Bronze analysis by k0-NAA and PIXE

Five copper alloys were prepared with modern powder metallurgical processes in the frame of the European project Improvement of Means of Measurement on Archaeological Copper-Alloys for Characterisation and Conservation (IMMACO) and certified for As, Pb, Sn and Zn mass fractions. Similar in their composition to archaeological bronze alloys, these Certified Reference Materials (CRMs) are to be used for calibration of XRF instruments for characterization of archaeological samples either in the laboratory or in the field. This paper presents and compares the successful contribution of our non-destructive analytical methods (k ₀-NAA and PIXE) to the IMMACO project and to the certification of the five reference materials.     

Uncertainty Budget for k0-NAA

The concepts of the Guide to the expression of Uncertainties in Measurements for chemical measurements (GUM) and the recommendations of the Eurachem document "Quantifying Uncertainty in Analytical Methods" are applied to set up the uncertainty budget for k ₀-NAA. The "universally applicable spreadsheet technique", described by Kragten, is applied to the k ₀-NAA basic equations for the computation of uncertainties. The variance components — individual standard uncertainties — highlight the contribution and the importance of the different parameters to be taken into account.     

A Web tool for calculating k0-NAA uncertainties

The calculation of uncertainty budgets is becoming a standard step in reporting analytical results. This gives rise to the need for simple, easily accessed tools to calculate uncertainty budgets. An example of such a tool is the Excel spreadsheet approach of Robouch et al. Here, we present an internet application which calculates uncertainty budgets for k ₀-NAA. The Web application has built in Literature values for standard isotopes and accepts as inputs fixed information such as the thermal to epithermal neutron flux ratio, as well as experiment specific data such as the mass of the sample. The application calculates and displays intermediate uncertainties as well as the final combined uncertainty of the element concentration in the sample. The interface only requires access to a standard browser and is thus easily accessible to researchers and laboratories. This may facilitate and standardize the calculation of k ₀-NAA uncertainty budgets.     

Quality assessment in a Brazilian laboratory performing k0-NAA

This work is focused at the demonstration of the overall adequacy of the procedures introduced in a Brazilian laboratory for conducting the k ₀-standardized NAA. Concentrations of 29 elements determined in certified reference materials of plants and geological matrices are evaluated. Most of the experimentally determined values agreed well with the reference data and no consistent bias could be attributed to the analytical system adopted.     

The robustness of k 0-NAA in large multi-purpose research reactors

The challenges and opportunities associated with performing k ₀-NAA in high-powered, multi-purpose research reactors are examined and recommendations are made concerning the conditions that need to be met in such facilities in order to allow the potential for this method of elemental analysis to be fully realised.     

k0-NAA, a valuable tool for reference-material producers

The main concern of producers of certified reference materials (CRM) is the preparation of high-quality products with demonstrated homogeneity and stability, combined with a well established set of certified characteristics. CRM producers must, furthermore, comply with other constraints imposed by the ISO Guide 34: ·*production processes, production control, and certification analyses should be performed by expert laboratories, using validated protocols documented in their respective quality assurance manuals; ·*laboratory mean values and the corresponding “expanded” uncertainties, must be used for the determination of the certified values, as recommended by the ISO Guide to the Expression of Uncertainties in Measurements (GUM); and ·*when possible, traceability of the certified value to the SI units, using appropriately validated and/or primary methods, must be ensured. k₀-NAA, i.e. neutron activation analysis with k₀ standardization, is one of the analytical techniques implemented at the Reference Material Unit of IRMM; it meets the first two requirements.     

k 0-NAA for determination of REE in reference materials of ore sources

Journal of Radioanalytical and Nuclear Chemistry - Multielements, including some rare earth elements, have been determined by k 0-NAA in three types of ore reference materials from Australia...     

The impact of polyethylene vials on reactor channel characterization in k 0 -NAA

Reactor channel characterization is commonly performed by irradiating bare and cadmium-covered “fluence rate monitors”, avoiding as much as possible the use of irradiation vials and spacers to position the monitors inside the channel. However, in routine k ₀ -Neutron Activation Analysis often samples are packed in small polyethylene vials prior to irradiation. This work aims at studying the impact of typical NAA polyethylene vials (~1 mm wall thickness) on the determination of the f and α channel-specific parameters through the “Bare”, “Cadmium-Covered” and “Cadmium-Ratio” methods. The impact of these vials on each method was studied for 3 irradiation channels of the Belgian Reactor 1 at SCK·CEN (Mol, Belgium) with low to high f and α-values. The net impact was 1% on each parameter. Inconsistencies between the different methods were found when the impact of the polyethylene was neglected, implying that all determination methods must be pooled and thin monitors should be used for an accurate channel characterization.     

k0-NAA, a valuable tool for reference-material producers.

The main concern of producers of certified reference materials (CRM) is the preparation of high-quality products with demonstrated homogeneity and stability, combined with a well established set of certified characteristics. CRM producers must, furthermore, comply with other constraints imposed by the ISO Guide 34: production processes, production control, and certification analyses should be performed by expert laboratories, using validated protocols documented in their respective quality assurance manuals; laboratory mean values and the corresponding "expanded" uncertainties, must be used for the determination of the certified values, as recommended by the ISO Guide to the Expression of Uncertainties in Measurements (GUM); and when possible, traceability of the certified value to the SI units, using appropriately validated and/or primary methods, must be ensured. k0-NAA, i.e. neutron activation analysis with k0 standardization, is one of the analytical techniques implemented at the Reference Material Unit of IRMM; it meets the first two requirements.     

Determination of major and trace elements in iron reference materials using k0-NAA

Major and trace element contents in iron ore reference materials were investigated using k ₀-instrumental neutron activation analysis (k ₀-INAA). To avoid iron interferences, radiochemical separation was developed (k ₀-RNAA). The determination of the investigated elements in the inorganic phase from hydrochloric acid solution was performed after radiochemical separation of iron by diisopropyl ether. It was found that after the Fe elimination, the limit of detection for some elements was much lower that enables their direct determination. The distribution of 39 elements (with intermediate/medium and long half-life radionuclides) after Fe removal was investigated.     

Determination and evaluation of fission k0-factors for correctionof the 235U(n,f) interference in k0-NAA

In order to provide a tailored solution for the correction of the ²³⁵U interference in k₀-NAA, fission k₀-factors for the analytically relevant radionuclides/gamma-lines (versus gold as the comparator), are experimentally determined in four channels of the Gent THETIS reactor. A comparison is made with former data from the literature. The new evaluated results are to be implemented in the forthcoming upgrade of the DSMKayzero software package for k₀-NAA.     

k0-NAA quality assessment by analysis of different certified reference materials using the KAYZERO/SOLCOI software

A suite of natural matrix reference materials (RMs) were used to assess the quality of analytical results obtained by k ₀-instrumental neutron activation analysis (k ₀-INAA) at the Joef Stefan Institute (IJS). Five certified reference materials (CRMs) from the Institute for Reference Materials and Measurements (IRMM), two standard reference materials (SRMs) from the National Institute of Standards and Technology (NIST), three RMs from the International Atomic Energy Agency (IAEA) and one RM from IJS were analyzed. Altogether, results for twenty-four elements in inorganic matrices and twenty-nine elements in organic matrices, obtained by k ₀-INAA, were compared to certified values. Results obtained show good agreement with certified or assigned values except for Fe, La, Nd, Sm and U in inorganic matrices, and Ag, Al and Cr in organic matrices.     

Comparison of 14 MeV-NAA, k0-NAA and ED-XRF for air pollution bio-monitoring

In this paper the performances and the limitations of three multi-elementary analysis techniques are compared applied to a study of air pollution biomonitoring in Morocco. These techniques are: (1) 14 MeV neutron activation analysis (14 MeV-NAA), (2) thermal neutron activation analysis using the k ₀ quasi-absolute method (k ₀-NAA) and (3) energy dispersive X-ray fluorescence analysis (ED-XRF). The experimental procedures and the control of the analytical results using certified reference materials are described and discussed. The three methods were confronted for the analysis of lichens, mosses and tree-barks. The complementarity of these methods enabled us to determine 43 elements in different samples. The most suitable method for each element was selected according to the sensitivity and selectivity necessitating the minimum corrections of the matrix effects and/or the interfering reactions.     

Determination of 135Cs in nuclear power plant wastes by ICP-MS and k 0-NAA

A radiochemical method for the determination of ¹³⁵Cs in radioactive wastes has been adopted/developed. For the separation of cesium from other elements ammonium-molybdophosphate precipitation and cation exchange chromatography were used. The chemical yield of the method was about 60–100 %. ¹³⁵Cs was measured by two methods. In neutron activation analysis (NAA), Cs was irradiated with reactor neutrons. ¹³⁶Cs was detected by gamma spectrometry, wherefrom the activity/mass of ¹³⁵Cs was calculated according to the k ₀-standardization technique. The Cs containing fractions were measured by inductive coupled plasma mass spectrometry, as well. NAA and ICP-MS techniques were comparatively evaluated and a good agreement between the results was found. The activity concentration of ¹³⁵Cs in a couple of waste samples originating from VVER-440 type nuclear reactors was in the range of 1–5 Bq L^?1 (20–120 ng L^?1) while ¹³⁷Cs activity concentrations varied between 0.1 and 1 MBq L^?1.     

Determination of α and f for k0-NAA in irradiation sites with high thermalized neutrons

We have measured the ⁵⁷Fe Mössbauer spectra of the Hofmann pyridine complex Fe(pyridine)₂Ni(CN)₄ sample before and after exposure to high pressure of gaseous xenon. The temperature dependence of the high spin molar fraction has been determined from the ⁵⁷Fe Mössbauer spectra. The spin transition of the sample without the high pressure treatment occurs between 175 and 220 K with a hysteresis width of 15 K. Although the ⁵⁷Fe Mössbauer spectra suggest that the spin crossover behavior of the sample before and after the high pressure treatment are almost the same, the hysteresis of the latter sample is somewhat larger.     

A simplified method to replace the Westcott formalism in k 0-NAA using non-1/v nuclides

The Westcott formalism was developed to accurately describe the activation of nuclides whose neutron capture cross-sections do not follow the 1/v-law and it was incorporated in the k ₀-method about 20 years ago. However, its implementation in the original fashion is not easy, requiring the use of a different formalism for the non-1/v nuclides, with a g(T _n) factor for the thermal neutron activation and an s ₀ factor for epithermal activation, the measurement of the neutron spectral index of the irradiation channel and the irradiation of a temperature monitor with each batch of samples as well. In this work we investigated the accuracy of maintaining the simpler formula of the Høgdahl convention for all nuclides and introducing the g(T _n) factor for the thermal neutron activation for non-1/v nuclides. The epithermal activation is calculated using a Q ₀-value estimated from the measured s ₀-value for non-1/v nuclides. This new approach has been shown, by calculations with the parameters of the neutron spectra of five irradiation channels, not to give a significant loss of accuracy relative to the Westcott formalism.     

Thirty years of k 0-NAA at JSI,Ljubljana: implementation,progress, achievements

Journal of Radioanalytical and Nuclear Chemistry - A survey is given of the installation, applications and main achievements of the k 0 method of neutron activation analysis as implemented at the...     

The role of k0-NAA in the assessment of the annual radiation dose for use in TL/OSL dating of sediments

An account is given of the role and the strength of k ₀-INAA to assess the annual radiation dose (contribution of U, Th, K and Rb) for use in TL/OSL dating of sediments. Mention is made of: (1) its simplicity of sample preparation, (2) its accuracy and even its reference character for other elemental determination methods, (3) the possibility of obtaining the Rb content with no extra effort and (4) its capability to easily and reliably quantify U and Th in a small amount of etched quartz grains, followed by evaluating the importance of their presence in the quartz inclusion technique.     

Establishment of the k 0, \bar{E}_{\rm r}, Q 0, and cascade coincidence correction factors for the determination of 129I by k 0-NAA

A k ₀-NAA procedure used in the determination of ¹²⁹I is established. For this purpose, the k ₀-values for the reaction ¹²⁹I (n, ??) ¹³⁰I are determined, the Q ₀- and $\bar{E}_{\rm r}$ -values are calculated, and the correction procedure for the cascade coincidence effects is established by calculation of the correction factor COI for five ¹³⁰I ??-rays (418.0, 536.1, 668.5, 739.5, and 1157.5 keV).     

The preparation and homogeneity study of synthetic multi-element standards (SMELS) for QC/QA of k0-NAA

Three new synthetic multi-element standards (SMELS) were developed for testing the performance of the k ₀-standardization neutron activation analysis (k ₀-NAA) method when implemented in a laboratory. SMELS consist of a phenol-formaldehyde polymer matrix spiked with different groups of elements according to the half-lives of the formed radionuclides. They are classified as Type I for short-, Type II for medium- and Type III for long-lived radionuclides. This article presents the preparation of SMELS including different aspects such as choice of the matrix and spiking elements, chemical compounds, target concentrations, purity of the matrix and spiking procedure and the homogeneity study for all the spiked elements in order to demonstrate the quality of the produced materials.