Instrumental neutron activation analysis of samples with volumes from 2 to 350 ml

Usually neutron activation analyses are performed in point-source geometry. However, specially designed irradiation positions and carefully planned measuring conditions enabled the activation and analysis of samples with weights up to several tens of kilograms. A dedicated character of irradiation and of measuring conditions was the main reason for a very limited application of such activation analysis. The use of routine irradiation facilities and standard conditions for analytical gamma-spectrometric measurements is described. Starting with samples of some hundred milligrams usually used in activation, through multi-gram samples to several hundred gram samples, irradiation and measuring conditions were studied and tested for development of the method. This work began in 1991 in Denmark, using the Danish DR-3 reactor. Since then different aspects of the method have been investigated on 6 reactors; in Denmark on DR-3, in Austria on Triga-MkII (in Vienna), and Astra (in Seibersdorf), in the German Federal Republic on FRG-1 in Geesthacht, in Norway on Jeep II (in Kjeller), and in Kazakhstan on VVR-K (in Alatau). Altogether more than 1000 samples have been irradiated and measured. In total, the roughly 30 kg of irradiated materials included almost 300 large samples of more than 30 gram weight. The following theoretical and practical aspects were investigated during the work: theoretical problems concerning neutron self-absorption in common organic and inorganic materials, as well as gamma-attenuation during the measurement. From a more practical point of view: health physics and radiation hazards during irradiation, measurement, transportation and storage of samples with several hundred grams weight. Special requirements to irradiation containers were formulated and various containers were tested. Main advantages and drawbacks of the method are discussed.     

High-Flux Irradiation of Open Samples

The irradiation of large samples of biological material in a high neutron flux enables the extention of trace element analysis into the ng to pg range, but raises several problems as gamma heating and radiolysis degrade the samples. Gamma heating increases the pressure to a point where either a very large irradiation container is necessary or a container which can endure the high pressure. Several methods to overcome these problems have been published. The irradiation of open samples was performed as an alternative to these methods. Temperature effects on biological material during irradiation in a high and in a low neutron flux were compared. As an example, wheat was irradiated in open containers allowing simultaneous temperature measurement in the sample during irradiation.     

An accurate and sensitive analysis of trace and ultratrace metallic impurities in plastics by NAA

Neutron activation analysis (NAA) has been studied to improve the accuracy and sensitivity of the analysis of trace and ultratrace metallic impurities in plastic materials. There are two main problems in the analysis of plastics by NAA. First the contamination during sample preparation, especially sample crushing procedure is very serious for ultratrace analysis. Another problem is the destruction of the sample capsule due to the pressure build-up by the gases formed during neutron irradiation. A simple preparation technique of the sample crushing method using liquid nitrogen and reducing the capsule pressure by a pin hole was developed to solve the above problems. Two different irradiation and seven cooling conditions were also investigated to optimize the experimental conditions. A SRM from NIST (1632b coal) has been used to investigate the accuracy of the analysis. More than thirty elements could be analyzed in the range of sub-ppb to percent. Samples analyzed in this work were polyethylene and polypropylene which were made by different manufacturing procedure, and pigments. Two kinds of plastic products used for food and drug containers were also analyzed. It was found that NAA could be a powerful technique for the analysis of metallic impurities in plastics even though their concentrations were at ultratrace levels.     

Instrumental neutron activation analysis of samples with masses from micrograms to hectograms

The rotating rig at the Danish DR-3 reactor was used for irradiation of samples with masses from a hundred micrograms to several hundred grams. The pneumatic post for uranium delayed neutron counting was used for automatic sequential irradiation of samples subdivided into up to 24 aliquots, each with a volume of 7 cm³. The cumulative samples were measured in polyethylene irradiation containers in a specially designed radial holder.     

Low-cost activation analysis at small research reactors

A software implementation of a loss-free counting multichannel analyzer, storing immediately into the multimegabyte memory of a low-cost 486 or Pentium type PC, enables the real-time control of a rabbit system as well as the collection of up to 1000 pairs of simultaneously recorded loss-corrected and non-corrected spectra of 16 k channels each, in a true sequence without time gaps in between, at throughput rates of up to 200 kc/s.¹ Intended for activation analysis of short-lived isomeric transitions, the system renders possible peak to background optimizations and separations of lines with different half-lives without an a priori knowledge of sample composition by summing up appropriate numbers of spectra over appropriate intervals of time. By automatically adapting the noise filtering time to individual pulse intervals, the Preloaded Digital Filter (PLDF) combines low- to medium-rate resolutions comparable to those of high-quality Gaussian amplifiers with throughput rates of up to 100 kc/s, and high-rate resolutions superior to those of state-of-the-art gated integrator systems. In contrast to commercially available digital filters, the PLDF in its new implementation performs pulse shortening as well as pole zero cancellation in the analog domain. This not only results in a simpler digital core but also, for the first time, makes possible the use of a low-cost ADC in a spectrometric application.² A simple but highly effective rabbit system is made from an aluminum incore part, inexpensive plastic tubing and an industrial pressurized air generator. Large sample containers have a volume of 25 cm³. Smaller containers of 5 cm³ are automatically separated from a transport capsule. A transport time of below 0.5 s enables activation analysis of short-lived isomeric transitions. The combination of rabbit system, PLDF and software based multichannel analyzer provides a low-cost but powerful solution for NAA at Triga reactors in developing countries, a forthcoming research project of the IAEA, Vienna.     

Determination of the calibration factor for CR-39 based indoor radon detector

CR-39 based radon detectors are widely used in measuring indoor radon. In this regard, different groups have developed their own systems. However, before using any system for indoor radon measurements, it has, first, to be calibrated with a known source of radon. In the current study, CR-39 based NRPB type radon detector has been calibrated and presented. In this regard, about 200 holders for CR-39 were obtained from the Radiation Protection Division of the Health Protection Agency (former NRPB), UK and several thousand more similar detector holders, hereafter called NRPB type holders, were fabricated locally in Pakistan. Uranium ore samples of known grade were placed into the plastic containers of volume 5.4 × 10³ cm³ and CR-39 detectors were placed in the NRPB type holders and were then installed into the containers at a distance of 25 cm from the surface of the known grade ore samples. The containers were hermetically sealed and the detectors were allowed to expose to radon for 3 weeks. After 16 h etching in 25 % NaOH at 80 °C, the measured track densities were related to the radon concentration. The calibration factor of 2.563 tracks cm^?2 h^?1/kBq m^?3 was obtained.     

Determination of rare earth elements in rice by INAA and ICP-MS

In order to improve the accuracy of reactor neutron activation analysis, flux gradients and spectrum changes in the irradiation capsule have been studied at the Kyoto University Reactor (KUR). The flux and spectrum monitoring samples of Fe, Co, Au, Sb, U and Ni were placed at several positions in a polyethylene irradiation capsule of 24 mm inner diameter and 98 mm length, and were irradiated in a pneumatic irradiation facility (Pn-2). The flux gradients were found to be rather negligible in the vertical (axial) direction while they were considerable in the radial one. The flux gradient was around 5%/cm for thermal neutrons and 10%/cm for epithermal and fast neutrons. The spectrum changes were dependent on the materials (polyethylene and silica) filled in the capsule. Based on these observations, the effect of the flux gradients and spectrum changes on the accuracy of reactor neutron activation analysis was discussed.     

The long-time reactor irradiation of biological material at reduced temperature

When biological material in closed quartz ampoules is irradiated gaseous reaction products are formed as a result of radiation damage and thermal decomposition. The pressure thus created in the ampoules puts a limit to the time of irradiation or the sample mass and thereby to the detection limit of neutron activation analysis. The investigation will show how the internal pressure of the ampoules is reduced by cooling the sample containers in a nitrogen bath during irradiation so that a number of trace elements also in fresh biological material can be detected by means of neutron activation analysis with long-time irradiation. It will further contain a methodical study of the mechanical strength of quartz ampoules used as sample containers and the change in sample temperature using different sample containers and cooling through different media. The results of two irradiation studies of biological material in the low temperature irradiation unit of the reactor Melusine of the CENG Grenoble will be discussed.     

Method for determination of silicon in plant materials by neutron activation analysis

Silicon has been found to be an essential element for the growth and development of many ecomomically important plants such as sugarcane, rice, oats, and wheat. A method is described for the quantitative determination of silicon in plant samples. Measurements were made with two Ge(Li) detectors matched with a multiplexing unit to provide a single amplified signal to a computerized analyzer system. For those materials containing greater than 0.5 weight percent silicon, the reaction²⁹Si(n, p)²⁹Al (1273 keV) provides a direct measurement of the quantity of silicon provided the irradiation is done in a special boron nitride capsule to reduce interferences from thermal neutron reactions and a correction is made for the single escape line from²⁸Al (1268 keV). For lesser quantities of silicon, a technique which utilizes the fast neutron reaction²⁸Si(n, p)²⁸Al is preferred. Corrections for the interference produced by the presence of phosphorus³¹P(n, α)²⁸Al are made by determining the phosphorus content following the instrumental analysis using a unique application of neutron activation analysis, i. e., measurement of tungsten in tungstomolybdophosphoric acid produced when molybdate and tungstate ions are added to dissolved samples of the plant material containing phosphorus. Aluminum, which may also produce an interference by thermal neutron reaction²⁷Al(n, γ)²⁸Al, is determined directly from the original activation data after subtracting out the effect of the phosphorus. Thus, three irradiations in the pneumatic sample irradiator are necessary; one short irradiation (1 min) without thermal neutron shielding, a longer irradiation (6 min) in the boron capsule, and a final irradiation of the tungstomolybdophosphoric acid provide all data required to accurately determine silicon in plant materials. A computer program has been developed that provides rapid reduction of the data in final report format. Elements such as sodium, chlorine, calcium, manganese, potassium, and magnesium extrinsic to the analysis for silicon are also determined by this method. The method has been tested on a large number of samples and reliable results are obtained with less than 0.2 g of sample. This work was supported by Grant 533 from the Michigan Memorial—Phoenix Project.     

Determination of Tellurium by Gas Phase Molecular Absorption Spectrometry After Hydrogen Telluride Generation

Abstract

A method for determination of tellurium(IV) or tellurium(VI) is described that involves hydrogen telluride generation by reduction with sodium tetrahydro-borate(III), evolution of hydride with HCl solution, transport into a flow-cell placed in a UV-visible molecular absorption spectrophotometer and measurement of gas at 190 nm. Hydride generation and determination procedures are optimized, based on height and area of absorbance versus time profile of hydrogen telluride generated. Using the best experimental conditions found the calibration curve is linear from 5 to 100 μg/ml of tellurium, 1.1 μg/ml of tellurium(IV) or 3.1 μg/ml of tellurium(VI) can be detected, and relative standard deviation ranges from 4 to 7%. The method is applied to the analysis of additives for synthetic rubber making.     

A Peanut‐Shaped Polyaromatic Capsule: Solvent‐Dependent Transformation and Electronic Properties of a Non‐Contacted Fullerene Dimer

Synthesis of molecular containers capable of incorporating multiple fullerenes remains challenging. Reported here is that room‐temperature mixing of metal ions with W‐shaped bispyridine ligands featuring polyaromatic panels results in the quantitative formation of a peanut‐shaped M₂L₄ capsule. The capsule reversibly converts into two molecules of an ML₂ double tube in response to changes in the solvent. Notably, the capsule allows the incorporation of two fullerene molecules into the connected two spherical cavities at room temperature. The close proximity yet non‐contact of the encapsulated C₆₀ molecules, with a separation of 6.4 Å, was revealed by X‐ray crystallographic analysis. The resultant, unusual fullerene dimer undergoes sequential reduction within the capsule to generate (C₆₀^.?)₂, C₆₀^.??C₆₀^2?, and (C₆₀^2?)₂ species. Furthermore, temperature‐controlled stepwise incorporation of two C₆₀ molecules into the capsule is demonstrated.     

Compositional analysis of American southwestern ceramics by neutron activation analysis

Mercury, a known neurotoxin, has been implicated in the etiology and pathogenesis of such disease states as Alzheimer's and Parkinson's diseases. There is concern that the exposure to mercury vapor released from dental amalgam restorations is a potential health hazard. Measurement of mercury concentrations in blood or urine may be useful in diagnosis of mercury poisoning and in assessing the extent of exposure. This study describes the optimization of pre-neutron activation analysis procedures such as sampling, selection of irradiation and counting vials and acid digestion in order to minimize mercury loss via volatilization and/or permeation through containers. Therefore, the determination of mercury can be complicated by these potential losses. In the optimized procedure 20 mL of urine was spiked with three different concentrations of mercury, digested with concentrated nitric acid, and placed in polypropylene vials for irradiation and counting. Analysis was performed by subtracting the Se-75 photopeak contribution to the 279 keV Hg-203 photopeak and applying the method of standard additions. Urinary mercury concentrations in normal human subjects were determined to be of the order of 10 ng/mL.     

Estimation of gas transport coefficients from differential permeation, integral permeation, and sorption rate data

Experimental methods for studying the transport of gases in polymers may be divided into three categories: integral permeation rate measurement, in which the cumulative amount of a penetrant that has passed through a membrane is determined; differential permeation rate measurement, in which the rate of penetration through a membrane is measured directly; and sorption rate measurement, or determination of the cumulative amount of a penetrant absorbed in a polymer sample. This paper reviews commonly used techniques for estimating diffusion coefficients from transport data of all three types. Several new estimation formulas are presented, and the relative merits of different measurement and estimation methods are discussed. A general relationship between the traditional time lag method for integral rate data analysis and a recently developed moment method for differential rate data analysis is established, extending the applicability of the moment approach to the analysis of non-ideal transport in membranes of arbitrary geometry and composition.     

Hazardous and other element characterization of new and used domestic plastic food containers using INAA and AAS

Instrumental Neutron Activation Analysis (INAA) and Atomic Absorption Spectroscopy methodology was developed to characterize the hazardous and other inorganic trace element constituents in new and used domestic plastic food containers. INAA due to its non destructive, highly sensitive, multielement and low detection limits characteristics was found to be a good technique for the characterization of polymeric products. Through the variation of irradiation, cooling and counting protocols Al, Ba, Br, Co, Cr, Eu, Fe, Hg, K, Mn, Na, Nd, Sb, Sc, Th, Ti, V and Zn were determined, while Atomic Absorption Spectroscopy was used as complementary technique to quantify toxic inorganic elements such as Cd, Pb and Cu. These elements are thought to originate from the polymer manufacturing processes. It was found that there was gradual increase in the concentration of most of these elements from new to used plastic samples. Moreover it was also observed that these inorganic elements are present in higher concentrations in the lower grade containers as compared to the high quality containers. It was also observed that the good quality containers even with the long usage do not degrade to such an extent as the low quality containers.     

Determination of Trace Leaching Phthalate Esters in Water and Urine from Plastic Containers by Solid-Phase Microextraction and Gas Chromatography-Mass Spectrometry

A sensitive method has been developed for determination of trace leaching phthalate esters (PAEs) in water and urine from plastic containers by direct immersion solid-phase microextraction (DI-SPME) coupled to gas chromatography-mass spectrometry (GC-MS). The limits of detection (LODs) for PAEs in water and urine had values between 0.2–8 ng L^?1 and 4–70 ng L^?1, respectively. The proposed method was successfully used for quantification of trace PAEs in water in microwavable polypropylene containers heated by microwave irradiation and in the urine of patients treated with a glucose injection using polyvinyl chloride tubing.     

Uniform saturation of a strongly coupled spin system by two-frequency irradiation

The theoretical basis of two-frequency saturation is given here in the framework of Provotorov theory. The parameters influencing the saturation efficiency are discussed and studied experimentally using a liquid-crystalline test system. It is shown that double-frequency irradiation can be extremely efficient when the irradiation frequencies are placed at opposite sides of the characteristic frequency of the spin system, and that the frequency separation in the double-frequency irradiation can be varied over a large range. Provotorov theory is also shown to provide good insights into the experimental findings, which would otherwise be difficult to obtain from simulations.     

A clean laboratory for ultralow concentration heavy metal analysis

Summary Laboratory facilities and methods are described which have been developed in our laboratory in collaboration with C. Patterson's group at the California Institute of Technology for the reliable measurement of various heavy metals at extremely low concentration levels down to the sub pg/g level in Antarctic and Greenland snow and ice. All analytical work is performed inside a clean laboratory pressurized with air filtered through high efficiency particle air filters and equipped with all-plastic laminar flow clean benches. High-purity water is produced by ion-exchange resins, and high purity acids from the US National Institute of Science and Technology are used. The various containers which are in contact with the samples are made of conventional low density polyethylene and FEP teflon. These containers are cleaned by immersion during several weeks in a succession of heated acid baths of increasing purity. Extremely careful blank determinations are made in order to quantitatively determine how much of the investigated metals is added to the samples from each separate reagent, from the walls of the various containers and from the air of the clean laboratory.     

Characterization and use of the new NIST rapid pneumatic tube irradiation facility

Recently a new rapid pneumatic tube facility was inserted into a long unused location in the NIST 20 MW nuclear reactor. This facility was designed and constructed specifically for rapid INAA using short lived activation products. Included is a computer controlled console which uses fast sensors to accurately measure the irradiation capsule flight time, and a loss-free counting system connected to a 32% efficient PHGe detector with a transistor reset preamplifier. Measurement of travel, times from end-of-irradiation to detector were 473±8 ms. Measurement of the thermal neutron fluence rate was 5.0·10¹³ n·cm⁻²·s⁻¹. The other three pneumatic tubes in the NIST reactor have transfer times of 3 to 15 seconds, and no timing capability more accurate than human response. This new facility substantially improves our ability to accurately determine activation products with half-lives from 1 to 100 seconds. Characterization information reported on this new irradiation facility includes absolute fluence measurements, fluence rate variations within the capsule and variations with time, and determination of analytical sensitivities for fluorine-20 selenium-77m, and silver-110g.     

Practical results of Co production at RBMK-reactors

The paper presents practical results of ⁶⁰Co production in irradiation assemblies (IAs) in RBMK-1000 reactor during 1100 effective days of irradiation. Operational support of irradiation was performed by means of certified software system SAPFIR&RC-RBMK_RT. Integrity of IA in operating reactor was monitored by design system: no leaks in IAs were detected. Activity of ⁶⁰Co contained in each capsule was measured in the hot cell by comparison, using reference dosimeter with absorbed gamma-dose rate measurement uncertainty not more than ±3% at confidence probability P=0.95. Total amount of ⁶⁰Co produced was 2 MCi, average specific activity of ⁶⁰Co—52±7 Ci/g. Achievable specific activity of ⁶⁰Co in RBMK-reactor is 90±7 Ci/g and annual production capacity—about 8 MCi.