Radiochemical methods instrumentation

The following instrumental analysis textbooks may be consulted for further information on the detectors and signal analyzers used in radiochemical methods of analysis. 

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]. 

Radioactivity of uranium can be measured by alpha counters. The metal is digested in nitric acid. Alpha activity is measured by a counting instrument, such as an alpha scintillation counter or gas-flow proportional counter. Uranium may be separated from the other radioactive substances by radiochemical methods. The metal or its compound(s) is first dissolved. Uranium is coprecipitated with ferric hydroxide. Precipitate is dissolved in an acid and the solution passed through an anion exchange column. Uranium is eluted with dilute hydrochloric acid. The solution is evaporated to near dryness. Uranium is converted to its nitrate and alpha activity is counted. Alternatively, uranium is separated and electrodeposited onto a stainless steel disk and alpha particles counted by alpha pulse height analysis using a silicon surface barrier detector, a semiconductor particle-type detector. 

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. 

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 ... 

The availability of natuml and artificial ra-dioactiDc isotopes has made possible, the development of sensitufC and specific radiochemical methods. These procedures arc usually accurate and of widespread applicability. Some radiochemical methods also minimize or eliminate the separations required in other analytical methods. This chapter introduces the principles, instrumentation, and applications of radiochemical methods. 

See also Extraction Solid-Phase Extraction. Food and Nutritional Analysis Oils and Fats Fruits and Fruit Products. Lab-on-a-Chip Technologies. Liquid Chromatography Liquid Chromatography-Nuclear Magnetic Resonance Spectrometry. Nuclear Magnetic Resonance Spectroscopy Oven/iew Principles Instrumentation. Nuclear Magnetic Resonance Spectroscopy Applications Food. Nuclear Magnetic Resonance Spectroscopy Techniques Solid-State. Peptides. Radiochemical Methods Radiotracers Pharmaceutical Applications. 

Radiochemical methods can be successfully applied to separate elements and/or radionuclides that cannot be directly analyzed in the radioactive matrix by instrumental methods, e.g., pure beta emitters, short-lived nuclides in the presence of long-lived matrix components. In this case, there is no instrumental alternative to RAA. 

Classical or wet chemistry analysis techniques such as titrimetry and gravimetry remain in use in many laboratories and are still widely taught in Analytical Chemistry courses. They provide excellent introductions to the manipulative and other skills required in analytical work, they are ideal for high-precision analyses, especially when small numbers of samples are involved, and they are sometimes necessary for the analysis of standard materials. However, there is no doubt that most analyses are now performed by instrumental methods. Techniques using absorption and emission spectrometry at various wavelengths, many different electrochemical methods, mass spectrometry, gas and liquid chromatography, and thermal and radiochemical methods, probably account for at least 90% of all current analytical work. There are several reasons for this. 

One of the reviews cited earlier enumerates spectrophotometric methods for the determination of cyanide up to 1962 [8]. Also, instrumental methods such as colorimetric and spectrophotometric methods, electroanalytical methods, catalytic methods, gas chromatography methods, radiochemical methods, and miscellaneous methods for determination of cyanide up to 1977 have been summarized by Williams [7]. The instrumental methods developed since 1977 are considered here. 

The radiochemical methods of analysis to be discussed in this chapter will be divided into two groups for convenience tracer methods will be defined as those methods where the radioisotope is introduced into the analytical technique independently of the sample, and activation methods those where the radioisotope is incorporated into the sample by nuclear reaction. The different types of method may each have advantages in a particular situation, depending upon the availability of particular isotopes, the concentration at which the method is to be applied, and the instrumental facilities available to the individual analyst. 

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. 

All items of equipment must be considered, including balances and volumetric measuring devices, not just the expensive equipment. In terms of instrumentation, while a method using a mass spectrometer may be ideal for the study, if no such equipment is available the job will have to be contracted out to another laboratory, or another approach agreed with the customer. Neutron activation or radiochemical measurements require special equipment and dedicated laboratory facilities and safety procedures. Such techniques are often not generally available and are better left to specialist laboratories. 

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 experimental technique devised in this work is based on a NAA method. Neutron irradiation of solid waste forms of simulated HLW (see Table II) produces activation of the elements in the sample. The activation products can be readily measured before and after leaching by radiochemical and/or instrumental techniques. In order to be useful for these purposes, the activation product must have a sufficiently energetic and abundant radiation (either 6 or y) to be easily detected, as well as a sufficiently long half-life several days or more) to be useful for relatively... 

The increase in accuracy afforded by a radiochemical separation is absolutely necessary in the determination by NAA of trace elements in the coals selected as standards. The fact that interferences from the coal matrix are removed by a radiochemical separation is the advantage of this method of analysis over such instrumental methods as x-ray fluorescence and emission spectroscopy. 

Weaver and von Lehmden (20), under sponsorship of the EPA, evaluated two instrumental NAA methods and one with radiochemical separation for determining mercury in coal. 

Run Module The run module is used to set up the LC conditions, including the pump (e.g., gradient method), UV methods (e.g., wavelength), and autosampler (e.g., sequence setup). Apart from the LC, the method for radiochemical detection and the volume of liquid scintillant for radioactivity counting is also programmed in this module. The autosampler (as set up by the mn module) is used to trigger the Start Run for all other instruments through external contact closures. 

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. 

The NAA method can be divided into NAA (Instrumental NAA) and RNAA (Radiochemical NAA). In the latter, the various neutron-induced products are separated chemically to minimize interferences. There are several comprehensive review papers on INAA published in the literature 1,2,3,4). Briefly, the basic parameters controlling sensitivity for a multi-element determination are neutron flux, irradiation time, delay interval prior to counting, half-life and gamma-ray energy of the induced activity, and eflBciency and resolution of the detector. Table I outlines the irradiation parameters used for each of the two sequential irradiations. The final count occurring 40-50 days after the second irradiation is performed on an anti-coincidence-shielded Ge(Li) system developed recently in our laboratory. 

A wide variety of instrumental methods have been used to quantitate enzymes and their substrates. The choice of method depends primarily on the physical properties of the species being measured, and this is generally the product of the enzymatic or indicator reaction. In this section, instrumental detection methods are broadly classified as optical, electrochemical or other , where other techniques include radiochemical and manometric methods. 

Reproduced (adjusted) from Nuclear Instruments and Methods, 174(3), Hickmann U, Greulich N, Trautmann N, Gaggeler H, Gaggeler-Koch H, Eichler B, Herrmann G, Rapid continuous radiochemical separations by thermochromatography in connection with a gas-jet recoil system, 507-513, 1980, with permission from Elsevier. 

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