Pb(II)-mediated precipitate transformation promotes Cr(VI) immobilization by biogenic hydroxyapatite

Abstract

In this work, the mechanism of Pb(II)-mediated precipitation transformation to improve the removal of Cr(VI)-oxyanion on biogenic hydroxyapatite (BHAp) were investigated. The Pb(II)-preloading formed pyromorphite [Pb5(PO4)3Cl] precipitate on the BHAp surface (Pb@BHAp), thus causing an increase of 2.2 times in the uptake of Cr(VI) by Pb@BHAp at pH of 2.4. It was primarily due to the dissolution of Pb5(PO4)3Cl accompanied with the release of Pb(II), resulting in the rapid formation of crocoite (PbCrO4). Although the Ksp of Pb5(PO4)3Cl was approximately 23 orders of magnitude lower than that of PbCrO4, Pb(II)-mediated precipitation transformation could still occur. XRD and SEM-EDX analyses demonstrated that the process was a time-dependent that included rapid crystal precipitation in the initial 10 min and subsequent precipitate accumulation for several hours. The Pb(II) released from the dissolution of Pb5(PO4)3Cl was immediately immobilized by Cr(VI); therefore, it did not cause any retention risk of Pb(II) in the solution. Furthermore, a small quantity of Cr(VI) could be reduced to Cr(III) by BHAp, and Cr(III) could enter into the BHAp lattice for the exchange of Ca(II). This study provides a new insight into the resource utilization of Pb-bearing BHAp and a potential method for the successive removal of Pb(II) and Cr(VI).