Abstract
Heavy metals including Cd, Pb, and Zn are prevalent stormwater and groundwater contaminants derived from natural and human activities, and there is a lack of cost-effective treatment for their removal. Recently, biochar has been increasingly recognized as a promising low-cost sorbent that can be used to remediate heavy metal contaminated water. This study evaluates the immobilization/release performance of dairy manure-derived biochar (DM-BC) as a sustainable material for competitive removal of coexisting heavy metal ions from water and explains the underlying mechanism for regeneration/reusability of biochar. Results showed that the metal ions exhibited competitive removal in the order of Pb(2+) ≫ Zn(2+) > Cd(2+). The pH played a decisive role in influencing metal ion speciation affecting the electrostatic attraction/repulsion and surface complexation. Higher pH led to greater removal for Pb(2+) and Cd(2+), whereas Zn(2+) showed maximum removal at pH ≈ 7.5. Diffuse reflectance infrared spectroscopy, scanning electron microscopy, and X-ray diffraction confirmed the interactions and precipitation reactions of oxygen-containing functional groups (e.g., ─OH, CO32-, and Si─O) as key participants in metal immobilization. Langmuir, Freundlich, and Redlich-Peterson isotherm modeling data showed varied and unique results depending on the metal ion and concentration. The removal kinetics and model fitting showed that the three steps of intraparticle diffusion might be more representative for describing the immobilization processes of metal ions on the external surface and internal pores. In the flow-through columns, DM-BC effectively retained the mixed metal ions of Cd(2+), Pb(2+), and Zn(2+) showing 100% removal for the duration of the column run over three cycles of regeneration and reuse.