.77%; ⁹⁸Tc, 15.03%; ⁹⁹Tc, 0.20%).     

Determination of99Tc in fuel leachates using extraction chromatography

A simple technique using a combination of cation exchange and solid phase extraction chromatographic resins has been developed for the separation of⁹⁹Tc from other radionuclides present in nuclear fuel leachates. Quantification of the isolated⁹⁹Tc is accomplished using liquid scintillation counting. The method provides consistently high recoveries (>96%), generates small amounts of waste compared to classical methods, and requires less analysis time.     

Automated radiochemical analysis of total <Superscript>99</Superscript>Tc in aged nuclear waste processing streams

Summary A fully automated analysis procedure and instrument for the measurement of total ⁹⁹Tc in aged nuclear waste has been developed. The overall analysis approach is based on a fully automated wet radiochemical analysis method. Microwave-assisted sample oxidation is used prior to a chemical separation step in order to oxidize all of the non-pertechnetate species to pertechnetate. Separation of the pertechnetate from interfering radioactive and stable matrix species is carried out using an anion-exchange column. The separated ⁹⁹Tc is quantified using a flow-through solid cell scintillation detector. The instrument is capable of an analysis time of <13 minute per sample with a detection limit of 2000 dpm/ml. Nuclear waste samples from the Hanford site with a high content of non-pertechnetate species were successfully analyzed using this method.     

Determination of <Superscript>137</Superscript>Cs and <Superscript>90</Superscript>Sr in the bottom sediments from the Barents Sea

The aim of this paper was to determine the extent of contamination by anthropogeneous radionuclides ¹³⁷Cs and ⁹⁰Sr in the bottom sediments from the Barents Sea based on the radioactive activity of the samples taken up in August 1991, among others, from the area close to New Land Island and Francis Joseph Archipelago. The results are based on the phenomenon of vertical migration, in the bottom sediments which is of significant importance from the natural environment point of view.