Activation analysis with reactor neutrons

Activation with reactor neutrons allows the determination of a wide range of metallic and non-metal lie elements. It can in general not be used for the determination of traces of carbon, nitrogen and oxygen. Among the elements considered in this book, boron can be determined by prompt methods based on the B(n,ay) i reaction (2), whereby the a-particles or y-rays emitted are measured during the irradiation. Phosphorus and sulphur can be determined by reactor neutron activation analysis as described in chapters VIII and IX. 

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Figure 2.13 Schematic diagram of the nuclear processes involved in neutron activation analysis. Prompt gamma neutron activation analysis (PGNAA) occurs within the reactor delayed gamma NAA (DGNAA) occurs at some remote site. (After Glascock, 1994 Fig. 1. John Wiley Sons Limited. Reproduced with permission.)...

The fundamental principle behind analysis by activation analysis is activation or excitation of an atomic nucleus by exposure to radiation such as neutrons, protons or high-energy photons with subsequent measurement of emitted sub-atomic particles or radiation. The most common aspect of the technique involves activation with neutrons in a nuclear reactor and measurement of delayed emitted gamma rays, denoted neutron activation analysis, either instrumental neutron activation analysis (INAA) or neutron activation followed by radiochemical separation (RNAA) in which the element of interest is chemically separated from the matrix after irradiation to provide for better, unimpeded counting. 

Neutron Activation Analysis Few samples of interest are naturally radioactive. For many elements, however, radioactivity may be induced by irradiating the sample with neutrons in a process called neutron activation analysis (NAA). The radioactive element formed by neutron activation decays to a stable isotope by emitting gamma rays and, if necessary, other nuclear particles. The rate of gamma-ray emission is proportional to the analyte s initial concentration in the sample. For example, when a sample containing nonradioactive 13AI is placed in a nuclear reactor and irradiated with neutrons, the following nuclear reaction results. 

The concentration of Mn in steel can be determined by a neutron activation analysis using the method of external standards. A 1.000-g sample of an unknown steel sample and a 0.950-g sample of a standard steel known to contain 0.463% w/w Mn, are irradiated with neutrons in a nuclear reactor for 10 h. After a 40-min cooling period, the activities for gamma-ray emission were found to be 2542 cpm (counts per minute) for the unknown and 1984 cpm for the standard. What is the %w/w Mn in the unknown steel sample ... 

All impactor and filter samples were analyzed for up to 45 elements by instrumental neutron activation analysis (INAA) as described by Heft ( ). Samples were irradiated simultaneously with standard flux monitors in the 3-MW Livermore pool reactor. The x-ray spectra of the radioactive species were taken with large-volume, high-resolution Ge(Li) spectrometer systems. The spectral data were transferred to a GDC 7600 computer and analyzed with the GAMANAL code (1 ), which incorporates a background-smoothing routine and fits the peaks with Gaussian and exponential functions. 

The concentration of silver nanoparticles and ions in solntions was determined by neutron activation analysis [15]. Samples were irradiated in the nuclear reactor at the Institute of Nuclear Physics, Tashkent, Uzbekistan. The product of nuclear reaction ° Ag(n,y)" Ag has the half-life Tj j=253 days. The silver concentration was determined by measnring the intensity of gamma radiation with the energy of 0.657 MeV and 0.884 MeV emitted by "" Ag. A Ge(Li) detector with a resolution of about 1.9 keV at 1.33 MeV and a 6,144-channel analyzer were used for recording gamma-ray quanta. 

Neutron activation analysis (NAA), based on the interaction of the object material with fast neutrons, has been used in the identification and determination of the content of elements present in pigments, coins and alloys, stone, glass, and pottery [26]. Multi-elemental analysis (about 20 elements) can be performed on small samples off less than 5 mg, with sensitivities in the ppm range. The requirement of a nuclear reactor, the handling of radioactive materials, and the time-consuming procedures required for preparing the samples are the main drawbacks of this technique. 

During the late 1960s and early 1970s, neutron activation analysis provided a new way to measure bulk chemical composition. Neutron activation analysis utilizes (n,y) reactions to identify elements. A sample is placed in a nuclear reactor where thermal neutrons are captured by atoms in the sample and become radioactive. When they decay, the radioactive isotopes emit characteristic y-rays that are measured to determine abundances. Approximately 35 elements are routinely measured by neutron activation analysis. A number of others produce radioactive isotopes that emit y-rays, but their half-lives are too short to be useful. Unfortunately, silicon is one of these elements. Other elements do not produce y-ray-emitting isotopes when irradiated with neutrons. There are two methods of using neutron activation to determine bulk compositions, instrumental neutron activation analysis (INAA) and radiochemical neutron activation analysis (RNAA). 

The amount of unreacted target element that eluted was determined by measuring its radioactivity directly in the case of actinides, and by activation analysis in the case of lanthanides. The distribution of the radioactive neutron capture product was determined by counting both the eluate and the eluted zeolite. All irradiations were done in the Oak Ridge Research reactor in a pneumatic tube facility with a thermal neutron flux of about 4 X 1013 neutrons cm-2 sec-1 or, for a few long irradiations, in a tube adjacent to the reactor core at the fluxes stated in Table VI. 

The second step in an activation analysis concerns the choice of nuclear reaction to change X into X, plus the irradiation facility in which the reaction will be carried out. In addition, the length of irradiation and decay prior to counting must be chosen so the produced X activity is enhanced relative to all other activities produced. Most activation analysis is done with thermal neutrons produced in nuclear reactors for the following reasons ... 

Until now, little attention has been given to the analysis of ancient copper alloys with LA-ICP-MS. This type of material is usually analyzed with fast or instrumental neutron activation analysis (FNAA or INAA), particle induced X-ray emission (PIXE), X-ray fluorescence (XRF), inductively coupled plasma-atomic emission spectrometry or inductively coupled plasma-atomic absorption spectrometry (ICP-AES or ICP-AAS). Some of these techniques are destructive and involve extensive sample preparation, some measure only surface compositions, and some require access to a cyclotron or a reactor. LA-ICP-MS is riot affected by any of these inconveniences. We propose here an analytical protocol for copper alloys using LA-ICP-MS and present its application to the study of Matisse bronze sculptures. 

Instrumental neutron activation analysis was conducted at the University of Missouri Research Reactor (MURR). Samples of approximately 50-100 mg were subjected to long and short irradiations using the same methodology used on pottery and other materials with appropriate reference standards (23). The analysis provided abundances of 33 elements for 72 samples. 

Activation analysis is based on the production of radioactive nuclides by means of induced nuclear reactions on naturally occurring isotopes of the element to be determined in the sample. Although irradiations with charged particles and photons have been used in special cases, irradiation with reactor thermal neutrons or 14 MeV neutrons produced by Cockcroft-Walton type accelerators are most commonly used because of their availability and their high probability of nuclear reaction (cross section). The fundamental equation of activation analysis is given below ... 

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. 

Neutron activation analysis is a two-step technique (3). The sample to be analysed is first irradiated with the neutron flux of a nuclear reactor. The nuclei of a small bit predictable fraction of the atcms of each element in the sample will capture neutrons and beocme radioactive. These will subsequently emit radiation at a time which depends on the half-life of the radioactive isotope. At the end of the pre-determined irradiation time the sample is removed from the reactor it is now radioactive and the activity will decrease with time as the individual atcms emit radiation and... 

Even in relatively large programs, few laboratories will justify the initial expense and calibration effort required for development of the emission spectrographic method. As reported by Scott etal. [3], sample preparation will generally not differ significantly from that required for AAS. Instrumental neutron activation analysis (INAA) is only attractive where a reactor is already available, and multielement analysis by this technique requires the use of high resolution Ge(Li) crystals and multiple irradiations for elements with differing activation product half-lives. The key elements, cadmium, nickel and lead still require analysis by AAS because of limitations of the INAA method [4]. 

Many trace element studies of archaeological samples have used neutron activation analysis (NAA). Although this technique is not useful for all elements, it is very sensitive for many of those that have proved to be valuable indicators of geochemical processes (e.g., the rare earth elements). The precision of the actual measurements is usually high and easy to determine. Samples can be irradiated with little or no sample preparation, so there are few chances of contamination during the analysis. However, the limited number of nuclear reactors severely limits access to this type of analysis. When samples are sent to a distant laboratory for analysis, the critical interaction between archaeologist and analyst can be lost. 

Throughout this investigation we have been greatly aided in many ways by the efforts of Emlen Myers. We acknowledge the important support provided by the personnel of the Reactor Operations Division and the Nuclear Methods Group (Inorganic Analytical Research Division) of the National Bureau of Standards, who have made their facilities available to us both for this project and the numerous other projects that the Conservation Analytical Laboratory is carrying out with neutron activation analysis. 

Analysis of Major Elements. Major elements were determined quantitatively by neutron activation analysis at the University of Toronto SLOWPOKE reactor. This technique was chosen because the available sample size was small. Differential scanning calorimetry with a Perkin-Elmer DSC-1B was used to establish the plaster composition further and to investigate its thermal behavior. 

Thermal neutrons in the reactor are efficient in producing ( , y) neutron capture reactions e.g. Fe (n, y) f< Fe. The products of these reactions will have an excess of neutrons and generally decay by (/ ", y) emission. The major disadvantage is that the radioactive atoms will always be diluted with many -non-radioactive atoms and chemical separation is not possible, (n, y) reactions are however usefully exploited in neutron activation analysis (p. 471). With fast neutrons, proton, deuteron or alpha particle bombardment a change in atomic number accompanies the.reaction and chemical separation of the carrier free radiotracer becomes possible,... 

In practice, nuclear activation analysis is carried out by placing thesample to be examined in a nuclear reactor. The neutrons available in the reactor bring about the n/c (neutron/gamma ray) reactions described above. The radioactive sample is then removed from the reactor and examined with a gamma ray spectrometer. This device measures the type and intensity of radiation released by the sample. These data can then be compared to standard tables to determine which elements and the amounts of each are present in the sample. 

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