Oxidation of humic acids from an agricultural soil and a lignite deposit: Analysis of lipophilic and hydrophilic products

The composition of humic acids (HAs) isolated from an agricultural soil and a lignite deposit was examined via H₂O₂ and RuO₄ oxidation. The oxidation digests were separated into lipophilic and hydrophilic components. Information with regard to the source, degree of humification and preservation of easily degradable constituents of the HAs was obtained and results were compared with those obtained earlier for base hydrolysates of solvent-extracted fractions.H₂O₂ oxidation of both HAs afforded lipophilic fractions containing high molecular weight compounds. The composition of the base hydrolysates of the lipophilic fractions strongly differed with the origin of the HA. The lipophilic components of the soil HA derived mainly from the higher plant polyesters cutin and suberin. The lipophilic components of the lignite HA predominantly comprised long chain alkanoic acids and alkanols. The patterns for the hydrophilic components released upon H₂O₂ oxidation were found to be identical irrespective of the origin of the HA. The hydrophilic fractions comprised aliphatic (poly)carboxylic acids related to carbohydrate moieties and benzene polycarboxylic acids. The relative abundance of benzene polycarboxylic acids increased with the degree of humification.For both HAs, RuO₄ oxidation resulted in a lipophilic fraction containing low molecular weight products identical to those found in the base hydrolysate of the lipophilic fraction released upon H₂O₂ oxidation. The hydrophilic components released upon RuO₄ oxidation were independent of the HA origin and consisted mainly of monosaccharides and disubstituted aromatic compounds. In agreement with the greater aromaticity of lignite HA, the aromatic compound/carbohydrate ratio was higher for lignite HA than soil HA. The results show that the fused aromatic structures had a small size and that carbohydrates could escape degradation during the humification process.