The role of Fe dissolution in olivine-hydroxylamine-induced Fenton reaction for enhanced oxidative degradation of organic pollutant.

In this study, a dye pollutant (methyl orange, MO) was effectively oxidized in a hydroxylamine (HA)-assisted Fenton system using various Al/Si/Fe- and Fe-containing minerals. The fastest degradation kinetics of MO were observed in the olivine-HA Fenton system, whereas other Al/Si/Fe and Fe-rich minerals (magnetite and lepidocrocite) demonstrated much slower degradation kinetics. The degradation rate constants were proportional to dissolved Fe(II) quantities in mineral suspensions (R = 0.98), indicating the crucial role of dissolved Fe(II) quantity in HA-assisted Fenton reactions. Radical scavenging and electron spin resonance results revealed that MO was dominantly oxidized by ·HO produced in the olivine-HA Fenton system. The continuous production of aqueous Fe(II) via direct Fe(II) dissolution at a pH of 3 and further Fe dissolution from the reductive dissolution of surface Fe(III) by HA was the main driving force for efficient MO degradation. Furthermore, lowering the pH by the addition of hydroxylamine hydrochloride resulted in the effective removal of MO under various pH conditions (3-9), indicating the additional advantage of HA use in Fenton reactions. Liquid chromatography-mass spectroscopy analysis revealed that the cleavage of C-N and C-C bonds, demethylation, hydroxylation, and dehydroxylation were the main processes for MO oxidation in the olivine-HA Fenton system.