A selective separation method for <Superscript>93</Superscript>Zr in radiochemical analysis of low and intermediate level wastes from nuclear power plants

The zirconium isotope ⁹³Zr is a long-lived pure β-particle-emitting radionuclide produced from ²³⁵U fission and from neutron activation of the stable isotope ⁹²Zr and thus occurring as one of the radionuclides found in nuclear reactors. Due to its long half life, ⁹³Zr is one of the radionuclides of interest for the performance of assessment studies of waste storage or disposal. Measurement of ⁹³Zr is difficult owing to its trace level concentration and its low activity in nuclear wastes and further because its certified standards are not frequently available. A radiochemical procedure based on liquid–liquid extraction with 1-(2-thenoyl)-3,3,3-trifluoroacetone in xylene, ion exchange with Dowex resin and selective extraction using TRU resin has to be carried out in order to separate zirconium from the matrix and to analyze it by liquid scintillation spectrometry technique (LSC). To set up the radiochemical separation procedure for ⁹³Zr, a tracer solution of ⁹⁵Zr was used in order to follow the behavior of zirconium during the process by γ-ray spectrometry through measurement of the ⁹⁵Zr. Then, the protocol was applied to low level waste (LLW) and intermediate level waste (ILW) from nuclear power plants. The efficiency detection for ⁶³Ni was used to determination of ⁹³Zr activity in the matrices analyzed. The limit of detection of the 0.05 Bq l⁻¹ was obtained for ⁶³Ni standard solutions by using a sample:cocktail ratio of 3:17 mL for OptiPhase HiSafe 3 cocktail.     

Comparison of thermal ionization mass spectrometry and Multiple Collector Inductively Coupled Plasma Mass Spectrometry for cesium isotope ratio measurements

In the nuclear domain, precise and accurate isotopic composition determination of elements in spent nuclear fuels is mandatory to validate neutron calculation codes and for nuclear waste disposal. The present study presents the results obtained on Cs isotope ratio by mass spectrometric measurements. Natural cesium is monoisotopic (¹³³Cs) whereas cesium in spent fuels has 4 isotopes (¹³³Cs, ¹³⁴Cs, ¹³⁵Cs, and ¹³⁷Cs). As no standard reference material is available to evaluate the accuracy of Cs isotopic measurements, a comparison of cesium isotopic composition in spent nuclear fuels has been performed between Thermal Ionization Mass Spectrometry (TIMS) and a new method involving Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) measurements. For TIMS measurements, isotopic fractionation has been evaluated by studying the behavior of cesium isotope ratios (¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs) during the analyses. For MC-ICPMS measurements, the mass bias effects have been corrected with an external mass bias correction using elements (Eu and Sb) close to cesium masses. The results obtained by the two techniques show good agreement: relative difference on ¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs ratios for two nuclear samples, analyzed after chemical separation, ranges from 0.2% to 0.5% depending on the choice of reference value for mass bias correction by MC-ICPMS. Finally the quantification of the ¹³⁵Cs/²³⁸U ratio by the isotope dilution technique is presented in the case of a MOx (mixed oxide) spent fuel sample. Evaluation of the global uncertainties shows that this ratio could be defined at an uncertainty of 0.5% (k = 2). The intercomparison between two independent mass spectrometric techniques is fundamental for the evaluation of uncertainty when no isotopic standard is available.     

Mass Spectrometric Determination of Zirconium from a Resin Bead

Abstract

A sensitive, isotope dilution technique has been developed for the analysis of sub-microgram amounts of zirconium. The analysis is based on the increased thermal ion emission for Zr adsorbed on a single anion resin bead. Zr is isolated from a solution containing the sample and a highly enriched ⁹⁴Zr (96%) spike. The determination is made possible by using a high-sensitivity pulse-counting 2-stage 30-cm radius mass spectrometer. The detection limit depends upon the amount of the isotope spike added and the desired precision. Fifty nanograms of zirconium (sample plus spike) produce sufficient ion signals for reliable isotopic analysis so that fission Zr can be measured with blank correction to a precision of 3%. By this method for fission Zr in spent reactor fuel particles, contamination from normal Zr and Mo can be corrected out by making isotopic measurements before and after spiking and scanning masses 90 and 95 during analysis. Since neither masses 90 nor 95 are stable fission products, their presence is due to sample contamination and can be used for correction based on their normal isotopic distributions. Zone-refined tantalum ribbon, essentially free of normal Zr and Mo was selected as the ionizing filament. This method can be adapted to a wide variety of samples.     

Development of a method for the determination of 93Zr and 94Nb in radioactive waste using TEVA® resin

The behaviour of ⁹⁵Zr and ⁹⁵Nb isotopes on TEVA^® resin column was studied. The influence of hydrofluoric, hydrochloric, oxalic and sulphuric acids on the separation and chemical yield of zirconium and niobium was tested. The method is suitable for the separation of ⁹³Zr and ⁹⁴Nb isotopes from hydrofluoric, hydrochloric and sulphuric acid by using different concentrations of the acid for the load or elutes solutions. Samples from reactor and fuel assemblies such as the control-rod connection rod, shielding/absorber parts of fuel rods, neutron in-core measurement channels, pressure vessel basic construction material and internal cladding, core barrel and reactor protection tube unit were analysed.     

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.     

Use of zirconium and ruthenium isotope correlations in the analysis of spent nuclear fuels

An approach is proposed to use the isotope ratios⁹³Zr/⁹⁶Zr,⁹¹Zr/⁹⁶Zr and¹⁰¹Ru/¹⁰⁴Ru for the determination of plutonium contriubtion to the total burnup of a spent nuclear reactor fuel of low initial enrichment in²³⁵U (3.6%). This approach was verified by determining the total burnup of the fuel from the¹³⁷Cs and¹⁴⁸Nd monitors and subtracting the partial burnup due to²³⁵U from the value obtained.     

Vertical distribution of uranium concentrations and 235U/238U atom ratios in the coastal water off Aomori, Japan: A survey prior to the operation of a nuclear fuel reprocessing facility

Summary From the viewpoint of environmental radioactivity monitoring, the determination of uranium and its isotope ratio is important for identifying and assessing the environmental impact of any unexpected release from nuclear facilities. In this work, a survey was conducted to determine ²³⁸U concentrations and ²³⁵U/²³⁸U atom ratios in coastal waters off Rokkasho Village, Aomori, Japan, where several uranium-related nuclear facilities have been operating since 1992, and a newly constructed nuclear fuel reprocessing plant is scheduled to be commissioned in 2006. Seawater samples were analyzed directly after a 10-fold dilution using isotope dilution sector-field ICP-MS. Based on the results, we concluded that there is no observable uranium contamination in the investigated sites. In addition, for the first time, a correlation between uranium concentration and salinity was established in coastal waters using the SF-ICP-MS technique.     

Determination of zirconium traces in polymers by ICP-IDMS – a powerful and fast method for routine testing of zirconium residues in polyolefins

Zirconium trace analyses play an important role for polyolefins produced by modern catalytic processes with zirconium metallocenes. A reliable and fast routine testing method by inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) was therefore developed, which allows the determination of zirconium in polymers down to the low ng/g level. With respect to its precision, accuracy, and time-consumption this method is suitable for routine testing of production processes. A spike solution, enriched in the stable isotope ⁹¹Zr, was prepared and used for the isotope dilution procedure, which has the advantage of being an internal “one point” calibration method. The polyolefin samples were dissolved by microwave assisted digestion with a mixture of concentrated HNO₃/HF.     

Design of Homogeneous Hybrid Materials through a Careful Control of the Synthetic Procedure

Sols for the synthesis of hybrid organic-inorganic materials have been prepared by mixing zirconium n-propoxide and methacryloxypropyltrimethoxysilane (MPS). The synthesis was done in two steps: a 15 minute hydrolysis of a MPS : H₂O : EtOH 1 : 1 : 2 mixture and then addition of 0.5 molar equivalent of zirconium alkoxide. All the experimental parameters—hydrolysis ratio, pH, dilution, pre-hydrolysis time—have been optimized through a detailed ²⁹ Si and ¹⁷O NMR analysis. Immediately after the addition, 94% of the initial water was consumed for the formation of Si–O–Zr bridges. Cleavage of these bonds, associated with formation of Si–O–Si and Zr–O–Zr bridges are then observed during the aging time.     

Determination of 90Sr / 238U ratio by double isotope dilution inductively coupled plasma mass spectrometer with multiple collection in spent nuclear fuel samples with in situ 90Sr / 90Zr separation in a collision-reaction cell

Strontium-90 is one of the most important fission products generated in nuclear industry. In the research field concerning nuclear waste disposal in deep geological environment, it is necessary to quantify accurately and precisely its concentration (or the ⁹⁰Sr / ²³⁸U atomic ratio) in irradiated fuels. To obtain accurate analysis of radioactive ⁹⁰Sr, mass spectrometry associated with isotope dilution is the most appropriated method. But, in nuclear fuel samples the interference with ⁹⁰Zr must be previously eliminated. An inductively coupled plasma mass spectrometer with multiple collection, equipped with an hexapole collision cell, has been used to eliminate the ⁹⁰Sr / ⁹⁰Zr interference by addition of oxygen in the collision cell as a reactant gas. Zr⁺ ions are converted into ZrO⁺, whereas Sr⁺ ions are not reactive.A mixed solution, prepared from a solution of enriched ⁸⁴Sr and a solution of enriched ²³⁵U was then used to quantify the ⁹⁰Sr / ²³⁸U ratio in spent fuel sample solutions using the double isotope dilution method. This paper shows the results, the reproducibility and the uncertainties that can be obtained with this method to quantify the ⁹⁰Sr / ²³⁸U atomic ratio in an UOX (uranium oxide) and a MOX (mixed oxide) spent fuel samples using the collision cell of an inductively coupled plasma mass spectrometer with multiple collection to perform the ⁹⁰Sr / ⁹⁰Zr separation. A comparison with the results obtained by inductively coupled plasma mass spectrometer with multiple collection after a chemical separation of strontium from zirconium using a Sr spec resin (Eichrom) has been performed. Finally, to validate the analytical procedure developed, measurements of the same samples have been performed by thermal ionization mass spectrometry, used as an independent technique, after chemical separation of Sr.     

Determination of zirconium traces in polymers by ICP-IDMS – a powerful and fast method for routine testing of zirconium residues in polyolefins

Zirconium trace analyses play an important role for polyolefins produced by modern catalytic processes with zirconium metallocenes. A reliable and fast routine testing method by inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) was therefore developed, which allows the determination of zirconium in polymers down to the low ng/g level. With respect to its precision, accuracy, and time-consumption this method is suitable for routine testing of production processes. A spike solution, enriched in the stable isotope ⁹¹Zr, was prepared and used for the isotope dilution procedure, which has the advantage of being an internal “one point” calibration method. The polyolefin samples were dissolved by microwave assisted digestion with a mixture of concentrated HNO₃/HF. Received: 16 November 1998 / Revised: 29 January 1999 / Accepted: 18 February 1999     

The Determination of Impurities in 233UO2 by Spark Source Mass Spectrometry

Abstract

A method for the determination of impurities in ²³³UO₂ has been developed and applied to the analysis of a product stream of ceramic grade ²³³UO₂ powder. The analytical method has combined isotope dilution and internal standard methods to permit the determination of impurities at concentrations between 0.1 and 500 ppm in a single sample.     

Determination of U/U atom ratio in uranium samples using liquid scintillation counting (LSC)

A correlation has been developed for the determination of ²³⁵U/²³⁸U atom ratio in uranium samples using liquid scintillation counting (LSC). The ²³⁵U/²³⁸U atom ratio determined by thermal ionization mass spectrometry (TIMS) was correlated to the ratio of (i) α-count rate and (ii) Cerenkov count rate due to ^234mPa in the sample; both measured by LSC. This correlation is linear over the range of ²³⁵U/²³⁸U atom ratio encountered in the nuclear fuel samples, i.e. the low enriched uranium (LEU) samples with ²³⁵U < 20 atom%. The methodology based on this correlation will be useful for the quick determination and verification of ²³⁵U/²³⁸U atom ratios in fuel samples using cost effective technique of LSC.     

Determination of zirconium in U−Zr−Al and Pu−Zr−Al alloys by isotope dilution thermal ionization mass spectrometry

An isotope dilution thermal ionization mass-spectrometric (ID-TIMS) method is described for the determination of Zr in U?Zr?Al and Pu?Zr?Al alloy samples. Problems encountered in the chemical exchange between the zirconium isotopes in the spike and sample, particularly Pu?Zr?Al samples, are discussed and a method has been standardized to eliminate it. Separation of Zr from U, Pu and Al was achieved by employing ion exchange procedures. A precision of better than 1% is possible in the determination of Zr with the method reported here.     

A new approach to determine Pm in irradiated fuel solutions

Developments carried out in the Laboratory of Isotopic, Nuclear and Elementary Analyses in order to quantify ¹⁴⁷Pm in spent nuclear fuels analyzed at the CEA within the framework of the Burn Up Credit research program for neutronic code validation are presented here. This determination is essential for safety-criticality studies.The quantity and the nature of the radionuclides in irradiated fuel solutions force us to separate the elements of interest before measuring their isotopic content by mass spectrometry. The main objective of this study is to modify the separation protocol used in our laboratory in order to recover and to measure the ¹⁴⁷Pm at the same time as the other lanthanides and actinides determined by mass spectrometry.A very complete study on synthetic solution (containing or not ¹⁴⁷Pm) was undertaken in order to determine the yield of the various stages of separation carried out before obtaining the isolated Pm fraction from the whole of the elements present in the spent fuel solutions. With the lack of natural tracer to carry out the measurement with the isotope dilution technique, the great number of isotopes in fuel, the originality of this work rests on the use of another present lanthanide in fuel to define the output of separation. The yields were measured at the conclusion of each stage of separation with two others lanthanides in order to show that one of them could be used as a tracer to correct the measurement of the ¹⁴⁷Pm with the separation yield. The total yield (at the conclusion of the two stages of separation) was measured at the same time by ICP-MS and liquid scintillation. This last determination made it possible to validate the use of the ¹⁴⁷Sm (natural) to measure the ¹⁴⁷Pm in ICP-MS since the outputs determined in liquid scintillation and ICP-MS (starting from the radioactive decrease of the source having been used to make the synthetic solution) were equivalent. It is the first time that such measurement is performed in ICP-MS.The measurement of the ¹⁴⁷Pm was finally taken on fuels UOx and MOx by using the ¹⁵³Eu like a tracer of the separation yield. The results obtained are in very good agreement with those obtained from neutronic calculation code.     

Chemical and microstructural characterization of remelted Zircaloy by X-ray fluorescence techniques and metallographic analysis

Brazilian nuclear power reactor (PWR type) use, as nuclear fuel, sintered UO₂ pellets with Zircaloy cladding. The cladding material has to present high mechanical strength and corrosion resistance, which are related to the material chemical composition and microstructural characteristics. Zircaloy machining scraps were remelted using VAR process, resulting in a billet, and its elemental composition was determined. The major elements Zr, Sn, Fe, Cr and Ni were determined by EDXRFS; Hf and contaminants were determined by WDXRFS. The chemical analysis did not show changes in the alloy elemental composition, except for Fe and Cr, which their out-off content can be attributed to contamination from steel scraps. The found Cu contamination may be related to the contact of the melted Zircaloy droplets with copper crucible. The billet microstructure was evaluated using optical and scanning electron microscopy and showed the typical zirconium alloy microstructures (needle and plates) resulting from the high cooling rate and thermal gradients, present during the solidification.     

Mass spectrometry of long-lived radionuclides

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, for quality assurance and determination of the burn-up of fuel material in a nuclear power plant, for reprocessing plants, nuclear material accounting and radioactive waste control. Inorganic mass spectrometry, especially inductively coupled plasma mass spectrometry (ICP-MS) as the most important inorganic mass spectrometric technique today, possesses excellent sensitivity, precision and good accuracy for isotope ratio measurements and practically no restriction with respect to the ionization potential of the element investigated—therefore, thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements of long-lived radionuclides for many decades, is being replaced increasingly by ICP-MS. In the last few years instrumental progress in improving figures of merit for the determination of isotope ratio measurements of long-lived radionuclides in ICP-MS has been achieved by the application of a multiple ion collector device (MC-ICP-MS) and the introduction of the collision cell interface in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing noble gas ions (e.g. of ¹²⁹Xe⁺ for the determination of ¹²⁹I). The review describes the state of the art and the progress of different inorganic mass spectrometric techniques such as ICP-MS, laser ablation ICP-MS vs. TIMS, glow discharge mass spectrometry, secondary ion mass spectrometry, resonance ionization mass spectrometry and accelerator mass spectrometry for the determination of long-lived radionuclides in quite different materials.     

Development of a species-specific isotope dilution GC-ICP-MS method for the determination of thiophene derivates in petroleum products

A species-specific isotope dilution technique for accurate determination of sulfur species in low- and high-boiling petroleum products was developed by coupling capillary gas chromatography with quadrupole ICP-MS (GC-ICP-IDMS). For the isotope dilution step ³⁴S-labeled thiophene, dibenzothiophene, and mixed dibenzothiophene/4-methyldibenzothiophene spike compounds were synthesized on the milligram scale from elemental ³⁴S-enriched sulfur. Thiophene was determined in gasoline, ‘sulfur-free’ gasoline, and naphtha. By analyzing reference material NIST SRM 2296, the accuracy of species-specific GC-ICP-IDMS was demonstrated by an excellent agreement with the certified value. The detection limit is always limited by the background noise of the isotope chromatograms and was determined for thiophene to be 7 pg absolute, which corresponds to 7 ng sulfur/g sample under the experimental conditions used. Dibenzothiophene and 4-methyldibenzothiophene were determined in different high-boiling petroleum products like gas oil, diesel fuel, and heating oil. In this case a large concentration range from about < 0.04 to more than 2,000 μg g⁻¹ was covered for both sulfur species. By parallel GC-ICP-MS and GC-EI-MS experiments (EI-MS electron impact ionization mass spectrometry) the substantial influence of co-eluting hydrocarbons on the ICP-MS sulfur signal was demonstrated, which can significantly affect results obtained by external calibration but not those by the isotope dilution technique.     

Comparison of ICP-MS and SIMS techniques for determining uranium isotope ratios in individual particles

The determination of uranium isotope ratios in individual particles is of great importance for nuclear safeguards. In the present study, an analytical technique by inductively coupled plasma mass spectrometry (ICP-MS) with a desolvation sample introduction system was applied to isotope ratio analysis of individual uranium particles. In ICP-MS analysis of individual uranium particles with diameters ranging from 0.6 to 4.2 μm in a standard reference material (NBL CRM U050), the use of the desolvation system for sample introduction improved the precision of ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope ratios. The performance of ICP-MS with desolvation was compared with that of a conventionally used method, i.e., secondary ion mass spectrometry (SIMS). The analysis of test swipe samples taken at nuclear facilities implied that the performance of ICP-MS with desolvation was superior to that of SIMS in a viewpoint of accuracy, because the problems of agglomeration of uranium particles and molecular ion interferences by other elements could be avoided. These results indicated that ICP-MS with desolvation has an enough ability to become an effective tool for nuclear safeguards.     

Determination of cadmium,mercury and lead in coal fly ash by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

Ultrasonic slurry sampling electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (USS-ETV-ID-ICP-MS) has been applied to the determination of Cd, Hg and Pb in coal fly ash samples. Thioacetamide (TAC) was used as the modifier. Since the sensitivities of the elements studied in coal fly ash slurry and aqueous solution were quite different, isotope dilution method was used for the determination of Cd, Hg and Pb in these coal fly ash samples. The isotope ratios of each element were calculated from the peak areas of each injection peak. This method has been applied to the determination of Cd, Hg and Pb in NIST SRM 1633a coal fly ash reference material and a coal fly ash sample collected from Kaohsiung area. Analysis results of reference sample NIST SRM 1633a coal fly ash agreed satisfactorily with the certified values. The other sample determined by isotope dilution and method of standard additions was agreed satisfactorily. Precision was better than 6% for most of the determinations and accuracy was better than 4% with the USS-ETV-ID-ICP-MS method. Detection limits estimated from standard addition curves were in the range of 24–58, 6–28 and 108–110 ng g⁻¹ for Cd, Hg and Pb, respectively.