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Abstract: Selenium (Se) is a toxic contaminant with multiple anthropogenic sources, including 79Se from nuclear fission. Se mobility in the geosphere is generally governed by its oxidation state, therefore understanding Se speciation under variable redox conditions is important for the safe management of Se contaminated sites. Here, we investigate Se behavior in sediment groundwater column systems. Experiments were conducted with environmentally relevant Se concentrations, using a range of groundwater compositions, and the impact of electron-donor (i.e., biostimulation) and groundwater sulfate addition was examined over a period of 170 days. X-Ray Absorption Spectroscopy and standard geochemical techniques were used to track changes in sediment associated Se concentration and speciation. Electron-donor amended systems with and without added sulfate retained up to 90% of added Se(VI)(aq), with sediment associated Se speciation dominated by trigonal Se(0) and possibly trace Se(-II); no Se colloid formation was observed. The remobilization potential of the sediment associated Se species was then tested in reoxidation and seawater intrusion perturbation experiments. In all treatments, sediment associated Se (i.e., trigonal Se(0)) was largely resistant to remobilization over the timescales of the experiments (170 days). However, in the perturbation experiments, less Se was remobilized from sulfidic sediments, suggesting that previous sulfate-reducing conditions may buffer Se against remobilization and migration.

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Abstract: Globally, the need for radioactive waste disposal and contaminated land management is clear. Here, gaining an improved understanding of how biogeochemical processes, such as Fe(III) and sulfate reduction, may control the environmental mobility of radionuclides is important. Uranium (U), typically the most abundant radionuclide by mass in radioactive wastes and contaminated land scenarios, may have its environmental mobility impacted by biogeochemical processes within the subsurface. This study investigated the fate of U(VI) in an alkaline (pH ∼9.6) sulfate-reducing enrichment culture obtained from a high-pH environment. To explore the mobility of U(VI) under alkaline conditions where iron minerals are ubiquitous, a range of conditions were tested, including high (30 mM) and low (1 mM) carbonate concentrations and the presence and absence of Fe(III). At high carbonate concentrations, the pH was buffered to approximately pH 9.6, which delayed the onset of sulfate reduction and meant that the reduction of U(VI)(aq) to poorly soluble U(IV)(s) was slowed. Low carbonate conditions allowed microbial sulfate reduction to proceed and caused the pH to fall to ∼7.5. This drop in pH was likely due to the presence of volatile fatty acids from the microbial respiration of gluconate. Here, aqueous sulfide accumulated and U was removed from solution as a mixture of U(IV) and U(VI) phosphate species. In addition, sulfate-reducing bacteria, such as Desulfosporosinus species, were enriched during development of sulfate-reducing conditions. Results highlight the impact of carbonate concentrations on U speciation and solubility in alkaline conditions, informing intermediate-level radioactive waste disposal and radioactively contaminated land management.

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Abstract: Metaschoepite is commonly found in U contaminated environments and metaschoepite-bearing wastes may be managed via shallow or deep disposal. Understanding metaschoepite dissolution and tracking the fate of any liberated U is thus important. Here, discrete horizons of metaschoepite (UO3●nH2O) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield site. The column systems either remained oxic or became anoxic due to electron donor additions, and the columns were sacrificed after 6- and 12-months for analysis. Solution chemistry, extractions, and bulk and micro-/nano-focus X-ray spectroscopies were used to track changes in U distribution and behavior. In the oxic columns, U migration was extensive, with UO22+ identified in effluents after 6-months of reaction using fluorescence spectroscopy. Unusually, in the electron-donor amended columns, during microbially-mediated sulfate reduction, significant amounts of UO2-like colloids (>60% of the added U) were found in the effluents using TEM. XAS analysis of the U remaining associated with the reduced sediments confirmed the presence of trace U(VI), non-crystalline U(IV), and biogenic UO2, with UO2 becoming more dominant with time. This study highlights the potential for U(IV) colloid production from U(VI) solids under reducing conditions and the complexity of U biogeochemistry in dynamic systems.

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Abstract: Iron nanoparticles are a promising new technology to treat contaminated groundwater, particularly as they can be engineered to optimise their transport properties. Technetium is a common contaminant at nuclear sites and can be reductively scavenged from groundwater by iron(II). Here we investigated the potential for a range of optimised iron nanoparticles to remove technetium from contaminated groundwater, and groundwater/sediment systems. Nano zero-valent iron and Carbo-iron stimulated the development of anoxic conditions while generating Fe(II) which reduced soluble Tc(VII) to sparingly soluble Tc(IV). Similar results were observed for Fe(II)-bearing biomagnetite, albeit at a slower rate. Tc(VII) remained in solution in the presence of the Fe(III) mineral nano-goethite, until acetate was added to stimulate microbial Fe(III)-reduction after which Tc(VII) concentrations decreased concomitant with Fe(II) ingrowth. The addition of iron nanoparticles to sediment microcosms caused an increase in the relative abundance of Firmicutes, consistent with fermentative/anoxic metabolisms. Residual bacteria from the synthesis of the biomagnetite nanoparticles were out-competed by the sediment microbial community. Overall the results showed that iron nanoparticles were highly effective in removing Tc(VII) from groundwater in sediment systems, and generated sustained anoxic conditions via the stimulation of beneficial microbial processes including Fe(III)-reduction and sulfate reduction.

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Abstract: At nuclear contaminated sites, microbially-mediated Fe(III) reduction under alkaline conditions opens up the potential for co-treatment of the groundwater contaminants 99Tc, though reduction to less mobile Tc(IV) phases, and 90Sr, through increased sorption and/or precipitation promoted at higher pH. In the experiments described here, microbial enrichment cultures derived from representative Sellafield sediments were used to probe the effect of microbially-mediated Fe(III) reduction on the mobility of 99Tc and Sr (as stable Sr2+ at elevated concentrations and 90Sr2+ at ultra-trace concentrations) under both neutral and alkaline conditions. The reduction of Fe(III) in enrichment culture experiments at an initial pH of 7 or 9 resulted in the precipitation of an Fe(II) bearing biomineral comprised of siderite and vivianite. Results showed that added at 1.6 × 10−6 M was removed (>80%) from solution concurrent with Fe(III) reduction at both pH 7 and pH 9. Furthermore, X-ray absorption spectroscopy of the reduced biominerals confirmed reduction of Tc(VII) to Tc(IV). To understand Sr behaviour in these systems, Sr2+ was added to enrichment cultures at ultra-trace concentrations (2.2 × 10−10 M (as 90Sr2+)) and at higher concentrations (1.15 × 10−3 M (as stable Sr2+)). In ultra-trace experiments at pH 7, microbially active systems showed enhanced removal of 90Sr compared to the sterile control. This was likely due to sorption of 90Sr2+ to the Fe(II)-bearing biominerals that formed in situ. By contrast, at pH 9, the sterile control showed comparable removal of 90Sr to the microbially active experiment even though the Fe-minerals formed were of very different character in the active (vivianite, siderite) versus sterile (an amorphous Fe(III)-phase) systems. Overall, 90Sr bioreduction experiments showed 60–70% removal of the added 90Sr across the different systems: this suggests that treatment strategies involving bioreduction and the promotion of Fe(III)-reducing conditions to scavenge Tc(IV) are not incompatible with treatment of groundwater 90Sr contamination. In systems with elevated Sr2+ concentrations and an initial pH of 7, microbially active systems showed <20% removal of added Sr2+ following Fe(III) reduction with little or no removal in sterile controls. At pH 9, significant Sr2+ was removed from solution in both sterile and microbially active experiments and was attributed to Sr-sorption to mineral phases both chemically precipitated in sterile controls, and biologically precipitated in the microbially active systems. These results confirm that in systems with an elevated natural or anthropogenic Sr2+ loading, bioreduction at modestly alkaline pH is compatible with co-treatment of both and 90Sr2+. These data are discussed in terms of aqueous geochemistry trends, X-ray diffraction and morphological data, and thermodynamic modelling. The results demonstrate the potential for removal of trace levels of 99Tc and 90Sr2+ from groundwaters during stimulated bioreduction and highlight that in the presence of stable Sr2+, optimal removal for technetium and strontium is likely to occur under mildly alkaline, reducing conditions.