The wet oxidation of aqueous humic acids

Humic acids are highly distributed in aqueous environments. This article examines in depth the advanced oxidation of humic acid aqueous solutions, in order to understand more complex oxidation processes such as those of the sewage sludge or landfill leachate, or the matrix effects triggered by the humic acids of natural organic matter (NOM) in the oxidation of other aqueous compounds as herbicides. Humic acids were efficiently oxidized; higher temperatures (180−220 °C) involved higher mineralization, the formation of intermediates with lower colour and also led to a higher concentration of organic acids at the end of the treatment, particularly acetic and oxalic ones. Nevertheless, humic acid wet oxidation was not sensitive to changes in the pressure, at least in the range tested (65−95 bar), but the initial pH (4–13) was found to be a key factor. Thus, alkaline media accelerated the humic acid removal, but more refractory intermediates were generated, and the organic acids, excepting malic acid, were more stable than in neutral or acidic media. Eventually, a lumped kinetic model was proposed and successfully fitted to the experimental data, including the effect of all the operating variables studied.