Redox Behavior of Secondary Solid Iron Species and the Corresponding Effects on Hydroxyl Radical Generation during...

During the pyrite oxidation process, aqueous ferrous/ferric ions (Fe²⁺/Fe³⁺), as well as surface-adsorbed Fe²⁺/Fe³⁺, have been widely recognized to dominate hydroxyl radical (^•OH) generation, while this study reveals that the secondary solid iron species also play non-negligible roles. Based on the different forms and the presence of sites, the secondary solid iron species were classified as Fe_coat (iron-containing coating on the pyrite surface) and Fe_dep (ex situ-deposited iron (oxyhydr)oxide that is not in contact with pyrite). Instead of participating in building a stubborn passivation layer on the pyrite surface, Fe_coat is easy to fall off from the pyrite surface as the oxidation of pyrite deepens, while large fractions of Fe_dep and Fe_coat are found to be extractable with nitrilotriacetic acid (NTA). Achieved by cyclically oxidizing pyrite within different NTA levels (0/0.1/10 mM), Fe_coat and Fe_dep were proved to have distinct redox behavior during the pyrite oxidation process. Amorphous Fe_dep, originated from the hydrolyzation of dissolved Fe³⁺, accelerates the nonradical decay of hydrogen peroxide (H₂O₂); as a result, the accumulation of Fe_dep always decreases the ^•OH production during the pyrite oxidation process. However, part of Fe_dep adsorbs on the pyrite surface through electrostatic attraction and converts into Fe_coat. The electron conduction between Fe_coat and pyrite was verified, which accelerates the oxidative dissolution of pyrite, produces reactive Fe(II), and therefore favors ^•OH generation. This study improves our understanding of the redox behavior of pyrite in complex media such as natural processes and practical engineering systems.