PNNL

Abstract

Technetium (Tc) remains a priority remediation concern due to persistent challenges, including rapid re-oxidation of immobilized Tc, and competing contaminants, e.g. Cr(VI), that inhibit targeted Tc reduction and incorporation into stable mineral phases. Here Fe(OH)2(s) is investigated as a comprehensive solution for overcoming these challenges, by serving as both the reductant, (Fe(II)), and immobilization agent to form Tc-incorporated magnetite (Fe3O4). Trace metal analysis suggests removal of Tc(VII) and Cr(VI) from solution occurs simultaneously; however, complete removal and reduction of Cr(VI) is achieved earlier than the removal/reduction of co-mingled Tc(VII). Bulk oxidation state analysis of the magnetite solid phase by XANES confirms that the majority of Tc is Tc(IV), which is corroborated by XPS. Furthermore, EXAFS results show successful Tc(IV) incorporation into magnetite octahedral sites without additional substitution of Cr or Tc into neighboring Fe octahedral sites. XPS analysis of Cr confirms reduction to Cr(III) and the formation of a Cr-incorporated spinel, Cr2O3, and Cr(OH)3 phases. Spinel (modeled as Fe3O4), goethite, and feroxyhyte are detected in all reacted solid phase samples analyzed by XRD, where Tc(IV) incorporation has little effect on the spinel lattice structure. In the presence of Cr(III) a spinel phase along the magnetite-chromite (Fe3O4 ? FeCr2O4) solid-solution line is formed.