Bioreduction of Fe-bearing clay minerals and their reactivity toward pertechnetate (Tc-99)
- Miami University
99Technetium (99Tc) is a fission product of uranium-235 and plutonium-239 and poses a high environmental hazard due to its long half-life (t1/2 = 2.13 x 105 y), abundance in nuclear wastes, and environmental mobility under oxidizing conditions [i.e., Tc(VII)]. Under reducing conditions, Tc(VII) can be reduced to insoluble Tc(IV). Ferrous iron [Fe(II)], either in aqueous form or in mineral form, has been used to reduce Tc(VII) to Tc(IV). However, the reactivity of Fe(II) from clay minerals, other than nontronite, toward immobilization of Tc(VII) and its role in retention of reduced Tc(IV) have not been investigated. In this study the reactivity of a suite of clay minerals toward Tc(VII) reduction and immobilization was evaluated. The clay minerals chosen for this study included five members in the smectite-illite (S-I) series, (montmorillonite, nontronite, rectorite, mixed layered I-S, and illite), chlorite, and palygorskite. Fe-oxides were removed from these minerals with a modified dithionite-citrate-bicarbonate (DCB) procedure. The total Fe content of these clay minerals, after Fe-oxide removal, ranged from 0.7 to 30.4% by weight, and the Fe(III)/Fe(total) ratio ranged from 44.9 to 98.5%. X-ray diffraction (XRD) and Mossbauer spectroscopy results showed that after Fe oxide removal the clay minerals were free of Fe-oxides. Scanning electron microscopy (SEM) revealed that little dissolution occurred during the DCB treatment. Bioreduction experiments were performed in bicarbonate buffer (pH-7) with Fe(III) in the clay minerals as the sole electron acceptor, lactate as the sole electron donor, and Shewanella Putrifaciens CN32 cells as mediators. In select tubes, anthraquinone-2,6-disulfate (AQDS) was added as electron shuttle to facilitate electron transfer. The extent of Fe(III) bioreduction was the highest for chlorite (~43 wt%) and the lowest for palygorskite (~4.17 wt%). In the S-I series, NAu-2 was the most reducible (~31 %) and illite the least (~0.4 %). The extent and initial rate of bioreduction were positively correlated with the percent smectite in the S-I series (i.e., layer expandability). Fe(II) in the bioreduced clay minerals subsequently was used to reduce Tc(VII) to Tc(IV) in PIPES buffer. Similar to the trend of bioreduction, in the S-I series, reduced smectite showed the highest reactivity toward Tc(VII), and reduced illite exhibited the least. The initial rate of Tc(VII) reduction, after normalization to clay and Fe(II) concentrations, was positively correlated with the percent smectite in the S-I series. Fe(II) in chlorite and palygorskite was also reactive toward Tc(VII) reduction. These data demonstrate that crystal chemical parameters (layer expandability, Fe and Fe(II) contents, and surface area etc.) play important roles in controlling the extent and rate of bioreduction and the reactivity toward Tc(VII) reduction. Reduced Tc(IV) resides within clay mineral matrix, and this association could minimize any potential of reoxidation over long term.
- Research Organization:
- Miami Univ., Oxford, OH (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- FG02-07ER64369
- OSTI ID:
- 1042655
- Report Number(s):
- DOE/07ER64369
- Journal Information:
- Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Journal Issue: 18 Vol. 75; ISSN 0016-7037
- Publisher:
- Elsevier; The Geochemical Society; The Meteoritical Society
- Country of Publication:
- United States
- Language:
- English
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