Altering environmental conditions induce shifts in simulated deep terrestrial subsurface bacterial communities-Secretion of primary and secondary metabolites.

The deep terrestrial subsurface (DTS) harbours a striking diversity of microorganisms. However, systematic research on microbial metabolism, and how varying groundwater composition affects the bacterial communities and metabolites in these environments is lacking. In this study, DTS groundwater bacterial consortia from two Fennoscandian Shield sites were enriched and studied. We found that the enriched communities from the two sites consisted of distinct bacterial taxa, and alterations in the growth medium composition induced changes in cell counts. The lack of an exogenous organic carbon source (ECS) caused a notable increase in lipid metabolism in one community, while in the other, carbon starvation resulted in low overall metabolism, suggesting a dormant state. ECS supplementation increased CO2 production and SO4 2- utilisation, suggesting activation of a dissimilatory sulphate reduction pathway and sulphate-reducer-dominated total metabolism. However, both communities shared common universal metabolic features, most probably involving pathways needed for the maintenance of cell homeostasis (e.g., mevalonic acid pathway). Collectively, our findings indicate that the most important metabolites related to microbial reactions under varying growth conditions in enriched DTS communities include, but are not limited to, those linked to cell homeostasis, osmoregulation, lipid biosynthesis and degradation, dissimilatory sulphate reduction and isoprenoid production.

Biogeochemical Cycling of 99Tc in Alkaline Sediments.

99Tc will be present in significant quantities in radioactive wastes including intermediate-level waste (ILW). The internationally favored concept for disposing of higher activity radioactive wastes including ILW is via deep geological disposal in an underground engineered facility located ∼200-1000 m deep. Typically, in the deep geological disposal environment, the subsurface will be saturated, cement will be used extensively as an engineering material, and iron will be ubiquitous. This means that understanding Tc biogeochemistry in high pH, cementitious environments is important to underpin safety case development. Here, alkaline sediment microcosms (pH 10) were incubated under anoxic conditions under "no added Fe(III)" and "with added Fe(III)" conditions (added as ferrihydrite) at three Tc concentrations (10-11, 10-6, and 10-4 mol L-1). In the 10-6 mol L-1 Tc experiments with no added Fe(III), ∼35% Tc(VII) removal occurred during bioreduction. Solvent extraction of the residual solution phase indicated that ∼75% of Tc was present as Tc(IV), potentially as colloids. In both biologically active and sterile control experiments with added Fe(III), Fe(II) formed during bioreduction and >90% Tc was removed from the solution, most likely due to abiotic reduction mediated by Fe(II). X-ray absorption spectroscopy (XAS) showed that in bioreduced sediments, Tc was present as hydrous TcO2-like phases, with some evidence for an Fe association. When reduced sediments with added Fe(III) were air oxidized, there was a significant loss of Fe(II) over 1 month (∼50%), yet this was coupled to only modest Tc remobilization (∼25%). Here, XAS analysis suggested that with air oxidation, partial incorporation of Tc(IV) into newly forming Fe oxyhydr(oxide) minerals may be occurring. These data suggest that in Fe-rich, alkaline environments, biologically mediated processes may limit Tc mobility.

Metaschoepite Dissolution in Sediment Column Systems-Implications for Uranium Speciation and Transport.

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 Ltd. 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), noncrystalline 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.

Uranium Dioxides and Debris Fragments Released to the Environment with Cesium-Rich Microparticles from the Fukushima Daiichi Nuclear Power Plant.

Trace U was released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) during the meltdowns, but the speciation of the released components of the nuclear fuel remains unknown. We report, for the first time, the atomic-scale characteristics of nanofragments of the nuclear fuels that were released from the FDNPP into the environment. Nanofragments of an intrinsic U-phase were discovered to be closely associated with radioactive cesium-rich microparticles (CsMPs) in paddy soils collected ∼4 km from the FDNPP. The nanoscale fuel fragments were either encapsulated by or attached to CsMPs and occurred in two different forms: (i) UO2+X nanocrystals of ∼70 nm size, which are embedded into magnetite associated with Tc and Mo on the surface and (ii) Isometric (U,Zr)O2+X nanocrystals of ∼200 nm size, with the U/(U+Zr) molar ratio ranging from 0.14 to 0.91, with intrinsic pores (∼6 nm), indicating the entrapment of vapors or fission-product gases during crystallization. These results document the heterogeneous physical and chemical properties of debris at the nanoscale, which is a mixture of melted fuel and reactor materials, reflecting the complex thermal processes within the FDNPP reactor during meltdown. Still CsMPs are an important medium for the transport of debris fragments into the environment in a respirable form.

Novel Method of Quantifying Radioactive Cesium-Rich Microparticles (CsMPs) in the Environment from the Fukushima Daiichi Nuclear Power Plant.

Highly radioactive cesium-rich microparticles (CsMPs) were released from the Fukushima Daiichi nuclear power plant (FDNPP) to the surrounding environment at an early stage of the nuclear disaster in March of 2011; however, the quantity of released CsMPs remains undetermined. Here, we report a novel method to quantify the number of CsMPs in surface soils at or around Fukushima and the fraction of radioactivity they contribute, which we call "quantification of CsMPs" (QCP) and is based on autoradiography. Here, photostimulated luminescence (PSL) is linearly correlated to the radioactivity of various microparticles, with a regression coefficient of 0.0523 becquerel/PSL/h (Bq/PSL/h). In soil collected from Nagadoro, Fukushima, Japan, CsMPs were detected in soil sieved with a 114 µm mesh. There was no overlap between the radioactivities of CsMPs and clay particles adsorbing Cs. Based on the distribution of radioactivity of CsMPs, the threshold radioactivity of CsMPs in the size fraction of <114 µm was determined to be 0.06 Bq. Based on this method, the number and radioactivity fraction of CsMPs in four surface soils collected from the vicinity of the FDNPP were determined to be 48-318 particles per gram and 8.53-31.8%, respectively. The QCP method is applicable to soils with a total radioactivity as high as ∼106 Bq/kg. This novel method is critically important and can be used to quantitatively understand the distribution and migration of the highly radioactive CsMPs in near-surface environments surrounding Fukushima.

Quantifying Technetium and Strontium Bioremediation Potential in Flowing Sediment Columns.

The high-yield fission products 99Tc and 90Sr are found as problematic radioactive contaminants in groundwater at nuclear sites. Treatment options for radioactively contaminated land include bioreduction approaches, and this paper explores 99mTc and 90Sr behavior and stability under a range of biogeochemical conditions stimulated by electron donor addition methods. Dynamic column experiments with sediment from the Sellafield nuclear facility, completed at site relevant flow conditions, demonstrated that Fe(III)-reducing conditions had developed by 60 days. Sediment reactivity toward 99Tc was then probed using a 99mTc(VII) tracer at <10-10 mol L-1 and γ camera imaging showed full retention of 99mTc in acetate amended systems. Sediment columns were then exposed to selected treatments to examine the effects of different acetate amendment regimes and reoxidation scenarios over 55 days when they were again imaged with 99mTc. Here, partially oxidized sediments with no further electron donor additions remained reactive toward 99mTc under relevant groundwater O2 and NO3- concentrations over 55 days. Immobilization of 99mTc was highest where continuous acetate amendment had resulted in sulfate-reducing conditions. Interestingly, the sulfate reducing system showed enhanced Sr retention when stable Sr2+ was added continuously as a proxy for 90Sr. Overall, sediment reactivity was nondestructively imaged over an extended period to provide new information about dynamic iron and radionuclide biogeochemistry throughout realistic sediment redox cycling regimes.

Impacts of Repeated Redox Cycling on Technetium Mobility in the Environment.

Technetium is a problematic contaminant at nuclear sites and little is known about how repeated microbiologically mediated redox cycling impacts its fate in the environment. We explore this question in sediments representative of the Sellafield Ltd. site, UK, over multiple reduction and oxidation cycles spanning ∼1.5 years. We found the amount of Tc remobilised from the sediment into solution significantly decreased after repeated redox cycles. X-ray Absorption Spectroscopy (XAS) confirmed that sediment bound Tc was present as hydrous TcO2-like chains throughout experimentation and that Tc's increased resistance to remobilization (via reoxidation to soluble TcO4-) resulted from both shortening of TcO2 chains during redox cycling and association of Tc(IV) with Fe phases in the sediment. We also observed that Tc(IV) remaining in solution during bioreduction was likely associated with colloidal magnetite nanoparticles. These findings highlight crucial links between Tc and Fe biogeochemical cycles that have significant implications for Tc's long-term environmental mobility, especially under ephemeral redox conditions.

Uranium Immobilization and Nanofilm Formation on Magnesium-Rich Minerals.

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO3] and brucite [Mg(OH)2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (PCO2 = 10(-3.5)) or reduced partial pressures of carbon dioxide (PCO2 = 10(-4.5)). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented with its Oaxial═U(VI)═Oaxial linkage at high angles (60-80°) to both magnesite (101̅4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the "effective" number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ∼ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. These results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Redox Interactions of Tc(VII), U(VI), and Np(V) with Microbially Reduced Biotite and Chlorite.

Technetium, uranium, and neptunium are contaminants that cause concern at nuclear facilities due to their long half-life, environmental mobility, and radiotoxicity. Here we investigate the impact of microbial reduction of Fe(III) in biotite and chlorite and the role that this has in enhancing mineral reactivity toward soluble TcO4(-), UO2(2+), and NpO2(+). When reacted with unaltered biotite and chlorite, significant sorption of U(VI) occurred in low carbonate (0.2 mM) buffer, while U(VI), Tc(VII), and Np(V) showed low reactivity in high carbonate (30 mM) buffer. On reaction with the microbially reduced minerals, all radionuclides were removed from solution with U(VI) reactivity influenced by carbonate. Analysis by X-ray absorption spectroscopy (XAS) confirmed reductive precipitation to poorly soluble U(IV) in low carbonate conditions and both Tc(VII) and Np(V) in high carbonate buffer were also fully reduced to poorly soluble Tc(IV) and Np(IV) phases. U(VI) reduction was inhibited under high carbonate conditions. Furthermore, EXAFS analysis suggested that in the reaction products, Tc(IV) was associated with Fe, Np(IV) formed nanoparticulate NpO2, and U(IV) formed nanoparticulate UO2 in chlorite and was associated with silica in biotite. Overall, microbial reduction of the Fe(III) associated with biotite and chlorite primed the minerals for reductive scavenging of radionuclides: this has clear implications for the fate of radionuclides in the environment.

Formation of stable uranium(VI) colloidal nanoparticles in conditions relevant to radioactive waste disposal.

The favored pathway for disposal of higher activity radioactive wastes is via deep geological disposal. Many geological disposal facility designs include cement in their engineering design. Over the long term, interaction of groundwater with the cement and waste will form a plume of a hyperalkaline leachate (pH 10-13), and the behavior of radionuclides needs to be constrained under these extreme conditions to minimize the environmental hazard from the wastes. For uranium, a key component of many radioactive wastes, thermodynamic modeling predicts that, at high pH, U(VI) solubility will be very low (nM or lower) and controlled by equilibrium with solid phase alkali and alkaline-earth uranates. However, the formation of U(VI) colloids could potentially enhance the mobility of U(VI) under these conditions, and characterizing the potential for formation and medium-term stability of U(VI) colloids is important in underpinning our understanding of U behavior in waste disposal. Reflecting this, we applied conventional geochemical and microscopy techniques combined with synchrotron based in situ and ex situ X-ray techniques (small-angle X-ray scattering and X-ray adsorption spectroscopy (XAS)) to characterize colloidal U(VI) nanoparticles in a synthetic cement leachate (pH > 13) containing 4.2-252 µM U(VI). The results show that in cement leachates with 42 µM U(VI), colloids formed within hours and remained stable for several years. The colloids consisted of 1.5-1.8 nm nanoparticles with a proportion forming 20-60 nm aggregates. Using XAS and electron microscopy, we were able to determine that the colloidal nanoparticles had a clarkeite (sodium-uranate)-type crystallographic structure. The presented results have clear and hitherto unrecognized implications for the mobility of U(VI) in cementitious environments, in particular those associated with the geological disposal of nuclear waste.

Microbial reduction of U(VI) under alkaline conditions: implications for radioactive waste geodisposal.

Although there is consensus that microorganisms significantly influence uranium speciation and mobility in the subsurface under circumneutral conditions, microbiologically mediated U(VI) redox cycling under alkaline conditions relevant to the geological disposal of cementitious intermediate level radioactive waste, remains unexplored. Here, we describe microcosm experiments that investigate the biogeochemical fate of U(VI) at pH 10-10.5, using sediments from a legacy lime working site, stimulated with an added electron donor, and incubated in the presence and absence of added Fe(III) as ferrihydrite. In systems without added Fe(III), partial U(VI) reduction occurred, forming a U(IV)-bearing non-uraninite phase which underwent reoxidation in the presence of air (O2) and to some extent nitrate. By contrast, in the presence of added Fe(III), U(VI) was first removed from solution by sorption to the Fe(III) mineral, followed by bioreduction and (bio)magnetite formation coupled to formation of a complex U(IV)-bearing phase with uraninite present, which also underwent air (O2) and partial nitrate reoxidation. 16S rRNA gene pyrosequencing showed that Gram-positive bacteria affiliated with the Firmicutes and Bacteroidetes dominated in the post-reduction sediments. These data provide the first insights into uranium biogeochemistry at high pH and have significant implications for the long-term fate of uranium in geological disposal in both engineered barrier systems and the alkaline, chemically disturbed geosphere.

Incorporation and retention of 99-Tc(IV) in magnetite under high pH conditions.

Technetium incorporation into magnetite and its behavior during subsequent oxidation has been investigated at high pH to determine the technetium retention mechanism(s) on formation and oxidative perturbation of magnetite in systems relevant to radioactive waste disposal. Ferrihydrite was exposed to Tc(VII)(aq) containing cement leachates (pH 10.5-13.1), and crystallization of magnetite was induced via addition of Fe(II)aq. A combination of X-ray diffraction (XRD), chemical extraction, and X-ray absorption spectroscopy (XAS) techniques provided direct evidence that Tc(VII) was reduced and incorporated into the magnetite structure. Subsequent air oxidation of the magnetite particles for up to 152 days resulted in only limited remobilization of the incorporated Tc(IV). Analysis of both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data indicated that the Tc(IV) was predominantly incorporated into the magnetite octahedral site in all systems studied. On reoxidation in air, the incorporated Tc(IV) was recalcitrant to oxidative dissolution with less than 40% remobilization to solution despite significant oxidation of the magnetite to maghemite/goethite: All solid associated Tc remained as Tc(IV). The results of this study provide the first direct evidence for significant Tc(IV) incorporation into the magnetite structure and confirm that magnetite incorporated Tc(IV) is recalcitrant to oxidative dissolution. Immobilization of Tc(VII) by reduction and incorporation into magnetite at high pH and with significant stability upon reoxidation has clear and important implications for limiting technetium migration under conditions where magnetite is formed including in geological disposal of radioactive wastes.

Incorporation of Uranium into Hematite during crystallization from ferrihydrite.

Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments.

Detecting radioactive particles in complex environmental samples using real-time autoradiography.

Radioactive particles often contain very high radioactivity concentrations and are widespread. They pose a potential risk to human health and the environment. Their detection, quantification, and characterization are crucial if we are to understand their impact. Here, we present the use of a real-time autoradiography gaseous detector (using parallel ionization multiplier) to expedite and improve the accuracy of radioactive particle screening in complex environmental samples. First, standard particles were used to assess the detector capabilities (spatial resolution, spectrometry, and artefact contributions), then, we applied the technique to more complex and environmentally relevant samples. The real-time autoradiography technique provides data with a spatial resolution (≲100 µm) suitable for particle analysis in complex samples. Further, it can differentiate between particles predominantly emitting alpha and beta radiation. Here, the technique is applied to radioactive cesium-rich microparticles collected from the Fukushima Daiichi nuclear exclusion zone, showing their accurate detection, and demonstrating the viability of real-time autoradiography in environmental scenarios. Indeed, for more complex samples (radioactive particles in a less radioactive heterogeneous background mix of minerals), the technique permits relatively high selectivity for radioactive particle screening (up to 61.2% success rate) with low false positive percentages (~ 1%).

"Invisible" radioactive cesium atoms revealed: Pollucite inclusion in cesium-rich microparticles (CsMPs) from the Fukushima Daiichi Nuclear Power Plant.

Understanding radioactive Cs contamination has been a central issue at Fukushima Daiichi and other nuclear legacy sites; however, atomic-scale characterization of radioactive Cs in environmental samples has never been achieved. Here we report, for the first time, the direct imaging of radioactive Cs atoms using high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). In Cs-rich microparticles collected from Japan, we document inclusions that contain 27 - 36 wt% of Cs (reported as Cs2O) in a zeolite: pollucite. The compositions of three pollucite inclusions are (Cs1.86K0.11Rb0.19Ba0.22)2.4(Fe0.85Zn0.84X0.31)2.0Si4.1O12, (Cs1.19K0.05Rb0.19Ba0.22)1.7(Fe0.66Zn0.32X0.41)1.4Si4.6O12, and (Cs1.27K0.21Rb0.29Ba0.15)1.9(Fe0.60Zn0.32X0.69)1.6Si4.4O12 (X includes other cations). HAADF-STEM imaging of pollucite, viewed along the [111] zone axis, revealed an array of Cs atoms, which is consistent with a simulated image using the multi-slice method. The occurrence of pollucite indicates that locally enriched Cs reacted with siliceous substances during the Fukushima meltdowns, presumably through volatilization and condensation. Beta radiation doses from the incorporated Cs are estimated to reach 106 - 107 Gy, which is more than three orders of magnitude less than typical amorphization dose of zeolite. The atomic-resolution imaging of radioactive Cs is an important advance for better understanding the fate of radioactive Cs inside and outside of nuclear reactors damaged by meltdown events.

Improved Radio-Cesium Detection Using Quantitative Real-Time Autoradiography.

Cesium-134 and -137 are prevalent, long-lived, radio-toxic contaminants released into the environment during nuclear accidents. Large quantities of insoluble, respirable Cs-bearing microparticles (CsMPs) were released into the environment during the Fukushima Daiichi nuclear accident. Monitoring for CsMPs in environmental samples is essential to understand the impact of nuclear accidents. The current detection method used to screen for CsMPs (phosphor screen autoradiography) is slow and inefficient. We propose an improved method: real-time autoradiography that uses parallel ionization multiplier gaseous detectors. This technique permits spatially resolved measurement of radioactivity while providing spectrometric data from spatially heterogeneous samples-a potential step-change technique for use after nuclear accidents for forensic analysis. With our detector configuration, the minimum detectable activities are sufficiently low for detecting CsMPs. Further, for environmental samples, sample thickness does not detrimentally affect detector signal quality. The detector can measure and resolve individual radioactive particles ≥465 µm apart. Real-time autoradiography is a promising tool for radioactive particle detection.

Vadose-zone alteration of metaschoepite and ceramic UO2 in Savannah River Site field lysimeters.

Uranium dioxide (UO2) and metaschoepite (UO3•nH2O) particles have been identified as contaminants at nuclear sites. Understanding their behavior and impact is crucial for safe management of radioactively contaminated land and to fully understand U biogeochemistry. The Savannah River Site (SRS) (South Carolina, USA), is one such contaminated site, following historical releases of U-containing wastes to the vadose zone. Here, we present an insight into the behavior of these two particle types under dynamic conditions representative of the SRS, using field lysimeters (15 cm D x 72 cm L). Discrete horizons containing the different particle types were placed at two depths in each lysimeter (25 cm and 50 cm) and exposed to ambient rainfall for 1 year, with an aim of understanding the impact of dynamic, shallow subsurface conditions on U particle behavior and U migration. The dissolution and migration of U from the particle sources and the speciation of U throughout the lysimeters was assessed after 1 year using a combination of sediment digests, sequential extractions, and bulk and µ-focus X-ray spectroscopy. In the UO2 lysimeter, oxidative dissolution of UO2 and subsequent migration of U was observed over 1-2 cm in the direction of waterflow and against it. Sequential extractions of the UO2 sources suggest they were significantly altered over 1 year. The metaschoepite particles also showed significant dissolution with marginally enhanced U migration (several cm) from the sources. However, in both particle systems the released U was quantitively retained in sediment as a range of different U(IV) and U(VI) phases, and no detectable U was measured in the lysimeter effluent. The study provides a useful insight into U particle behavior in representative, real-world conditions relevant to the SRS, and highlights limited U migration from particle sources due to secondary reactions with vadose zone sediments over 1 year.

Retention of immobile Se(0) in flow-through aquifer column systems during bioreduction and oxic-remobilization.

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 timescale 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.

Plutonium mobilization from contaminated estuarine sediments, Esk Estuary (UK).

Since 1952, liquid radioactive effluent containing238-242Pu, 241Am, 237Np, 137Cs, and 99Tc has been released with authorization from the Sellafield nuclear complex (UK) into the Irish Sea. This represents the largest source of plutonium (Pu) discharged in all western Europe, with 276 kg having been released. In the Eastern Irish Sea, the majority of the transuranic activity has settled into an area of sediments (Mudpatch) located off the Cumbrian coast. Radionuclides from the Mudpatch have been re-dispersed via particulate transport in fine-grained estuarine and intertidal sediments to the North-East Irish Sea, including the intertidal saltmarsh located at the mouth of the Esk Estuary. Saltmarshes are highly dynamic systems which are vulnerable to external agents (sea level change, erosion, sediment supply, and freshwater inputs), and their stability remains uncertain under current sea level rise projections and possible increases in storm activity. In this work, we examined factors affecting Pu mobility in contaminated sediments collected from the Esk Estuary by conducting leaching experiments under both anoxic and oxic conditions. Leaching experiments were conducted over a 9-month period and were periodically sampled to determine solution phase Pu via multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS), and to measure redox indicators (Eh, pH and extractable Fe(II)). Microbial community composition was also characterized in the sediments, and at the beginning and end of the anoxic/oxic experiments. Results show that: 1) Pu leaching is about three times greater in solutions leached under anoxic conditions compared to oxic conditions, 2) the sediment slurry microbial communities shift as conditions change from anoxic to oxic, 3) Pu leaching is enhanced in the shallow sediments (0-10 cm depth), and 4) the magnitude of Pu leached from sediments is not correlated with total Pu, indicating that the biogeochemistry of sediment-associated Pu is spatially heterogeneous. These findings provide constraints on the stability of redox sensitive Pu in biogeochemically dynamic/transient environments on a timescale of months and suggests that anoxic conditions can enhance Pu mobility in estuarine systems.