Cyclodextrin-enhanced 1,4-dioxane treatment kinetics with TCE and 1,1,1-TCA using aqueous ozone.

ABSTRACT

Enhanced reactivity of aqueous ozone (O3) with hydroxypropyl-ß-cyclodextrin (HPßCD) and its impact on relative reactivity of O3 with contaminants were evaluated herein. Oxidation kinetics of 1,4-dioxane, trichloroethylene (TCE), and 1,1,1-trichloroethane (TCA) using O3 in single and multiple contaminant systems, with and without HPßCD, were quantified. 1,4-Dioxane decay rate constants for O3 in the presence of HPßCD increased compared to those without HPßCD. Density functional theory molecular modeling confirmed that formation of ternary complexes with HPßCD, O3, and contaminant increased reactivity by increasing reactant proximity and through additional reactivity within the HPßCD cavity. In the presence of chlorinated co-contaminants, the oxidation rate constant of 1,4-dioxane was enhanced. Use of HPßCD enabled O3 reactivity within the HPßCD cavity and enhanced 1,4-dioxane treatment rates without inhibition in the presence of TCE, TCA, and radical scavengers including NaCl and bicarbonate. Micro-environmental chemistry within HPßCD inclusion cavities mediated contaminant oxidation reactions with increased reaction specificity.