Few studies have been carried out on the effects of ligands on rare earth element (REE) bioaccumulation processes. In this study, the effects of phosphate (Pi, an inorganic ligand) and citrate (an organic ligand) on accumulation and fractionation of REEs in wheat were investigated using aqueous culture with extraneous mixed REEs (MRE). The results show that initial Pi solution culture at various levels followed by exposure to a fixed-MRE solution did not significantly change the total concentrations of REEs (SigmaREE) in roots, whereas the SigmaREE in leaves dramatically decreased with increasing levels of Pi applied. Simultaneous culture of wheat with mixture of MRE and citrate solutions caused obvious decreases of the SigmaREE in both roots and leaves. Compared with MRE, significant fractionations of REEs were found in wheat organs when no ligand was applied. Notable middle REE (MREE) enrichment and M-type tetrad effect were observed in the roots, and heavy REE (HREE) enrichment and W-type tetrad effect existed in the leaves. Pi treatments did not significantly affect the fractionations of REEs in the roots, but enrichment of HREEs in the leaves slightly increased at the highest level of Pi applied. Fractionations of REEs in both roots and leaves decreased with increasing levels of citrate applied; at higher levels of citrate (> or =150 microM), no above fractionation features were observed in wheat, but light REE (LREE) enrichment existed in the roots and leaves. The results indicate that ligands might play important roles in accumulation and fractionation of REEs during bioaccumulation processes.