Water actinides

In most natural waters actinides are usually coordinated with hydroxide and carbonate ligands however, waters from ancient salt formations that are proposed as disposal sites for nuclear waste, such as the Waste Isolation Pilot Plant (WIPP) in New Mexico or the Gorleben site in Germany, are saturated with chloride salts. Chloride has been shown to affect the solubility and speciation of actinides significantly compared with their chemistry in inert electrolyte solutions ofsimilar ionic strengths. Radiolytic formation of hypochlorite in chloride brines may resnh in (he... 

Potential fusion appHcations other than electricity production have received some study. For example, radiation and high temperature heat from a fusion reactor could be used to produce hydrogen by the electrolysis or radiolysis of water, which could be employed in the synthesis of portable chemical fuels for transportation or industrial use. The transmutation of radioactive actinide wastes from fission reactors may also be feasible. This idea would utilize the neutrons from a fusion reactor to convert hazardous isotopes into more benign and easier-to-handle species. The practicaUty of these concepts requires further analysis. 

The primary issue is to prevent groundwater from becoming radioactively contaminated. Thus, the property of concern of the long-lived radioactive species is their solubility in water. The long-lived actinides such as plutonium are metallic and insoluble even if water were to penetrate into the repository. Certain fission-product isotopes such as iodine-129 and technicium-99 are soluble, however, and therefore represent the principal although very low level hazard. Studies of Yucca Mountain, Nevada, tentatively chosen as the site for the spent fuel and high level waste repository, are underway (44). 

Solvent for Electrolytic Reactions. Dimethyl sulfoxide has been widely used as a solvent for polarographic studies and a more negative cathode potential can be used in it than in water. In DMSO, cations can be successfully reduced to metals that react with water. Thus, the following metals have been electrodeposited from their salts in DMSO cerium, actinides, iron, nickel, cobalt, and manganese as amorphous deposits zinc, cadmium, tin, and bismuth as crystalline deposits and chromium, silver, lead, copper, and titanium (96—103). Generally, no metal less noble than zinc can be deposited from DMSO. 

The Table shows a great spread in Kd-values even at the same location. This is due to the fact that the environmental conditions influence the partition of plutonium species between different valency states and complexes. For the different actinides, it is found that the Kd-values under otherwise identical conditions (e.g. for the uptake of plutonium on geologic materials or in organisms) decrease in the order Pu>Am>U>Np (15). Because neptunium is usually pentavalent, uranium hexavalent and americium trivalent, while plutonium in natural systems is mainly tetravalent, it is clear from the actinide homologue properties that the oxidation state of plutonium will affect the observed Kd-value. The oxidation state of plutonium depends on the redox potential (Eh-value) of the ground water and its content of oxidants or reductants. It is also found that natural ligands like C032- and fulvic acids, which complex plutonium (see next section), also influence the Kd-value. 

For Pond 3513, the cycle of 2 3 8U and 239,2 °pu concentrations in water (filtered with a 0.22y membrane) is out of phase with the cycle of plutonium concentrations in Lake Michigan. In this shallow pond, the concentrations of the two actinides peak in summer and decline in winter. An explanation for this cycle of plutonium is that photosynthetic activity depletes dissolved CO2 which results in an increase in pH and this in turn shifts the oxidation state in favor of Pu(V) which is desorbed from the sediments(26). 

The highly fractionated nature of the and Th series nuclides is illustrated by the measured activities in some representative waters in Figure 1. The highest activities are typically observed for Rn, reflecting the lack of reactivity of this noble gas. Groundwater Rn activities are controlled only by rapid in situ decay (Table 1) and supply from host rocks, without the complications of removal by adsorption or precipitation. The actinide U, which is soluble in oxidizing waters, is present in intermediate activities that are moderated by removal onto aquifer rocks. The long-lived... 

Geckeis H, Klenze R, Kim J1 (1999) Solid-water interface reactions of actinides and homologues sorption onto mineral surfaces. Radiochim Acta 87 13-21... 

Murray CN, Kautsky H, Hoppenheit M, et al. 1978. Actinide activities in water entering the northern North Sea. Nature 276 225-230. 

Rate Constants and Activation Parameters for Water Exchange on Actinides or Actinyl Aqua Ions... 

The elucidation of actinide chemistry in solution is important for understanding actinide separation and for predicting actinide transport in the environment, particularly with respect to the safety of nuclear waste disposal.72,73 The uranyl CO + ion, for example, has received considerable interest because of its importance for environmental issues and its role as a computational benchmark system for higher actinides. Direct structural information on the coordination of uranyl in aqueous solution has been obtained mainly by extended X-ray absorption fine structure (EXAFS) measurements,74-76 whereas X-ray scattering studies of uranium and actinide solutions are more rare.77 Various ab initio studies of uranyl and related molecules, with a polarizable continuum model to mimic the solvent environment and/or a number of explicit water molecules, have been performed.78-82 We have performed a structural investigation of the carbonate system of dioxouranyl (VI) and (V), [U02(C03)3]4- and [U02(C03)3]5- in water.83 This study showed that only minor geometrical rearrangements occur upon the one-electron reduction of [U02(C03)3]4- to [U02(C03)3]5-, which supports the reversibility of this reduction. 

The actinides. The actinides metals are electropositive and very reactive they are pyrophoric in finely divided form. They tarnish rapidly in air forming an oxide protective coating in the case of Th, but more slowly for the other actinides. The metals react with most non-metals. With steam or boiling water, oxide is formed on the surface of the metal and H2 evolves in this way hydrides are produced that react rapidly with water and facilitate further attack on the metals. The oxidation states observed in the chemistry of lanthanides and actinides are shown in Fig. 5.9. Notice the predominant oxidation state III for the lanthanides... 

The trivalent actinide state resembles that of the lanthanides. In an aqueous solution some M3+ ions exist (Am3+, Cm3+) ions the U3+ ions is readily oxidised by air or more slowly by water. Tetravalent U and Pu are reasonably stable in solution, whereas Am(IV) and Cm(IV) are readily reduced and exist only as complex ions in... 

---