Mackinawite (FeS) activation of persulfate for the degradation of p-chloroaniline: Surface reaction mechanism and sulfur-mediated cycling of iron species

Among the numerous iron-based materials for persulfate (PS) activation, mackinawite (FeS) particles have gained considerable interest as a ubiquitous natural mineral due to their high reactivity. However, the iron and sulfur co-mediated reaction mechanism of PS activation by FeS remains ambiguous. In this study, FeS was applied as a catalyst to activate PS for p-chloroaniline (PCA) degradation and mineralization over a wide initial pH range (3.0-11.0). The reaction was found to follow pseudo-first-order kinetics, with rate constants ranging from 0.0044 to 0.0144 min(-1). The reaction mechanism was elucidated by electron spin resonance (ESR) and quenching studies. A heterogeneous activation mechanism, in which surface Fe(II) species activated PS to produce center dot OHads and SO4ads center dot-, controlled by surface reaction and diffusion was proposed, whereas (OHfree)-O-center dot and SO4free center dot- diffusing from the FeS surface were mainly responsible for PCA degradation. The sulfur-mediated cycling of iron species was investigated by comparing PS activation by zero-valent iron (ZVI) and FeS, exogenous Fe(III) addition and X-ray photoelectron spectroscopy (XPS). The results suggested that Fe(II) and S(-II) experienced independent oxidations and that S(-II) species could regenerate Fe(II) from Fe(III) at the FeS surface. Therefore, the S(-II)-promoted Fe(II)/Fe(III) cycle resulted in less PS decomposition but a higher PCA mineralization efficiency. The findings of this study elucidated the novel surface activation mechanism of PS by FeS and provided useful information for utilizing FeS to remediate contaminated water.