Handbook of Nuclear Chemistry

This chapter gives a brief overview of the development of nuclear and radiochemistry from Mme. Curie’s chemical isolation of radium toward the end of the twentieth century. The first four sections deal with fairly distinct time periods: (1) the pioneering years when the only radioactive materials available were the naturally occurring ones; (2) the decade of rapid growth and expansion of both the fundamental science and its applications following the discoveries of the neutron and artificial radioactivity; (3) the World War II period characterized by the intense exploration of nuclear fission and its ramifications; (4) what can be called the “golden era” – the 3 to 4 decades following World War II when nuclear science was generously supported and therefore flourished. In the final section, research trends pursued near the end of the century are briefly touched upon.

In this chapter, four topics are treated. (1) Fundamental constituents and interactions of matter and the properties of nuclear forces (experimental facts and phenomenological and meson-field theoretical potentials). (2) Properties of nuclei (mass, binding energy, spin, moments, size, parity, isospin, and characteristic level schemes). (3) Nuclear states and excitations and individual and collective motion of the nucleons in the nuclei. Description of basic experimental facts and their interpretation in the framework of shell, collective, interacting boson, and cluster models. The recent developments, few nucleon systems, and ab initio calculations are also shortly discussed. (4) In the final section, the α- and β-decays, as well as the special decay modes observed far off the stability region are treated.

The investigation and application of nuclear reactions play a prominent role in modern nuclear chemistry research. After a discussion of basic principles and reaction probabilities that govern collisions between nuclei, an overview of reaction theory is presented and the various reaction mechanisms that occur from low to high energies are examined. The presentation strives to provide links to more standard chemical disciplines as well as to nuclear structure.

This chapter first gives a survey on the history of the discovery of nuclear fission. It briefly presents the liquid-drop and shell models and their application to the fission process. The most important quantities accessible to experimental determination such as mass yields, nuclear charge distribution, prompt neutron emission, kinetic energy distribution, ternary fragment yields, angular distributions, and properties of fission isomers are presented as well as the instrumentation and techniques used for their measurement. The contribution concentrates on the fundamental aspects of nuclear fission. The practical aspects of nuclear fission are discussed in Chap. 57 of Vol. 6.

This chapter gives a survey of the latest results obtained for the fission process that takes place when the energy of the compound system is smaller than the energy of the fission barrier. The tunneling and resonant tunneling processes play a role in this energy region. The transmission resonances were studied in high-energy-resolution experiments and the excitation energies, Jπ and K values of the states were determined. Rotational bands were constructed, from which the moment of inertia and the degree of the deformation were determined. The implications of these results to the present knowledge of the fission potential extracted from experiments are discussed.

This chapter is devoted to the fundamental concepts of nuclear fusion. To be more precise, it is devoted to the theoretical basics of fusion reactions between light nuclei such as hydrogen, helium, boron, and lithium. The discussion is limited because our purpose is to focus on laboratory-scale fusion experiments that aim at gaining energy from the fusion process. After discussing the methods of calculating the fusion cross section, it will be shown that sustained fusion reactions with energy gain must happen in a thermal medium because, in beam-target experiments, the energy of the beam is randomized faster than the fusion rate. Following a brief introduction to the elements of plasma physics, the chapter is concluded with the introduction of the most prominent fusion reactions ongoing in the Sun.

At present there are over 3,000 known nuclides (see the Appendix in Vol. 2 on the “Table of the Nuclides”), 265 of which are stable, while the rest, i.e., more than 90% of them, are radioactive. The chemical applications of the specific isotopes of chemical elements are mostly connected with the latter group, including quite a number of metastable nuclear isomers, making the kinetics of radioactive decay an important chapter of nuclear chemistry. After giving a phenomenological and then a statistical interpretation of the exponential law, the various combinations of individual decay processes as well as the cases of equilibrium and nonequilibrium will be discussed. Half-life systematics of the different decay modes detailed in Chaps. 2 and 4 of this volume are also summarized.

The effects of interactions of the various kinds of nuclear radiation with matter are summarized with special emphasis on relations to nuclear chemistry and possible applications. The Bethe–Bloch theory describes the slowing down process of heavy charged particles via ionization, and it is modified for electrons and photons to include radiation effects like bremsstrahlung and pair production. Special emphasis is given to processes involved in particle detection, the Cherenkov effect and transition radiation. Useful formulae, numerical constants, and graphs are provided to help calculations of the stopping power of particles in simple and composite materials.

The term “stochastics” in the title roughly translates into “random features.” So it refers to anything related to probability theory, statistics, and, of course, stochastic processes. Some of the facts of probability and statistics, including special distributions relevant to nuclear measurements, have been summarized. Examples of the nuclear applications of stochastic processes have also been given. A separate section has been devoted to the analysis of nuclear spectra.

The present experimental evidence seems to support the Standard Model of elementary particles, which interprets the world as consisting of 12 basic fermions: six quarks and six leptons with their antiparticles, 13 bosons mediating the strong, electromagnetic and weak interactions, and the mysterious Higgs boson. This chapter attempts to overview the basic features of the Standard Model with a minimal mathematical apparatus.

The modern metric system of measurement has become the standard in scientific practice. The official name is International System of Units, abbreviated SI from the French Le Système International d’Unitès. The SI was established in 1960 by the 11th General Conference on Weights and Measures. The defining document, commonly called the SI Brochure, has been published by the International Bureau of Weights and Measures (BIPM) in French original and in English translation (BIPM 1991). It has been complemented with a series of international consensus standards to promote international uniformity in the practical use of the SI in science and technology (ISO 1993). Several national standards organizations have prepared practical guides to promote the implementation and practical use of the SI in their country. This chapter is mainly based on the guide prepared by the National Institute of Standards and Technology (NIST), USA (Taylor 1995), which is also available electronically on the NIST Web site on constants, units, and uncertainty (NIST 2003).

This chapter provides the necessary background from astrophysics, nuclear, and particle physics to understand the cosmic origin of the chemical elements. It reflects the year 2008 state of the art in this extremely quickly developing interdisciplinary research direction. The discussion summarizes the nucleosynthetic processes in the course of the evolution of the Universe and the galaxies contained within, including primordial nucleosynthesis, stellar evolution, and explosive nucleosynthesis in single and binary systems.

Shell effects on nuclear stability have created an island of relative stability for nuclides near A = 230–240 and Z = 90–92. Three nuclides, 232Th, 238U, and 235U, have half-lives long enough for significant amounts to have survived since the heavy elements in the Earth’s crust were created. When one of these nuclides decays, it starts a journey that ends with an isotope of lead (Z = 82, A ≈ 208). The predominant steps in this journey are α and β decays, so that each of the long-lived parents heads a distinct chain. Each chain, as well as a fourth one that is extinct, is described.

Technetium (Tc) (Z = 43) and promethium (Z = 61) are the only elements below bismuth (Z = 83) in atomic number that have no stable isotopes. The discovery of these unusual elements is described, and the physical factors leading to their instability are discussed.

Isotope effects, that is, differences brought about by isotopic substitution in the physical and chemical properties of atoms and molecules, are reviewed from the point of view of spectroscopy, chemical equilibria, phase equilibria, physicochemical properties, reaction kinetics, and biology. The theory of isotope effects is discussed in some detail.

Paleotemperature scales were calculated by H. C. Urey and others in the 1950s to assess past temperatures, and later work using the stable isotopes of oxygen, hydrogen, and carbon employed standards such as Peedee belemnite (PDB) and Standard Mean Ocean Water (SMOW). Subsequently, subjects as diverse as ice volume and paleotemperatures, oceanic ice and sediment cores, Pleistocene/Holocene climatic changes, and isotope chronostratigraphy extending back to the Precambrian were investigated.

This chapter provides a necessarily brief summary of radioactive dating techniques, which can produce dates (“ages”) ranging from tens to thousands through millions to billions of years often with assumptions not universally accepted, especially those involving the assessments of half-lives and radioactive decay constants.

This chapter reviews the historical perspective of transuranium elements and the recent progress in the production and study of nuclear properties of transuranium nuclei. Exotic decay properties of heavy nuclei are also introduced. Chemical properties of transuranium elements in aqueous and solid states are summarized based on the actinide concept. For new application of studying transuranium elements, an X-ray absorption fine structure (XAFS) method and computational chemistry are surveyed.

Microscopic nuclear theories predict a region of superheavy elements (SHEs) at the next doubly magic shell closure above 208Pb. Early models locate the shell closure at Z = 114, more recent calculations place it at Z = 120. The closed neutron shell is located at N = 184. These predictions motivated the search for superheavy elements in nature and in the laboratory to explore the limits of the chart of nuclides toward its upper end. A new region of shell stabilization, centered at Z = 108 and N = 162 has been discovered. It interconnects the transuranium region and the superheavy elements. As of 2009, the heaviest element accepted by the Union of Pure and Applied Chemistry is Z = 112. The discovery of elements 113 to 116 and 118 has been reported. All of these elements have been created by the complete fusion of heavy ions. Production rates decrease to less than one atom per month for the heaviest species. Half-lives range down to below microseconds. The elements at the top of the nuclear chart have been discovered on the basis of single-atom decays after separation in-flight. The production and investigation of the transactinide elements with Z = 104 and beyond form the subject matter of this chapter. After a brief history of their discoveries and experimental methods, nuclear structure and the production of heavy elements will be discussed. The prospects for the synthesis and investigation of heavy elements using advanced technologies such as new high-current heavy-ion accelerators, radioactive beams, and ion traps will be outlined. The importance of closed nuclear shells for the existence and production of the heaviest elements will be addressed briefly.

In this chapter, the chemical properties of the man-made transactinide elements rutherfordium, Rf (element 104), dubnium, Db (element 105), seaborgium, Sg (element 106), bohrium, Bh (element 107), hassium, Hs (element 108), and copernicium, Cn (element 112) are reviewed, and prospects for chemical characterizations of even heavier elements are discussed. The experimental methods to perform rapid chemical separations on the time scale of seconds are presented and comments are given on the special situation with the transactinides where chemistry has to be studied with single atoms. It follows a description of theoretical predictions and selected experimental results on the chemistry of elements 104 through 108, and element 112.

The long quest to detect superheavy elements (SHEs) that might exist in nature and the efforts to artificially synthesize them at accelerators or in multiple-neutron capture reactions is briefly reviewed. Recent reports of the production and detection of the SHEs 113, 114, 115, 116, and 118 are summarized and discussed. Implications of these discoveries and the prospects for the existence and discovery of additional SHE species are considered.

This chapter presents the table of nuclides, i.e., experimental nuclear data concerning isotopes and isomers of the elements.

Ionizing radiation causes chemical changes in the molecules of the interacting medium. The initial molecules change to new molecules, resulting in changes of the physical, chemical, and eventually biological properties of the material. For instance, water decomposes to its elements H₂ and O₂. In polymers, degradation and crosslinking take place. In biopolymers, e.g., DNS strand breaks and other alterations occur. Such changes are to be avoided in some cases (radiation protection), however, in other cases they are used for technological purposes (radiation processing). This chapter introduces radiation chemistry by discussing the sources of ionizing radiation (radionuclide sources, machine sources), absorption of radiation energy, techniques used in radiation chemistry research, and methods of absorbed energy (absorbed dose) measurements. Radiation chemistry of different classes of inorganic (water and aqueous solutions, inorganic solids, ionic liquids (ILs)) and organic substances (hydrocarbons, halogenated compounds, polymers, and biomolecules) is discussed in concise form together with theoretical and experimental backgrounds. An essential part of the chapter is the introduction of radiation processing technologies in the fields of polymer chemistry, food processing, and sterilization. The application of radiation chemistry to nuclear technology and to protection of environment (flue gas treatment, wastewater treatment) is also discussed.

Various aspects of hot atom chemistry are described, reviewing it from fundamentals to applications. In gas, liquid, and solid systems, recoil atom reactions show characteristic features. Chemical behavior of implanted atoms that is specific to them and somewhat different from that of ordinary recoil atoms is also described. Examples of radioisotope enrichment are included.

Mössbauer spectroscopy, based on the recoilless resonance emission and absorption of γ photons observed with certain atomic nuclei, is a powerful investigating tool in most disciplines of natural science ranging from physics to chemistry to biology. This nuclear method makes it possible to measure the energy difference between nuclear energy levels to an extremely high resolution (up to 13–15 decimals). This resolution is required to measure the slight variation of nuclear energy levels caused by electric monopole, electric quadrupole, and magnetic dipole interactions between the electrons and the nucleus. Mössbauer nuclides being at different microenvironments act as local probes for the sensitive detection of the hyperfine interactions. Such interactions reflect changes in the electronic, magnetic, geometric, or defect structure as well as in the lattice vibrations, serving as a basis for a variety of applications. In this chapter, the principles and some practical aspects of Mössbauer spectroscopy are described.

The use of synchrotron radiation has opened up new areas in nuclear resonant scattering studies. It has permitted measurements that are difficult with conventional radioactive sources, such as the measurement of element-specific dynamics. Recent progress in studies using nuclear resonant scattering of synchrotron radiation is reviewed in this chapter.

This chapter demonstrates the applicability of positrons in nuclear chemistry and material sciences. From the very basics to highly developed spectroscopic methods, a brief outline of positron annihilation spectroscopies is given. The possibilities of these methods are emphasized, and the characteristic applications are outlined for every one of them.

In exotic atoms, one of the atomic electrons is replaced by a negatively charged particle, whereas muonium consists of a positive muon and an electron. After a general review of the theoretical and experimental aspects, the present knowledge of this field is summarized. These include muonium and the application of the muon spin resonance method in solid-state physics and chemistry, muonic hydrogen atoms, muonic molecules and muon-catalyzed fusion, pionic hydrogen atoms and their use in chemistry, testing quantum electrodynamics on heavy muonic atoms, measuring particle and nuclear properties using hadronic atoms, and testing basic symmetry principles with antiprotonic helium atoms and antihydrogen.

Starting with basic properties of the neutron, this chapter reviews the most important neutron scattering methods that provide valuable information for a chemist. The range of such methods is amazingly wide, from standard methods of crystallography to neutron spin echo spectroscopy. Experimental techniques like neutron reflectometry and small angle neutron scattering are able to probe large-scale structures on the surface and in the bulk, thus providing access to the “nano-world.” Apart from traditional areas of solid-state physics, like studying phonons, a particular emphasis is placed on the microscopic and mesoscopic structure and dynamics in the liquid state. Practical aspects, such as main components of the instrumentation, are also touched upon.

This chapter presents the basic principles of activation analysis and details its different types. Emphasis is given to instrumental neutron activation analysis and radiochemical separations for the determination of trace and ultra-trace elements. Location sensitive analysis is also included.

This section presents the principles, the practical aspects, and the applications of neutron-induced prompt gamma activation analysis (PGAA). The fundamentals of the method, the characteristics of the analytical technique, and the instrumentation are introduced. The measurements of samples and standards together with the procedures of the quantitative analysis are described. High-energy gamma-ray spectroscopy, enabling reliable chemical analyses, is discussed in detail. A comprehensive section of the most recent applications of the PGAA method is also given.

Miscellaneous applications of low-voltage neutron generators providing 3 and 14 MeV neutrons via the D-D and D-T reactions, respectively, are reviewed. New experimental methods are reported, and emerging applications in the areas of prompt and delayed neutron activation analysis, fast neutron imaging and profiling, irradiation effects, fast neutron radiobiology, and shielding design are highlighted.

This chapter discusses the basic principles of analytical methods based on positive ion beams from particle accelerators. The methods, namely, particle-induced X-ray emission (PIXE), Rutherford backscattering spectroscopy (RBS), and nuclear reaction analysis (NRA) are described in detail. Besides the underlying physical processes, methodical questions, analytical capabilities, and typical fields of application are also discussed.

This chapter deals with the analytical applications of synchrotron radiation sources for trace-level analysis of materials on microscopic and submicroscopic scales. Elemental analysis with X-ray fluorescence is described in detail. Two-dimensional (2D) and three-dimensional (3D) analyses are discussed in their quantitative aspects. Related methods of analysis based on absorption edge phenomena such as X-ray absorption spectrometry (XAS) and near-edge scanning spectrometry (XANES) yielding molecular information, computerized X-ray fluorescence microtomography (XFCT) based on the penetrative character of X-rays, and microscopic X-ray diffraction (XRD) providing structural data on the sample are also briefly discussed. The methodological treatment is illustrated with a number of applications.

In radioactive tracer technique, radioactive nuclides are used to follow the behavior of elements or chemical species in chemical and other processes. This is realized by means of radioactivity measurement. In 1913, Hevesy and Paneth succeeded in determining the extremely low solubility of lead salts by using naturally occurring 210Pb as a radioactive tracer. As various radioactive nuclides became artificially available, this technique has been widely employed in studies of chemical equilibrium and reactions as well as in chemical analysis. It is also an essential technique in biochemical, biological, medical, geological, and environmental studies. Medical diagnosis and industrial process control are the fields of its most important practical application. In this chapter, fundamental ideas concerning radioactive tracers will be described followed by their application with typical examples. Detailed description on their application to life sciences and medicine is given in Vol. 4.

For the first time, a Handbook of Nuclear Chemistry systematically and comprehensively acknowledges the various aspects of radiopharmaceutical chemistry. It thus reflects the significant progress that has been made over the last decades leading to the establishment of an independent field of modern science. The development of radiopharmaceutical chemistry was, nevertheless, a century-long route. It is paved by persons, their ideas and scientific results, being of historical dimensions.

The therapeutic use of radionuclides in nuclear medicine, oncology, and cardiology is the most rapidly growing use of medical radionuclides. Since most therapeutic radionuclides are neutron rich and decay by β− emission, they are reactor-produced. This chapter deals mainly with production approaches with neutrons. Neutron interactions with matter, neutron transmission and activation rates, and neutron spectra of nuclear reactors are discussed in some detail. Further, a short discussion of the neutron-energy dependence of cross sections, reaction rates in thermal reactors, cross section measurements and flux monitoring, and general equations governing the reactor production of radionuclides are presented. Finally, the chapter is concluded by providing a number of examples encompassing the various possible reaction routes for the production of a number of medical radionuclides in a reactor.

Cyclotron products are gaining in significance in diagnostic investigations via PET and SPECT, as well as in some therapeutic studies. The scientific and technological background of radionuclide production using a cyclotron is briefly discussed. Production methods of the commonly used positron and photon emitters are described and developments in the production of some new positron emitters and therapeutic radionuclides outlined. Some perspectives of cyclotron production of medical radionuclides are considered.

Radionuclide generator systems continue to play a key role in providing both diagnostic and therapeutic radionuclides for various applications in nuclear medicine, oncology, and interventional cardiology. Although many parent/daughter pairs have been evaluated as radionuclide generator systems, there are a relatively small number of generators, which are currently in routine clinical and research use. Essentially every conceivable approach has been used for parent/separation strategies, including sublimation, thermochromatographic separation, solvent extraction, and adsorptive column chromatography. The most widely used radionuclide generator for clinical applications is the 99Mo/99mTc generator system, but recent years have seen an enormous increase in the use of generators to provide therapeutic radionuclides, which has paralleled the development of complementary technologies for targeting agents for therapy and in the general increased interest in the use of unsealed therapeutic radioactive sources. More recently, use of the 68Ge/68Ga generator is showing great potential as a source of positron-emitting 68Ga for positron emission tomography (PET)/CT imaging. Key advantages for the use of radionuclide generators include reasonable costs, the convenience of obtaining the desired daughter radionuclide on demand, and availability of the daughter radionuclide in high specific activity, no-carrier added form.

Methods for the synthesis of compounds labeled with the short-lived positron emitting radionuclide 11C are described. Important aspects on how to achieve high specific radioactivity and the need for technical solutions to establish a reproducible routine tracer production are pointed out. Examples of positron emission tomography (PET) as a tool in drug development are also included.

Positron emission tomography (PET) is a unique tool for the investigation, localization, and quantification of physiological activities in vivo by tracing the involved or accompanying biochemical processes. Because of its nuclear and chemical properties, fluorine-18, which is commonly produced by a cyclotron using the 18O(p,n)18F or the 20Ne(d,α)18F nuclear process, is a nearly ideal positron emitting radionuclide. Its half-life of 109.7 min permits tracer syntheses and imaging protocols extending over hours and allows distribution of 18F-radiopharmaceuticals to hospitals and facilities lacking a cyclotron. The low maximum positron energy of 635 keV results in low radiation doses, short ranges in tissue, and therefore in excellent imaging resolution. Introduction of 18F-fluorine, either via nucleophilic strategies using [18F]F− or electrophilic routes using molecular [18F]F₂, permits the synthesis of a broad spectrum of compounds within a time compatible with the half-life. Although fluorine is only slightly larger than a hydrogen atom, changes in the physiological behavior of bioactive compounds as a result of alteration in metabolic stability, lipophilicity, affinity to the target, or other structures, etc., are often observed even after F-for-H or F-for-OH substitutions. In this chapter, an overview of the scope and limitations of the 18F-chemistry is given. Fluorination strategies, routes, and synthetic aspects are exemplified, as far as possible, by established and selected 18F-radiopharmaceuticals with clinical relevance or with potential for further clinical application.Further ReadingA review of the clinical use and the potential of 18F-labeled radiopharmaceuticals are by far beyond the scope of this chapter. Excellent reviews have been published, e.g., on PET tracers for mapping cardiac nervous system (Langer and Halldin 2002), on the production (Stöcklin 1995) and future of clinical 18F-labeled radiopharmaceuticals (Stöcklin 1998; Shiue and Welch 2004) for the heart and brain (Stocklin 1992; Halldin et al. 2001), for the 5-HT system (Crouzel et al. 1992), on targeting peptide receptors by PET (Lundquist and Tolmachev 2002; Okarvi 2001, 2004; Schottelius and Wester 2009; Tolmachev and Stone-Elander 2010) on general aspects in “working against time” during rapid radiotracer synthesis (Fowler and Wolf 1997), on radiotracers for endogenous competition (Laruelle and Huang 2001), on molecular imaging of cancer with PET (Gambhir 2002), on hypoxia PET tracers (Grierson and Patt 1999), on 18F-fluorine chemistry (Lasne et al. 2002; Stöcklin and Pike 1993; Stöcklin 1995; Ametamey et al. 2008; Miller et al. 2008; Cai et al. 2008), on microwave heating (Stone-Elander and Elander 2002), or on fluorinase-based 18F-labeling (Onega et al 2009), to mention only a few.

This chapter reviews the radiopharmaceutical chemistry of technetium related to the synthesis of perfusion agents and to the labeling of receptor-binding biomolecules. To understand the limitations of technetium chemistry imposed by future application of the complexes in nuclear medicine, an introductory section analyzes the compulsory requirements to be considered when facing the incentive of introducing a novel radiopharmaceutical into the market. Requirements from chemistry, routine application, and market are discussed. In a subsequent section, commercially available 99mTc-based radiopharmaceuticals are treated. It covers the complexes in use for imaging the most important target organs such as heart, brain, or kidney. The commercially available radiopharmaceuticals fulfill the requirements outlined earlier and are discussed with this background. In a following section, the properties and perspectives of the different generations of radiopharmaceuticals are described in a general way, covering characteristics for perfusion agents and for receptor-specific molecules. Technetium chemistry for the synthesis of perfusion agents and the different labeling approaches for target-specific biomolecules are summarized. The review comprises a general introduction to the common approaches currently in use, employing the N _x S_4−x , [3+1] and 2-hydrazino-nicotinicacid (HYNIC) method as well as more recent strategies such as the carbonyl and the TcN approach. Direct labeling without the need of a bifunctional chelator is briefly reviewed as well. More particularly, recent developments in the labeling of concrete targeting molecules, the second generation of radiopharmaceuticals, is then discussed and prominent examples with antibodies/peptides, neuroreceptor targeting small molecules, myocardial imaging agents, vitamins, thymidine, and complexes relevant to multidrug resistance are given. In addition, a new approach toward peptide drug development is described. The section has a focus on coordination and labeling chemistry, but biological results are briefly summarized as well. The last (and shortest) section finally intends to give a (subjective) outlook for the future role of 99mTc-based radiopharmaceuticals. Critical comments are spread over the whole article but are concentrated in this section. Despite the increasing competition of diagnostic radiopharmacy by other commonly applied methods in medicine such as magnetic resonance imaging (MRI) or ultrasound, the authors are convinced that 99mTc will play a key role also in future if novel approaches are added and the requirements from chemistry biology and the market considered in research to a stronger extent.

An overview of the chemistry of radioiodination is presented. The focus is directed on the labeling of iodine-containing radiopharmaceuticals, with emphasis on practical aspects of the various radioiodination methods. The advantages and disadvantages of these methods with respect to efficiency and ease of handling are discussed. Examples of the labeling methods are illustrated by protocols.

Radiometals are of increased current interest because of the growing use of targeted radiotherapy for tumors and the development of generators that produce positron-emitting radiometals. In addition, biomedical cyclotrons allow the cheap production of some relevant radiometals. The design of the corresponding radiopharmaceuticals includes the synthesis of bifunctional chelators, which carry a functional unit for the immobilization of the radiometal and a functional group for the covalent attachment to a vector molecule. Radiometals of interest for therapeutic applications are some lanthanides, 67Cu, and 90Y. For diagnostic applications 61Cu, 62Cu, 64Cu, 89Zr, and 68Ga are currently used and corresponding radiopharmaceuticals are being designed. In this chapter, some properties and the synthesis of bifunctional chelators including metal ion selectivity and special aspects of coupling chemistry are being described.

Radionuclide therapy utilizes unsealed sources of radionuclides as a treatment for cancer or other pathological conditions such as rheumatoid arthritis. Radionuclides that decay by the emission of β and α particles, as well as those that emit Auger electrons, have been used for this purpose. In this chapter, radiochemical aspects of radionuclide therapy, including criteria for radionuclide selection, radionuclide production, radiolabeling chemistry, and radiation dosimetry are discussed.

The extension of the use of ionizing radiation and the new biological information on the effects of radiation exposure that is now becoming available, present new challenges to the development of concepts and methodology in determination of doses and assessment of hazards for the protection of living systems. Concise information is given on the deterministic and stochastic effects, on the debate concerning the effects of low doses, the detection of injuries by biological assays, and the radiation sickness.

Most radiation related to nuclear properties is outside the visible part of the electromagnetic spectrum or involves submicroscopic particles, hence is invisible. Detectors – devices to sense the radiation, and perhaps measure its properties – are essential. The emphasis in research has moved from the characterization of radioactivity, through simple nuclear reactions, to explorations of the extremes of nuclear matter, but the central importance of suitable radiation detectors has persisted. This chapter emphasizes detectors associated with measurements of radioactivity, as opposed to nuclear reactions. Thus, much of the current creative work is excluded, but otherwise the scope of these volumes would at least double. Detectors are classified broadly as based on ionization of gases, conduction in semiconductors, or scintillation. The concluding section is an introduction to systems based on two or more components of one of these basic types.

Chemical and physical radiation dosimetry methods, used for the measurement of absorbed dose mainly during the practical use of ionizing radiation, are discussed with respect to their characteristics and fields of application.

This chapter is designed to serve as a review and reference for the wide and still-evolving field of particle sources and accelerators. The object of this chapter is to give a comprehensive and easily understandable survey of the field in greater detail to the users of accelerators, nuclear physicists and chemists, as well as students. The field of particle accelerators covers facilities from hand-size mass separators through room-scale cyclotrons to huge storage rings. In spite of their important differences, all of them own a key subsystem, the ion source. The parameters of the ion beam generated in and extracted from the ion source determine the features of the accelerated beam on the target. Therefore, in Sect. 50.1, the ion sources of particle accelerators are reviewed. Section 50.2 is devoted to the electrostatic accelerators. The cyclic and linear accelerators are summarized in Sect. 50.3 where a survey on beam parameters is also given.

Methods of isotope enrichment and isotope separation are reviewed. Several examples of commercially important or historically important separative processes are discussed.

In 1805, Bucholz extracted uranium from a nitric acid solution into ether and back-extracted it into pure water. This is probably the first reported solvent-extraction investigation. During the following decades, the distribution of neutral compounds between aqueous phases and pure solvents was studied, e.g., by Peligot, Berthelot and Jungfleisch, and Nernst. Selective extractants for analytical purposes became available during the first decades of the twentieth century. From about 1940, extractants such as organophosphorous esters and amines were developed for use in the nuclear fuel cycle. This connection between radiochemistry and solvent-extraction chemistry made radiochemists heavily involved in the development of new solvent extraction processes, and eventually solvent extraction became a major separation technique in radiochemistry. About 160 years ago, Thompson and Way observed that soil can remove potassium and ammonium ions from an aqueous solution and release calcium ions. This is probably the first scientific report on an ion-exchange separation. The first synthesis of the type of organic ion exchangers that are used today was performed by Adams and Holmes in 1935. Since then, ion-exchange techniques have been used extensively for separations of various radionuclides in trace as well as macro amounts. During the last 4 decades, inorganic ion exchangers have also found a variety of applications. Today, solvent extraction as well as ion exchange are used extensively in the nuclear industry and for nuclear, chemical, and medical research. Some of these applications are discussed in the chapter.

The history, theoretical fundamentals, and practical application of thermochromatography are briefly reviewed. The main advantages of the method – the speed and selectivity of chemical separation of complex mixtures of short-lived radionuclides, including transactinide ones – are analyzed. Prospects of thermochromatography in production of radionuclides widely used in science and technology are considered on the basis of the performed systematic investigations of the thermochromatographic behavior of volatile compounds of the elements of the periodic table.

Some radionuclides, like 10Be (T_1/2 = 1.5 Ma), 14C (T_1/2 = 5,730 years), 26Al (T_1/2 = 0.716 Ma), 53Mn (T_1/2 = 3.7 Ma), and 60Fe (T_1/2 = 1.5 Ma), 146Sm (T_1/2 = 103 Ma), 182Hf (T_1/2 = 9 Ma), 244Pu (T_1/2 = 80 Ma) are either being produced continuously by the interaction of cosmic rays (CR) or might have been produced in supernovae millions of years ago. Analysis of these radionuclides in ultratrace scale has strong influence in almost all branches of sciences, starting from archaeology to biology, nuclear physics to astrophysics. However, measurement of these radionuclides appeared as a borderline problem exploiting their decay properties because of scarcity in natural archives and long half-life. The one and only way seemed to be that of mass measurement. Accelerator mass spectrometry (AMS) is the best suited for this purpose. Apart from AMS, other mass measurement techniques like inductively coupled plasma-mass spectrometry (ICP-MS), thermal ionization mass spectrometry (TIMS), resonant laser ionization mass spectrometry (RIMS), secondary ionization mass spectrometry (SIMS) have also been used with limited sensitivity and approach.This chapter gives an essence of measurement of cosmogenic or supernova-produced radionuclides with various mass spectrometric techniques with special emphasis on AMS. The challenges of AMS measurement like isobaric interference, and development of chemical methods for separation of isobars have also been discussed. An abridged discussion has been made on the other techniques like ICP-MS, TIMS, RIMS, and SIMS.

The environmental distribution of radionuclides, released from nuclear facilities and other sources, and the principles of the emergency countermeasures for radiation protection of the public and workers are discussed in this chapter. The concentration levels of radionuclides in various aquatic and terrestrial environments and the exposure levels of the population due to the various sources of radiation (natural and artificial radionuclides, cosmic radiation, diagnostic medical examinations, atmospheric nuclear tests, etc.) are presented.

The conversion of wavelengths to energies in keV is done by multiplying the reciprocal wavelength with the conversion factor 1.239841857(49) × 10−9 keV m (Mohr and Taylor 1999, 2000; CODATA 2003). The database of X-ray wavelengths for elements (Bearden 1967) has recently been updated, adjusted to the new standards, and compared with new calculations using the Dirac–Fock method (Deslattes et al. 2003a).

The chapter is devoted to the practical application of the fission process, mainly in nuclear reactors. After a historical discussion covering the natural reactors at Oklo and the first attempts to build artificial reactors, the fundamental principles of chain reactions are discussed. In this context chain reactions with fast and thermal neutrons are covered as well as the process of neutron moderation. Criticality concepts (fission factor η, criticality factor k) are discussed as well as reactor kinetics and the role of delayed neutrons. Examples of specific nuclear reactor types are presented briefly: research reactors (TRIGA and ILL High Flux Reactor), and some reactor types used to drive nuclear power stations (pressurized water reactor [PWR], boiling water reactor [BWR], Reaktor Bolshoi Moshchnosti Kanalny [RBMK], fast breeder reactor [FBR]). The new concept of the accelerator-driven systems (ADS) is presented. The principle of fission weapons is outlined. Finally, the nuclear fuel cycle is briefly covered from mining, chemical isolation of the fuel and preparation of the fuel elements to reprocessing the spent fuel and conditioning for deposit in a final repository.

This chapter describes, in two parts, new-generation nuclear energy systems that are required to be in harmony with nature and to make full use of nuclear resources. The issues of transmutation and containment of radioactive waste will also be addressed. After a short introduction to the first part, Sect. 58.1.2 will detail the requirements these systems must satisfy on the basic premise of peaceful use of nuclear energy. The expected designs themselves are described in Sect. 58.1.3. The subsequent sections discuss various types of advanced reactor systems. Section 58.1.4 deals with the light water reactor (LWR) whose performance is still expected to improve, which would extend its application in the future. The supercritical-water-cooled reactor (SCWR) will also be shortly discussed. Section 58.1.5 is mainly on the high temperature gas-cooled reactor (HTGR), which offers efficient and multipurpose use of nuclear energy. The gas-cooled fast reactor (GFR) is also included. Section 58.1.6 focuses on the sodium-cooled fast reactor (SFR) as a promising concept for advanced nuclear reactors, which may help both to achieve expansion of energy sources and environmental protection thus contributing to the sustainable development of mankind. The molten-salt reactor (MSR) is shortly described in Sect. 58.1.7. The second part of the chapter deals with reactor systems of a new generation, which are now found at the research and development (R&D) stage and in the medium term of 20–30 years can shape up as reliable, economically efficient, and environmentally friendly energy sources. They are viewed as technologies of cardinal importance, capable of resolving the problems of fuel resources, minimizing the quantities of generated radioactive waste and the environmental impacts, and strengthening the regime of nonproliferation of the materials suitable for nuclear weapons production. Particular attention has been given to naturally safe fast reactors with a closed fuel cycle (CFC) – as an advanced and promising reactor system that offers solutions to the above problems. The difference (not confrontation) between the approaches to nuclear power development based on the principles of “inherent safety” and “natural safety” is demonstrated.

This chapter contains the information about nuclear power sources for space systems. Reactor nuclear sources are considered that use the energy of heavy nuclei fission generated by controlled chain fission reaction, as well as the isotope ones producing heat due to the energy of nuclei radioactive decay. Power of reactor nuclear sources is determined by the rate of heavy nuclei fission that may be controlled within a wide range from the zero up to the nominal one. Thermal power of isotope sources cannot be controlled. It is determined by the type and quantity of isotopes and decreases in time due to their radioactive decay. Both, in the reactor sources and in the isotope ones, nuclear power is converted into the thermal one that may be consumed for the coolant heating to produce thrust (Nuclear Power Propulsion System, NPPS) or may be converted into electricity (Nuclear Power Source, NPS) dynamically (a turbine generator) or statically (thermoelectric or thermionic converters). Electric power is supplied to the airborne equipment or is used to produce thrust in electric (ionic, plasma) low-thrust engines. A brief description is presented of the different nuclear systems with reactor and isotopic power sources implemented in Russia and the USA. The information is also given about isotopic sources for the ground-based application, mainly for navigation systems.

This chapter gives the conditions for achieving power production using nuclear fusion reactions. The two basic schemes for plasma confinement, inertial and magnetic, are briefly considered and the present technical solutions are outlined. The physical and chemical processes taking place between the hot plasma and the containing vessel wall are discussed in more detail. At the end of the chapter, the present status of research and the planned future development plans are summarized.

Issues related to the management of radioactive wastes are presented with specific emphasis on high-level wastes generated as a result of energy and materials production using nuclear reactors. The final disposition of these high-level wastes depends on which nuclear fuel cycle is pursued, and range from once-through burning of fuel in a light water reactor followed by direct disposal in a geologic repository to more advanced fuel cycles (AFCs) where the spent fuel is reprocessed or partitioned to recover the fissile material (primarily 235U and 239Pu) as well as the minor actinides (MAs) (neptunium, americium, and curium) and some long-lived fission products (e.g., 99Tc and 129I). In the latter fuel cycle, the fissile materials are recycled through a reactor to produce more energy, the short-lived fission products are vitrified and disposed of in a geologic repository, and the minor actinides and long-lived fission products are converted to less radiotoxic or otherwise stable nuclides by a process called transmutation. The advantages and disadvantages of the various fuel cycle options and the challenges to the management of nuclear wastes they represent are discussed.

A short history and treatment of the various aspects of nuclear forensic analysis is followed by a discussion of the most common chemical procedures, including applications of tracers, radioisotopic generators, and sample chronometry. Analytic methodology discussed includes sample preparation, radiation detection, various forms of microscopy, and mass-spectrometric techniques. The chapter concludes with methods for the production and treatment of special nuclear materials and with a description of several actual case studies conducted at Livermore.

This chapter deals with the “nuclear safeguards” verification system and describes procedures and measurement methods that allow the safeguards inspectorates/authorities to verify that nuclear materials or facilities are not used to further undeclared military activities. These procedures and methods provide the strong technical basis upon which the safeguards inspectorates/authorities issue their conclusions and receive the broadest international acceptance regarding the compliance of participating states with their obligations.