The Chemical Degradation of a Humic Acid

A humic acid (HA) extracted from the A 1 horizon of a Brunizem soil was degraded in the unmethylated and methylated form by sequential reaction with oxidants of increasing strength. The HA was first oxidized with alkaline cupric oxide; the products were then further degraded by oxidation with first alkaline KMnO 4 and then with H 2 O 2 in alkaline solution. Unmethylated HA was also degraded by Na-amalgam reduction. The degradation products were extracted into organic solvents, methylated, and separated by preparative gas chromatography into relatively pure components which were analyzed by mass spectrometry and micro-i.r. spectrophotometry. A matching of the mass and i.r. spectra and gas chromatographic retention times of the isolated components with those of authentic specimens led to their identification.The experimental data show that the HA contains a relatively easily degradable portion, which comprises guaiacyl and syringyl units and which may be lignin-derived (about 10% of the total weight). This material is degraded by CuO–NaOH oxidation and Na-amalgam reduction. The bulk of the HA structure, however, consists of a more condensed, chemically complex "core", which degrades on more drastic oxidation into complex phenolic and benzenepolycarboxylic acids. It is likely that the "core" originates in part from condensed lignin and in part from products of microbial synthesis. Of the methods investigated, the CuO–NaOH and the KMnO 4 oxidation of methylated HA appear most promising for providing information on the chemical structure of the HA.