We investigated the influences of humic acid on the removal of Al tridecamer (Al13) from a hydroxyaluminum (HyA) solution at various humic acid/Al ratios. The Al species contained in the solution were analyzed by using a liquid-state 27Al-NMR and an atomic absorption spectrometer and fractionated into three Al species: (i) Al13, (ii) Al monomer and dimer (AlSYM), and (iii) other undefined species including aggregated/precipitated Al (AlNON). By the addition of humic acid to the HyA solution, the concentration of Al13 was rapidly decreased within 0.007 d (10 min). The decrease in Al13 and the increase in AlNON were more pronounced at a higher humic acid/Al ratio. When the molar ratio of humic acid carboxylic groups to Al exceeded 0.8, Al13 was undetected from solution within 0.007 d. The formation of Al 13-humic acid complexes and the aggregation/precipitation of those complexes were a predominant mechanism in removing aqueous Al13 at the early stage of the reaction. Approximately 10 mol of carboxylic groups in humic acid were required to remove 1 mol of Al13 from the HyA solution. Aqueous Al13 had greater preference in precipitating with humic acid than AlSYM. After 5 to 570 d of aging, the concentration of Al13 and AlNON also decreased and increased, respectively, both in the presence and absence of humic acid. In conclusion, aqueous Al13 would not exist in soil solution under a high humic acid condition.
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