Direct observation of Cm(III)-fulvate species on fulvic acid-montmorillonite hybrid by laser-induced fluorescence spectroscopy

Particulate matter plays an important role in the removal of metal ions from water in natural aquifers. Some of the most important of these materials consist of associations of inorganic particles (clay minerals, oxides) with humic substances, associations that can form readily in such an environment due to the strong affinity between inorganic particles and humic substances. These associations are referred to in this paper as organic-inorganic hybrids. However, it is not clear whether the sorbed species of metal ions in such organic-inorganic hybrids are organic or inorganic species because of the complexity of such hybrids and the lack of appropriate methods for characterizing the trace metal ions incorporated in them. In this study, laser-induced fluorescence spectroscopy (LIF) was used successfully to characterize the Cm(III) species on an FA(fulvic acid)-montmorillonite hybrid, an example of such organic-inorganic hybrids. The LIF clearly showed that Cm(III) can be sorbed as Cm(III)-fulvate complex in the FA-montmorillonite hybrid. These results were consistent with those of experiments of solid-water partitioning of Cm(III) (or Eu(III) used as an analogue) and speciation calculations based on the stability constants of Cm(III)-fulvate complexes determined in this study. The results of LIF and the partitioning experiments showed that the solid-water distribution of humic substances governed that of Cm(III) under our experimental conditions. The Cm(III) preference for forming Cm(III)-fulvate complexes was also evident under a condition that would be found in a natural aquifer with a fairly low concentration of organic matter in freshwater (dissolved organic carbon: 2 mg/dm³), as determined by our speciation calculations. These findings on the importance of humic substances in the migration of Cm(III) indicate that the clarification of the environmental behavior of humic substances is necessary to understand fully the behavior of Cm(III), or actinide(III) and lanthanide(III) ions, in natural aquifers.