Neutron activation analysis sensitivity

Methods for iodine deterrnination in foods using colorimetry (95,96), ion-selective electrodes (94,97), micro acid digestion methods (98), and gas chromatography (99) suffer some limitations such as potential interferences, possibHity of contamination, and loss during analysis. More recendy neutron activation analysis, which is probably the most sensitive analytical technique for determining iodine, has also been used (100—102). 

Instiximental neutron activation analysis (INAA) is considered the most informative and highly sensitive. Being applied, it allows detecting and determination of 30-40 elements with the sensitivity of 10 -10 g/g in one sample. The evident advantage of INAA is the ability to analyze samples of different nature (filters, soils, plants, biological tests, etc.) without any complex schemes of preliminai y prepai ation. 

Atomic absorption spectroscopy of VPD solutions (VPD-AAS) and instrumental neutron activation analysis (INAA) offer similar detection limits for metallic impurities with silicon substrates. The main advantage of TXRF, compared to VPD-AAS, is its multielement capability AAS is a sequential technique that requires a specific lamp to detect each element. Furthermore, the problem of blank values is of little importance with TXRF because no handling of the analytical solution is involved. On the other hand, adequately sensitive detection of sodium is possible only by using VPD-AAS. INAA is basically a bulk analysis technique, while TXRF is sensitive only to the surface. In addition, TXRF is fast, with an typical analysis time of 1000 s turn-around times for INAA are on the order of weeks. Gallium arsenide surfaces can be analyzed neither by AAS nor by INAA. 

A modem technique for nitrogen detn is known as fast neutron activation analysis. Materials such as RDX are exposed to a high density fast neutron flux which converts the 14N content of the sample into unstable 13N. The N is detd by measuring the 13 N produced by the 14N (n, 2n) 13N reaction. This technique is extremely sensitive, but requires specialized instrumentation (Refs 44, 51 61)... 

This can result in a radioactive product from the A(n, t)A reaction where A is the stable element, n is a thermal neutron, A is the radioactive product of one atomic mass unit greater than A, and y is the prompt gamma ray resulting from the reaction. A is usually a beta and/or gamma emitter of reasonably long half-life. Where access to a nuclear reactor has been convenient, thermal neutron activation analysis has proven to be an extremely valuable nondestructive analytical tool and in many cases, the only method for performing specific analyses at high sensitivities... 

This section will deal briefly with some aspects of expls safety peculiar to neutron activation analysis expts. We are concerned here with a) the possible effect of the ionizing radiation dose on the energetic material which will cause it to be more sensitive or hazardous to normal handling as an expl, and b) the potential direct expl hazards involved in the physical and mechanical transportation of samples to and horn the irradiation source and in a nuclear counting system... 

Calcium-selective electrodes have long been in use for the estimation of calcium concentrations - early applications included their use in complexometric titrations, especially of calcium in the presence of magnesium (42). Subsequently they have found use in a variety of systems, particularly for determining stability constants. Examples include determinations for ligands such as chloride, nitrate, acetate, and malonate (mal) (43), several diazacrown ethers (44,45), and methyl aldofuranosides (46). Other applications have included the estimation of Ca2+ levels in blood plasma (47) and in human hair (where the results compared satisfactorily with those from neutron activation analysis) (48). Ion-selective electrodes based on carboxylic polyether ionophores are mentioned in Section IV.B below. Though calcium-selective electrodes are convenient they are not particularly sensitive, and have slow response times. 

To date, a few methods have been proposed for direct determination of trace iodide in seawater. The first involved the use of neutron activation analysis (NAA) [86], where iodide in seawater was concentrated by strongly basic anion-exchange column, eluted by sodium nitrate, and precipitated as palladium iodide. The second involved the use of automated electrochemical procedures [90] iodide was electrochemically oxidised to iodine and was concentrated on a carbon wool electrode. After removal of interference ions, the iodine was eluted with ascorbic acid and was determined by a polished Ag3SI electrode. The third method involved the use of cathodic stripping square wave voltammetry [92] (See Sect. 2.16.3). Iodine reacts with mercury in a one-electron process, and the sensitivity is increased remarkably by the addition of Triton X. The three methods have detection limits of 0.7 (250 ml seawater), 0.1 (50 ml), and 0.02 pg/l (10 ml), respectively, and could be applied to almost all the samples. However, NAA is not generally employed. The second electrochemical method uses an automated system but is a special apparatus just for determination of iodide. The first and third methods are time-consuming. 

Although the neutron activation analysis is inherently more sensitive than the atomic absorption spectrometry, both procedures yield a reliable measurement of vanadium in seawater at the natural levels of concentration. 

Table 10.2 Sensitivity of neutron activation analysis in determination of elements by (n,...

Neutron activation analysis is an attractive method in many trace element problems, or where the total amount of sample is limited. Many geochemical studies of trace constituents and semi-conductor developments have used the technique, whilst in recent years pollution investigations have provided a new focus. In forensic science small flakes of paint, single hairs and a variety of other small samples have been analysed and identified by activation analysis. In recent years activation analysis has lost further ground to ICP-MS which provides more comprehensive information and is more readily operated. Sensitivity is also comparable in many cases. 

It was not until the application of neutron activation analysis (NAA) that the problem of overlapping sources could be tackled. NAA is a highly sensitive and essentially non-destructive technique, although samples have to be taken which remain radioactive for some time after analysis. The use of NAA in characterizing obsidian was first demonstrated in the early 1970s (Aspinall... 

The number of protons is unique to the element but most elements can exist with two or more different numbers of neutrons in their nucleus, giving rise to different isotopes of the same element. Some isotopes are stable, but some (numerically the majority) have nuclei which change spontaneously - that is, they are radioactive. Following the discovery of naturally radioactive isotopes around 1900 (see Section 10.3) it was soon found that many elements could be artificially induced to become radioactive by irradiating with neutrons (activation analysis). This observation led to the development of a precise and sensitive method for chemical analysis. 

Until it was known that the half-life of Tc is much shorter than 10 years Herr looked for technetiimi-98 in a munber of minerals from Norway and South Africa by neutron activation analysis. This most sensitive method was also used by Alperovitch et al. and Anders et al. to detect this isotope in nature. According to the nuclear reaction... 

A method has been developed for the determination of technetium-99 in mixed fission products by neutron activation analysis Tc is separated from most fission products by a cyclohexanone extraction from carbonate solution, the stripping into water by addition of CCI4 to the cylohexanone phase, and the adsorption on an anion exchange column. Induced Tc radioactivity is determined using X-ray spectrometry to measure the 540 and 591 keV lines. The sensitivity of the analysis under these conditions is approximately 5 ng. The method has been successfully applied to reactor fuel solutions. 

Some of the methods commonly used for the determination of thorium in biological materials are given in Table 6-1. The colorimetric methods are not capable of isotope-specific determination of thorium isotopes. Alpha spectrometric and neutron activation analysis are useful in the quantification of isotope-specific thorium and thorium-232, respectively, and have better sensitivities than colorimetric methods. Alpha spectrometry is the commonly used isotope-specific analysis for the determination of thorium-232 and the thorium-230 derived from the decay of uranium-238 (Wrenn et al. 1981). Standard reference materials (SRMs) containing thorium in human liver (SRM-4352) and human lung (SRM-4351) necessary for the determination of absolute recovery in a given sample are available from the National Institute of Standards and Technology (Inn 1987). 

Gold may be identified by its physical properties. Trace quantities of gold may be analyzed by flame atomic absorption spectrophotometry (to 1 ppm) or by neutron activation analysis (to 1 ppb). The metal may be dissolved in aqua regia and the solution diluted appropriately prior to analysis. The most sensitive wavelength for this element is 242.8nm. 

Rhodium may be analyzed by flame atomic absorption spectrophotometry using the direct air-acetylene flame method. The metal, its oxide and insoluble salts may be solubilized by digesting with sulfuric acid—hydrochloric acid mixture. Rhodium also may by analyzed by ICP-AES and ICP/MS techniques. ICP/MS is the most sensitive method. Also, it may be analyzed by neutron activation analysis. 

Samarium may be analyzed by spectrographic and spectrophotometric methods. In solution, the trivalent samarium shows sharp and intense absorption bands at 362.5, 347.5 and 402.0 nm. Trace analysis may be carried out most accurately by flame AA, ICP-AES, ICP/MS and neutron activation analysis. ICP/MS is the most sensitive method. The metal and its insoluble salts may be solubilized by digestion with acids and diluted appropriately for most instrumental measurements. 

Zinc in trace amounts may be measured in solutions by flame-and fumace-AA, ICP-AES, and ICP/MS methods. It also can be identified by x-ray fluorescence and neutron activation analysis. Flame-AA measurement is done at 213.9nm using an air-acetylene flame. The ICP-AES measurement may be done at 213.86 nm or 206.20nm or alternative wavelengths. ICP/MS is the most sensitive method. 

With analytical methods such as x-ray fluorescence (XRF), proton-induced x-ray emission (PIXE), and instrumental neutron activation analysis (INAA), many metals can be simultaneously analyzed without destroying the sample matrix. Of these, XRF and PEXE have good sensitivity and are frequently used to analyze nickel in environmental samples containing low levels of nickel such as rain, snow, and air (Hansson et al. 1988 Landsberger et al. 1983 Schroeder et al. 1987 Wiersema et al. 1984). The Texas Air Control Board, which uses XRF in its network of air monitors, reported a mean minimum detectable value of 6 ng nickel/m (Wiersema et al. 1984). A detection limit of 30 ng/L was obtained using PIXE with a nonselective preconcentration step (Hansson et al. 1988). In these techniques, the sample (e.g., air particulates collected on a filter) is irradiated with a source of x-ray photons or protons. The excited atoms emit their own characteristic energy spectrum, which is detected with an x-ray detector and multichannel analyzer. INAA and neutron activation analysis (NAA) with prior nickel separation and concentration have poor sensitivity and are rarely used (Schroeder et al. 1987 Stoeppler 1984). 

First, we analyzed samples for a large number of elements to Identify any elements, regardless of toxicity or typical concentration, that would provide signals for the presence of material from certain types of sources. Both ambient samples and particles from sources were analyzed by Instrumental neutron activation analysis (INAA), by which one can often measure about 35 elements In Individual samples (17), As the Important elements Pb, N1 and Cd are not consistently, If ever, observed by INAA, they were often measured by other methods. As INAA Is sensitive to very small amounts of obscure elements, we have obtained reliable data for elements such as Ga, Hf, Sc, In, W and many rare earths which pose no known health hazard at present levels and contribute Insignificant amounts of mass to TSP. However, as discussed below, many trace elements have already been shown to be Important In receptor... 

We have operated the University of Washington MKV impactor as a low-pressure impactor to provide for chemical analysis, four discretely sized fly-ash fractions in the sub-half-micrometer- diameter aerosol accumulation region. Instrumental neutron activation analysis provided the sensitivity to determine accurately the concentrations of 28 major, minor, and trace elements with sufficient precision to reveal fine structure in the elemental distributions that might be missed by techniques of lesser accuracy and precision. 

The concentration levels of most trace metals and metalloids lie below 1000 pg P . Therefore, the classical methods of analysis do not have the required sensitivity. Among the instrumental techniques that have been extensively used for the analysis of biological materials include, atomic absorption spectrometry, plasma emission spectrometry, anodic stripping voltammetry and neutron activation analysis. 

---