Coexisting ferrihydrite-enhanced contaminant degradation during pyrite oxygenation

Oxygenation of pyrite (Py) is known to mediate generation of reactive oxygen species (ROS) with these species capable of inducing contaminants degradation, whereas the possible participation of coexisting Fe(III) minerals in these processes is still unclear. This study finds that freshly formed ferrihydrite (Fh) significantly enhances the Py-mediated sulfamethoxazole (SMX) degradation process. Through the ⁵⁶Fe isotope tracer experiment and a series of control experiments, Fh is found to be reduced by Py to form secondary solid-phase Fe(II) species (Fe(II)_RF) which in turn facilitates generation of H₂O₂ from the O₂ reduction pathway. However, Py was found to mediate rapid structural transformation of Fh to form more thermodynamically stable goethite and hematite with these less redox active minerals unable to sustainably promote the Py-mediated SMX degradation process. Therefore, the improvement of Fh on Py-mediated SMX degradation process is not readily observable in reaction systems with low concentrations of coexisting Fh. In comparison, continuing input of 10 mM Fh increased the degradation efficiency of SMX by 60 % over three days. Our results demonstrate that the oxidative degradation of organic contaminants over the oxygenation of Py when coexisting with Fh can be more significant but currently underestimated.