The influence of different soil constituents on the reaction kinetics of wet oxidation of the creosote compound quinoline

Abstract

Creosote contaminated sites have become a widespread problem in industrialized countries. Recently, wet oxidation using high temperature, pressure, water and oxygen followed by activated sludge treatment proved to be an efficient method for removing a wide selection of creosote compounds in contaminated soils. Wet oxidation of the creosote compound quinoline was carried out in the presence of montmorillionite, quartz and humic acid. The products derived from wet oxidation were identified and treated biologically by activated sludge testing their biodegradability. The influence on the oxidation kinetics of quinoline during wet oxidation was pH dependent. Humic acid supported the oxidation of quinoline, whereas the addition of montmorillionite and quartz had either an inhibiting effect or led only to a slight increase in oxidation. In mixtures of soil constituents, especially at low contents of humic acid, the adsorption of quinoline on montmorillionite prevented oxidation at neutral pH. Thus, alkaline extraction of both quinoline and humic acid was needed for an efficient oxidation. A proposed reaction mechanism suggests that quinoline was oxidized by hydroxyl radicals formed during the oxidation of the humic acid. A wide selection of reaction products (mainly carboxylic acids, benzene and pyridine derivatives) derived from the wet oxidation of humic acid and quinoline. The reaction products from humic acid degradation had a rate limiting effect on the wet oxidation of quinoline leaving small residues of quinoline after the treatment. On the contrary, these reaction products also improved the biodegradation of products from the quinoline oxidation due to co-digestion of carboxylic acids. Therefore, the presence of soil components (mainly humic acid) improved the combined wet oxidation and biological activated sludge treatment of quinoline.