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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 wa