Reactions of thiocarbamate, triazine and urea herbicides, RDX and benzenes on EPA Contaminant Candidate List with ozone and with hydroxyl radicals

Second-order rate constants of the direct ozone reactions (kO3,MkO3,M) and the indirect OH radical reactions (kOH,M) for nine chemicals on the US EPA's Drinking Water Contaminant Candidate List (CCL) were studied during the ozonation and ozone/hydrogen peroxide advanced oxidation process (O3/H2O2 AOP) using batch reactors. Except for the thiocarbamate herbicides (molinate and EPTC), all other CCL chemicals (linuron, diuron, prometon, RDX, 2,4-dinitrotoluene, 2,6-dinitrotoluene and nitrobenzene) show low reactivity toward ozone. The general magnitude of ozone reactivity of the CCL chemicals can be explained by their structures and the electrophilic nature of ozone reactions. The CCL chemicals (except RDX) are highly reactive toward OH radicals as demonstrated by their high kOH,M values. Ozonation at low pH, which involves mainly the direct ozone reaction, is only efficient for the removal of the thiocarbamates. Ozonation at high pH and O3/H2O2 AOP will be highly efficient for the treatment of all chemicals in this study except RDX, which shows the lowest OH radical reactivity. Removal of a contaminant does not mean complete mineralization and reaction byproducts may be a problem if they are recalcitrant and are likely to cause health concerns.