Molecular rigidity and diffusivity of Al3+ and Ca2+ humates as revealed by NMR spectroscopy

NMR techniques were applied to follow changes in molecular rigidity and diffusion of complexes formed between a humic acid (HA) and either aluminum or calcium ions, added in amounts ranging from 0.05% to 1% of HA carboxylic acidity. Spin-lattice relaxation time in the rotating frame (T1rho,(H)) and diffusion coefficients (D) of humic-metal complexes were obtained from 13C cross-polarization magic angle spinning (CP-MAS), and 1H-diffusion order spectroscopy (DOSY) spectra, respectively. Molecular rigidity of humic complexes increased significantly with metal addition throughout the full carbon spectral region, being more pronounced for triple-charged Al than for double-charged Ca. However, T1rho(H) values of spectral intervals suggested that molecular rigidity increase was generally in the following order: aliphatic C > aromatic/double bonds C > carboxyl C. Concomitantly, DOSY spectra showed that addition of both Al and Ca decreased substantially the diffusivity of humic alkyl components and increased that of aromatic and hydroxyalkyl components, thereby indicating that complexation induced a molecular-size increase in the former and a decrease in the latter. These results suggest that saturated and unsaturated long-chain alkanoic acids in HA were preferentially involved in metal complexation with Al and Ca, with consequentincrease of conformational rigidity and molecular size of humic hydrophobic domains. Conversely, more hydrophilic or mobile humic components appeared relatively less affected by the molecular and intermolecular rearrangements induced in HA by complexation with metals. Such NMR approach appears thus liable to evaluate the response to metal complexation of specific chemical entities present in the bulk HA and provides a further insight in the molecular architecture of humic-metal complexes.