Unraveling the molecular mechanisms of Cd sorption onto MnO_x-loaded biochar produced from the Mn-hyperaccumulator Phytolacca americana

Engineered biochar represents a promising material for green remediation practices. In this paper, we present an innovative approach to produce MnO_x-loaded biochars by pyrolyzing the biomass of a Mn-hyperaccumulator species (Phytolacca americana). Batch sorption and stirred-flow kinetic experiments were combined with spectroscopic techniques to elucidate the mechanisms behind the Cd sorption onto those biochars, named here as PABCs. The incorporation of MnO_x into the PABCs increased their surface densities of oxygen-containing functional groups. The average Mn leaching (< 9%) from PABCs was lower than that measured for the non-pyrolyzed biomass of P. americana (30-43%). PABCs pyrolyzed at 500 °C had Cd sorption capacities as high as 212-337 mg/g, which achieved by far the best performance reported for biochar materials. The stirred-flow experiments showed that MnO_x loading was instrumental in increasing both the Cd sorption onto PABCs as well as its irreversibility. Extended X-ray absorption fine structure spectroscopy revealed that the Cd immobilization occurred mainly through its association with organic matter (Cd-OM) and, to a lesser extent, with carbonate (CdCO₃) and MnO_x (Cd-MnO_x). In short, MnO_x-loaded biochar prepared from the biomass of a Mn-hyperaccumulator species proved to be an effective, sustainable, and eco-friendly material for remediating Cd-contaminated waters.