Geomicrobiological redox cycling of the transuranic element neptunium.

Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.

The behaviour of technetium during microbial reduction in amended soils from Dounreay, UK.

Radioactive technetium-99 forms during nuclear fission and has been found as a contaminant at sites where nuclear wastes have been processed or stored. Here we describe results from microcosm experiments containing soil samples representative of the UKAEA site at Dounreay to examine the effect of varying solution chemistry on the fate of technetium during microbial reduction. Analysis of a suite of stable element redox indicators demonstrated that microbial activity occurred in a range of microcosm experiments including unamended Dounreay sediments, carbonate buffered sediments, and microcosms amended with ethylenediaminetetraacetic acid (EDTA) a complexing ligand used in nuclear fuel cycle operations. During the development of anoxia mediated by indigenous microbial populations, TcO4- was removed from solution in experiments. In all cases, the removal of TcO4- from solution occurred during active microbial Fe(III)-reduction when Fe(II) was growing into the microcosms. Tc removal was most likely via reduction of TcO4- to poorly soluble Tc(IV) which is retained on the sediments. The potential stability of Tc associated with the soil to remobilisation via complexation with EDTA was examined as reduced Tc-labelled sediments were contacted with a de-oxygenated EDTA solution. No remobilisation of Tc(IV) in the presence of EDTA was observed.