Actinide speciation in the environment

Nuclear test explosions and nuclear reactor wastes and accidents have released large amounts of radioactivity into the environment. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides are introduced into the aquatic system. Chemical speciation, oxidation state, redox reactions, and sorption characteristics are necessary in predicting solubility of the different actinides, their migration behaviors and their potential effects on marine biota. The most significant of these variables is the oxidation state of the metal ion as the simultaneous presence of more than one oxidation state for some actinides in a solution complicates actinide environmental behavior. Both Np(V)O-2(+) and Pu(V)O-2(+) , the most significant soluble states in natural oxic waters, are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation. The solubility of NpO2+ can be as high as 10 (4) M while that of PuO2+ is much more limited by reduction to the insoluble tetravalent species, Pu(OH)(4), (pK(sp)>= 56) but which can be present in the pentavalent form in aqautic phases as colloidal material. The solubility of hexavalent UO22+ stop in sea water is relatively high due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(OH)(CO3) is the limiting species for the solubility of Am(III) in sea water. Thorium(IV) is present as Th(OH)(4), in colloidal form. The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in natural waters which must be considered in assessing the environmental behavior of actinides. Much is understood about sorption of actinides on surfaces, the mode of migration of actinides in such waters and the potential effects of these radioactive species on marine biota, but much more understanding of the behavior of the actinides in the environment is needed to allow proper and reliable modeling needed for disposition of nuclear waste over many thousands of years.