Reaction kinetics of ozone in variably saturated porous media

A kinetic model based on the mass balance principle with equilibrium partitioning of gaseous ozone into pore water was developed to delineate the reactions of ozone in variably saturated porous media contaminated with phenanthrene. Dimensionless fraction factors were used in the kinetic model to account for the reactions of ozone with soil organic matter (SOM), metal oxide (MO), and phenanthrene as a function of water saturation. The enhanced removal of phenanthrene resulting from heterogeneous catalytic reactions between ozone and soil organic matter and metal oxide was incorporated as lumped parameters in the reaction rate coefficients of gaseous and dissolved ozone with phenanthrene. Laboratory experiments employing 5 cm long mini column reactor systems were conducted to estimate the reaction constants for three porous medium types (glass beads, baked field soil, and field soil) at various water-saturation levels. Water saturation and SOM were found to significantly affect the decomposition of gaseous ozone in both uncontaminated and contaminated porous media. It was found that water saturation over 75% completely eliminates gas-to-solid interfacial ozone reactions with SOM and MO. The kinetic model, with the reaction parameters estimated in this study, predicted reasonably well the experimental data obtained from both the mini column reactor and 20 cm long columns packed with field soil, suggesting that the kinetic model would be suitable for describing the fate and reactions of ozone in variably saturated porous media for soil types and experimental conditions similar to those tested in this study.