Revealing methane production potential from waste activated sludge through citric acid-assisted hydrogen corrosion of zero valent iron

Anaerobic digestion of waste activated sludge (WAS) for biofuel recovery is one key step for developing energy-self-sufficient and carbon–neutral wastewater treatment plants. Although zero valent iron (ZVI) is an alternative additive to promote methane production from WAS, low hydrogen corrosion of ZVI is one important limitation. This study explored whether methane production potential could be further enhanced while using citric acid (CA) to accelerate hydrogen corrosion of ZVI. Results showed that the maximum methane production reached 92.77 mL/g volatile suspended solid (VSS) with ZVI of 30 mM and CA of 6 mM, which increased by 63.8% compared to that with solo ZVI. Mechanism analysis demonstrated that the proposed strategy could accelerate the solubilization of WAS, increase the accumulation of short-chain fatty acids (SCFAs), and optimize the composition of SCFAs. Meanwhile, both the efficiencies of hydrogen yield and production rate obtained with ZVI and CA were the highest. The accumulation of hydrogen with ZVI and CA reached 5 mL/g VSS during the 9-hour period, which was 2.42 times higher than that with solo ZVI, and the hourly hydrogen production rate was 2.47 mL/g VSS⁻¹h⁻¹, which was higher than those with either solo CA or ZVI. Thus, the effectiveness of 1 + 1＞2 was obtained. Correspondingly, the concentration of ferrous ion with ZVI and CA increased to 2.32 times higher than that with solo ZVI. In addition, the microbial community analysis indicated that hydrogenotrophic methanogens were predominated with ZVI and CA. These findings may provide some new solutions for promoting the role of nano-ZVI in enhancing methane production from anaerobic digestion.