Irradiation, neutron activation

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 ... 

Another application involves the measurement of copper via the radioisotope Cu (12.6-hour half-life). Since Cu decays by electron capture to Ni ( Cu Ni), a necessary consequence is the emission of X rays from Ni at 7.5 keV. By using X-ray spectrometry following irradiation, sensitive Cu analysis can be accomplished. Because of the short range of the low-energy X rays, near-surface analytical data are obtained without chemical etching. A combination of neutron activation with X-ray spectrometry also can be applied to other elements, such as Zn and Ge. 

The HFBR at Brookhaven National Laboratory is a heavy water moderated and cooled reactor designed to provide an intense beam of neutrons to the experimental area. In addition using thimbles i oiitaincd within the vessel, it provides isotopic production, neutron activation analysis, ami muiemi irradiations. It began operation in 1965 at a power of 40 MW to be upgraded to 60 MW m 19S2. 

Special Self-shielded Irradiation Cells for Fast Neutron Activation of... 

The concrete block walls of the cell housing the generator tube and associated components are 1.7 meters thick. The facility also includes a Kaman Nuclear dual-axis rotator assembly for simultaneous transfer and irradiation of reference and unknown sample, and a dual Na iodide (Nal) scintillation detector system designed for simultaneous counting of activated samples. Automatic transfer of samples between load station to the rotator assembly in front of the target, and back to the count station, is accomplished pneumatically by means of two 1.2cm (i.d.) polyethylene tubes which loop down at both ends of the system and pass underneath the concrete shielding thru a pipe duct. Total one-way traverse distance for the samples is approx 9 meters. In performing quantitative analysis for a particular element by neutron activation, the usual approach is to compare the count rates of an unknown sample with that of a reference standard of known compn irradiated under identical conditions... 

For fast neutron activations, the samples were irradiated with a Kaman nuclear neutron generator (Model A711) under conditions similar to those described In this article under the section... 

At PicArsn (Ref 19), the fast neutron activation approach for detection of expls in suitcases was extended to the activation of both nitrogen and oxygen using two 7-ray detector stations in sequence. After 14 MeV neutron irradiation, the baggage is first monitored for 6.1 MeV 7-rays from the l60(n,p),6N reaction (7.5 sec half-life), followed by measurement of the 10 min 13N. Because expls are also rich in oxygen and have characteristic ratios of N/O, it was felt that this approach would increase the probability of detection with a corresponding decrease in the false alarm rate... 

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... 

With regard to the hazard concern from physical and mechanical handling, the expl nature of the materials can pose a special problem. For example, during pneumatic transfer of samples in fast neutron activation, the polyethylene vials containing the expl approach speeds of 15m/sec and come to rest against a metal stop at both irradiation and count stations. However at PicArsn (Ref 13), in over 1000 irradiations and pneumatic transfers with up to 2.3g of shock-resistant secondary expls such as TNT, HMX,... 

The apphed pretreatment techniques were digestion with a combination of acids in the pressurized or atmospheric mode, programmed dry ashing, microwave digestion and irradiation with thermal neutrons. The analytical methods of final determination, at least four different for each element, covered all modern plasma techniques, various AAS modes, voltammetry, instrumental and radiochemical neutron activation analysis and isotope dilution MS. Each participating laboratory was requested to make a minimum of five independent rephcate determinations of each element on at least two different bottles on different days. Moreover, a series of different steps was undertaken in order to ensure that no substantial systematic errors were left undetected. 

Byrne AR, and Kucera J (1991) Radiochemical neutron activation analysis of traces of vanadium in biological samples A comparison of prior dry ashing with post-irradiation wet ashing. Fresenius f Anal Chem 340 48-52. 

The two Mossbauer levels of Pt, 99 keV and 130 keV, are populated by either EC of Au(fi/2 = 183 days) or isomeric transition of Pt(fi/2 = 4.1 days). Only a few authors, e.g., [323, 324] reported on the use of Pt, which is produced by thermal neutron activation of " Pt via " Pt(n, y) Pt. The source used in the early measurements by Harris et al. [322, 325] was carrier-free Au diffused into platinum metal. Walcher [326] irradiated natural platinum metal with deuterons to obtain the parent nuclide Au by (d, xn) reactions. After the decay of short-lived isotopes, especially Au(fi/2 = 6.18 days), Au was extracted with ethyl acetate, and the Au/Pt source prepared by induction melting. Buym and Grodzins [323] made use of (a, xn) reactions when bombarding natural iridium with... 

Principles and Characteristics In neutron activation analysis (NAA) the sample is irradiated by neutrons. The principal reaction in NAA is ... 

Neutron activation analysis (NAA) is a technique for the qualitative and/or quantitative determination of atoms possessing certain types of nuclei. Bombarding a sample with neutrons transforms some stable isotopes into radioactive isotopes measuring the energy and/or intensity of the gamma rays emitted from the radioactive isotopes created as a result of the irradiation reveals information on the nature of the elements in the sample. NAA Is widely used to characterize such archaeological materials as pottery, obsidian, chert, basalt, and limestone (Keisch 2003). 

The neutron activation method for the determination of arsenic and antimony in seawater has been described by Ryabin et al. [66]. After coprecipitation of arsenic acid and antimony in a 100 ml sample of water by adding a solution of ferric iron (10 mg iron per litre) followed by aqueous ammonia to give a pH of 8.4, the precipitate is filtered off and, together with the filter paper, is wrapped in a polyethylene and aluminium foil. It is then irradiated in a silica ampoule in a neutron flux of 1.8 x 1013 neutrons cm-2 s 1 for 1 - 2 h. Two days after irradiation, the y-ray activity at 0.56 MeV is measured with use of a Nal (Tl) spectrometer coupled with a multichannel pulse-height analyser, and compared with that of standards. 

Cerium was included in a list of 14 elements determined by Lee et al. [627] in seawater using neutron activation analysis. The metals were first precon-centraed on a mixture of Chelex 100 and glass powder. The elements were desorbed from the column by 4 M nitric acid, and aqueous solution was irradiated for 3 days and subjected to y-ray spectrometry method with a Ge(Ii) detector coupled to a 4000-channel analyser. Cerium was found to be present to the extent of 16.7 xg/l in water taken from the Kwangyang Bay (South Korea). 

Holzbecker and Ryan [825] determined these elements in seawater by neutron activation analysis after coprecipitation with lead phosphate. Lead phosphate gives no intense activities on irradiation, so it is a suitable matrix for trace metal determinations by neutron activation analysis. Precipitation of lead phosphate also brings down quantitatively the insoluble phosphates of silver (I), cadmium (II), chromium (III), copper (II), manganese (II), thorium (IV), uranium (VI), and zirconium (IV). Detection limits for each of these are given, and thorium and uranium determinations are described in detail. Gamma activity from 204Pb makes a useful internal standard to correct for geometry differences between samples, which for the lowest detection limits are counted close to the detector. 

If the samples are irradiated by fast neutrons, 39Ar is produced from K by the reaction 39K (n, p) 39Ar. The K can be determined by neutron activation on the identical sample for which the 40Ar is determined, resulting in a K-Ar age. 

Nuclear bombardment reactions in which the product is radioactive constitute the basis of radioactivation analysis (p. 456). Although in principle any bombardment-decay sequence may be used the analyst is largely concerned with thermal neutron activation. Equation (10.13) relates the induced activity to the amount of the parent nucleide (analyte). However, practical difficulties arise because of flux inhomogeneities. It is common therefore to irradiate a standard with very similar characteristics alongside the sample, e.g. for a silicate rock sample a standard solution would be evaporated on to a similar amount of pure silica. On the assumption that identical specific activities for the analyte are then induced in the sample and standard, the amount w2 of analyte is readily calculated from... 

The y particle is emitted virtually instantaneously on the capture of the neutron, and is known as a prompt y - it can be used analytically, in a technique known as prompt gamma neutron activation analysis (PGNAA), but only if such y s can be measured in the reactor during irradiation. Under the conditions normally used it would be lost within the nuclear reactor. In this reaction, no other prompt particle is emitted. The isotope of sodium formed (24Na) is radioactively unstable, decaying by beta emission to the element magnesium (the product nucleus in Figure 2.13), as follows ... 

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. 

The most sensitive method for determining trace amounts of technetium is the neutron activation . The Tc sample is irradiated by slow neutrons. The radioactive isotope Tc with a half-life of 15.8 s is formed by the reaction Tcfn, y) Tc, the neutron capture cross section of which is comparatively large (20 bams), so that it is possible to determine amounts < 2x 10 " g of Tc. However, the method is not widely used since the half-life of Tc is very short. Moreover, this method is only convenient when a reactor or a neutron source is available. 

A technique for the determination of Tc amounts as little as 4 x 10 g by neutron activation analysis has been described by Foti et al. . Tc in triply distilled water is irradiated in a thermal neutron flux of 5 x 10 neutrons per cm and per second to produce °°Tc. Other radionuclides are removed by co-precipi-tation with Fe(OH)j. Then, °°Tc is co-precipitated twice with tetraphenylarsonium perrhenate which can be removed by sublimation. The chemical purification of °°Tc requires 40-45 s and the technetium yield is about 53%. 

Trace amounts of Tc are also determined in filter paper and vegetable samples by neutron activation analysis The procedure consists of the following major steps separation of technetium from the sample, thermal neutron irradiation of the Tc fraction to produce °°Tc, post-irradiation separation and purification of °°Tc from other activated nuclides, and counting of the 16 s Tc in a low-background P counter. The estimated detection limits for Tc in this procedure are 5 x 10 g in filter paper and 9 x 10 g in vegetable samples. 

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). 

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