Tc(VII) reduction kinetics by titanomagnetite (Fe3−xTixO4) nanoparticles

Abstract

Technetium contamination remains a major environmental problem at nuclear reprocessing sites, such as at the Hanford nuclear reservation, Washington, USA. Here we investigate the heterogeneous reduction of the highly soluble pertechnetate anion [Tc(VII)O4−] to sparingly soluble Tc(IV)-bearing solids by a novel and well-characterized set of mixed-valent titanium-doped magnetite nanoparticles, structurally and chemically analogous to titanomagnetites naturally present in Hanford sediments. Titanomagnetite (Fe3−xTixO4) nanoparticles (10–12nm) with varying Ti content (0⩽x⩽0.53) were synthesized in aqueous suspension. Reaction with 10 and 30μM Tc(VII) solution yielded fast exponentially decaying reduction kinetics with rates that increased with increasing solid-state Fe(II)/Fe(III) ratio in the nanoparticles, a characteristic systematically controlled by the Ti-content. Nanoparticles before and after reduction experiments and surface-associated products of Tc(VII) reduction were characterized using transmission electron microscopy (TEM), X-ray absorption near-edge spectroscopy (XANES), extended X-ray absorption fine structure spectroscopy (EXAFS), micro X-ray diffraction (μ-XRD), X-ray absorption (XA) and X-ray magnetic circular dichroism (XMCD). A mechanistic reaction model was developed involving reduction of Tc(VII) to form Tc(IV)/Fe(III) solids by structural Fe(II) enriched at the nanoparticle surface, a reactive Fe(II) pool that during reaction is resupplied and sustained by outward migration of Fe(II) from the particle interior with concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1. The reaction process was quantitatively linked to mass and electron balanced changes in the Fe3−xTixO4 nanoparticles, and the accessibility of structural Fe(II) from these phases was determined.