Pertechnetate (TcO4-) reduction by reactive ferrous iron forms in naturally anoxic, redox transition zone sediments from the Hanford Site, USA
Technetium is an important environmental contaminant introduced by the processing and disposal of irradiated nuclear fuel and atmospheric nuclear tests. Under oxic conditions technetium is soluble and exists as pertechnatate anion (TcO4-), while under anoxic conditions Tc is usually insoluble and exists as precipitated Tc(IV). Here we investigated abiotic Tc(VII) reduction in mineralogically heterogeneous, Fe(II)-containing sediments. The sediments were collected from a 55 m borehole that sampled a semi-confined aquifer at the Hanford Site, USA that contained a dramatic redox transition zone. One oxic facies (18.0-18.3 m) and five anoxic facies (18.3-18.6 m, 30.8-31.1 m, 39.0-39.3 m, 47.2-47.5 m and 51.5-51.8 m) were selected for this study. Chemical extractions, X-ray diffraction, electron microscopy, and Mössbauer spectroscopy were applied to characterize the Fe(II) mineral suite that included: Fe(II)-phyllosilicates, pyrite, magnetite and siderite. The Fe(II) mineral phase distribution differed between the sediments. Sediment suspensions were adjusted to the same 0.5 M HCl extracted Fe(II) concentration (0.6 mM) for Tc(VII) reduction experiments. Aqueous Fe was low in all sediment suspensions (<2 μM) and below the Fe(II)aq detection limit (10 μM). Technetium(VII) reduction occurred in all anoxic sediments at depths greater than 18.3 m and reaction time differed significantly between the sediments (8-219 d). Mössbauer analysis of the Tc-reacted, 30.8-31.1 m sediment confirmed that Tc(VII) was reduced by solid-phase Fe(II), with siderite and Fe(II)-containing phyllosilicates implicated as redox reactive phases. Technetium-XAS analysis demonstrated that Tc associated with sediments was in the Tc(IV) valence state and immobilized as clusters of a TcO2·nH2O-like phase. The speciation of redox product Tc(IV) was not affected by reduction rate or Fe(II) mineralogy.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1052514
- Report Number(s):
- PNNL-SA-84692; 42318; KP1702030
- Journal Information:
- Geochimica et Cosmochimica Acta, 92:48-66, Vol. 92; ISSN 0016-7037
- Country of Publication:
- United States
- Language:
- English
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