Selective dissolution of Am in basic media in the presence of ferricyanide ions: a mechanistic and structural study on Am(V) and Am(VI) compounds

Americium exhibits a soluble form in aqueous alkaline media in the presence of ferricyanide ions (Fe(CN)(6)(3-)), which is not the case for the other transplutonium elements (TPE). This soluble Am compound can be obtained by addition of a concentrated basic solution of ferricyanide ions on a trivalent americium hydroxide precipitate. Thus, this technique enables a complete and rapid extraction of americium through its soluble form in alkaline solutions whereas under these conditions, other TPE and the lanthanides remain in the solid state as trivalent hydroxides. In the case of dissolution involving large amounts of americium, the formation of the soluble americium species is followed by the appearance of a reddish precipitate in the basic solution. Dissolution of the reddish solid in NaOH or NaOH/Fe(CN)(6)(3-) media demonstrated the existence of a media-dependent solubility of the precipitate, and therefore the existence of at least two forms of soluble Am. Spectroscopic (UV-visible, EXAFS-XANES, Raman) and electrochemical investigations were carried out on the different forms of americium to determine the nature of the compounds. This study points out that the reddish solid Am compound is probably a Am(V) hydroxide: Na2AmO2(OH)(3).3H(2)O while the other Am species is a mixed americyl-ferricyanide complex. This work demonstrates that this dissolution of Am(III) solid compound is much more complex than a simple oxidation by the ferricyanide ions. The existence of a molecular interaction between Am(V)O-2(+) and ferricyanide ions is highly probable. This selective dissolution of americium by a basic ferricyanide solution can be used to define a separation process of Am from lanthanides and other transplutonium elements in the field of high level liquid waste treatment.