Combined AFM and STXM in situ study of the influence of Eu(III) on the agglomeration of humic acid

Humic acid (HA) agglomerates formed in aqueous solutions in the presence of trivalent Eu cations were investigated in situ with a combination of atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM). The micromorphologies of both natural HA and a melanoidine based synthetic HA observed by AFM in electrolyte solution are in fair agreement with previous AFM studies on humic substances. STXM micrographs of Eu(III) induced HA agglomeration reveal zones of high and low optical density with markedly distinct C K-NEXAFS, indicative of different humic functionalities. Particulate agglomerates observed by AFM can be correlated to the dense zones, whereas fibrous structures in AFM images can be associated with the low density areas. The Eu cation distribution within the agglomerates cannot be unambiguously deduced from their C K-NEXAFS spectra. The near edge X-ray absorption fine structure spectra can be correlated to a segregation of different HA fractions, possibly due to the presence of humic species with different affinities for metal cation complexation. STXM micrographs of purified Aldrich HA exhibit the presence of other yet unidentified, carbon-rich particles, independent of the addition of Eu(III). Both AFM and STXM results for the synthetic melanoidine based HA demonstrate a homogeneous morphology and chemical structure.