Applied Research Center, Florida International University, 10555W Flagler St, Miami, FL 33174, USA.
Applied Research Center, Florida International University, 10555W Flagler St, Miami, FL 33174, USA.
J Hazard Mater. 2023 Mar 5;445:130546. doi: 10.1016/j.jhazmat.2022.130546. Epub 2022 Dec 5.
Radioactive technetium-99 (Tc) present in waste streams and subsurface plumes at legacy nuclear reprocessing sites worldwide poses potential risks to human health and environment. This research comparatively evaluated efficiency of zero-valent iron (ZVI) toward reductive removal of Tc(VII) in presence of Cr(VI) from NaCl and NaSO electrolyte solutions under ambient atmospheric conditions. In both electrolytes, anticorrosive Cr(VI) suppressed oxidation of ZVI at elevated concentrations resulting in the delay of initiation of Tc(VII) reduction to Tc(IV). In the absence of Cr(VI), no delay was observed in the analogous systems. At low ionic strength (IS), retarded ZVI oxidation inhibited Tc(VII) reduction. Higher IS favored reduction of both Tc(VII) and Cr(VI), which followed second-order reaction rates in both electrolytes attributed to the more efficient iron oxidation as evident from solids characterization studies. Magnetite was the primary iron oxide phase, and its higher fraction in the SO solutions facilitated reductive removal of Tc(VII) and Cr(VI). In the Cl matrix, Cr(VI) promoted further oxidation of magnetite as well as formation of chromite diminishing overall reductive capacity of this system and resulting in less effective removal of Tc(VII) compared to the SO solutions.
放射性锝-99(Tc)存在于世界各地的核废料和地下羽流中,对人类健康和环境构成潜在威胁。本研究比较了零价铁(ZVI)在环境大气条件下,从 NaCl 和 NaSO 电解质溶液中还原去除 Tc(VII)的效率,同时存在 Cr(VI)。在两种电解质中,腐蚀性 Cr(VI)抑制了 ZVI 在高浓度下的氧化,导致 Tc(VII)还原为 Tc(IV)的起始延迟。在没有 Cr(VI)的情况下,在类似的系统中没有观察到延迟。在低离子强度(IS)下,延迟的 ZVI 氧化抑制了 Tc(VII)的还原。较高的 IS 有利于 Tc(VII)和 Cr(VI)的还原,这归因于更有效的铁氧化,这在固体特性研究中很明显,两种电解质中的还原速率均遵循二级反应速率。磁铁矿是主要的氧化铁相,其在 SO 溶液中的较高分数有利于 Tc(VII)和 Cr(VI)的还原去除。在 Cl 基体中,Cr(VI)促进了磁铁矿的进一步氧化以及铬铁矿的形成,从而降低了该体系的整体还原能力,导致 Tc(VII)的去除效果不如 SO 溶液。