INAA of Zr,La, Ce and Nd in geological samples in the presence of different uranium concentratios

Rock samples which contain relatively high concentrations of uranium may create problems of interference produced by fission products, when instrumental neutron activation analysis is used. The isotopes⁹⁵Zr,¹⁴⁰La,¹⁴¹Ce, 143Ce and 147Nd, which are commonly used in the neutron activation analysis of the corresponding elements, are also produced as fission products of²³⁵U. For each of these radioisotopes, a contribution factor is calculated theoretically and meaured experimentally using geological samples with different uranium contents.     

Determination of uranium fission interference factors for INAA

Instrumental neutron activation analysis (INAA) is a very suitable technique for the determination of several elements in different kinds of matrices. However, when the sample contains high uranium concentration this method presents interference problems of uranium fission products. The same radioisotopes used in INAA are formed in uranium fission. Among these radioisotopes are ¹⁴¹Ce, ¹⁴³Ce, ¹⁴⁰La, ⁹⁹Mo, ¹⁴⁷Nd, ¹⁵³Sm and ⁹⁵Zr. The purpose of this study was to evaluate uranium fission interference factors to be used in the INAA of environmental and geological samples containing high levels of U. The obtained interference factors agreed with literature reported values. The results point to the viability of using these experimentally determined interference factors for the correction of uranium fission products.     

Feasibility of using dendroanalysis of uranium as a biomarker for environmental contamination

A study was initiated to investigate the chronological deposition of uranium in certain species of trees growing on the site of a former uranium metal processing facility. The Feed Materials Production Center (FMPC) is located in Fernald, Ohio, and for roughly 40 years operated as a large scale uranium processing center. Core samples from several species of trees growing in different locations throughout the site were extracted using a 12.5 mm incremental wood boring drill bit. After extraction, each core sample was cut and packaged into individual sections representing 4 annual growth rings and submitted for instrumental neutron activation analysis (INAA). The reaction ²³⁵U(n,f)¹⁴⁰Ba→¹⁴⁰La+γ was evaluated using high resolution germanium gamma-spectroscopy to detect the 1.596 MeV photon emission from the fission product ¹⁴⁰La following a minimum of a 3 week decay. A total of 106 samples representing 7 individual trees of 3 unique species were irradiated. In addition to the tree-core samples, 18 quality control (QC) samples and 18 standard reference material (SRM) Fly Ash samples were irradiated with the core samples for determining neutron flux. The activity in any one sample in a batch was determined by comparison with the amount of natural uranium in the QC standards. No significantly measurable amount of uranium was detected in any of the tree core samples, although 3 tree core samples were in excess of the minimum detectable amount (30 ng).     

Search for uranium in high purity silicon

Detection of small quantities of uranium in silicon wafers has been carried out by neutron activation followed by observation of fission product¹⁴⁰La. Irradiations of about one week were made at a flux of 6·10¹⁴n cm⁻² s⁻¹ and the activity of the 1596 keV line was determined. Counting rates of as low as 1 count per minute have been observed. This indicates uranium concentrations of about 5·10¹⁰ atoms per cubic centimeter of silicon or about 0.01 mg/g, assuming activity from other fissionable nuclides to be negligible.     

Multielement analysis of uraniferous rocks by INAA: Special reference to interferences due to uranium and fission of uranium

The presence of uranium in a sample enhances the true values of La, Ce, Nd, Sm determined by INAA if appropriate corrections are not made for the interference. The enhancement of the true values comes about because the (n, γ) activation products of these elements, viz.¹⁴⁰La,¹⁴¹Ce,¹⁴⁷Nd,¹⁵³Sm, are also produced from the fission of²³⁵U (～0.72% natural isotopic abundance) even when La, Ce, Nd, Sm are totally absent in the given sample. In a 5 hour irradiation 1 μg of U is found to be equal to 0.28 μg of Ce and 0.23 μg of Nd while the equivalent La is found to be dependent upon the delay from end of irradiation to sample counting time. A numerical procedure is given to correct for these interferences. Spectral interferences from fission and (n, γ) β products of uranium in the determination of other trace elements by INAA is also investigated. Uranium is found to be determined best using the 278 keV gamma-ray of²³⁹Np.     

Neutron activation analysis of pure uranium: Preconcentration of impurity elements

We have developed a radiochemical neutron activation analysis technique (RNAA) of pure uranium with using extraction chromatographic separation of ²³⁹Np from impurity elements in TBP-6M HNO₃ media. The estimation of influence of fission products of ²³⁵U on the results by radiochemical neutron activation analysis has been carried out. For it we have performed NAA with preconcentration of impurity elements. Experiments show that in this case the apparent concentration of Y, Zr, Mo, Cs, La, Ce, Pr, Nd exceeds the true concentration by 2500–3000 times. Therefore, determination of these elements is not possible by RNAA. This technique allowed to use the determination of 26 impurity elements with detection limit 10⁻⁵–10⁻⁹% by mass. This developed technique may be used for the determination of impurities in uranium and its compounds.     

Fission product yields in the fast-neutron fission of238U

The fission yields of 38 fission products in the fast-neutron induced fission of²³⁸U have been determined using a rapid, multiscaling gamma-ray spectroscopic method. To obtain absolute yields for fission products having half-lives ranging from 32 s to 40 d, a total of 56 multi-scaling gamma-ray spectra were collected using various irradiation and cooling periods. Gamma-rays and photopeak areas of interest were assigned to the fission products by their energies and half-lives. Fission product activities were evaluated from spectral data using growth and decay calculations and fission yields were determined by normalizing the¹⁴⁰Ba yield to the average value from reported data. The depleted uranium target, covered with a boron-cadmium thermal neutron shield, was used to keep interference from the fission of²³⁵U minimal. Results for the cumulative fission yields, including 17 mostly short-lived fission products measured for the first time, are compared with previous measurements and with the recommended yields in recent evaluations. The agreement, and some discrepancies, in the comparisons are discussed. No explicit even-odd pairing effects are observed in the fission yield data for fast-neutron induced fission of²³⁸U.     

Intereferences from uranium fission in neutron-activation analysis in an Argonaut-type Low Flux Reactor

The interferences by uranium fission on the determination by neutron activation analysis of Zr, Mo, Ru, La, Ce, Nd and Sm are investigated for the Argonaut-type Low Flux Reactor at ECN, Petten, The Netherlands. In addition, the spectral interference of the determination of Sm by²³⁹Np is considered. The experimental values for fission yields are found to be in good agreement with calculated values based on recent cross-section compilations.     

Neutron activation analysis of rare earth impurities in metallic uranium

A method with a sensitivity of 2·10⁻⁷ to 1·10⁻¹⁰% has been developed for determining Yb, Ho, Dy, Gd, Eu, Sm and La impurities in metallic uranium by means of neutron activation. The method is based on a preliminary chromatographic separation of the total amount of rare earth elements from uranium by passing the solution in sulphuric acid through KU-2 cation exchange resin and eluting the traces of uranium retained by the resin with a solution of ascorbic acid. The rare earth impurities are then eluted from the resin with 4–5N HCl, evaporated, and irradiated for 20 hours with a neutron flux of 1.2·10¹³ n·cm⁻²·sec⁻¹. Subsequently the traces of the rare earth elements are co-precipitated with Fe(OH)₃, dissolved in concentrated HCl and separated from the iron and other impurities by passing the solution through Dowex 1X8 anion exchange resin in the chloride form. The individual rare earth elements are then separated from each other using KU-2 cation exchange resin and a solution of ammonium α-hydroxyisobutyrate as the eluant.     

Determination of235U abundance in uranium by neutron activation on the basis of the molybdenum fission interference

The purpose of the present paper is to suggest a method for determining the²³⁵U abundance in uranium samples (compounds, metallic alloys or other uranium materials, where this element may be natural or not) through a particular application of neutron activation analysis, based on the fission interference by molybdenum. The method lies on an a priori calibration with natural uranium, thus it does not require²³⁵U certified standards.     

On-stream nuclear activation of trace uranium and thorium using a 14 MeV neutron generator

A method for the continuous on-stream determination of trace concentrations of uranium and thorium in flowing streams is developed. The 14 MeV neutron generator was used for irradiation and the delayed neutron counting technique was employed in counting the induced neutron activity. The dependence of the minimum detectable concentration on the irradiation, decay and counting times, liquid flow-rate and the background was studied. At optimal conditions, uranium and thorium concentrations were determined down to 20 and 100 ppm, respectively. The interference of the neutron emitting nuclide^17m O was reduced to an insignificant level by optimizing the decay time.     

Evaluation of methods for the assay of neptunium and other long-lived actinides in environmental matrices

Inductively coupled plasma mass spectrometry (ICP-MS) and neutron activation analysis (NAA) have been investigated as alternatives to alpha-spectrometry for the low-level determination of²³⁷Np and other actinides in environmental matrices. ICP-MS in particular, has been shown here to offer suitable sensitivity, precision and accuracy compared to the other techniques, with considerably faster sample throughput relative to radiometric and activation approaches. Added advantages of ICP-MS are found to include the abilities to determine other long-lived actinides simultaneously and to quantify²³⁹Pu:²⁴⁰Pu ratios. The neutron activation analysis approach was found to be particularly prone to interference especially from uranium nuclides.     

Solvent extraction studies using tetracycline as complexing agent

The behaviour of tetracycline as an extracting agent for strontium, iodine, barium, molybdenum, technetium, zirconium, niobium, cesium, ruthenium, tellurium and uranium has been studied and the influence of the acidity of the aqueous phase upon extraction of the elements mentioned has been examined. Experiments have been made to determine whether or not the species extracted into the organic phase is the complex formed between tetracycline and the elements considered as well as to determine the time of shaking necessary so that the equilibrium between the phases is attained. As a practical application, the possibility of using the tetracycline-benzyl alcohol system for separating the fission products¹³⁷Cs,¹⁴⁰Ba,¹⁴⁰La,¹⁴¹Ce,¹⁰³Ru,⁹⁵Zr and⁹⁵Nb from each other and from uranium is presented. The same study has been made for¹³¹I,^99mTc,⁹⁹Mo,¹³²Te,²³⁹Np and uranium and the steps necessary for the separation of these elements are proposed.From a thesis submitted by I. I. L. CUNHA to the Instituto de Pesquisas Energéticas e Nucleares-University of São Paulo in partial fulfillment of the requirements for a Doctor of Science's Degree. Work supported by Comissão Nacional de Energia Nuclear.     

Determination of rare-earth eleemnts in rock samples by neutron activation analysis

A Ge(Li) detector combined with cation exchange separation has been used for the determination of 12 rare-earth elements (La, Ce, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, and Lu) in rock samples by neutron activation analysis. After purification by the conventional hydroxide-fluoride precipitation, the rare-earth elements are separated into two fractions, light (La-Tb) and heavy (Ho-Lu), by EDTA cation exchange, and the γ-activities of the two fractions are measured by a Ge(Li) detector. The heavy rare-earths, such as Ho, Er, and Tm, can be easily γ-counted without serious interference from the intense Compton background and photopeaks due to the light rare-earths such as¹⁴⁰La,¹⁵³Sm,¹⁵²Eu, and¹⁶⁰Tb. The chemical yields (60%) for the individual rare-earths are determined by a reactivation technique. The results obtained for the U.S. Geological Survey standard rocks G-1 and W-1 are compared with the previously reported data.     

Neutron activation analysis of uranium in human bone,drinking water and daily diet

Uranium in human bone, drinking water and daily diet has been determined by neutron activation analysis using the²³⁸U(n, γ)²³⁹U reaction. An improved scheme for the separation of the²³⁹U is proposed; with this scheme, after neutron irradiation in a 100 kW TRIGA reactor, a uranium content as low as 5·10⁻¹¹ g can be determined reliably, rapidly and easily. A wide range of uranium concentrations, from about 0.1 ppb up to about 10 ppb has been found in the bones of normal Japanese. Water from several Japanese city water services, and the daily diet taken in two Japanese cities, have been found to contain an average 9·10⁻⁹ g/l and 1.5 μg per person-day uranium, respectively.     

Determination of hafnium and zirconium in geological materials by neutron activation analysis

In this work, neutron activation analysis was applied to analyze the geological standard materials: GSP-1 and W-1 from USGS, GB-1 and BB-1 from the University of Bahia, Brazil and a sample of uraniferous rock. Hf was determined by instrumental method and the obtained results was shown with relative standard deviations varying from 1.1 to 14%. In the case of Zr analyses, both instrumental and radiochemical neutron activation analyses were used. The interference of¹⁵⁴Eu radioisotope that emits -rays too close to those emitted by⁹⁵Zr was eliminated by retention of Zr in an anionic exchange resin column. The contribution of uranium fission product was considered in the Zr determination by using an interference factor. Results of Zr were presented with relative standard deviations varying from 2.0 to 25.7%. More precise results were obtained by using radiochemical separation. The concentration obtained for Hf and Zr in reference materials agreed well with respective certified values or information values.     

Adsorption of fission products on a metal surface in nitric acid solutions: Radiochemical study using a multitracer

Adsorption behavior of fission products in nitric acid solution on various alloys and metals was studied by using a multitracer produced by neutron irradiation of UO₂. The adsorption behavior of the fission products ⁹⁹Mo, ¹³¹I, ¹³²Te, ¹⁴⁰La, and ¹⁴³Ce, and ²³⁹Np was simultaneously studied. Some chemical decontamination tests were also examined. Clear adsorption of ⁹⁹Mo, ¹³¹I, and ¹³²Te was observed, whereas adsorption of ¹⁴⁰La, ¹⁴³Ce, and ²³⁹Np was not. The adsorption characteristics were discussed by considering anion-exchange reaction and surface complexation.     

Neutron activation analysis for ultra low contents of uranium and thorium in aluminium and silica

Highly sensitive neutron activation analysis of uranium and thorium in high quality silica and aluminium has been investigated using the Japan Materials Testing Reactor (JMTR), having a thermal neutron flux higher than 10¹⁴ n/cm²/s. In order to determine ultra-low contents of uranium and thorium,²³⁹Np and²³³Pa as activation products were separated by using anion exchange and LaF₃ coprecipitation methods. As a result, a number of interfering radioactive isotopes containing double neutron capture product such as¹⁸³Ta were removed completely from the isolated²³⁹Np and²³³Pa fraction and the detection limits for uranium and thorium were found to be 2·10^–12 g and 4·10^–13 g, respectively.     

Elemental analysis in bed sediment samples of Karnafuli estuarine zone in the Bay of Bengal by instrumental neutron activation analysis

The concentration of rare earths and other elements have been determined in the bed sediment samples of Karnafuli estuarine zone in the Bay of Bengal by instrumental neutron activation analysis (INAA). The samples and the standards soil-5, soil-7, coal fly ash and pond sediment were prepared and simultaneously irradiated for short and long time at the TRIGA Mark-II research reactor facility of Atomic Energy Research Establishment, Savar, Dhaka. The maximum themal neutron flux was of the order of 10¹³ n·cm^–2·s^–1. After irradiation the radioactivity of the product nuclides was measured by using a high resolution high purity germanium detector system. Analysis of -ray spectra and quantitative analysis of the elemental concentration were done via the software GANAAS, it has been possible to determine the concentration level of 27 elements including the rare earths La, Ce, Sm, Eu, Tb, Dy and Yb and uranium and thorium.     

U determination in environmental samples by delayed neutron activation analysis in Korea

A delayed neutron counting system has been implemented at the HANARO research reactor in 2007. Thermal neutron flux measured at the NAA #2 irradiation hole coupled to the delayed counting system, was higher than 3 × 10¹³ n cm⁻² s⁻¹. The delayed neutron counting system is composed of 18 ³He detectors which are divided into three groups with six detectors and the collected signals of each group are processed to a digital signal. The count numbers were measured with the uranium mass by using NIST SRMs under fixed analytical condition and their correlation could be determined. Finally, delayed neutron activation analysis has been carried out for the determination of uranium mass fraction in the collected environmental samples.