Synergistic role of inherent calcium and iron minerals in paper mill sludge biochar for phosphate adsorption

Phosphate adsorption using metal-based biochar has awakened much attention and triggered extensive research. In this study, novel Ca/Fe-rich biochars were prepared via a one-step process of pyrolyzing paper mill sludge (PMS) at various temperatures (300, 500, 700, and 800 °C) under a CO2 atmosphere for phosphate removal. Batch adsorption experiments showed that the biochar obtained at 800 °C (PB-800), which could be easily separated magnetically, exhibited the best phosphate adsorption capacity in a wide range of solution pH (5-11). Based on the Langmuir model, the maximum phosphate adsorption capacity for PB-800 was 17.33 mg/g. Besides, the effects of ambient temperature as well as coexisting ions on phosphate removal were also investigated. Kinetic and thermodynamic analysis revealed that chemisorption dominated the adsorption process. The calcium carbonate and ferric salts in the sludge were converted into CaO and Fe3O4 through pyrolysis at 800 °C. The CaO inherent in PB-800 was proved to serve as active sites for the chemical precipitation, showing its synergistic effect with iron oxide compounds (i.e., Fe3O4, α-Fe2O3) on phosphate removal through chemical precipitation, ligand exchange, and complexation. This study not only provides a feasible waste-to-wealth strategy for converting PMS into a Ca/Fe-rich magnetic biochar that can be used as an effective phosphate adsorbent, but also offers new insights into the synergistic effect of calcium and iron species for the adsorption of phosphate using biochar.