NIR Spectroscopic Study of the Complexation of Neptunium(V) with Humic Acids: Influence of Phenolic OH Groups on the Complex Formation

The influence of phenolic OH groups on the Np(V) complexation by humic acids was studied at pH 7 and pH 8 under nitrogen atmosphere applying chemically modified humic acids with blocked phenolic OH groups in comparison to their corresponding unmodified humic acids. The studies were performed by near-infrared (NIR) absorption spectroscopy using the metal ion charge neutralization model for evaluation of the experimental data. For all humic acids under investigation comparable complexation constants were determined. However, the studied modified humic acids Aldrich and M42 show significantly lower loading capacities for NpO2+ ions (e.g., pH 7: 7.2 ± 1.1 % and 5.3 ± 1.0 %, respectively) than the corresponding unmodified humic acids (e.g., pH 7: 10.0 ± 1.5 % and 11.2 ± 1.1 %, respectively). This result points to a lower amount of maximal available humic acid ligand sites after blocking of phenolic OH groups. From that, it can be concluded that humic acid phenolic OH groups contribute to the interaction between humic acid and Np(V) under the studied conditions. The comparison of the loading capacities obtained for unmodified and modified Aldrich humic acid at pH 7 and pH 8 shows that the impact of phenolic OH groups on the Np(V) complexation by humic acids is increased with increasing pH value.