Competitive adsorption of heavy metals onto xanthate-modified sludge hydrochar and its solidification as secondary...

In this study, a sulfur-modified magnetic hydrochar was synthesized by grafting thiol-containing groups onto the sludge-derived hydrochar. The modified hydrochar exhibited effective adsorption of Cu²⁺, Pb²⁺, Zn²⁺, and Cd²⁺ over a wide pH range and in the presence of coexisting ions, and showed almost no secondary leaching in three acidic solutions. In the mult-metal ion system, the modified hydrochar exhibited maximum adsorption capacities were 39.38, 105.74, 26.53, and 38.11 mg g^-1 for Cu²⁺, Pb²⁺, Zn²⁺, and Cd²⁺, respectively. However, the binding capacity and adsorption amount of modified hydrochar for metal ions were lower in the mult-metal ion system compared to the unit-metal ion system. Notably, Pb²⁺ showed a strong inhibitory effect on the adsorption of other heavy metal ions by modified hydrochar due to strong competition for xanthate functional groups. The Pb²⁺ occupied the xanthate and native functional groups (-OH, -NH₂, and Fe-O etc.), leaving only a small amount of adsorption sites for Cu²⁺, Zn²⁺ and Cd²⁺. Simulation results further supported these findings, indicating that Pb²⁺ had the highest density profiles near the four functional groups, and the density profiles of the four heavy metals near the xanthate functional groups were greater compared to the other three functional groups. Furthermore, the SEM-EDS, TOF-SIMI, and XPS results indicated that modified hydrochar achieved excellent mineral binding mainly through electrostatic interaction, ion exchange, and chelation. Overall, these results highlight the sulfur-modified magnetic hydrochar as a highly efficient adsorbent for heavy metals in environmental applications.