Enhancement of Cr(VI) reduction by indigenous bacterial consortia using natural pyrite: A detailed study to elucidate the mechanisms involved in the highly efficient and possible sustainable system.

Pyrite was applied to Cr(VI) bioremediation as an inorganic electron donor due to the ability to provide electrons, while the role of pyrite in Cr(VI) bioremediation where organics as electron donors remains unknown. Herein a pyrite-based Cr(VI) bioreduction process in the sediment system containing lactate was demonstrated to be effective to detoxify Cr(VI): over 2200 mg L-1 Cr(VI) was continuously removed within 210 h with high reactivity (10.5 mg/(L·h)) all along. High-throughput 16S rDNA gene sequencing indicated that the pyrite could shape a functioning community that electrochemically active bacteria dominated (such as Fusibacter sp. and Rhodobacteraceae) instead of iron-oxidizing bacteria and sulfur-oxidizing bacteria. Mineralogy analysis results indicated that Fe(III), S22- and S0 formed on the pyrite surface after the oxidation of Cr(VI) might serve as the electron acceptor of microflora, then the S2- and Fe(II) with strong Cr(VI) reduction ability were formed by microbial reduction to enhance the removal of Cr(VI). This study provides new insights into thoroughly understanding the role of pyrite in the practical application of Cr(VI) bioreduction.

Conductive property of secondary minerals triggered Cr(VI) bioreduction by dissimilatory iron reducing bacteria.

Although secondary minerals have great potential for heavy metal removal, their impact on chromium biogeochemistry in subsurface environments associated with dissimilatory iron reducing bacteria (DIRB) remains poorly characterized. Here, we have investigated the mechanisms of biogenic secondary minerals on the rate of Cr(VI) bioreduction with shewanella oneidensis MR-1. Batch results showed that the biogenic secondary minerals, schwertmannite and jarosite, appreciably increased the Cr(VI) bioreduction rate. UV-vis diffuse reflection spectra showed that schwertmannite and jarosite are semiconductive minerals, which can be activated by MR-1, followed by transferred conduction electrons toward Cr(VI). Cyclic voltammetry and Tafel analysis suggested that the resistance of secondary minerals is a dominant factor controlling Cr(VI) bioreduction. In addition, Cr(VI) adsorption on secondary minerals through ligand exchange promoted Cr(VI) bioreduction by decreasing the electron transfer distance between MR-1 and chromate. Fe(III)/Fe(II) cycling in schwertmannite and jarosite also contributed to Cr(VI) bioreduction as reflected by X-ray photoelectron spectroscopy and Fourier transform infrared spectrometer. Complementary characterizations further verified the contributions of Fe(III)/Fe(II) cycling, Cr(VI) adsorption, and conduction band electron transfer to enhanced Cr(VI) bioreduction. This study provides new insights on the understanding of Cr(VI) bioreduction by semiconductor minerals containing sulfate in subsurface environments.