Radiochemical methods neutron activation analysis

Nuclear Methods - Neutron Activation Analysis with Radiochemical Separation (RNAA)... 

Detection limits are presented for 61 elements by ten analytical determinative methods FAAS flame atomic absorption spectrometry ETAAS electrothermal atomization atomic absorption spectrometry HGAAS hydride generation atomic absorption spectrometry including CVAAS cold vapor atomic absorption spectrometry for Hg ICPAES(PN) inductively coupled plasma atomic emission spectrometry utilizing a pneumatic nebulizer ICPAES(USN) inductively coupled plasma atomic emission spectrometry utilizing an ultrasonic nebulizer ICPMS inductively coupled plasma mass spectrometry Voltammetry TXRF total reflection X-ray fluorescence spectrometry INAA instrumental activation neutron analysis RNAA radiochemical separation neutron activation analysis also defined in list of acronyms. 

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. 

The characteristics of radiochemical methods are well known [435]. An overview of the determination of elements by nuclear analytical methods has appeared [436]. Some selected reviews of nuclear methods of analysis are available charged particle activation analysis [437,438], instrumental neutron activation analysis [439-441] and ion-beam analysis [442]. 

The need for special facilities for work involving neutron activation analysis and radiochemical measurements has been referred to above in Section 4.3.6. Other safety factors may also influence your choice of method. For example, you may wish to avoid the use of methods which require toxic solvents, such as benzene and certain chlorinated hydrocarbons, or toxic reagents, such as potassium cyanide, if alternative procedures are available. Where Statutory Methods have to be used, there may be no alternative. In such cases, it is essential that staff are fully aware of the hazards involved and are properly supervised. Whatever method is used, the appropriate safety assessment must be carried out before the work is started. Procedures should be in place to ensure that the required safety protocols are followed and that everyone is aware of legislative requirements. 

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). 

Procedures for the determination of 11 elements in coal—Sb, As, Br, Cd, Cs, Ga, Hg, Rb, Se, U, and Zn—by neutron activation analysis with radiochemical separation are summarized. Separation techniques include direct combustion, distillation, precipitation, ion exchange, and solvent extraction. The evaluation of the radiochemical neutron activation analysis for the determination of mercury in coal used by the Bureau of Mines in its mercury round-robin program is discussed. Neutron activation analysis has played an important role in recent programs to evaluate and test analysis methods and to develop standards for trace elements in coal carried out by the National Bureau of Standards and the Environmental Protection Agency. 

Neutron activation analysis techniques are frequently used for trace element analyses of coal and coal-related materials (Weaver, 1978). Precision of the method is 25%, based on all elements reported in coal and other sample matrices. Overall accuracy is estimated at 50%. Neutron activation analysis utilizing radiochemical separations (NAA-RC) is employed by investigators when the sensitivity for a particular element or group of elements is inherently low or when spectral interference for a given element in a specific matrix is too great to be detected adequately. This situation was more prevalent before the advent of Ge(Li) spectrometry when only low-resolution Nal(TI) detectors were available. 

Neutron activation analysis (NAA) with a rapid radiochemical separation has been the method generally used in recent years, but requires substantial investment, has high operating cost and limited availability. Modem flameless atomic absorption (AAS) instruments provide sensitivity approaching that of NAA and offer a viable alternative for the detection of firearms discharge residue. 

Uranium in nature may be measured either radiometrically or chemically because the main isotope - 238U - has a very long half life (i.e., relatively few of its radioactive atoms decay in a year). Its isotopes in water and urine samples usually are at low concentrations, for which popular analytical methods are (1) radiochemical purification plus alpha-particle spectral analysis, (2) neutron activation analysis, (3) fluorimetry, and (4) mass spectrometry. The radiochemical analysis method is similar in principle to that of the measurement of plutonium isotopes in water samples (Experiments 15 and 16). Mass spectrometric measurement involves ionization of the individual atoms of the uranium analyte, separation of the ions by isotopic mass, and measurement of the number of separated isotopic ions (see Chapter 17 of Radioanalytical Chemistry text). 

Direct measurement of dietary zinc availability in humans requires development of the stable isotope tracer methodology. Several aspects of this integrated methodology are considered and briefly discussed. These are analytical isotopic measurement methodology, consequences of the finite precision of isotopic measurements, validation of in vivo measurements, and several aspects of biological labeling of human foods. It is shown that Radiochemical Neutron Activation Analysis provides a suitable method for accurate measurement of the stable isotopes Zn,... 

Stable Isotope methodology has recently become sufficiently developed to permit relatively precise measurement of zinc absorption In human subjects. The methodology using Radiochemical Neutron Activation Analysis has been validated and Is now being applied to the study of the effects of various dietary and host factors on the availability of dietary zinc. However, additional analytical developments and refinements will be necessary before a maximum utilization of this safe and non-lnvaslve method Is... 

Destructive method (radiochemical neutron activation analysis, RNAA) based on the chemical separation of radioelements into fractions, each of which contains some radionuclides [17-20]. 

Activation analysis may be applied in many variants. Neutron activation analysis (NAA) is the most widely used, but often charged particle activation or photon activation are more advantageous. If the energy of the projectiles can be varied, many variations are possible. The application of the manifold methods of activation depends on the availability of research reactors and accelerators. In addition, purely instrumental or radiochemical methods may be used. In instrumental activation analysis, the samples are measured after irradiation without chemical separation, whereas radiochemical activation analysis includes chemical separation. 

The availability of high flux thermal neutron irradiation facilities and high resolution intrinsic Ge and lithium drifted germanium (Ge(Li)) or silicon (Si(Li)) detectors has made neutron activation a very attractive tool for determining trace elemental composition of petroleum and petroleum products. This analytical technique is generally referred to as instrumental neutron activation analysis (INAA) to distinguish it from neutron activation followed by radiochemical separations. INAA can be used as a multi-elemental method with high sensitivity for many trace elements (Table 3.IV), and it has been applied to various petroleum materials in recent years (45-55). In some instances as many as 30 trace elements have been identified and measured in crude oils by this technique (56, 57). 

Earlier methods used to determine mercury in biological tissue and fluids were mainly colorimetric, using dithizone as the com-plexing agent. However, during the past two to three decades, AAS methods - predominantly the cold vapor principle with atomic absorption or atomic fluorescence detection - have become widely used due to their simplicity, sensitivity, and relatively low price. Neutron activation analysis (NAA), either in the instrumental or radiochemical mode, is still frequently used where nuclear reactors are available. Inductively coupled plasma mass spectrometry (ICP-MS) has become a valuable tool in mercury speciation. Gas and liquid chromatography, coupled with various detectors have also gained much importance for separa-tion/detection of mercury compounds (Table 17.1). 

Some relevant terms for activation analysis are activation analysis, neutron activation analysis (NAA), instrumental neutron activation analysis (INAA), neutron activation analysis with radiochemical separation (RNAA), photon activation, neutron capture prompt gamma activation analysis (PGAA), charged particle activation, autoradiography, liquid scintillation counting, nuclear microprobe analysis, radiocarbon (and other element) dating, radioimmunoassay, nuclear track technique, other nuclear and radiochemical methods. Briefly, the salient features of some of the more popular techniques are as follows ... 

Neutron activation analysis is a sensitive and versatile method of rock analysis, chiefly applicable to trace elements and capable of determining a large number of elements simultaneously without necessarily destroying the sample. There are two approaches. Instrumental neutron activation analysis (INAA) employs a powdered rock or mineral sample radiochemical neutron activation analysis (RNAA) involves the chemical separation of selected elements. The range of elements analysed is given in Table 1.5 and the methods are described in detail by Muecke (1980). 

Electrothermal vaporization isotopa dilution inductively coupled plasma mass spectrometry (ETV-ID-ICP-MS) has been utilized for the analysis of cadmium in fish samples. Radiochemical neutron activation analysis (RNAA), differential pulse anodic stripping voltametry (ASV) and the calorimetric dithizone method may also be employed. The AAS techniques appear to be most sensitive, with cadmium recoveries ranging from 94 to 109% (Koplan, 1999). 

Activation analysis is the other field of radiochemical analysis that has become of major importance, particularly neutron activation analysis. In this method nuclear transformations are carried out by irradiation with neutrons. The nature and the intensity of the radiation emitted by the radionuclides formed are characteristic, respectively, of the nature and concentrations of the atoms irradiated. Activation analysis is one of the most sensitive methods, an important tool for the analysis of high-purity materials, and lends itself to automation. The technique was devised by Hevesy, who with Levi in 1936 determined dysprosium in yttrium by measuring the radiation of dysprosium after irradiation with neutrons from a Po-Be neutron source. At the time the nature of the radiation was characterized by half-life, and the only available neutron sources were Po-Be and Ra-Be, which were of low efficiency. Hevesy s paper was not followed up for many years. The importance of activation analysis increased dramatically after the emergence of accelerators and reactors in which almost all elements could be activated. Hevesy received the 1943 Nobel prize in chemistry for work on the use of isotopes as tracers in the study of chemical processes . 

The second purpose is to extend the scope of the radiochemical neutron activation analysis (RNAA) method. Preirradiation of inorganic samples to induce fission products prior to oxygen flask ignition and solvent extraction can be used to distinguish ionic and nonionic form. The use of double irradiation in RNAA allows the determination of nuclides with short, medium, and long lives in a single experiment. This enables simultaneous determination of 13 1, and " Hg. 

The nondestructive instrumental (INAA) and destructive radiochemical (radiochemical neutron activation analysis — RNAA) procedures of this method are discussed later in this chapter. Specific problems, such as chain decays, cyclic activation, and interferences, as well as typical appKcations have recently been discussed by Alfassi (2001) and the references therein. 

In radiochemical activation analysis (RAA), the various techniques of activation analysis (AA), i.e., neutron activation analysis (NAA), photon activation analysis (PAA), and charged particle activation analysis (CPAA) are combined with radiochemical separation procedures with the intention of extending the capabilities offered by the purely instrumental methods. 

Neutron activation analysis, including nondestructive as weh as radiochemical techniques, has been successfully used for the determination of trace elements in metals, especially high purity metals. In the past, radiochemical separations were extensively used for the removal of matrix interferences. Later this procedure was extended to the group separation of trace elements. Radiochemical methods are also applied to the accurate and sensitive determination of single difficult-to-determine elements. 

Glover et al. (1998, 2001) developed an ultra-sensitive method for the analysis of Th in bioassay and environmental samples and pre-concentration radiochemical neutron activation analysis (PC-RNAA) was applied. In the pre-irradiation procedure, Th was concentrated using... 

Accelerator mass spectrometry (AMS) is useful to measure extremely low-abundance nuclides (isotope ratio of 10 to 10 relative to its stable isotope), such as Be, C, A1, C1, " Ca, and I, in natural samples. Small amounts of C and T can be measured by AMS on mg size samples of carbon and iodine extracted from 500-ml seawater samples (Povinec et al. 2000). Neutron activation analysis (NAA), radiochemical neutron activation analysis (RNAA), and inductively coupled plasma mass spectrometry (ICP-MS) are useful for the determination of ultra-trace Th and U in geological and cosmochemical samples, and for determination of the concentration of Pu and Pu. Reference marine-biological samples are necessary to test the performance of the analytical methods employed in surveying and monitoring radioactive materials in the sea. An ocean shellfish composite material containing 0.1% w/w Irish Sea mussel, 12% w/w White Sea mussel, and 87.9% w/w Japan Sea oyster has been prepared as the NIST SRM 4358 (The National Institute of Standards and Technology, SRM) in the natural-matrix, environmental-level radioactive SRM series (Altzitzoglou 2000). This NIST SRM 4358 sample will be useful for the determination of the activity of K, Cs, Pb, Ra, Th, and Am. 

---