Remediation of TCE-contaminated groundwater using KMnO4 oxidation: laboratory and field-scale studies

The objectives of this study were to (1) conduct laboratory bench and column experiments to determine the oxidation kinetics and optimal operational parameters for trichloroethene (TCE)-contaminated groundwater remediation using potassium permanganate (KMnO₄) as oxidant and (2) to conduct a pilot-scale study to assess the efficiency of TCE remediation by KMnO₄ oxidation. The controlling factors in laboratory studies included soil oxidant demand (SOD), molar ratios of KMnO₄ to TCE, KMnO₄ decay rate, and molar ratios of Na₂HPO₄ to KMnO₄ for manganese dioxide (MnO₂) production control. Results show that a significant amount of KMnO₄ was depleted when it was added in a soil/water system due to the existence of natural soil organic matters. The presence of natural organic material in soils can exert a significant oxidant demand thereby reducing the amount of KMnO₄ available for the destruction of TCE as well as the overall oxidation rate of TCE. Supplement of higher concentrations of KMnO₄ is required in the soil systems with high SOD values. Higher KMnO₄ application resulted in more significant H⁺ and subsequent pH drop. The addition of Na₂HPO₄ could minimize the amount of produced MnO₂ particles and prevent the clogging of soil pores, and TCE oxidation efficiency would not be affected by Na₂HPO₄. To obtain a complete TCE removal, the amount of KMnO₄ used to oxidize TCE needs to be higher than the theoretical molar ratio of KMnO₄ to TCE based on the stoichiometry equation. Relatively lower oxidation rates are obtained with lower initial TCE concentrations. The half-life of TCE decreased with increased KMnO₄ concentrations. Results from the pilot-scale study indicate that a significant KMnO₄ decay occurs after the injection due to the reaction of KMnO₄ with soil organic matters, and thus, the amount of KMnO₄, which could be transported from the injection point to the downgradient area, would be low. The effective influence zone of the KMnO₄ oxidation was limited to the KMnO₄ injection area (within a 3-m radius zone). Migration of KMnO₄ to farther downgradient area was limited due to the reaction of KMnO₄ to natural organic matters. To retain a higher TCE removal efficiency, continuous supplement of high concentrations of KMnO₄ is required. The findings would be useful in designing an in situ field-scale ISCO system for TCE-contaminated groundwater remediation using KMnO₄ as the oxidant.