Oxidative Functionalization of Woody Biochar for Hexavalent Chromium Detoxification: Adsorption-Coupled Reduction and...

To address the ecological risks associated with highly mobile hexavalent chromium [Cr(VI)], woody biochar was functionalized with hydrogen peroxide (H₂O₂) to develop a dual-phase remediation material (H-BC) for aqueous and soil environments. Batch post-contact isotherm fitting yielded a Langmuir-fitted/extrapolated apparent retention capacity q_m of 77.44 mg/g at 328 K. This value reflects enhanced overall Cr(VI)-derived retention within the tested concentration range, rather than increased electrostatic affinity for chromate oxyanions. Empirical kinetic diagnostics and FTIR/XPS results were consistent with adsorption-coupled interfacial reduction, while DFT analysis provided qualitative support for the enhanced electronic responsiveness of H-BC. The OFG-enriched interface may facilitate short-range, non-electrostatic interfacial interactions and stabilize surface-associated Cr(III). Temperature-dependent apparent isotherm fitting suggested that elevated temperature favored the overall Cr(VI)-derived retention process under the tested conditions, and should not be interpreted as rigorous standard-state adsorption thermodynamics. Continuous-flow column leaching and accelerated wet-dry (W-D) aging experiments demonstrated that H-BC substantially suppressed the mobility of operationally filtered Cr(VI), achieving a maximum filtered-Cr(VI)-based retention efficiency of 99.98% under cyclic drying-rewetting conditions. Spatial configuration analysis indicated that homogeneous incorporation of H-BC improved soil-biochar contact and was more effective than stratified placement in limiting vertical filtered-Cr(VI) migration. Overall, oxidatively functionalized H-BC shows promise as a biomass-derived amendment for reducing Cr(VI) mobility in complex environmental matrices, although complete chromium mass redistribution will require future total-Cr and Cr(III)-resolved analyses.