An EXAFS and TRLFS study of the sorption of trivalent actinides onto smectite and kaolinite

The structure parameters of the Am3+ aquo ion and of Am(III) sorbed onto smectite and kaolinite at varying pH are analyzed using EXAFS. An Am-O distance of 2.47-2.49 Å is found and a coordination number of 8-9 oxygen atoms is observed for the Am3+ and its hydration sphere. Combined TRLFS (Cm(III)) and EXAFS (Am(III)) results show that An(III) sorbs onto smectite at pH 4, forming an outer-sphere complex and retains its complete primary hydration sphere. With increasing pH, inner-sphere sorption onto smectite and kaolinite occurs. The overall number of oxygen atoms coordinating the actinide ion remains about the same at pH 6, with four water molecules being replaced by oxygen atoms from the mineral surface during inner-sphere complex formation. The coordination number of sorbed Am(III) at pH 8 exhibits an apparent decrease, which may be affected by the formation of ternary OH-/Am/clay mineral surface species.