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.

Removal of phosphate from water by paper mill sludge biochar.

Biochar modification by metals and metal oxides is considered a practical approach for enhancing the adsorption capacity of anionic compounds such as phosphate (P). This study obtained paper mill sludge (PMS) biochar (PMSB) via a one-step process by pyrolyzing PMS waste containing ferric salt to remove anionic P from water. The ferric salt in the sludge was transformed into ferric oxide and zero-valent-iron (Fe0) in N2 atmosphere at pyrolysis temperatures ranging from 300 to 800 °C. The maximum adsorption (Qm) of the PMSBs for P ranged from 9.75 to 25.19 mg P/g. Adsorption is a spontaneous and endothermic process, which implies chemisorption. PMSB obtained at 800 °C (PMSB800) exhibited the best performance for P removal. Fe0 in PMSB800 plays a vital role in P removal via adsorption and coprecipitation, such as forming the ≡Fe-O-P ternary complex. Furthermore, the possible chemical precipitation of P by CaO decomposed from calcite (CaCO3; an additive of paper production that remains in PMS) may also contribute to the removal of P by PMSB800. Moreover, PMSBs can be easily separated magnetically from water after application and adsorption. This study achieved a waste-to-wealth strategy by turning waste PMS into a metal/metal oxide-embedded biochar with excellent P removal capability and simple magnetic separation properties via a one-step pyrolysis process.

Effects of aging and weathering on immobilization of trace metals/metalloids in soils amended with biochar.

Biochar is an effective amendment for trace metal/metalloid (TMs) immobilization in soils. The capacity of biochar to immobilize TMs in soil can be positively or negatively altered due to the changes in the surface and structural chemistry of biochar after soil application. Biochar surfaces are oxidized in soils and induce structural changes through physical and biochemical weathering processes. These changes in the biochar surface and structural chemistry generally increase its ability to immobilize TMs, although the generation of dissolved black carbon during weathering may increase TM mobility. Moreover, biochar modification can improve its capacity to immobilize TMs in soils. Over the short-term, engineered/modified biochar exhibited increased TM immobilization capacity compared with unmodified biochar. In the long-term, no large distinctions in such capacities were seen between modified and unmodified biochars due to weathering. In addition, artificial weathering at laboratories also revealed increased TM immobilization in soils. Continued collection of mechanistic evidence will help evaluate the effect of natural and artificial weathering, and biochar modification on the long-term TM immobilization capacity of biochar with respect to feedstock and synthesis conditions in contaminated soils.