We recently demonstrated common oxidants simply coupled with ZVI to continuously drive the accelerated Fe-0 corrosion and hence achieve fast and very efficient removal of heavy metals and metalloids from groundwater. In this study, we aimed first to answer a basic question of the oxidant dosage theoretically required to sequester a certain amount of selenite. The specific ratio of oxidant dosage to Se(IV) removal, which reflected the theoretically minimal oxidant dosage required to sequester one mole of Se(IV), was almost independent of the initial Se (IV) concentration but significantly affected by the difference in oxidant species. To sequester one mole of Se (IV), the minimum dosage of the required oxidant was calculated to be 3.94-4.09 for NaClO, 3.90-4.33 for H2O2, and 3.29-3.54 for KMnO4, respectively. Simultaneous aeration increased the removal efficiency of Se(IV) and substantially reduced the required dosage of oxidants. To form a strong contrast with very limited Se(IV) removal by ZVI alone, the coupling of NaClO and H2O2 into the ZVI system remarkably enhanced the performance of Se(IV) removal during the long term fixed-bed experiments with a real groundwater background. The ZVI columns coupled by NaClO and H2O2 steadily treated 10,000 volumes (BV) of real groundwater. X-ray adsorption near edge structure (XANES) demonstrated that more than 85% of the selenium was reduced to Se-0 and Se2-, with Se-0 as the dominant selenium species sequestered in the solid phase. Synchrotron-based scanning transmission soft X-ray microscopy (STXM) explicitly revealed the ubiquitous spatial distribution of selenium in the corrosion products and hence demonstrated a high accessibility of these corrosion products to selenite.