Thorium and Uranium

2 Uranium and thorium. It appears almost certain that thorium does not deviate from the tetravalent state in the environment. It is very strongly particle reactive (Kd 107) and there is no evidence to suggest that thorium isotopes migrate in sedimentary materials (Bernat and Goldberg, 1969). 

Total tetravalent uranium may be precipitated as an insoluble oxalate or fluoride (Grinberg et at., 1957) or in trace amounts co-precipitated for example with neodymium fluoride (cf. Pu ). Such a procedure can be used to show whether uranium is present in the lower oxidation state, for example, in anoxic waters because hexavalent uranium does not co-precipitate in this way. 

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Much of the internal heat of the earth is thought to be attributable to the presence of uranium and thorium. 

Lead occurs naturally as a mixture of four non-radioactive isotopes, and Pb, as well as the radioactive isotopes ° Pb and Pb. All but Pb arise by radioactive decay of uranium and thorium. Such decay products are known as radiogenic isotopes. 

A more constrained opportunity for nitrate bioremediation arose at the US-DoE Weldon Spring Site near St. Louis, Missouri. This site had been a uranium and thorium processing faciUty, and treatment of the metal had involved nitric acid. The wastestream, known as raffinate, was discharged to surface inpoundments and neutralized with lime to precipitate the metals. Two pits had nitrate levels that requited treatment before discharge, but heavy rains in 1993 threatened to cause the pits to overflow. Bioremediation by the addition of calcium acetate as a carbon source successfully treated more than 19 million liters of water at a reasonable cost (75). 

Radioactivity occurs naturally in earth minerals containing uranium and thorium. It also results from two principal processes arising from bombardment of atomic nuclei by particles such as neutrons, ie, activation and fission. Activation involves the absorption of a neutron by a stable nucleus to form an unstable nucleus. An example is the neutron reaction of a neutron and cobalt-59 to yield cobalt-60 [10198 0-0] Co, a 5.26-yr half-life gamma-ray emitter. Another is the absorption of a neutron by uranium-238 [24678-82-8] to produce plutonium-239 [15117 8-5], Pu, as occurs in the fuel of a nuclear... 

The same chemical separation research was done on thorium ores, leading to the discovery of a completely different set of radioactivities. Although the chemists made fundamental distinctions among the radioactivities based on chemical properties, it was often simpler to distinguish the radiation by the rate at which the radioactivity decayed. For uranium and thorium the level of radioactivity was independent of time. For most of the radioactivities separated from these elements, however, the activity showed an observable decrease with time and it was found that the rate of decrease was characteristic of each radioactive species. Each species had a unique half-life, ie, the time during which the activity was reduced to half of its initial value. 

By this time, the Periodic Table of elements was well developed, although it was considered a function of the atomic mass rather than atomic number. Before the discovery of radioactivity, it had been estabUshed that each natural element had a unique mass thus it was assumed that each element was made up of only one type of atom. Some of the radioactivities found in both the uranium and thorium decays had similar chemical properties, but because these had different half-Hves it was assumed that there were different elements. It became clear, however, that if all the different radioactivities from uranium and thorium were separate elements, there would be too many to fit into the Periodic Table. 

C. Frondel, Systematic Mineralogy of Uranium and Thorium, U.S. Geological Survey Bulletin 1064, Washington, D.C., 1958. 

Carbides of the Actinides, Uranium, and Thorium. The carbides of uranium and thorium are used as nuclear fuels and breeder materials for gas-cooled, graphite-moderated reactors (see Nuclearreactors). The actinide carbides are prepared by the reaction of metal or metal hydride powders with carbon or preferably by the reduction of the oxides uranium dioxide [1344-57-6] UO2 tduranium octaoxide [1344-59-8], U Og, or thorium... 

Table 3. Physical Properties of Uranium and Thorium Carbides...

ISOLATION OF URANIUM AND THORIUM FROM NATURAL SAMPLES... 

Uranium and thorium are the first members of natural radioactive chain which makes their determination in natural materials interesting from geochemical and radioecological aspect. They are quantitatively determined as elements by spectrophotometric method and/or their radioisotopes by alpha spectrometry. It is necessary to develop inexpensive, rapid and sensitive methods for the routine researches because of continuous monitoring of the radioactivity level. 

SI 1962/2710 Radioactive Substances (Uranium and Thorium) Exemption Order... 

SI 1962/2711 Radioactive Substances (Prepared Uranium and Thorium Compounds) Order... 

Spectral Gamma Ray Log. This log makes use of a very efficient tool that records the individual response to the different radioactive minerals. These minerals include potassium-40 and the elements in the uranium family as well as those in the thorium family. The GR spectrum emitted by each element is made up of easily identifiable lines. As the result of the Compton effect, the counter records a continuous spectrum. The presence of potassium, uranium and thorium can be quantitatively evaluated only with the help of a computer that calculates in real time the amounts present. The counter consists of a crystal optically coupled to a photomultiplier. The radiation level is measured in several energy windows. 

The examination and analysis of minerals have provided x-ray emission spectrography with a challenge and an opportunity. This situation has arisen because of a great growth of interest in uranium and thorium minerals in the rare-earth oxides and in metals such as tantalum and niobium, or hafnium and zirconium. On the whole, x-ray emission spectrography has met the challenge successfully, and the investigations that prove this also demonstrate the versatility and the value of the method.70"72... 

Our information on AHf(PuF4,c) is based on high temperature reactions (600-900 K) already assessed in 1966 by Rand (21) and on extrapolation of uranium and thorium tetrafluoride data. Thus we have... 

Astatine is a radioactive element that occurs in nature in uranium and thorium ores, but only to a minute extent. Samples are made by bombarding bismuth with a particles in a cyclotron, which accelerates the particles to a very high speed. Astatine isotopes do not exist long enough for its properties to be studied, but it is thought from spectroscopic measurements to have properties similar to those of iodine. 

The deposition of pyrolytic graphite in a fluidized bed is used in the production of biomedical components such as heart valves, ] and in the coating of uranium- and thorium-carbides nuclear-fuel particles for high temperature gas-cooled reactors, for the purpose of containing the products of nuclear fission.fl" The carbon is obtained from the decomposition of propane (CgHg) or propylene (CgHg) at 1350°C, or of methane (CH4) at 1800°C. Its structure is usually isotropic (see Ch. 4). 

These methods deal with specific cases. The list of examples is not exhaustive. The low-T (200-300°C) decomposition of the transition-metal borohydrides M(BH4> , e.g., leads to titanium, zirconium, halfnium, uranium and thorium borides . Alternatively, the uranium diboride may be obtained by reacting uranium hydride with diborane in hydrogen at 200-400°C. 

Ernest Rutherford observed that the paths taken by energetic particles emitted by radioactive uranium and thorium responded in three ways to magnetic fields slightly bent, strongly bent, and unaffected. He gave them the designations or, fi, and y. Even though scientists soon identified the particles, they still use these names to emphasize that they are nuclear decay products. 

The structural chemistry of the actinides is often similar to that of lighter transition metals, such as Zr and Hf, and to that of the lanthanides however, the diffuse nature of the 5/ orbitals leads to some differences and specifically to interesting magnetic and electrical properties. The actinide sulfides are generally isostructural with the selenides, but not with the analogous tellurides. The binary chalcogenides of uranium and thorium have been discussed in detail [66], but the structural... 

Narducd AA, Ibers JA (1998) Ternary and quaternary uranium and thorium chalcogenides. Chem Mater 10 2811-2823... 

Curie M (1898) Rays emitted by compounds of uranium and thorium. Comptes Rendus de Seances de I academie de Sciences 126 1101-1103... 

The uranium and thorium decay-series contain radioactive isotopes of many elements (in particular, U, Th, Pa, Ra and Rn). The varied geochemical properties of these elements cause nuclides within the chain to be fractionated in different geological environments, while the varied half-lives of the nuclides allows investigation of processes occurring on time scales from days to 10 years. U-series measurements have therefore revolutionized the Earth Sciences by offering some of the only quantitative constraints on time scales applicable to the physical processes that take place on the Earth. 

Van Orman JA, Grove TL, Shimizu N (1998) Uranium and thorium diffusion in diopside. Earth Planet Sci Lett 160 505-519... 

In this chapter we discuss improvements documented in the literature over the past decade in these areas and others. Chemical procedures, decay-counting spectroscopy, and mass spectrometric techniques published prior to 1992 were previously discussed by Lally (1992), Ivanovich and Murray (1992), and Chen et al. (1992). Because ICPMS methods were not discussed in preceding reviews and have become more commonly used in the past decade, we also include some theoretical discussion of ICPMS techniques and their variants. We also primarily focus our discussion of analytical developments on the longer-lived isotopes of uranium, thorium, protactinium, and radium in the uranium and thorium decay series, as these have been more widely applied in geochemistry and geochronology. 

Subsequently, a wide array of developments in TIMS methods for uranium-series measurement occurred during the past decade including initiation of methods for measurement of long-lived radium (Volpe et al. 1991 Cohen and O Nions 1991) and protactinium isotopes (Pickett et al. 1994 Bourdon et al. 1999), development of improved sources or ionization methods for TIMS analysis, and introduction of commercially available multi-collector TIMS instruments designed specifically for uranium and thorium isotopic measurement. 

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