Actinide elements production

Ion exchange (qv see also Chromatography) is an important procedure for the separation and chemical identification of curium and higher elements. This technique is selective and rapid and has been the key to the discovery of the transcurium elements, in that the elution order and approximate peak position for the undiscovered elements were predicted with considerable confidence (9). Thus the first experimental observation of the chemical behavior of a new actinide element has often been its ion-exchange behavior—an observation coincident with its identification. Further exploration of the chemistry of the element often depended on the production of larger amounts by this method. Solvent extraction is another useful method for separating and purifying actinide elements. 

Hamilton, J. G. (1948a). The metabolic properties of the fission products and actinide elements, Rev. Mod. Phys. 10, 718. 

Dr. Darleane C. Hoffman of the Nuclear Science Division of the Lawrence Berkeley National Laboratory and Department of Chemistry at the University of California at Berkeley has written and presented several papers documenting her work and that of her team on the laboratory production of transactinide and actinide elements one-atom-at-a-time. She explains the difficulty of determining the chemistry of heavy elements How long does an atom need to exist before it s possible to do any meaningful chemistry on it Is it possible to learn anything at all about the reactions of an element for which no more... 

Thorium is commonly found in combination with other actinide elements, with organic and inorganic chemicals, and with acids and bases during occupational exposure. The health effects of occupational exposures to thorium on humans, therefore, cannot necessarily be attributed to thorium. The daughter products of thorium have unique properties that also add to the radiological toxicity of thorium. For further information, see the toxicological profiles on uranium, radon, and radium. 

Americium may be separated from other elements, particularly from the lanthanides or other actinide elements, by techniques involving oxidation, ion exchange and solvent extraction. One oxidation method involves precipitation of the metal in its trivalent state as oxalate (controlled precipitation). Alternatively, it may be separated by precipitating out lanthanide elements as fluorosilicates leaving americium in the solution. Americium may also he oxidized from trivalent to pentavalent state by hypochlorite in potassium carbonate solution. The product potassium americium (V) carbonate precipitates out. Curium and rare earth metals remain in the solution. An alternative approach is to oxidize Am3+ to Am022+ in dilute acid using peroxydisulfate. Am02 is soluble in fluoride solution, while trivalent curium and lanthanides are insoluble. 

The incorporation of more inorganic appendages into TSIL cations has also been achieved through the use of l-(3-aminopropyl)imidazole. Phosphoramide groups are readily synthesized by treatment of phosphorous(V) oxyhahdes with primary or secondary amines. In just such an approach, l-(3-aminopropyl)imidazole was allowed to react with commerdaUy available (C H5)2POCl2 in dichloromethane. After isolation, the resulting phosphoramide was then quaternized at the imidazole N(3) position by treatment with ethyl iodide (Scheme 2.3-2). The viscous, oily product was found to mix readily with more conventional ionic Hquids such as [HMIM][PF ], yielding a more tractable material. This particular TSIL has been used to extract a number of actinide elements from water. Similarly, the thiourea-appended TSILs discussed earlier have been used for the extraction of Hg and Cd from IL-immiscible aqueous phases. 

The lanthanide elements are very difficult to separate because of their highly similar chemistry, but the earlier actinide elements have sufficiently different redox chemistry to allow easy chemical separations. This is important in the nuclear power industry, where separations have to be made of the elements produced in fuel rods of nuclear power stations as fission products, and of the products Np and Pu, which arise from the neutron bombardment of the uranium fuel. 

This paper describes a new reaction which may yield useful amounts of the product isotope following neutron capture by lanthanide or actinide elements. The trivalent target ion is exchanged into Linde X or Y zeolite, fixed in the structure by appropriate heat treatment, and irradiated in a nuclear realtor. The (n, y) product isotope, one mass unit heavier than the target, is ejected from its exchange site location by y recoil. It may then be selectively eluted from the zeolite. The reaction has been demonstrated with several rare earths, and with americium and curium. Products typically contain about 50% of the neutron capture isotope, accompanied by about 1% of the target isotope. The effect of experimental variables on enrichment is discussed. 

In the chemistry of the fuel cycle and reactor operations, one must deal with the chemical properties of the actinide elements, particularly uranium and plutonium and those of the fission products. In this section, we focus on the fission products and then chemistry. In Figures 16.2 and 16.3, we show the chemical composition and associated fission product activities in irradiated fuel. The fission products include the elements from zinc to dysprosium, with all periodic table groups being represented. 

Fly ash increases the density, decreases the permeability, and increases the leaching resistance of Ordinary Portland Cement (OPC). It is a truism that The leach resistance of solidified cement-waste systems can be improved by any process which accelerates curing, limits porosity, or chemically bonds fission product or actinide elements. (Jantzen et al., 1984). Supercritical C02 treatment of a modified Portland cement is expected to further increase the density over the untreated material, so that a reduced porosity and improved leachability should result. In addition, the high silica content of fly ash, with its well-known sorbent properties toward actinides and certain other radionuclides, enhances the immobilization characteristics. 

Most radioactive particles and vapours, once deposited, are held rather firmly on surfaces, but resuspension does occur. A radioactive particle may be blown off the surface, or, more probably, the fragment of soil or vegetation to which it is attached may become airborne. This occurs most readily where soils and vegetation are dry and friable. Most nuclear bomb tests and experimental dispersions of fissile material have taken place in arid regions, but there is also the possibility of resuspension from agricultural and urban land, as an aftermath of accidental dispersion. This is particularly relevant to plutonium and other actinide elements, which are very toxic, and are absorbed slowly from the lung, but are poorly absorbed from the digestive tract. Inhalation of resuspended activity may be the most important route of human uptake for actinide elements, whereas entry into food chains is critical for fission products such as strontium and caesium. 

Although ICP-MS has been used for analysis of nuclear materials, often the entire instrument must be in an enclosed hot enclosure [350]. Sample preparation equipment, inlets to sample introduction systems, vacuum pump exhaust, and instrument ventilation must be properly isolated. Many of the materials used in the nuclear industry must be of very high purity, so the low detection limits provided by ICP-MS are essential. The fission products and actinide elements have been measured by using isotope dilution ICP-MS [351]. Because isotope ratios are not predictable, isobaric and molecular oxide ion spectral overlaps cannot be corrected mathematically, so chemical separation is required. 

Actinides served already as targets, when neutron capture and subsequent P decay were used for the first synthesis of transuranium elements. Later, up to the synthesis of seaborgium, actinides were irradiated with light-ion beams from accelerators. At that time it was already known that cold fusion reactions yield higher cross sections for heavy element production. 

Since both the vacuum isolation foil and the target backing foil must hold a pressure difference of greater than 1 bar, relatively thick metal foils, such as 2.5 mg/cm2 Be or 1.8 mg/cm2 HAVAR, have been used. These thick foils are especially attractive when considering the mechanical stability of extremely radioactive actinide targets. Variations on the double-window target system have traditionally been used for heavy element production with actinide target materials. 

The location of berkelium, a beta emitter which cannot be monitored, can be estimated from the position of the californium in the column, as determined by the neutron peak (from 2 2cf), during the time that curium is in the effluent solution. Typical neutron peaks are shown in Fig. 2. By comparison of the relative distribution coeffients of the actinides, the berkelium location is known to be about midway between californium and curium. The last 5-10% of the americium-curium is purposely routed into the transcurium element product tank to minimize the berkelium loss. Subsequently, this americium-curium is recovered in a second-cycle LiCl AIX run. 

G. T. Seaborg and J. J. Katz, eds., The Actinide Elements, Positional Nuclear Energy Series, Div. IV, 14A, McGraw-Hill Book Co., Inc., New York, 1954 G. T. Seaborg, ed., Transuranium Elements Products of Modern Alchemy, Benchmark Papers, Dowden, Hutchinson Ross, Inc., Stroudsburg, Pa.,... 

The burning of the uranium-based nuclear fuel causes a cavalcade of chemical and physical transformations. Nuclear reactions lead to the formation of a variety of actinide elements, for example, Np, Pu, Am, and Cm, as radioactive fission products. As a result of the production of these highly radioactive elements, burnt nuclear fuel must be allowed to cool until the short-hved isotopes decay away and reduce the thermal generation. The cooling typically takes place in either water ponds or engineered dry casks/facilities. 

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