The application of S(IV) for the regeneration of Fe(II) has been widely investigated. As the common S(IV) sources, sodium sulfite (Na2SO3) and sodium bisulfite (NaHSO3) are soluble in the solution, resulting in excessive SO32− concentration and redundant radical scavenging problems. In this research, calcium sulfite (CaSO3) was applied as the substitution for the enhancement of different oxidant/Fe(II) systems. The advantages of CaSO3 could be summarized as follows: (1) it could sustainedly supplement SO32− for Fe(II) regeneration, preventing radical scavenging and unnecessary reagent waste; (2) the cost and toxicity of CaSO3 were extremely lower than that of other S(IV) sources; (3) the concentration of reactive species increased in the presence of CaSO3; and (4) after the reaction, SO42− would form CaSO4 precipitate, which would not increase the burden of SO42− in the solution. In the participation of CaSO3, the removal of trichloroethylene (TCE) and other organic contaminants were significantly promoted and different enhanced systems had high tolerance on complex solution conditions. The major reactive species in different systems were determined through qualitative and quantitative analyses. Eventually, the dechlorination and mineralization of TCE were measured and the differentiated degradation pathways in different CaSO3-enhanced oxidants/Fe(II) systems were elucidated.
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