Neutron activation analysis detection levels

In the modern forensic chemistry laboratory (Figure B) arsenic is detected by analysis of hair samples, where the element tends to concentrate in chronic arsenic poisoning. A single strand of hair is sufficient to establish the presence or absence of the element. The technique most commonly used is neutron activation analysis, described in Chapter 19. If the concentration found is greater than about 0.0003%, poisoning is indicated normal arsenic levels are much lower than this. 

Cadmium in acidified aqueous solution may be analyzed at trace levels by various instrumental techniques such as flame and furnace atomic absorption, and ICP emission spectrophotometry. Cadmium in solid matrices is extracted into aqueous phase by digestion with nitric acid prior to analysis. A much lower detection level may be obtained by ICP-mass spectrometry. Other instrumental techniques to analyze this metal include neutron activation analysis and anodic stripping voltammetry. Cadmium also may be measured in aqueous matrices by colorimetry. Cadmium ions react with dithizone to form a pink-red color that can be extracted with chloroform. The absorbance of the solution is measured by a spectrophotometer and the concentration is determined from a standard calibration curve (APHA, AWWA and WEF. 1999. Standard Methods for the Examination of Water and Wastewater, 20th ed. Washington, DC American Public Health Association). The metal in the solid phase may be determined nondestructively by x-ray fluorescence or diffraction techniques. 

Iron metal can be analyzed by x-ray spectroscopy, flame- and furnace atomic absorption, and ICP atomic emission spectroscopy at trace concentration levels. Other instrumental techniques include ICP-mass spectrometry for extreme low detection level and neutron activation analysis. 

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). 

Conventional analytical techniques generally operate at the part per million or higher levels. Some techniques such as laser photo acoustic spectroscopy are capable of measuring phenomena at the 10-8-10-6 mol/L level. The most sensitive conventional analytical techniques, time-resolved laser-induced fluorescence, and ICP-MS are capable of measuring concentrations at the part per trillion level, that is, 1 part in 1012, but rarely does one see detection sensitivities at the single atom level as routinely found in some radioanalytical techniques. While techniques such as ICP-MS are replacing the use of neutron activation analysis in the routine measurement of part per billion concentrations, there can be no doubt about the unique sensitivity associated with radioanalytical methods. 

The determination of 129I in low-level radioactive waste was accomplished by radioactive instrumental neutron activation analysis [3]. A different group reported the determination of both 129I and 127I by neutron activation analysis and inductively coupled plasma mass spectrometry [4]. The method was very rapid - a sample could be analysed in three minutes. However, interference from 129Xe resulted in limited sensitivity for 129I detection. 

In addition, some metals may be determined by other methods, including ion-selective electrode, ion chromatography, electrophoresis, neutron activation analysis, redox titration, and gravimetry. Atomic absorption or emission spectrophotometry is the method of choice, because it is rapid, convenient, and gives the low detection levels as required in the environmental analysis. Although colorimetry methods can give accurate results, they are time consuming and a detection limit below 10 pg/L is difficult to achieve for most metals. 

Neutron activation analysis (NAA) technique has also been used for determining low levels of barium in human blood (Olehy et al. 1966). This technique is based on the interaction of the nuclei of individual barium atoms with neutron irradiation, resulting in the emission of x-rays (photons). Detection limits of 7 pg barium/L of erythrocyte and 66 pg barium/L of plasma were obtained (Olehy et al. 1966). The advantages of the NAA technique are its nondestructive nature of sample and minimum sample manipulation. Disadvantages of this technique include its high costs and a nuclear reactor may not be readily available to many laboratories. 

Comparison of the levels of some trace elements detected by the non-destructive neutron activation analysis in five tapeworms - parasites of birds. Bulletin de I Academie Polonaise des Sciences (Sciences Biologiques), 25 49-54. 

Mercury and Gallium a General Electric TRIGA reactor provides slow neutrons for the neutron activation analysis of these metals at the 10-50-ppb detection level. 

While the inorganic matrix of human bones can survive, it can also be contaminated by the soil in which it was buried. Instrumental neutron activation analysis and X-ray fluorescence can be used to detect levels of contamination. Microscopic studies show that voids in the inorganic matrix can be filled with new mineral deposits that have resulted from diagenesis and contamination. 

Maintaining the quality of food is a far more complex problem than the quality assurance of non-food products. Analytical methods are an indispensable monitoring tool for controlling levels of substances essential for health and also of toxic substances, including heavy metals. The usual techniques for detecting elements in food are flame atomic absorption spectroscopy (FAAS), graphite furnace atomic absorption spectrometry (GF AAS), hydride generation atomic absorption spectrometry (HG AAS), cold vapour atomic absorption spectrometry (CV AAS), inductively coupled plasma atomic emission spectrometry (ICP AES), inductively coupled plasma mass spectrometry (ICP MS) and neutron activation analysis (NAA). 

Neutron Activation Analysis. Magnesium-26 has a small cross section of 0.03 b. The product of irradiation with thermal neutrons is Mg (1 9.5m). As shown in Table 1, several elements commonly present in biological materials give rise to radioactive nuclides with radiations at energy levels close to those characteristic of Mg. Neutron activation was used in the first trials of Mg as an in vivo tracer when measurements were made with a well-type Nal-Tl crystal detector (14,21). Under these conditions the presence of sodium, altuninum and manganese in the samples interfered in the accurate detection of Mg, but could be reduced or eliminated by sample purification. 

Many researchers have attempted to determine mercury levels in the blood, urine, tissues, and hair of humans and animals. Most methods have used atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS), or neutron activation analysis (NAA). In addition, methods based on mass spectrometry (MS), spectrophotometry, and anodic stripping voltametry (ASV) have also been tested. Of the available methods, cold vapor (CV) AAS is the most widely used. In most methods, mercury in the sample is reduced to the elemental state. Some methods require predigestion of the sample prior to reduction. At all phases of sample preparation and analysis, the possibility of contamination from mercury found naturally in the environment must be considered. Rigorous standards to prevent mercury contamination must be followed. Table 6-1 presents details of selected methods used to determine mercury in biological samples. Methods have been developed for the analysis of mercury in breath samples. These are based on AAS with either flameless (NIOSH 1994) or cold vapor release of the sample to the detection chamber (Rathje et al. 1974). Flameless AAS is the NIOSH-recommended method of determining levels of mercury in expired air (NIOSH 1994). No other current methods for analyzing breath were located. 

Matters to be considered in the selection of a method of chemical analysis include the suite of elements for which the method is useful, and the lower limit of concentration at which each element can be detected and measured, as well as the accuracy of the analysis and the cost in money and time. Few analytical methods are applicable at the concentration levels required, and none is optimum by all these criteria. This paper describes one method in common use, neutron activation analysis (NAA). The essential characteristics of NAA will... 

Other Metal-Peptide and -Protein Interactions.—The determination of protein-bound trace elements in biological material by neutron activation analysis has been described Zn, Hg, Cu, and Se were accurately detected in human liver samples, provided that most of the element concerned was protein bound. An interaction of mercury with a protein or a protein-DNA complex has been invoked to explain the partitioning of the metal in euchromatin over heterochromatin (from mouse liver nuclei) by a 10 1 ratio. " Bovine retinas, isolated rod outer segments and emul-phogene extracts of rod outer segments have been shown to contain appreciable amounts of Zn ", Ca and the zinc levels being light sensitive. 

NAA has been used to determine selenium levels in environmental samples. Dams et al. (1970) reported a detection limit of lxlO 10 g/m3 selenium using nondestructive NAA for determining selenium in air particulate matter. For determining selenium levels in soil, radiochemical variants of NAA have been commonly employed (Bern 1981). Instrumental neutron activation analysis (INAA) is frequently used to determine selenium concentrations in water and can also be used to distinguish between selenium(IV) and selenium(VI) oxidation states (Bern 1981). INAA is also used to determine selenium concentrations in air (Bern 1981). 

It is possible to detect selenium levels as low as 1 ng per cubic meter of air using neutron activation analysis. Standardized methods for selenium determination in different environmental samples such as water, soil, sludge, and industrial waste are available in the above-mentioned literature. 

Arsenic levels below 10 ng/g can be readily detected in petroleum by instrumental neutron activation analysis. The most convenient technique involves direct gamma counting based on the 75As (n, y) 76As reaction with a principle radiation of 559 keV. After a 1-hr irradiation at a neutron flux of 1012 n cm"2 sec-1, the arsenic may be counted in a relatively short time. The method requires a high resolution Ge(Li) detector to avoid interference from bromine (550 keV) or antimony (564 keV). 

The paucity of information on metals, other than Ni and V, in crude oil is due principally to the poor sensitivity of most common analytical techniques for trace metals in oil. Neutron activation analysis has been used for trace element measurement in crude oils by several workers °" and allows detection of many elements at the sub-ppm level in small samples (0.1-1.0 g). Shah, et have developed an in-... 

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