Lead competition alters the zinc adsorption mechanism on animal-derived biochar

In this study, the adsorption behaviors and mechanisms of Pb(II) and Zn(II) by animal-derived biochar (ADB) in single and binary metal systems were comparatively investigated. ADB contains considerable amounts of Ca/P components and is mainly composed of hydroxyapatite (HAP), which plays an important role in the adsorption of Pb(II) and Zn(II). The maximum adsorption capacities of Pb(II) and Zn(II) on ADB were in the order of Zn(II)-single (3.23 mmol g^-1) > Pb(II)-single (2.74 mmol g^-1) ≈ Pb(II)-binary (2.71 mmol g^-1) > Zn(II)-binary (2.31 mmol g^-1). In the single metal system, approximately 99.9% of the adsorbed Pb(II) existed as Pb₅(PO₄)₃Cl, while the dominant adsorption mechanism of Zn(II) was cation exchange, followed by precipitation, accounting for 78.0%-80.6% and 19.4%-21.5% of the adsorption capacity, respectively. These findings were verified by X-ray diffraction refinement, X-ray photoelectron spectroscopy, metal speciation modeling, and Ca(II) exchange experiment. In the binary metal system, the proportion and form of Pb(II) precipitate remained unchanged. However, the binding of Zn(II) to ADB was completely dependent on the cation exchange with Ca(II), and no remarkable Zn(II) precipitation was observed. Phosphate released from HAP preferentially precipitated with Pb(II) than with Zn(II) when they coexisted. Consequently, Pb(II) competition may alter the Zn(II) adsorption mechanism on ADB. Nonetheless, ADB could serve as an efficient biochar for the simultaneous immobilization of Pb(II) and Zn(II) via different mechanisms.