Metallic technetium sequestration in nickel Core/Shell microstructure during Fe(OH)2 transformation with Ni doping (2022)

Guohui Wang, Dong-Sang Kim, Matthew J. Olszta, Mark E. Bowden, Daniel K. Schreiber, Sarah A. Saslow, Wooyong Um, Brian J. Riley, Jing Wang, Albert A. Kruger

Journal of Hazardous Materials, Volume 425, 5 March 2022, 127779

DOI : https://doi.org/10.1016/j.jhazmat.2021.127779

ABSTRACT

This study investigates the impacts of Ni doping on technetium-99 (Tc) sequestration in aqueous solutions through transformation of Fe(OH)2(s) to iron spinel (magnetite) under alkaline conditions. Extensive solid characterization was performed for the mineral phases produced, as well as the Tc/Ni speciation and distribution within these phases. X-ray diffraction results show that iron spinel was the dominant mineral product without detectable Ni incorporation. The doped Ni ions mainly precipitated as fine Fe/Ni oxide/hydroxide particles, including strongly reduced nanometer˗sized spheroidal Ni-rich and metallic Ni phases. High-resolution analytical scanning transmission electron microscopy using energy dispersive X-ray spectroscopy and electron energy loss spectroscopy on the produced solid samples (focused ion beam-prepared specimens) revealed three Tc distribution domains dominated by nanocrystals and, especially, a Tc-rich metallic phase. Instances of metallic Tc were specifically found in spheroidal, Ni-rich and metallic nanoparticles exhibiting a core/shell microstructure that suggests strong reduction and sequential precipitation of Ni-Tc-Ni. Mass balance analysis showed nearly 100% Tc removal from the 4.8 × 10−4 M Tc solutions. The finding of the metallic Tc encapsulation indicates that Tc sequestration through Ni-doped Fe(OH)₂(s)˗to˗iron spinel transformation process likely provides an alternative treatment pathway for Tc removal and could be combined into further waste treatment approaches.