Chemical processes of Cr(VI) removal by Fe-modified biochar under aerobic and anaerobic conditions and mechanism characterization under aerobic conditions using synchrotron-related techniques.

Fe-modified biochar (FeBC) has been considered for aqueous hexavalent chromium (Cr(VI)) removal, but a better understanding is needed with respect to the removal behavior, chemical processes, and removal mechanisms under aerobic and anaerobic conditions. Aqueous Cr(VI) removal was evaluated using unmodified (BC) and FeBC. The Cr(VI) was completely removed in a pH range of 2-10. The removal behavior was properly depicted using pseudo-second-order (PSO) and Langmuir models under aerobic conditions, and using PSO and Freundlich models under anaerobic conditions. Removal rate and capacity were enhanced by up to 3.8 times under anaerobic conditions. Desorption experiments indicated removed Cr in FeBC was stable except under strong acid condition. X-ray absorption spectroscopy (XAS) analysis suggested removed Cr in FeBC was 100% in Cr(III) form and bound to Fe with a bond length of 3.01 Å in the stable form of Fe(III)nCr(III)(1-n)(OOH). The removal mechanisms of Cr(VI) under aerobic conditions by FeBC mainly included electrostatic adsorption, chemical reduction, and complex precipitation.

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.

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.