Mechanistic investigation of mercury removal by unmodified and Fe-modified biochars based on synchrotron-based methods

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 HgS 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.