Effect of sulfidation on nitrobenzene removal from groundwater by microscale zero-valent iron: Insights into reactivity, reaction sites and removal pathways

While it has been recognized that sulfidation can effectively improve the reactivity of microscale zero valent iron (mZVI), there is limited understanding of nitrobenzene (ArNO2) removal by sulfidated mZVI. To understand the reduction capacity and pathway of ArNO2 by sulfidated mZVI, ball-milling sulfidated mZVI (S-mZVIbm) with different S/Fe molar ratios (0–0.2) was used to conduct this experiment. The results showed that sulfidation could efficiently enhance ArNO2 removal under iron-limited and iron excess conditions, which was attributed to the presence of FeSx sites that could provide higher Fe(0) utilization efficiency and stronger passivation resisting for S-mZVIbm. The optimum ArNO2 reduction could be obtained by S-mZVIbm with S/Fe molar ratio at 0.1, which could completely transform ArNO2 to aniline (ArNH2) with a rate constant of 4.36 × 10−2 min−1 during 120-min reaction. FeSx phase could act as electron transfer sites for ArNO2 reduction and it could still be reserved in S-mZVIbm after reduction reaction. The product distribution indicated that sulfidation did not change the types of reduction products, while the removal of ArNO2 by S-mZVIbm was a step-by-step reduction progress along with the adsorption of ArNH2. In addition, a faster reduction of ArNO2 in groundwater/soil system further demonstrated the feasibility of S-mZVIbm in the real field remediation. [Display omitted] •Sulfidation significantly enhanced nitrobenzene removal by mZVIbm.•Fe(0) utilization of S-mZVIbm for nitrobenzene reduction was higher than that of mZVIbm.•FeSx phase acted as electron transfer sites for nitrobenzene reduction and still reserved after reaction.•Nitrobenzene removal by S-mZVIbm included a multi-step reduction process and adsorption of aniline.•S-mZVIbm exhibited a faster nitrobenzene removal in groundwater/soil system.