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Luminescence spectroscopic investigations of europium complexes formed in the kaolinite-humic acid/citric acid systems

Abstract In the present study, the nature of Eu(III) complexes (Eu(III) was used as a surrogate for Am(III)) formed in kaolinite–humic acid (HA)/citric acid (CA) system was investigated by luminescence spectroscopy. In addition to the ternary system (kaolinite + Eu + L(CA/HA)), the binary system (Eu-L) was also looked at for a better understanding of the complexes formed at the kaolinite surface. The lifetime and emission spectra of Eu-L complexes on the kaolinite surface differ considerably as compared to the same in the aqueous phase. The Eu-HA aqueous complexation shows differences in the excitation spectra with similar decay lifetimes with increasing aqueous HA concentrations. The ligand-to-metal charger transfer (LMCT) in the Eu-HA excitation spectra suggests the complexation of Eu(III) with HA at pH ∼ 4. Although the mode of Eu(III) binding to the kaolinite surface in the presence of CA/HA was the same i.e. metal-bridged ternary complex formation, the local surroundings around the sorbed Eu(III) differ in the two cases. The loading of HA in the Eu-HA-kaolinite system does not have a large effect on the local structure around the sorbed Eu(III) ion, but enhances the percentage of Eu(III) uptake onto the kaolinite surface. The number of H2O molecules in the primary hydration sphere of sorbed Eu(III) differs in the Eu-HA-kaolinite and Eu-CA-kaolinite systems. In addition, Eu(III) assisted precipitation of HA was also seen using a radiometric method.