Lead coprecipitation with iron oxyhydroxide nano-particles

Abstract

Pb 2+ and Fe 3+ coprecipitation was studied with sorption edge measurements, desorption experiments, sorbent aging, High Resolution Transmission and Analytical Electron Microscopy (HR TEM–AEM), and geochemical modeling. Companion adsorption experiments were also conducted for comparison. The macroscopic chemical and near atomic scale HRTEM data supplemented our molecule scale analysis with EXAFS ( Kelly et al., 2008). Coprecipitation of Pb 2+ with ferric oxyhydroxides occurred at ∼pH 4 and is more efficient than adsorption in removing Pb 2+ from aqueous solutions at similar sorbate/sorbent ratios and pH. X-ray Diffraction (XRD) shows peaks of lepidocrocite and two additional broad peaks similar to fine particles of 2-line ferrihydrite (2LFh). HRTEM of the Pb–Fe coprecipitates shows a mixture of 2–6 nm diameter spheres and 8–20 by 200–300 nm needles, both uniformly distributed with Pb 2+. Geochemical modeling shows that surface complexation models fit the experimental data of low Pb:Fe ratios when a high site density is used. Desorption experiments show that more Pb 2+ was released from loaded sorbents collected from adsorption experiments than from Pb to Fe coprecipitates at dilute EDTA concentrations. Desorbed Pb 2+ versus dissolved Fe 3+ data show a linear relationship for coprecipitation (CPT) desorption experiments but a parabolic relationship for adsorption (ADS) experiments. Based on these results, we hypothesize that Pb 2+ was first adsorbed onto the nanometer-sized, metastable, iron oxyhydroxide polymers of 2LFh with domain size of 2–3 nm. As these nano-particles assembled into larger particles, some Pb 2+ was trapped in the iron oxyhydroxide structure and re-arranged to form solid solutions. Therefore, the CPT contact method produced more efficient removal of Pb 2+ than the adsorption contact method, and Pb 2+ bound in CPT solids represent a more stable sequestration of Pb 2+ in the environment than Pb 2+ adsorbed on iron oxyhydroxide surfaces.