Plutonium oxides dissolution

Plutonium Oxide Dissolution. All four sites dissolve impure PuO, residues in concentrated HND3 (10 to 14M) containing HF (<0.3M). Whereas material calcined at temperatures of... 

Plutonium Oxide Dissolution Model. Based on the species observed dissolving from the oxide, a conceptualization of the fate of PUO2 in the environment might be represented by Fig. 2. 

Spent anode residues from electrorefining (which contain approximately 20-30 percent of the plutonium fed to the process) are either recycled back to electrorefining, or, if high enough in impurities, are oxidized and sent to oxide dissolution. The spent salt is sent to aqueous dissolution (see Figure 1). 

Hydrofluoric acid is best known for its ability to dissolve silica, but even small quantities exert a marked catalytic effect on the nitric acid dissolution of many refractory oxides, including ignited plutonium oxide, due to the high stability of the fluoride complexes. Consequently, use of hydrofluoric acid in leaching procedures generally gives more accurate results. However, erratic... 

The slow dissolution behaviour of the plutonium and americium isotopes was similar to that reported for insoluble plutonium oxides. The moderate uranium dissolution behaviour was similar to that reported on filters from personal air samplers of uranium miners. ... 

Fallout plutonium arrives in natural waters either by direct atmospheric deposition or by erosion and/or dissolution from the land. Although in the past, this plutonium was considered to be in a refractory form due to formation within the fire ball, it seems more likely that most of the plutonium originated in the stratosphere by the decay of 239Np (from 239U formed during the detonation)(4). Deposition occurs predominantly with one or a few atoms incorporated in a raindrop. Investigations by Fukai indicate that collected rain contains soluble plutonium which has oxidation states that are almost totally Pu(V+VI)05). 

Two of the study systems, Lake Michigan and Pond 3513, exhibit cyclic behavior in their concentrations of Pu(V) (Figure 2 and 3). The cycle in Lake Michigan seems to be closely coupled with the formation in the summer and dissolution in the winter of calcium carbonate and silica particles, which are related to primary production cycles in the lake(25). The experimental knowledge that both Pu(IV) and Pu(V) adsorb on calcium carbonate precipitates(20) confirms the importance of carbonate formation in the reduction of plutonium concentrations in late summer. Whether oxidation-reduction is important in this process has not been determined. 

An overview is presented of plutonium process chemistry at Rocky Flats and of research in progress to improve plutonium processing operations or to develop new processes. Both pyrochemical and aqueous methods are used to process plutonium metal scrap, oxide, and other residues. The pyrochemical processes currently in production include electrorefining, fluorination, hydriding, molten salt extraction, calcination, and reduction operations. Aqueous processing and waste treatment methods involve nitric acid dissolution, ion exchange, solvent extraction, and precipitation techniques. 

Dissolution. Plutonium is solubilized in nitric acid solutions at Rocky Flats. The feed material consists of oxide, metal and glass, dissolution heels, incinerator ash and sand, slag, and crucible from reduction operations. The residues are contacted with 12M HNO3 containing CaF2 or HF to hasten dissolution. Following dissolution, aluminum nitrate is added to these solutions to complex the excess fluoride ion. 

This PUCI3 also acts as a salt-phase buffer to prevent dissolution of trace impurities in the metal feed by forcing the anode equilibrium to favor production (retention) of trace impurities as metals, instead of permitting oxidation of the impurities to ions. Metallic impurities in the feed fall into two classes, those more electropositive and those less electropositive than plutonium. Since the cell is operated at temperatures above the melting point of all the feed components, and both the liquid anode and salt are well mixed by a mechanical stirrer, chemical equlibrium is established between all impurities and the plutonium in the salt even before current is applied to the cell. Thus, impurities more electropositive than the liquid plutonium anode will be oxidized by Pu+3 and be taken up by the salt phase, while impurities in the electrolyte salt less electropositive than plutonium will be reduced by plutonium metal and be collected in the anode. 

Oak Ridge National Laboratory (ORNL) is developing the glass material oxidation and dissolution system (GMODS) for the treatment and stabilization of plutonium- or halogen-containing... 

Distribution ratios and transport were carried out on real HAW arising from dissolution of a mixed oxide of uranium and plutonium (MOX) fuel (burnup 34,650 MW d/tU), where uranium and plutonium have been previously extracted by TBP.86 The experiments were performed in the CARMEN hot cell of CEA Fontenay aux Roses with two dialkoxy-calix[4]arene-crown-6 derivatives (diisopropoxy and dini-trophenyl-octyloxy). High cesium distribution ratios were obtained (higher than 50) by contacting the HAW solution with diisopropoxy calix[4]arene-crown-6 (0.1 M in NPHE). Moreover, the high selectivity observed with the simulated waste was confirmed for most of the elements and radionuclides (actinides or fission products Eu, Sb, Ce, Mo, Zr, and Nd). The residual concentration or activity of elements, other than cesium, was less than 1% in the stripping solution, except for iron (2%) and ruthenium (8%) the extraction of these two cations, probably under a complexed... 

Since publication of this work, Japanese researchers have undertaken an effort to demonstrate the feasibility of direct dissolution of U02 from spent nuclear fuels by the TBP-HN03 complex in SC-C02.49 Ultimately, the project is directed at the extraction of both uranium and plutonium from mixed oxide fuels and from irradiated nuclear fuel. Ideally, soluble uranyl and plutonium nitrate complexes will form and dissolve in the C02 phase, leaving the FPs as unwanted solids. As in the conventional... 

The process sequence currently used for waste salts (except those containing aluminum for which no process currently exists) is shown in Figure 1. The process includes (1) dilute hydrochloric acid dissolution of residues (2) cation exchange to convert from the chloride to the nitrate system and to remove gross amounts of monovalent impurities (3) anion exchange separation of plutonium (4) oxalate precipitation of americium and (5) calcination of the oxalate at 600°C to yield americium oxide. 

The flowsheet for the FFTF Pu02 production is shown in Figure 2. Briefly, the plutonium metal is converted to an impure oxide by burning the metal in air. This is followed by dissolution of the impure oxide in a 15.6 M HN03 - 0.5 M HF solution. The americium is separated from the plutonium by precipitation of the plutonium as the peroxide. Americium does not form an insoluble peroxide and stays in the filtrate with other cationic impurities. The active peroxide filtrate is slowly dripped into 9 M NaOH. The combination of strong alkali and heat destroys the peroxides and precipitates the americium as the hydroxide. Any residual plutonium in the filtrate, along with other cations, is precipitated also as the hydroxide. The flowsheet for the americium oxide production is shown in Figure 3. 

Other examples of redox-sensitive elements include heavy elements such as uranium, plutonium, and neptunium, all of which can exist in multiple oxidation states in natural waters. Redox conditions in natural waters are also indirectly important for solute species associated with redox-sensitive elements. For example, dissolution of iron (hydr)oxides under reducing conditions may lead to the solubilization and hence mobilization of associated solid phase species, e.g. arsenate, phosphate (see Sections 3.3.2.1, 3.3.3.2, and 3.3.4.1). 

Dissolution of the calcium fluoride in aluminum nitrate-nitric acid oxidizes the plutonium to the tetravalent hexanitrate complex (3), while the transplutonium nuclides remain in the trivalent state. The only actinides retained by a nitrate-form anion-exchange column are thorium, neptunium, and plutonium. The uranium distribution coeflBcient under these conditions is about ten, but uranium should not be present at this point since hexavalent uranium does not carry on calcium fluoride (4). 

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