[en] The uptake mechanism of plutonium by kaolinite was investigated by applying X-ray absorption spectroscopy to batch sorption samples (total Pu concentrations 1 and 10 μM; 4 g kaolinite/L in 0.1 M NaClO₄; 1 ≤ pH ≤ 9; presence and absence of ambient CO₂). For XAFS measurements, one sample was prepared from a Pu(III) solution at pH 6 under argon atmosphere. Three samples were obtained by sorption of Pu(IV) at pH I, 4, and 9 in an air-equilibrated system. The Pu L_III-edge XANES spectra indicated that in all samples, including the Pu(III) sample, plutonium is sorbed at the kaolinite surface as Pu(IV). The Pu L_III-edge k³-weighted EXAFS spectra showed eight oxygen atoms at an average Pu-O distance of 2.3 angstrom. Two Pu atoms were detected at ∼ 3.7 angstrom in all spectra, indicating the formation of polynuclear Pu(IV) species at the kaolinite surface. For the sample prepared from Pu(III) solution, an additional Pu-O shell at 3.2 angstrom was observed. The spectra of samples prepared from Pu(IV) included a Pu-Al/Si co-ordination shell at approximately 3.6 angstrom, indicating formation of inner-sphere sorption complexes. The structural models used in the least-squares fits were confirmed by an alternative EXAFS data analysis approach based on a modified Tikhonov regularization method. (authors)