Plutonium chemical separation

Chemical Separation. A reprocessing facility typically utilizes multiple extraction/reextraction (stripping) cycles for the recovery and purification of uranium and plutonium. For example, a co-decontamination and partitioning cycle is followed by one or more cycles of uranium and plutonium purification. The basic process is illustrated in Figure 3. 

Although the outline of a chemical separation process could be obtained by tracer-scale investigations, the process could not be defined with certainty until study of it was possible at the actual separation plants. Therefore, the question in the summer of 1942, was as follows How could any separations process be tested at the concentration of plutonium that would exist several years later in the production plants when, at this time, there was not even a microgram of plutonium available This problem was solved through an unprecedented series of experiments encompassing two major objectives. First, it was decided to attempt the production... 

Berkeley, and, essentially simultaneously, by Hindman and coworkers (1949) at the Metallurgical Laboratory and Mastick and Wahl (1944) at the Los Alamos Laboratory the latter two groups utilized the milligram amounts of plutonium made available at the time through the operation of the reactor and chemical separation plant at the Clinton Laboratories in Tennessee. The existence of the V oxidation state was established in the summer of 1944, through the use of plutonium obtained from the Clinton Laboratories, by Connick and coworkers (1949), at the University of California, Berkeley. 

Other reasons for investigating plutonium photochemistry in the mid-seventies included the widely known uranyl photochemistry and the similarities of the actinyl species, the exciting possibilities of isotope separation or enrichment, the potential for chemical separation or interference in separation processes for nuclear fuel reprocessing, the possible photoredox effects on plutonium in the environment, and the desire to expand the fundamental knowledge of plutonium chemistry. 

The plutonium concentration in marine samples is principally due to environmental pollution caused by fallout from nuclear explosions and is generally at very low levels [75]. Environmental samples also contain microtraces of natural a emitters (uranium, thorium, and their decay products) which complicate the plutonium determinations [76]. Methods for the determination of plutonium in marine samples must therefore be very sensitive and selective. The methods reported for the chemical separation of plutonium are based on ion exchange resins [76-80] or liquid-liquid extraction with tertiary amines [81], organophosphorus compounds [82,83], and ketones [84,85]. 

Hanford and Richland, Washington, was selected for industrial-scale plutonium production and chemical separations facilities on January 16, 1943. This site was named the Hanford Engineer Works (later named the Hanford Site). 

A primary goal of chemical separation processes in the nuclear industry is to recover actinide isotopes contained in mixtures of fission products. To separate the actinide cations, advantage can be taken of their general chemical properties [18]. The different oxidation states of the actinide ions lead to ions of charges from +1 (e.g., NpOj) to +4 (e.g., Pu" " ) (see Fig. 12.1), which allows the design of processes based on oxidation reduction reactions. In the Purex process, for example, uranium is separated from plutonium by reducing extractable Pu(IV) to nonextractable Pu(III). Under these conditions, U(VI) (as U02 ) and also U(IV) (as if present, remain in the... 

Actinides were determined at the ultratrace level in moss samples collected from the eastern Italian Alps (1500 m a.s.l.). The frozen samples were cut into 1-2 cm sections and analyzed separately to obtain the distribution curves of the vertical concentrations. For plutonium and americium isotope analysis, 1-2 g of the samples were ashed, leached, separated with respect to analytes and analyzed by alpha spectrometry and LA-ICP-MS after the plutonium or americium had been electroplated on a stainless steel disk.23 Estimated limits of quantification of LA-ICP-MS for actinide radionuclides deposited on stainless steel plates after chemical separation are summarized in Table 9.45. For most of the long-lived radionuclides in moss samples, lower limits of determination were found at the 10 15gg 1 concentration level compared to those of a - spectrometry 23... 

Apostolidis, C., Molinet, R., Richir, P., Ougier, M., and Mayer, K., Development and validation of a simple, rapid, and robust method for the chemical separation of uranium and plutonium, Radiochim. Acta, 83, 21-25, 1998. 

McLeod, K.W., Adriano, D.C., Boni, A.L., Corey, J.C., Horton, J.H., Paine, D. Pinder, J.E. Ill (1980) Influence of a nuclear fuel chemical separations facility on the plutonium content of a wheat crop. Journal of Environmental Quality, 9,306-15. 

Shinn, J.H., Homan, D.N. Gay, D.D. (1983) Plutonium aerosol fluxes and pulmonary exposure rates during re-suspension from bare soils near a chemical separation facility. In Precipitation Scavenging, Dry Deposition and Re-suspension, ed. H.R. Pruppacher, R.G. Semonin W.G.N. Slinn, pp. 1131 43. Amsterdam Elsevier. 

Table II. Interferences in Environmental Plutonium Measurements by Chemical Separation and a-Spectrometry...

Plutonium is manufactured in megagram quantities neptunium, americium, and curium in kilogram quantities californium in gram amounts berkelium in 100-milligram amounts and einsteinium in milligram quantities. Chemical separations play a key role in the manufacture of actinide elements, as well as in their recovery, and analysis in the nuclear fuel cycle. This collection of timely and state-of-the-art topics emphasizes the continuing importance of actinide separations processes. 

Plutonium. (74) Plutonium can be chemically separated from all other elements except neptunium and counted quantitatively by this procedure, and the 4.78 MeV Np peak can be resolved by its energy difference from 5.15 MeV The... 

This plutonium-239 can be chemically separated and used as a nuclear fuel in another reactor. 

Direct calcination of Pu(N03)4 involves no chemical separations that could remove impurities, so a highly pure plutonium nitrate feed solution is required. The plutonium dioxide product can be hydrofluorinated to PUF4, or it can be used as a feed for the formation of PUCI3. Direct calcination has received less industrial-scale application than the precipitation processes described above [C2]. 

Chemical separation. Current concepts for high-efficiency separation of actinides call for improved plutonium recovery, coextraction of uranium and neptunium with subsequent partitioning by valence control, and extraction of amercium and curium from the HAW stream. There are a number of major problems to be solved before a technically feasible process will be available. 

In Germany in 1938, Otto Hahn and Fritz Strassmann, skeptical of claims by Enrico Fermi and Irene Johot-Curie that bombardment of uranium by neutrons produced new so-called transuranic elements (elements beyond uranium), repeated these experiments and chemically isolated a radioactive isotope of barium. Unable to interpret these findings, Hahn asked Lise Meitner, a physicist and former colleague, to propose an explanation for his observations. Meitner and her nephew, Otto Frisch, showed that it was possible for the uranium nucleus to be spfit into two smaller nuclei by the neutrons, a process that they termed fission. The discovery of nuclear fission eventually led to the development of nuclear weapons and, after World War II, the advent of nuclear power to generate electricity. Nuclear chemists were involved in the chemical purification of plutonium obtained from uranium targets that had been irradiated in reactors. They also developed chemical separation techniques to isolate radioactive isotopes for industrial and medical uses from the fission products wastes associated with plutonium production for weapons. Today, many of these same chemical separation techniques are being used by nuclear chemists to clean up radioactive wastes resulting from the fifty-year production of nuclear weapons and to treat wastes derived from the production of nuclear power. 

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