Degradation of trichloroethene by siderite-catalyzed hydrogen peroxide and persulfate: Investigation of reaction mechanisms and degradation products

A binary catalytic system, siderite-catalyzed hydrogen peroxide (H₂O₂) coupled with persulfate (S₂O₈^2-), was investigated for the remediation of trichloroethene (TCE) contamination. Batch experiments were conducted to investigate reaction mechanisms, oxidant decomposition rates, and degradation products. By using high performance liquid chromatography (HPLC) coupled with electron paramagnetic resonance (EPR), we identified four radicals (hydroxyl (HO), sulfate (SO₄^-), hydroperoxyl (HO₂), and superoxide (O₂^-)) in the siderite-catalyzed H₂O₂-S₂O₈^2- system. In the absence of S₂O₈^2- (i.e., siderite-catalyzed H₂O₂), a majority of H₂O₂ was decomposed in the first hour of the experiment, resulting in the waste of HO. The addition of S₂O₈^2- moderated the H₂O₂ decomposition rate, producing a more sustainable release of hydroxyl radicals that improved the treatment efficiency. Furthermore, the heat released by H₂O₂ decomposition accelerated the activation of S₂O₈^2-, and the resultant SO₄^- was the primary oxidative agent during the first two hours of the reaction. Dichloroacetic acid was for the first time detected as a degradation product. The results of this study indicate a new insight to the reaction mechanism for the catalytic binary H₂O₂-S₂O₈^2- oxidant system, and the delineation of radicals and the discovery of the chlorinated byproduct provide useful information for efficient treatment of chlorinated-solvent contamination in groundwater.