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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 A 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.

Improved surface characteristics and incorporated Fe, S, and Cl species are reported in Fe-modified biochar, which makes it a prospective material for Hg(II) removal. In this study, aqueous Hg(II) was removed from solution by unmodified, FeCl3-modified, and FeSO4-modified biochars pyrolyzed at 300, 600, or 900 °C. Higher pyrolytic temperature resulted in higher removal efficiency, with the biochars pyrolyzed at 900 °C removing >96% of Hg(II). Fe-modification enhanced Hg(II) removal for biochars pyrolyzed at 600 °C (from 88% to >95%) or 900 °C (from 96% to 99%). Based on synchronous extended X-ray absorption fine structure (EXAFS) analysis, Hg coordinated to S in modified and unmodified biochars pyrolyzed at 900 °C, where thiol was reported, and in FeSO4-modified biochars pyrolyzed at 600 or 900 °C, where sulfide was recognized; in other biochars, Hg bound to O or Cl. Additionally, confocal micro-X-ray fluorescence imaging (CMXRFI) demonstrated Hg was distributed in agreement with S in biochars where Hg S was formed; otherwise, Hg distribution was influenced by Hg species in solution and the pore characteristics of the biochar. This investigation provides information on the effectiveness and mechanisms of Hg removal that is critical for evaluating biochar applications and optimizing modification methods in groundwater remediation.