Electrochemical and spectroelectrochemical properties of neptunium(VI) ions in nitric acid solution

A benchmark study was carried out to verify whether MCNP is useful in the design stage of a PGNAA facility for large samples up to 1 m length and 0.15 m diameter, using a 2.54 cm diameter thermal neutron beam. For this facility neutron self-shielding and gamma-attenuation correction methods have to be developed. The relative spatial neutron-density distributions within three samples with different macroscopic scattering and absorption cross sections were studied in a comparison between an MCNP simulation and an irradiation experiment using copper wires as neutron monitors. The neutron density in the sample was within statistical agreement between experiment and simulation. Typically the relative spatial neutron-density distributions agreed to within 1%. Therefore, MCNP can be used in design studies for the development of a large sample PGNAA facility as specified. This revised version was published online in July 2006 with corrections to the Cover Date.     

Complete thermal and epithermal neutron self-shielding corrections for NAA using a spreadsheet

An analytical expression has been developed to calculate the neutron self-shielding in a cylindrical sample using the elemental thermal neutron absorption cross sections, σ _abs , and the newly-defined epithermal neutron absorption cross-sections, σ _abs,ep . The σ _abs,ep were measured experimentally for 13 nuclides and calculated from resonance parameters for 76 nuclides. Agreement between the two was good to about 20% in most cases. A spreadsheet program was written to use these nuclear parameters to perform iterative self-shielding corrections of concentrations measured by NAA. In cases with up to 30% self-shielding, the correction factors had uncertainties varying from 2% to 3%.     

Influence of the effective mass on the relative neutron density distribution inside a large sample in prompt-gamma neutron activation analysis

A Monte Carlo study was carried out to determine the influence of the effective scattering mass (M _e) of the atoms on the neutron density profile inside and outside the sample illuminated by a thermal neutron beam as in large-sample prompt-gamma neutron activation analysis (LS-PGNAA). From theory it is known that the spatial neutron density distribution (n(r)) inside a large sample is not the same for atoms with the same macroscopic scattering and absorption cross-section (Σ _s and Σ _a) but different M _e, due to anisotropic scattering at low M _e. The probability of neutron absorption in the sample was found to be the same for materials with equal Σ _s and Σ _a but different M _e, even though the neutron density distribution in the sample was found to change slightly. In view of typical sample, collimator and detector dimensions, it is concluded that M _e does not need to be taken into account in a correction method for neutron self-shielding in LS-PGNAA.     

Neutron self-shielding correction for prompt gamma neutron activation analysis of large samples

Summary Facilities and methods for INAA of large samples (up to 30 kg) have been developed and successfully tested at IRI, Delft. The methods encompass corrections for neutron self shielding in an isotropic neutron field and gamma self-absorption. The sample’s neutron absorption and scattering characteristics are determined by monitoring the neutron fluence rate around the sample and comparing the neutron densities measured with unperturbed fluence rates. We report on the possibility of developing similar methods for PGNAA. Relative self-shielding factors were measured as well as obtained from Monte Carlo computations. The agreement is good except for the most extreme case, with respect to absorption, attempted (CCl₄).     

Large sample neutron activation analysis of a reference inhomogeneous sample

A benchmark experiment was performed for Neutron Activation Analysis (NAA) of a large inhomogeneous sample. The reference sample was developed in-house and consisted of SiO₂ matrix and an Al–Zn alloy “inhomogeneity” body. Monte Carlo simulations were employed to derive appropriate correction factors for neutron self-shielding during irradiation as well as self-attenuation of gamma rays and sample geometry during counting. The large sample neutron activation analysis (LSNAA) results were compared against reference values and the trueness of the technique was evaluated. An agreement within ±10% was observed between LSNAA and reference elemental mass values, for all matrix and inhomogeneity elements except Samarium, provided that the inhomogeneity body was fully simulated. However, in cases that the inhomogeneity was treated as not known, the results showed a reasonable agreement for most matrix elements, while large discrepancies were observed for the inhomogeneity elements. This study provided a quantification of the uncertainties associated with inhomogeneity in large sample analysis and contributed to the identification of the needs for future development of LSNAA facilities for analysis of inhomogeneous samples.     

Improving neutron activation analysis accuracy for the measurement of gold in the characterization of heterogeneous catalysts using a TRIGA reactor

To measure the gold content of a catalyst accurately, neutron activation analysis (NAA) is one of the methods of choice. NAA is preferred for such heterogeneous catalysts because: (1) it requires minimal sample preparation; (2) NAA provides consistent and accurate results; and (3) in most cases results are obtained much quicker than competing methods. NAA is also used as a referee for the other elemental techniques when results do not fall within expected statistical uncertainties. However, at very high gold concentrations, applying NAA to determine the gold in a heterogeneous catalyst is more challenging than a routine NAA procedure. On the one hand, the neutron absorption cross section for gold is very high, resulting in significant self-shielding related errors. On the other hand, gold exhibits low energy resonance neutron absorptions. In this application the self-shielding minimization effort was handled more rigorously than the classic suppression of neutron flux within a specimen. This non-routine approach was used because: (1) for most applications, high accuracy, <3 % relative, is desired, (2) the low energy resonances of gold make its neutron reaction rate complex and (3) the TRIGA reactor flux profile used in this study contains both thermal and significant epithermal neutron fluxes. Accuracy and precision, using this new approach, are expected to improve from 15 % to better than 3 % relative uncertainty. This has been accomplished through a rigorous assessment of the observed effects of low energy resonance on the neutron flux spectral shape within the sample and designing an experiment to minimize the effects.     

Development of a non-invasive method for the determination of the macroscopic neutron cross sections of a sample matrix in large-sample prompt-gamma neutron activation analysis

In order to correct for neutron self-shielding in large-sample prompt gamma NAA, a method has been developed to determine the macroscopic scattering and absorption cross sections, i.e., Σ _a and Σ _s, using four Cu flux monitors placed around the sample. With Monte Carlo computations, the neutron densities throughout the sample and the resulting and the corresponding self-shielding factor as calculated from the Σ _a and Σ _s as obtained through the Cu monitors were compared to the true values. The derived Σ _a and Σ _s were found to be sufficiently accurate as long as Σ _t = Σ _a + Σ _s was less than 0.6 cm⁻¹ and Σ _s/Σ _t was greater than 0.1.     

Validation experiment for large-sample prompt-gamma neutron activation analysis

A method is proposed for the implementation of large-sample prompt-gamma neutron activation analysis (LS-PGNAA). The method was tested with four different sample materials at the thermal PGNAA facility at JAERI, Japan. The macroscopic scattering cross section (Σ _s) and absorption cross section (Σ _a) of the samples were determined by monitoring the neutron flux in four positions just outside the sample container. With the Σ _s and Σ _a determined, the spatial neutron density distribution [n(r)] inside the sample material was derived. Taking n(r) and the gamma-ray self-absorption into account simultaneously, the effective geometric gamma-ray detection efficiency for large samples as a function of gamma-ray energy was calculated. Taking silicon as test element, the concentrations found agreed to within 7% with the known concentrations in the four sample materials examined, both when using relative standardization and with absolute standardization.     

Neutron activation analysis of manganese in Japanese iron reference standard materials, with large amounts of manganese

Effects of pile-up and neutron self-shielding were experimentally corrected in INAA of manganese and vanadium in iron and ferro- and silicon manganese samples supplied by the Japan Iron and Steel Federation. A pile-up correction curve was drawn as a function of total gamma count rate for each Ge detector by a ⁶⁰Co source set at a fixed position and ²⁴Na and ¹³⁷Cs sources moved to vary the gamma-ray intensities. The neutron self-shielding effect was examined by varying the weight of irradiated samples. The effect was negligible for iron samples containing a few percent manganese when samples of less than 0.2 g were irradiated. Good results were obtained for silicon and ferro-manganese by repeated analyses of samples less than 0.02 g in order to avoid the influence of the neutron self-shielding and sample inhomogeneity. A good result can be also obtained from the maximum point of a quadratic equation derived from the relationship between apparent manganese concentrations and sample weight in the range clearly affected by self-shielding. The water dilution after acid dissolution was also effective for samples of high manganese content if special caution was given to regulate the concentration of chloride having a large neutron absorption cross section.     

Towards routine NAA of materials rich in heavy elements with iterative gamma-ray attenuation and neutron self-shielding calculations

Solids and powders can be analysed directly and with good accuracy by neutron activation analysis without sample preparation because of the excellent penetrating powers of neutrons and gamma rays. However, if the sample contains high concentrations of gamma-absorbing heavy elements or neutron-absorbing elements, the analysis results must be corrected for neutron self-shielding and gamma-ray attenuation. These effects are coupled and depend on the chemical composition of the sample, which is the final result of the analysis. Thus, the correction calculation must be iterative. In this work we performed the first coupled iterative corrections of the two effects. Six test samples were prepared by mixing powders containing compounds of Cd, a neutron absorber, and the rare-earth elements Ce, Pr and Nd with concentrations as high as 47 %. The samples were irradiated in the SLOWPOKE research reactor and counted with a germanium gamma-ray detector. In the samples with the highest heavy element concentrations, the uncorrected Neutron activation analysis results were in error by as much as 55 %. The results were corrected iteratively using the neutron self-shielding model coupled with the gamma-ray attenuation model, and the final corrected results were accurate to 5 % or better.     

Implementation of a methodology to analyse cylindrical 5-g sample by neutron activation technique,k 0 method,at CDTN/CNEN,Belo Horizonte,Brazil

Neutron activation analysis (NAA) is routinely applied to geometrical point-source or small samples because there are technical and theoretical difficulties to analyse larger samples weighing more than 0.5 g. The analysis of larger samples is very advantageous, because the analytical procedure will be less time consuming, it may be possible to reach lower detection limit for several elements, it decreases cost and overcomes the difficulties related to the representativeness of the sample when dealing with inhomogeneous volume or several small samples. Thus, increasing the amount of sample is a way to compensate for low flux of neutrons. This paper is about the establishment of a method at Laboratory for Neutron Activation Analysis, CDTN/CNEN, to determine the elemental concentrations in 5 g-samples, 25 times larger than usual samples analysed by neutron activation, k ₀ method, keeping the current irradiation and gamma spectrometry facilities. To develop this method, several aspects were evaluated such as detector efficiency over the volume source, neutron self-shielding during neutron irradiation, axial neutron flux gradient and gamma ray attenuation within the sample during counting. The results suggest that if an appropriate adjustment of the above mentioned parameters is done, the k ₀ method of NAA can provide satisfactory results also for larger samples than the samples typically used in NAA. The KayWin software proved to be a robust program analysing the larger samples weighing 5 g and cylindrical geometry as if it were a small cylindrical sample, producing reliable results. It was successfully implemented at Belo Horizonte, Brazil, fully following the basic principles of the k ₀ standardization method.     

Instrumental neutron absorption activation analysis

We present and discuss a modification of instrumental neutron activation analysis (INAA) that is sensitive for nuclides that do not yield (suitable) activation products but have high cross sections for neutron absorption. Their presence in a sample may thwart INAA by neutron flux suppression inside the sample, but they remain undetected and thus unnoticed by the analyst. In particular, this refers to Li, B, Cd and Gd. The proposed method—instrumental neutron absorption activation analysis (INAAA)—takes advantage of the flux depression inside the sample caused by the neutron absorbers. It is made visible by addition of an activatable nuclide (indicator). The concentration of the neutron absorber (analyte) causes a decrease in activity of the indicator. The activity difference between a mixed sample (sample plus indicator) and the pure indicator carries the analytical information. The calibration curve hence follows a reciprocal exponential function. In a proof-of-principle experiment, the applicability for the quantification of boron was exemplified. In presence of only one neutron absorber (whose nature is known), INAAA can be applied easily for quantification of the analyte in powdered or liquid samples. Although INAAA is no trace sensitive method, it has the potential to increase the reliability of INAA analyses by fast and straightforward quality control (even in presence of two or more neutron absorbing nuclides). It is especially suited for research reactors that do not operate a prompt gamma neutron activation analysis (PGNAA) station.     

Extending NAA to materials with high concentrations of neutron absorbing elements

Summary The recently discovered universal functions for thermal and epithermal neutron self-shielding were adapted to NAA of cylindrical samples, expressing the magnitude as the product of a nuclear factor, a geometrical factor and the amount of the neutron absorbing element. The theory was tested and the nuclear factors were measured for 1 ml samples containing the halogens Cl, Br and I. Tests on samples containing these elements at a priori unknown concentrations, irradiated in a mixed thermal and epithermal neutron spectrum, showed that self-shielding as high as 30% could be corrected with an accuracy of about 1%, except in cases with significant epithermal shielding of one element by another.     

Accounting for flux decrease in neutron activation analysis

The problem of neutron flux decrease during the activation of samples is discussed. Data by different authors on the weight of spherical samples corresponding to a flux decrease of 10% are reported. The self-shielding effect due to the presence of constituents with large absorption cross-sections is discussed.     

Large sample neutron activation analysis: a challenge in cultural heritage studies

Large sample neutron activation analysis compliments and significantly extends the analytical tools available for cultural heritage and authentication studies providing unique applications of non-destructive, multi-element analysis of materials that are too precious to damage for sampling purposes, representative sampling of heterogeneous materials or even analysis of whole objects. In this work, correction factors for neutron self-shielding, gamma-ray attenuation and volume distribution of the activity in large volume samples composed of iron and ceramic material were derived. Moreover, the effect of inhomogeneity on the accuracy of the technique was examined.     

The NAA method at Polytechnique Montreal: an efficient alternative way to use the k 0 NAA models

At Ecole Polytechnique Montreal, the philosophy in performing neutron activation analysis (NAA) is long-term and application oriented. Thinking long-term implies a good understanding of the fundamentals of the method, of the samples, of the tools, reactor and detectors, and there must be constant innovation that is experimentally validated with extensive measurements. Application oriented means a NAA method developed to provide users with fast, sensitive, accurate and reliable analyses for various types of materials. This philosophy dictates the manner in which the developments in the areas of NAA software, peak-area calculation, dead-time correction, detection efficiency model, k ₀ and Q ₀ values, neutron moderation and neutron self-shielding are carried out. This paper presents a survey of the Laboratory’s methodology, reviewing a few of its unique features such as detector efficiency calibration and sample related perturbations of the neutron activation. These features are used as examples to provide the reader with an understanding of the philosophy and the evolution of the NAA method at Ecole Polytechnique.     

Trace-element determinations in very large samples: A new challenge for neutron activation analysis

At the Interfaculty Reactor Institute the development of large sample INAA has been started. A facility is being installed in the reactor's thermal column for irradiation of samples with, sizes up to 100 cm in length, and 15 cm in diameter and weights up to 50 kg. A gamma-ray spectrometer with a very large semiconductor detector and sample scanning options will be used for measurement of the induced radioactivity. Algorithms are being developed to correct for the neutron self-shielding and gamma-ray attenuation problems.     

Enhancement of thermal neutron self-shielding in materials surrounded by reflectors

Materials containing from 41 to 1124?mg chlorine and surrounded by polyethylene containers of various thicknesses, from 0.01 to 5.6?mm, were irradiated in a research reactor neutron spectrum and the ³⁸Cl activity produced was measured as a function of polyethylene reflector thickness. For the material containing the higher amount of chlorine, the ³⁸Cl specific activity decreased with increasing reflector thickness, indicating increased neutron self-shielding. It was found that the amount of neutron self-shielding increased by as much as 52% with increasing reflector thickness. This is explained by neutrons which have exited the material subsequently reflecting back into it and thus increasing the total mean path length in the material. All physical and empirical models currently used to predict neutron self-shielding have ignored this effect and need to be modified. A method is given for measuring the adjustable parameter of a self-shielding model for a particular sample size and combination of neutron reflectors.     

Neutron self-shielding in hydrogenous samples

Measurements performed in the past to determine sensitivity enhancements (later identified as neutron density increases) in PGNAA as a function of hydrogen concentration in slab-shaped samples are described. The results are compared to the results of Monte Carlo computations. It is concluded that, like H₂O, D₂O can also cause substantial neutron density increases. In one concentrated salt solution, however, D₂O seems to cause a neutron density decrease that cannot be explained from the macroscopic neutron scattering and absorption cross sections in the model used.     

Determination of iodine in diverse botanical and dietary matrices by pre-irradiation combustion followed by neutron activation analysis

Summary The method chosen for determination of iodine in this investigation is an extension of an existing analytical technique to food samples which was developed for environmental samples. The method is based on pre-irradiation combustion of the sample to liberate iodine, trapping the iodine on charcoal, and quantitating the element by neutron activation analysis (NAA). Existing botanical and dietary reference materials were used to check the validity of the method. Several mixed diet samples with high fat content from the U.S. Total Diet Study and composites of cereals with both low and high iodine content were analyzed. This method of pre-irradiation combustion followed by NAA has been shown to be a viable technique for the determination of iodine in dietary samples. However, with a detection limit of about 50 ng of iodine, large amounts of sample (>1 g) are typically required for each determination.