Self-enhanced oxidation of resistant monocyclic aromatic compounds during ozone treatment: Applicability in groundwater remediation

The Peroxone process—which utilizes a combination of ozone and hydrogen peroxide to generate hydroxyl radicals—is frequently used in groundwater remediation to effectively remove ozone-resistant contaminants. However, some monocyclic aromatic compounds with low ozone reactivity have been found to be removed by ozone solely (without the need for hydrogen peroxide) through a self-enhanced mechanism. This self-enhanced removal occurs when the interaction of ozone with hydroxide ion generates sufficient amount of hydroxyl radicals, initiating a radical reaction that subsequently propagates through the degradation intermediates. This study leverages the self-enhanced degradation mechanism for the treatment of ozone-resistant compounds during groundwater remediation. Key environmental conditions, including water alkalinity and contaminant concentration, were investigated for their effect on the self-enhanced degradation of para-chloro benzoic acid (pCBA), which served as a model for ozone-resistant compounds. High pCBA removal was observed during ozonation in the concentration range of 0.5–5 μM, where the decay kinetics of pCBA and ozone significantly dependent on the initial pCBA concentration. Furthermore, decreased pCBA removal was noted in water matrices with increased alkalinity, largely due to the scavenging of OH radicals by carbonate species. Finally, pCBA removal was investigated in natural groundwater, where co-existing substances acted as ozone/radical scavengers, leading to reduced pCBA removal. Overall, this study highlights the importance of the self-enhanced removal mechanism of monocyclic aromatic contaminants when treating water with high contamination levels and low-to-moderate alkalinities.