Plutonium isolation

The discovery of nuclear fission in 1938 proved the next driver in the development of coordination chemistry. Uranium-235 and plutonium-239 both undergo fission with slow neutrons, and can support neutron chain reactions, making them suitable for weaponization in the context of the Manhattan project. This rapidly drove the development of large-scale separation chemistry, as methods were developed to separate and purify these elements. While the first recovery processes employed precipitation methods (e.g., the bismuth phosphate cycle for plutonium isolation). 

Kilogram amounts of neptunium ( Np) have been isolated as a by-product of the large-scale synthesis of plutonium in nuclear reactors that utilise 235u and 238u as fuel. The following transmutations occur ... 

The wastes from uranium and plutonium processing of the reactor fuel usually contain the neptunium. Precipitation, solvent extraction, ion exchange, and volatihty procedures (see Diffusion separation methods) can be used to isolate and purify the neptunium. 

Transuranic Waste. Transuranic wastes (TRU) contain significant amounts (>3,700 Bq/g (100 nCi/g)) of plutonium. These wastes have accumulated from nuclear weapons production at sites such as Rocky Flats, Colorado. Experimental test of TRU disposal is planned for the Waste Isolation Pilot Plant (WIPP) site near Carlsbad, New Mexico. The geologic medium is rock salt, which has the abiUty to flow under pressure around waste containers, thus sealing them from water. Studies center on the stabiUty of stmctures and effects of small amounts of water within the repository. 

Plutonium was the first element to be synthesized in weighable amounts (6,7). Technetium, discovered in 1937, was not isolated until 1946 and not named until 1947 (8). Since the discovery of plutonium in 1940, production has increased from submicrogram to metric ton quantities. Because of its great importance, more is known about plutonium and its chemistry than is known about many of the more common elements. The metallurgy and chemistry are complex. MetaUic plutonium exhibits seven aUotropic modifications. Five different oxidation states are known to exist in compounds and in solution. 

The first preparation, isolation, and weighing of a pure compound of plutonium, plutonium(lV) oxide [12059-95-5] PUO2, was achieved in 1942 by... 

Plutonium occurs in natural ores in such small amounts that separation is impractical. The atomic ratio of plutonium to uranium in uranium ores is less than 1 10 however, traces of primordial plutonium-244 have been isolated from the mineral bastnasite (16). One sample contained 1 x 10 g/g ore, corresponding to a plutonium-244 [14119-34-7] Pu, terrestrial abundance of 7 x 10 to 2.8 x 10 g/g of mineral and to <10g of primordial Pu on earth. The content of plutonium-239 [15117 8-3], Pu, in uranium minerals is given in Table 2. 

Since the amount of fissile material in the fuel assemblies is only about 3 percent of the uranium present, it is obvious that there cannot be a large amount of radioactive material in the SNF after fission. The neutron flux produces some newly radioactive material in the form of uranium and plutonium isotopes. The amount of this other newly radioactive material is small compared to the volume of the fuel assembly. These facts prompt some to argue that SNF should be chemically processed and the various components separated into nonradioac-tive material, material that will be radioactive for a long time, and material that could be refabricated into new reactor fuel. Reprocessing the fuel to isolate the plutonium is seen as a reason not to proceed with this technology in the United States. 

Congress has decided that reprocessing will not be practiced in this country so that we will not be in the plutonium production business. This seems like a safe thing to do since this action will minimize terrorism threats. Reprocessing generates chemi cal wastes but greatly reduces the volume of the highly radioactive waste. It also isolates plutonium and unused fuel for possible use as new fuel. 

American nuclear chemist Glenn Seaborg s team of experimenters isolates plutonium, which proves to be a better fuel for nuclear reactors than uranium because of its greater energy yield. 

When the Plutonium Project was established early in 1942, for the purpose of producing plutonium via the nuclear chain reaction in uranium in sufficient quantities for its use as a nuclear explosive, we were given the challenge of developing a chemical method for separating and isolating it from the uranium and fission products. We had already conceived the principle of the oxidation-reduction cycle, which became the basis for such a separations process. This principle applied to any process involving the use of a substance which carried plutonium in one of its oxidation states but not in another. By use of this... 

The first isolation of plutonium was effected in room 405, Jones Laboratory, by starting with a concentrate containing the order of a microgram of plutonium in about 10 milligrams of rare earths prepared for us by Arthur C. Wahl and co-workers at Berkeley. My journal records this event as follows ... 

The descriptions of the first isolation and first weighing of plutonium that appeared in Metallurgical Laboratory Reports at that time have been reproduced in a Benchmark Book of reprints (Seaborg, 1978). 

The reason for the ultramicrochemical test was to establish whether the bismuth phosphate would carry the plutonium at the concentrations that would exist at the Hanford extraction plant. This test was necessary because it did not seem logical that tripositive bismuth should be so efficient in carrying tetrapositive plutonium. In subsequent months there was much skepticism on this point and the ultramicrochemists were forced to make repeated tests to prove this point. Thompson soon showed that Pu(Vl) was not carried by bismuth phosphate, thus establishing that an oxidation-reduction cycle would be feasible. All the various parts of the bismuth-phosphate oxidation-reduction procedure, bulk reduction via cross-over to a rare earth fluoride oxidation-reduction step and final isolation by precipitation of plutonium (IV) peroxide were tested at the Hanford concentrations of... 

For instance, observation of identical phases for zirconium and plutonium indicate that the zirconium compound would serve as a suitable matrix in which to isolate plutonium. Similarly, the appearance of identical phases for Th, U and Np makes possible the doping of uranium or neptunium into a thorium matrix. 

The only crystalline phase which has been isolated has the formula Pu2(OH)2(SO )3(HaO). The appearance of this phase is quite remarkable because under similar conditions the other actinides which have been examined form phases of different composition (M(OH)2SOit, M=Th,U,Np). Thus, plutonium apparently lies at that point in the actinide series where the actinide contraction influences the chemistry such that elements in identical oxidation states will behave differently. The chemistry of plutonium in this system resembles that of zirconium and hafnium more than that of the lighter tetravalent actinides. Structural studies do reveal a common feature among the various hydroxysulfate compounds, however, i.e., the existence of double hydroxide bridges between metal atoms. This structural feature persists from zirconium through plutonium for compounds of stoichiometry M(OH)2SOit to M2 (OH) 2 (S0O 3 (H20) i,. Spectroscopic studies show similarities between Pu2 (OH) 2 (SOO 3 (H20) i, and the Pu(IV) polymer and suggest that common structural features may be present. 

A1though quadrivalent plutonium forms complexes up to PuClg with the increasing HC1 concentration,quantitative data only exist for the cationic species.In fact, for complexes containing more than two chlorides only two results have been reported log 63(PuCl j = - 0.8 and - 1 in 4 M HCIO4 (103) and 1 to 5 M (HCIO4-KCI) (104), respectively.As these data are isolated, they... 

In what follows we briefly review some of the previous attempts to analyze the available spectra of plutonium (6). In addition, we estimate energy level parameters that identify at least the gross features characteristic of the spectra of plutonium in various valence states in the lower energy range where in most cases, several isolated absorption bands can be discerned. The method used was based on our interpretation of trivalent actinide and lanthanide spectra, and the generalized model referred to earlier in the discussion of free-ion spectra. 

Erdal, B.R. Aguilar, R.D. Bayhurst, B.P. Daniels, W.R. Duffy, C.J. Lawrence, F.O. Maestas, S. Oliver, P.Q. Wolfsberg, K. "Sorption-Desorption Studies on Granite. I. Initial Studies of Strontium, Technetium, Cesium, Barium, Cerium, Europium, Uranium, Plutonium, and Americium", in "Proceedings of the Task 4 Waste Isolation Safety Assessment Program Second Contractor Information Meeting", Vol. II, Report PNL-SA-7352, Battelle Pacific Northwest Laboratory, 1978, pp. 7-67. 

Difficulties in separating and isolating the lanthanoids delayed their widespread use in technology. However, today they are studied intensely, because superconducting materials often contain lanthanoids (Fig. 1.64). All the actinoids are radioactive. None of the elements following plutonium occurs naturally on Earth in any significant amount. Because they can be made only in nuclear reactors or particle accelerators, they are available only in small quantities. 

Work has also been conducted that involved the investigation, via infrared spectroscopy, of matrix-isolated, plutonium oxides (40), with the appropriate precautions being taken because of the toxicity of plutonium and its compounds. A sputtering technique was used to vaporize the metal. The IR spectra of PuO and PUO2 in both Ar and Kr matrices were identified, with the observed frequencies for the latter (794.25 and 786.80 cm", respectively) assigned to the stretchingmode of Pu 02. Normal-coordinate analysis of the PUO2 isotopomers, Pu 02, Pu 02, and Pu 0 0 in Ar showed that the molecule is linear. The PuO molecule was observed in multiple sites in Ar matrices, but not in Kr, with Pu 0 at 822.28 cm" in the most stable, Ar site, and at 817.27 cm" in Kr. No evidence for PuOa was observed. 

The reaction of plutonium metal with N2 in a sputtering device 41) resulted in the observation of matrix-isolated, plutonium nitride species. The species observed were PuN and PUN2, the latter being a linear species. 

The site and mechanism of absorption of ingested americium are not known. Based on studies of plutonium, it is likely that americium absorption occurs, at least to some extent, in the small intestine. Studies of the absorption of plutonium in preparations of in situ isolated segments of small intestine of immature miniature swine indicate that absorption of actinides can occur along the entire small intestine, with the highest rates of absorption occurring in the duodenum (Sullivan and Gorham 1982). 

Lee SC, Orlandini KA, Webb J, et al. 1998. Measurement of baseline atmospheric plutonium-239, 240 and americium-241 in the vicinity of the waste isolation pilot plant. J Radioanal Nucl Chem 234(l-2) 267-272. 

Although much of the preceding discussion involved the synthesis of new molecules by organic and inorganic chemists, there is another area of chemistry in which such creation is important—the synthesis of new atoms. The periodic table lists elements that have been discovered and isolated from nature, but a few have been created by human activity. Collision of atomic particles with the nuclei of existing atoms is the normal source of radioactive isotopes and of some of the very heavy elements at the bottom of the periodic table. Indeed nuclear chemists and physicists have created some of the most important elements that are used for nuclear energy and nuclear weapons, plutonium in particular. 

Robinson et al. (79) have demonstrated that extracellular products present in the media of microorganisms originally isolated from soil can alter the elution of plutonium on gel chromatograms and the mobility of plutonium on thin layer chromatograms. 

During the period 1960-1980, work was carried out in the United States [64] and in France [65] to isolate macro quantities of transpiutonium elements obtained from irradiated plutonium. Particular emphasis was placed upon separation and purification of gram to kilogram amounts of for use... 

Discovery and Isolation of Plutonium, http //science.kennesaw.edu/ mhermes/nuclear/nc-04.htm (accessed November... 

Bismuth hydroxide is used as an absorbent and in the hydrolysis of ribonucleic acid. It also is used in the isolation of plutonium from irradiated uranium. 

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