Humic acid addition sequence and concentration affect sulfur incorporation, electron transfer, and reactivity of sulfidated nanoscale zero-valent iron

Nanoscale zero-valent iron (nZVI) is extensively used in field remediation and can be sulfidated in situ with sulfide or sulfate-reducing bacteria to enhance its performance. Humic acid (HA) widely exists in nature, but its influence on both the sulfidation process of nZVI and the reactivity of sulfidated nZVI (S-nZVI) has been rarely reported. Herein, we first synthesized S-nZVI by one-pot (S-1-nZVI) and two-step (S-2-nZVI) approaches with adding HA before (pre-added) or after (post-added) FexSy generation, respectively. Then, we evaluated their reactivity on Cr(VI) removal and analyzed the effects of HA on sulfidation regarding electron transfer resistance, sulfur incorporation, and structure characterization. Pre-added HA inhibited the Cr(VI) removal by S-1-nZVI more seriously than by S-2-nZVI and nZVI, and stronger inhibition was observed at higher HA concentrations. The inhibitory effect can be attributed mainly to the adsorbed HA increasing the impedance of the material and the free HA impeding the generation and deposition of FexSy. Different from the inhibition of pre-added HA at all studied HA concentrations, the Cr(VI) removal by both S-1-nZVI and S-2-nZVI with post-added HA was enhanced at specific HA concentrations. The reason for this phenomenon was that the dispersion and specific surface area of S-nZVI were improved, thereby offsetting the inhibition from both impedance increase and sulfur loss. This work suggests that the presence of HA can affect the sulfidation process and the property of S-nZVI, which is conducive to evaluating the performance of S-nZVI produced both by injection and in situ in the subsurface contaminant remediation.

Automated summary

Nanoscale zero-valent iron (nZVI) is widely used for field remediation and can be sulfidated with sulfide or sulfate-reducing bacteria to enhance its performance. The presence of humic acid (HA) affects the sulfidation process and the properties of the sulfidated nZVI (S-nZVI). This study reveals that pre-added HA inhibits the removal of Cr(VI) by S-nZVI, while post-added HA enhances the removal at specific concentrations. The presence of HA can impact the performance of S-nZVI in subsurface contaminant remediation.