Metabisulfite as an Unconventional Reagent for Green Oxidation of Emerging Contaminants Using an Iron-Based Catalyst

In this work, contaminants of emerging concern were catalytically degraded in the homogeneous phase with the use of unconventional green reagents. Three reagents, namely, sulfite, metabisulfite, and persulfate, were tested and compared with conventional hydrogen peroxide in the degradation process activated by Fe-TAML. The latter is a biodegradable, homogeneous tetra-amido macrocyclic ligand catalyst containing iron(III). Metabisulfite showed the highest efficiency among the three tested reagents, and its reactivity was similar to that of H₂O₂. However, metabisulfite is a safer and cleaner reagent compared to H₂O₂. A comprehensive study of the activity of metabisulfite with Fe-TAML was carried out toward the oxidative degradation of eight contaminants of emerging concern. The catalytic process was tested at different pH values (7, 9, and 11). Metabisulfite showed the highest activity at pH 11, completely degrading some of the tested micropollutants, but in several cases, the system was active at pH 9 as well. In particular, metabisulfite showed the best efficiency toward phenolic compounds. A preliminary study on the reaction mechanism and the nature of the active species in the Fe-TAML/metabisulfite system was also conducted, highlighting that a high-valent iron-oxo species might be involved in the degradation pathways.