Radioactivity analysis

Sometimes a thorough examination of the artwork can determine authenticity. Forgers may use colors not available during the artist s life. Brushwork, themes, and techniques can be assessed. Unusual materials make a work suspect. Also, the usual methods can be applied to detect a forgery fluorescence, spectroscopy, X-rays, neutron activation analysis, radioactive dating and, more recently, digital analysis. 

In the method of activation analysis, radioactivity is induced in the sample to be analyzed. In the method of direct isotope dilution analysis (DIDA), a radioactive form of the component of interest is added to the sample. The component is then exhaustively purified without regard to quantitative recovery and a fraction of the pure component isolated. The amount and activity of the isolated component are measured and the quantity present in the original sample is calculated using that information. 

Metabolites are assigned based on retention times of radioactive peaks and LC/MS analysis. Radioactive peaks are reported as a percentage of dose (% of the sample multiplied by % excretion). Trace = <0.01% radioactivity and detected by LC/MS. 

Thermally Stimulated Emanation Measurement (Emanation Thermal Analysis) radioactive gas released ETA... 

For incubation each 4 discs vrere transferred to small petri dishes with 1 ml NL II containing the indicated concentration of cold L-Phe (0 - 75 /Ug/ml) and/ or other additions. Incubation was started by adding the same amount of U- C-L-Phe to all variants (0.15 - 0.6 /Ug/ml, total activity 4.4 - 17-6 x 105 dpm). After incubation discs were sucked on filter paper, floated 4 min, on ice water, again sucked on filter paper and aftervards frozen on dry ice. For analysis radioactivity in the TCA-soluble and the TCA-insoluble (protein) fractions as well as radioactivity of alkaloids excreted to the nutrient solution were determined (l, 3). 

Primers are often labeled with detectable groups to facilitate post-PCR analysis. Radioactive isotopes, haptens such as biotin, or fluorescent dyes are the most widely used. Labels attached to the 5 end of a primer have little or no effect on amplification. 

Seymour, R.S. and Cox, J.E. (1991). Library-Directed versus Peak-Search-Based Gamma-Ray Analysis, Radioact. Radiochem., 2, 10-18. 

There are many potential advantages to kinetic methods of analysis, perhaps the most important of which is the ability to use chemical reactions that are slow to reach equilibrium. In this chapter we examine three techniques that rely on measurements made while the analytical system is under kinetic rather than thermodynamic control chemical kinetic techniques, in which the rate of a chemical reaction is measured radiochemical techniques, in which a radioactive element s rate of nuclear decay is measured and flow injection analysis, in which the analyte is injected into a continuously flowing carrier stream, where its mixing and reaction with reagents in the stream are controlled by the kinetic processes of convection and diffusion. 

Although similar to chemical kinetic methods of analysis, radiochemical methods are best classified as nuclear kinetic methods. In this section we review the kinetics of radioactive decay and examine several quantitative and characterization applications. 

Three common quantitative applications of radiochemical methods of analysis are considered in this section the direct analysis of radioactive isotopes by measuring their rate of disintegration, neutron activation, and the use of radioactive isotopes as tracers in isotope dilution. 

Direct Analysis of Radioactive Analytes The concentration of a long-lived radioactive isotope is essentially constant during the period of analysis. As shown in Example 13.6, the sample s activity can be used to calculate the number of radioactive particles that are present. 

The direct analysis of short-lived radioactive isotopes using the method outlined in Example 13.6 is less useful since it provides only a transient measure of the isotope s concentration. The concentration of the isotope at a particular moment... 

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. 

Isotope Dilution Another important quantitative radiochemical method is isotope dilution. In this method of analysis a sample of analyte, called a tracer, is prepared in a radioactive form with a known activity. Ax, for its radioactive decay. A measured mass of the tracer, Wf, is added to a sample containing an unknown mass, w, of a nonradioactive analyte, and the material is homogenized. The sample is then processed to isolate wa grams of purified analyte, containing both radioactive and nonradioactive materials. The activity of the isolated sample, A, is measured. If all the analyte, both radioactive and nonradioactive, is recovered, then A and Ax will be equal. Normally, some of the analyte is lost during isolation and purification. In this case A is less than Ax, and... 

Equations 13.31 and 13.32 are only valid if the radioactive element in the tracer has a half-life that is considerably longer than the time needed to conduct the analysis. If this is not the case, then the decrease in activity is due both to the effect of dilution and the natural decrease in the isotope s activity. Some common radioactive isotopes for use in isotope dilution are listed in Table 13.1. 

In comparison with most other analytical techniques, radiochemical methods are usually more expensive and require more time to complete an analysis. Radiochemical methods also are subject to significant safety concerns due to the analyst s potential exposure to high-energy radiation and the need to safely dispose of radioactive waste. 

Radiochemical methods of analysis take advantage of the decay of radioactive isotopes. A direct measurement of the rate at which a radioactive isotope decays may be used to determine its concentration in a sample. For analytes that are not naturally radioactive, neutron activation often can be used to induce radioactivity. Isotope dilution, in which a radioactively labeled form of an analyte is spiked into the sample, can be used as an internal standard for quantitative work. 

For the naturally occurring elements, many new artificial isotopes have been made, and these are radioactive. Although these new isotopes can be measured in a mass spectrometer, this process could lead to unacceptable radioactive contamination of the instrument. This practical consideration needs to be considered carefully before using mass spectrometers for radioactive isotope analysis. 

Few of the naturally occurring elements have significant amounts of radioactive isotopes, but there are many artificially produced radioactive species. Mass spectrometry can measure both radioactive and nonradioactive isotope ratios, but there are health and safety issues for the radioactive ones. However, modem isotope instmments are becoming so sensitive that only very small amounts of sample are needed. Where radioactive isotopes are a serious issue, the radioactive hazards can be minimized by using special inlet systems and ion pumps in place of rotary pumps for maintaining a vacuum. For example, mass spectrometry is now used in the analysis of Pu/ Pu ratios. 

It is not necessary that there be two isotopes in both the sample and the spike. One isotope in the sample needs to be measured, but the spike can have one isotope of the same element that has been produced artificially. The latter is often a long-lived radioisotope. For example, and are radioactive and all occur naturally. The radioactive isotope does not occur naturally but is made artificially by irradiation of Th with neutrons. Since it is commercially available, this last isotope is often used as a spike for isotope-dilution analysis of natural uranium materials by comparison with the most abundant isotope ( U). 

National Institute of Standards and Technology (NIST). The NIST is the source of many of the standards used in chemical and physical analyses in the United States and throughout the world. The standards prepared and distributed by the NIST are used to caUbrate measurement systems and to provide a central basis for uniformity and accuracy of measurement. At present, over 1200 Standard Reference Materials (SRMs) are available and are described by the NIST (15). Included are many steels, nonferrous alloys, high purity metals, primary standards for use in volumetric analysis, microchemical standards, clinical laboratory standards, biological material certified for trace elements, environmental standards, trace element standards, ion-activity standards (for pH and ion-selective electrodes), freezing and melting point standards, colorimetry standards, optical standards, radioactivity standards, particle-size standards, and density standards. Certificates are issued with the standard reference materials showing values for the parameters that have been determined. 

Potential fusion appHcations other than electricity production have received some study. For example, radiation and high temperature heat from a fusion reactor could be used to produce hydrogen by the electrolysis or radiolysis of water, which could be employed in the synthesis of portable chemical fuels for transportation or industrial use. The transmutation of radioactive actinide wastes from fission reactors may also be feasible. This idea would utilize the neutrons from a fusion reactor to convert hazardous isotopes into more benign and easier-to-handle species. The practicaUty of these concepts requires further analysis. 

ImmunO lSS iy. Chemiluminescence compounds (eg, acridinium esters and sulfonamides, isoluminol), luciferases (eg, firefly, marine bacterial, Benilla and Varela luciferase), photoproteins (eg, aequorin, Benilld), and components of bioluminescence reactions have been tested as replacements for radioactive labels in both competitive and sandwich-type immunoassays. Acridinium ester labels are used extensively in routine clinical immunoassay analysis designed to detect a wide range of hormones, cancer markers, specific antibodies, specific proteins, and therapeutic dmgs. An acridinium ester label produces a flash of light when it reacts with an alkaline solution of hydrogen peroxide. The detection limit for the label is 0.5 amol. 

The analysis of steady-state and transient reactor behavior requires the calculation of reaction rates of neutrons with various materials. If the number density of neutrons at a point is n and their characteristic speed is v, a flux effective area of a nucleus as a cross section O, and a target atom number density N, a macroscopic cross section E = Na can be defined, and the reaction rate per unit volume is R = 0S. This relation may be appHed to the processes of neutron scattering, absorption, and fission in balance equations lea ding to predictions of or to the determination of flux distribution. The consumption of nuclear fuels is governed by time-dependent differential equations analogous to those of Bateman for radioactive decay chains. The rate of change in number of atoms N owing to absorption is as follows ... 

J. E. Till and H. R. Meyer, eds.. Radiological Assessment, A Textbook on Environmental Dose Analysis, NUREG/CR-3332, U.S. Nuclear Regulatory Commission, Washiagton, D.C., 1983 Disposal of Radioactive Waste Review of S afety Assessment Methods, Nuclear Energy Agency, Paris, 1991. 

Radiochemical tracers, compounds labeled with radioisotopes (qv), have become one of the most powerful tools for detection and analysis in research, and to a limited extent in clinical diagnosis (see Medical IMAGING TECHNOLOGY). A molecule or chemical is labeled using a radioisotope either by substituting a radioactive atom for a corresponding stable atom in the compound, such as substituting for H, for or for P, and for for... 

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