Impact of zero-valent iron nanoparticles on the activity of anaerobic granular sludge: From macroscopic to microcosmic investigation.

The study aimed at evaluating the influence of nano zero-valent iron (nZVI) on the activity of anaerobic granular sludge (AGS) from both macroscopic and microcosmic aspects using different methodologies. The tolerance response of AGS to nZVI was firstly investigated using short-term and long-term experiments, and also compared with anaerobic flocs. The Fe fate and distribution, the change of contents/structure of extracellular polymeric substances (EPS), and the variation of microbial community in the AGS after exposure to nZVI were further explored. Contrary to the anaerobic floc, insignificant inhibition of nZVI at dosage lower than 30 mmoL/L on the activity of AGS was observed. Additionally, the extra hydrogen gas released from the oxidation of nZVI was presumably suggested to stimulate the hydrogenotrophic methanogenesis process, resulting in 30% methane production enhancement when exposure to 30 mmoL/L nZVI. The microscopic analysis indicated that nZVI particles were mainly adsorbed on the surface of AGS in the form of iron oxides aggregation without entering into the interior of the granule, protecting most cells from contact damage. Moreover, surrounded EPS located outer surface of anaerobic granule could react with nZVI to accelerate the corrosion of nZVI and slow down H2 release from nZVI dissolution, thus further weakening the toxicity of nZVI to anaerobic microorganisms. The decrease in bacteria involved in glucose degradation and aceticlastic methanogens as well as the increase of hydrogenotrophic methanogens indicated a H2 mediated shift toward the hydrogenotrophic pathway enhancing the CH4 production.