Distribution and speciation of iron in Fe-modified biochars and its application in removal of As(V), As(III), Cr(VI), and Hg(II): An X-ray absorption study

Abstract

Characterization of the spatial distribution and speciation of iron (Fe) in Fe-modified biochars is critical for understanding the mechanisms of contaminant removal. Here, synchrotron-based techniques were applied to characterize the spatial distribution and speciation of Fe in biochars modified by FeCl₃ or FeSO₄ and pyrolyzed at 300, 600, and 900 °C, respectively. Confocal micro-X-ray fluorescence imaging (CMXRFI) results indicated Fe, sulfur (S), and chlorine (Cl) diffused into the basic porous structure of the biochars and aggregated to the surface as pyrolysis temperature increased. Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra revealed maghemite (γ-Fe₂O₃) as the primary Fe species in the modified biochars and Fe(0) was observed when pyrolyzed at 600 or 900 °C. Unmodified and FeCl₃-modified biochars pyrolyzed at 900 °C were evaluated in the removal of arsenate (As(V)), arsenite (As(III)), hexavalent chromium (Cr(VI)) and Hg(II) from aqueous solution and Fe-modification enhanced the removal efficiency from 42.0%, 62.5%, 19.6%, and 97.0%, respectively, to all 99.9%. X-ray absorption spectroscopy results indicate both adsorption and redox reaction contributed to the removal mechanisms. The present study provides a prospective and sustainable material and offers information relevant to tailoring Fe-modified biochars to specific environmental applications.

Keywords: Confocal micro-X-ray fluorescence imaging; Environmental removal; Extended X-ray absorption fine structure; Fe-modified biochar; X-ray absorption near-edge structure.