Iron mineral-humic acid complex enhanced Cr(VI) reduction by Shewanella oneidensis MR-1

Microorganisms, iron minerals, and humic acid are widely common in the soil and water environment and closely interact within environmental processes. In this study, the Cr(VI) removal by Shewanella oneidensis MR-1 (S. oneidensis) was examined in the presence of goethite and humic acid (HA) to mimic the real environment situation. Scanning electron microscopy (SEM) combined with energy disperse spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) technologies were used to probe the Cr(VI) reduction mechanism. Our results showed that S. oneidensis alone could reduce 65% of 1.0 mM Cr(VI) after 8 h of the reduction process. Meanwhile, Cr(VI) reduction rate was declined to 56% in the presence of goethite or humic acid. Contrary, the Cr(VI) reduction rate was mightily increased to 79% by the ternary complex of S. oneidensis-goethite-HA where reduced humic acid (HA_red) acted as electron shuttles and diminished the bacterial adhesion to the goethite surface thereby enhanced electron transfer and increased the extent of Cr(VI) reduction by 1.3 fold. XPS analysis indicated that Cr(VI) was reduced to Cr(III), and the final yields were Cr(OH)₃ and Cr₂O₃ precipitated on the surface of bacterial cells. S. oneidensis could also reduce Fe(III) in goethite to Fe(II), which in turn reduced Cr(VI). These results suggested that iron mineral-humic acid complex could enhance the microbial reduction of Cr(VI) and revealed the promotion role of HA in the Cr(VI) bioreduction process. This study affords inclusive insights on the Cr(VI) reduction kinetics and mechanisms in the most complicated systems.