Removal mechanisms of aqueous Cr(VI) by anaerobic fermentation sludge

After fermentation, activated sludge contains many acid-producing bacteria and their metabolites, which have a good reducing effect. Various active groups (e.g., hydroxyl, amino, carboxyl, and phosphate) on microbial cell surfaces can adsorb heavy metals through complexation or chelation, forming heavy metal precipitates and thereby reducing the toxicity of heavy metals. However, the effects and mechanisms of using sludge after anaerobic fermentation to remove Cr(VI) are unclear, such as the dominance of direct versus indirect biological reduction, the contribution of abiotic effects, and the influence of fermentation conditions. This paper compares Cr(VI) removal in fermented and unfermented sludges. After fermentation for 24 h, 99.9% of the Cr(VI) (50 mg/L) in anaerobic sludge was removed within 7 h, which was twice the rate in unfermented activated sludge. A series of comparative experiments demonstrated that Cr(VI) removal primarily occurred through biological effects (about 92%), which included biological reduction and biosorption. 16SrRNA gene sequencing revealed that Cr(VI) transformation primarily occurred through direct biological reduction, with the related genera being Trichococcus, Acetobacter, Aeromonas, and Tolumonas. Fourier-transform infrared (FTIR) spectroscopy results showed that the C = O and C-O functionalities on sludge were likely involved in the Cr(VI) conversion. Majority of the Cr(VI) in the system was reduced to Cr(III) and existed in the suspension, with a small amount deposited on the sludge surface. The X-ray photoelectron spectroscopy (XPS) results indicated that the majority of Cr was present as reduced Cr(III) on the sludge. These results demonstrate that after fermentation in an aqueous environment, activated sludge is an effective medium for the remediation of Cr(VI). These results are useful for designing a green and sustainable bioreduction system for the remediation of Cr(VI)-polluted water.