Highly efficient removal of Cr(VI) from aqueous solution by pinecone biochar supported nanoscale zero-valent iron coupling with Shewanella oneidensis MR-1

Nanoscale zero-valent iron (nZVI) has been extensively used to remove various pollutants. However, the rapid deactivation due to aggregation and surface passivation severely limits its practical application. In this study, a novel composite with nZVI supported by pinecone biochar (nZVI-PBC) was successfully synthesized and used for the removal of high concentration Cr(VI) from aqueous solution in the presence of Shewanella oneidensis MR-1 (MR-1). The results showed that the nZVI-PBC coupling with MR-1 (nZVI-PBC/MR-1) exhibited an excellent removal performance for high concentration Cr(VI) compared to the nZVI-PBC alone. Under optimal conditions, 100 mg/L Cr(VI) could be removed completely by nZVI-PBC/MR-1 within 48 h, while only 39.50% of Cr(VI) was removed by nZVI-PBC alone. The improvement of Cr(VI) removal is due to the dissolution of the surface passivation layer of nZVI-PBC, formation of sorbed Fe(II) in the presence of MR-1, and an important role of extracellular polymeric substance (EPS) derived from MR-1. X-ray photoelectron spectroscopy (XPS) and Cr K-edge X-ray absorption near-edge structure spectra (XANES) confirmed that most Cr(VI) was reduced to insoluble Cr(III) and formed Cr₂O₃, Cr_xFe_1-x(OH)₃ and FeCr₂O₄ precipitates, and a small amount of unreduced Cr(VI) was immobilized through adsorption and complexation. The results suggest that nZVI-PBC/MR-1 can effectively overcome the limitations of nZVI and achieve highly efficient removal of high concentration Cr(VI).