A 13C-NMR study of the interactions of soil organic matter with aluminium and allophane in podzols

The stabilization of organic matter in soil by interaction with aluminium (Al) or allophane is important in maintaining soil quality, and in retarding the decomposition of soil organic matter. Complexation of Al by soil organic matter may also ameliorate Al toxicity. Here we use C-13-NMR spectroscopy to assess the interaction of soil organic matter with both Al and allophane in two poorly drained podzols containing only trace amounts of iron. The C-13-NMR spectrum of the subsoil of the allophane-rich One Tree Point podzol shows an intense peak at 179 p.p.m., assigned to carbon in carboxylic acids. This peak shifts to 177 p.p.m. after removal of allophane (11% of the soil mass) by treatment with HF. We infer that the carboxyl groups in the organic matter are bonded to structural Al on the surface of allophane spherules. In the non-allophanic Te Kopuru podzol, on the other hand, the organic matter apparently interacts with Al ions in the soil solution. This soil also has more aromatic carbon and fewer carbons in carboxyl and carbohydrate structures than the allophanic sample. There is an indication that allophane stabilizes carbohydrate groups as well as carboxyl groups.