Preferential adsorption and surface precipitation of lead(II) ions onto anatase in artificially contaminated Dixie clay

During TEM-EDS (transmission electron microscopy coupled with an X-ray energy dispersive spectrometer) analysis of Dixie clay artificially contaminated with Pb(II), we observed that Pb(II) was preferentially adsorbed and precipitated on the surface of TiO2. To deepen the understanding of the mechanism and importance of this phenomenon, batch sorption experiments, XANES (X-ray absorption near edge spectroscopy) analysis, and sequential extraction analysis were performed. The TiO2 in Dixie clay was found to be anatase, and anatase showed a higher Pb(II) sorption propensity than rutile, α-FeOOH, and one of two MnO2 investigated in this study. Our experimental results indicated that the Pb precipitates preferentially formed on the surface of anatase was Pb(II) hydroxide or Pb(II) oxide. Additionally, sequential extraction analysis showed that at least 32% and 42% of Pb(II) was sorbed onto anatase in the Dixie clay contaminated with a Pb content of 736 mg Pb/kg and 1,958 mg Pb/kg, respectively. These results demonstrated that in addition to Fe and Mn oxides that are well-known metal oxides that serve as sinks for Pb(II) in the soil environment, TiO2 is also a metal oxide that controls the behavior and fate of Pb(II) in soils.