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Flow-through columns were used to assess potential long-term trends in 90Sr biogeochemistry and transport in a Finnish near-surface very low-level waste (VLLW) repository concept. Experiments simulated the effects of water intrusion and flow through the repository barrier and backfill materials, examining impacts on 90Sr migration. Artificial rainwater containing 2.0 mg/L stable Sr (as a proxy for 90Sr) was pumped through column systems that had varying compositions from a matrix of rock flour (backfill material), bentonite (backfill/sealing material), and carbon steel (waste encapsulation material), for 295 days. Effluent geochemistry was monitored throughout. Sr retention behaviour in all column systems was broadly similar. Sr removal from influent rainwater was marked (~95% removed) at the beginning of the experiments, and this degree of removal was maintained for 20 days. Thereafter, Sr concentrations in the effluents began to rise, reaching ~2 mg/L by 295 days. Further, 56%–67% of added Sr was retained in the repository materials over the 295-day reaction period. Analysis of the effluents indicated that colloids did not form; as such, Sr output was likely to be aqueous Sr2+. Upon completion of the experiment, solid-associated Sr distribution and speciation in the columns were assessed through column sectioning and post-mortem analyses, which encompassed the following: total acid digests, sequential extractions, and XAS analysis. The total acid digests and sequential extractions showed that Sr was evenly distributed throughout the columns and that the majority (68%–87%) of solid-associated Sr was in the exchangeable fraction (MgCl2). This suggested that a major part of the solid-phase Sr was weakly bound to the column materials via outer-sphere sorption. Interestingly, a smaller amount of Sr (7%–23%) could only be extracted by aqua regia, suggesting that a proportion of Sr may bind more strongly to the barrier materials. XAS analysis of select samples confirmed that the dominant Sr phase was sorbed to the rock flour and bentonite, but not corroded carbon steel. Columns were also subject to remobilisation experiments using artificial rain- and seawater without added Sr. While rainwater remobilised Sr slowly, high-ionic strength seawater remobilised Sr at much higher rates in the systems containing bentonite. Interestingly, Sr was well retained in the rock flour-only system following rain and seawater intrusion. Overall, the results indicate that the column materials provide reactive surfaces for Sr removal should it be released from waste packages; however, the backfill and barrier materials have limited retention capacity, and the dominant sorption interaction is relatively weak. The safety case for the shallow disposal of radioactive waste should consider the possibility of seawater intrusion and that the bentonite-bound Sr was significantly more susceptible to remobilisation following seawater, despite retaining slightly more Sr during sorption experiments.

Radiokemi står inför en väldokumenterad utbildning och rekryteringskris. Äldre radiokemister går i pension och färre unga studerar radiokemi. I sin tur leder detta till brist på nyutbildade radiokemister, såväl som förlust av historisk kunskap (eftersom kunskap ofta inte förmedlas). Här analyserade vi relevansen av studien av radiokemi i högre utbildning genom framtida radiokemists uppfattningar. Vårt mål var att ge inblick i framtida radiokemisternas tänkande och ge några tydliga exempel på hur man stöder relevans. En kvalitativ studie genomfördes genom en forskningsfråga: Vilka uppfattningar om relevans upplever framtida radiokemister om radiokemistudier och radiokemi som fält? Vi använde relevansmodellen av Stuckey et al. (2013) som ram för relevans. Detta valdes eftersom det erbjuder en omfattande definition av relevans inklusive individuella, samhälleliga och yrkesmässiga dimensioner. Uppgifterna samlades in från forskarstudenter i radiokemi (magister- och doktorsexamen) genom användning av ett kvalitativt frågeformulär som utformades med den valda relevansramen. Totalt deltog 15 framtida radiokemister i studien. Uppgifterna analyserades genom teoribaserad innehållsanalys med användning av det valda relevansramverket. Enligt våra uppgifter upplever framtida radiokemister att deras universitetsstudier och kemifältet är mycket relevanta. De upplevde att ämnen för radiokemi är intressanta (individuell relevans), fältet har stor samhällseffekt genom radiofarmaceutika, energilösningar och miljöproblemlösning (samhällsrelevans) och att deras professionella framtid var tydlig, till exempel ett jobb inom kärnkraftsområdet industri (yrkesrelevans). Dessa resultat kan användas för studentrekrytering och för att utveckla radiokemiundervisning mot en mer relevant inriktning. Radiokemialla on koulutus- ja rekrytointikriisi. Vanhemmat radiokemistit siirtyvät eläkkeelle, ja yhä vähemmän nuoria valitsee radiokemiaa opiskelualakseen. Asetelman vuoksi on pulaa pätevistä radiokemisteistä, ja hiljaista tietoa häviää. Tässä tutkimuksessa selvitetään tulevien radiokemistien kokemuksia radiokemian relevanssista. Tavoitteena on selvittää, miksi radiokemiaa valinneet opiskelijat ovat alan valinneet. Tutkimus oli luonteeltaan laadullinen tutkimus. Aineisto kerättiin sähköpostikyselyillä sisältäen kaksi aineistonkeruusykliä. Ainesot analysoitiin teoriapohjaisella sisällnöanalyysillä tunnetun Stuckeyn et al. (2013) relevanssia hyödyntäen. Tutkimuksen mukaan tulevat radiokemistit kokivat alan erittäin relevanssiksi. He kokivat, että radiokemian olevan mielenkiintoista (henkilökohtainen relevanssi), radiokemian yhteiskunnallisen merkityksen olevan suuri esim. lääke- ja energiateollisuuden kautta (yhteiskunnallinen relevanssi) ja heillä oli selkeä kuva tulevaisuuden työllistymisestä (ammatillinen relevanssi). Tutkimuksen tuloksia voidaan käyttää opiskelijoiden rekrytointiin ja radiokemian opetuksen relevanssin vahvistamiseen. Radiochemistry faces a well-documented training and recruitment crisis. Older radiochemists are retiring, and fewer young people are studying radiochemistry. In turn, this is leading to a shortage in newly qualified radiochemists, as well as a loss of historical knowledge (as know-how is often not passed-on). Here, we analyzed the relevance of the study of radiochemistry in higher education through future radiochemists’ perceptions. Our objective was to provide insights into future radiochemists’ thinking and provide some clear examples on how to support relevance. A qualitative study was conducted through a research question: What perceptions of relevance do future radiochemists experience about radiochemistry studies and radiochemistry as a field? We used the relevance model of Stuckey et al. (2013) as the relevance framework. This was selected because it offers a comprehensive definition of relevance including individual, societal, and vocational dimensions. The data were gathered from postgraduate radiochemistry students (masters and Ph.D. level) through use of a qualitative questionnaire that was designed using the selected relevance framework. In total, 15 future radiochemists participated in the study. The data were analyzed through theory-based content analysis using the selected relevance framework. According to our data, future radiochemists experience their university study and the chemistry field as being highly relevant. They experienced that radiochemistry topics are interesting (individual relevance), the field has great societal impact through radiopharmaceuticals, energy solutions, and environmental problem-solving (societal relevance), and that their professional future was clear, for example, a job in the nuclear industry (vocational relevance). These results can be used in student recruitment and in developing radiochemistry teaching toward a more relevance-oriented direction.

Boron carbide control rods remain in the fuel debris of the damaged reactors in the Fukushima Daiichi Nuclear Power Plant, potentially preventing re-criticality; however, the state and stability of the control rods remain unknown. Sensitive high-resolution ion microprobe analyses have revealed B-Li isotopic signatures in radioactive Cs-rich microparticles (CsMPs) that formed by volatilization and condensation of Si-oxides during the meltdowns. The CsMPs contain 1518-6733 mg kg

Article published under an ACS AuthorChoice License The Collaborative Materials Exercise (CMX) is organized by the Nuclear Forensics International Technical Working Group, with the aim of advancing the analytical capabilities of the participating organizations and providing feedback on the best approaches to a nuclear forensic investigation. Here, model nuclear fuel materials from the 5th CMX iteration were analyzed using a NanoSIMS 50L (CAMECA) in order to examine inhomogeneities in the U-235/U-238 ratio and trace element abundance within individual, micrometer scale particles. Two fuel pellets were manufactured for the exercise and labelled CMX-5A and CMX-5B. These pellets were created using different processing techniques, but both had a target enrichment value of U-235/U-238 = 0.01. Particles from these pellets were isolated for isotopic and trace element analysis. Fifteen CMX-5A particles and 20 CMX-5B particles were analyzed, with both sample types displaying inhomogeneities in the U isotopic composition at a sub-micrometer scale within individual particles. Typical particle diameters were similar to 1.5 to 41 mu m for CMX-5A and similar to 1 to 61 mu m for CMX-5B. The CMX-5A particles were shown to be more isotopically homogeneous, with a mean U-235/U-238 atom ratio of 0.0130 +/- 0.0066. The CMX-5B particles showed a predominantly depleted mean U-235/U-238 atom ratio of 0.0063 +/- 0.0094, which is significantly different to the target enrichment value of the pellet and highlights the potential variation of U-235/U-238 in U fuel pellets at the micrometer scale. This study details the successful application of the NanoSIMS 50L in a mock nuclear forensic investigation by optimizing high-resolution imaging for uranium isotopics.

Current methods for the decontamination of radioactively contaminated surfaces in nuclear facilities typically rely on the use of liquid agents to remove radionuclides. This generates large volumes of highly hazardous liquid waste which must then be treated in costly processes which often require purpose built plant. For the first time we report a nitric acid loaded polymer hydrogel based approach which gives a high decontamination factor for the removal of 137Cs and 90Sr on 304 L grade stainless steel surfaces. The generation of minimal liquid waste and no lateral spread or increased penetration of radionuclides helps mitigate many of the intrinsic hazards of liquid based decontamination methods. Once dried these gels are able to retain the contaminants for treatment as solid waste resulting in a concentrated, less mobile waste form presenting significantly reduced hazards and treatment constraints.

Stand-off, in-situ, laser induced breakdown spectroscopy (LIBS) offers a rapid, safe, and cost-effective method for discrimination of radioactive waste materials arising during the operation of nuclear plants and from decommissioning activities. Characterisation of waste materials is a critical activity in understanding the nature of the waste, ensuring hazardous material is managed safely and that waste can be segregated for reuse, recycle or sentenced for appropriate disposal. Characterisation of materials, often in hostile environments, requires the ability to remotely differentiate between materials in terms of their chemical composition and radioactivity. This proposition was tested using a case study on nuclear grade graphite. Graphite has been used extensively as a moderator material in many nuclear reactors. Internationally, over 250,000 tons of various nuclear-grade graphite, and graphite-bearing, materials exist. These are a major issue for nuclear decommissioning and radioactive waste management, due to the long half-lives of the associated 14C and 36Cl isotopes. LIBS offers a method for discrimination of nuclear grade graphites and other carbon and non-carbon-bearing wastes. This paper describes the development of a workflow method, including LIBS measurement analysis, for the discrimination of pre-irradiated nuclear ‘Pile Grade A’ (PGA) graphite moderator rod and domestic lumpwood charcoal, which act as surrogates for nuclear grade graphite and other carbon-bearing wastes. A new analysis workflow comprising the examination of spectral characteristics, multivariate analysis and molecular isotopic spectroscopy is proposed to enable rapid segregation of graphite from a heterogeneous waste stream. Enhanced characterisation techniques have the potential to significantly reduce the cost of decommissioning large parts of legacy nuclear generation plants.

International audience; 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

Understanding anthropogenic radionuclide biogeochemistry and mobility in natural systems is key to improving the management of radioactively contaminated environments and radioactive wastes. Here, we describe the contemporary depth distribution and phase partitioning of 137Cs, Pu, and 241Am in two sediment cores taken from the Irish Sea (Site 1: the Irish Sea Mudpatch; Site 2: the Esk Estuary). Both sites are located ~10 km from the Sellafield nuclear site. Low-level aqueous radioactive waste has been discharged from the Sellafield site into the Irish Sea for >50 y. We compare the depth distribution of the radionuclides at each site to trends in sediment and porewater redox chemistry, using trace element abundance, microbial ecology, and sequential extractions, to better understand the relative importance of sediment biogeochemistry vs. physical controls on radionuclide distribution/post-depositional mobility in the sediments. We highlight that the distribution of 137Cs, Pu, and 241Am at both sites is largely controlled by physical mixing of the sediments, physical transport processes, and sediment accumulation. Interestingly, at the Esk Estuary, microbially-mediated redox processes (considered for Pu) do not appear to offer significant controls on Pu distribution, even over decadal timescales. We also highlight that the Irish Sea Mudpatch likely still acts as a source of historical pollution to other areas in the Irish Sea, despite ever decreasing levels of waste output from the Sellafield site.

Understanding the long-term fate, stability, and bioavailability of uranium (U) in the environment is important for the management of nuclear legacy sites and radioactive wastes. Analysis of U behavior at natural analogue sites permits evaluation of U biogeochemistry under conditions more representative of long-term equilibrium. Here, we have used bulk geochemical and microbial community analysis of soils, coupled with X-ray absorption spectroscopy and mu-focus X-ray fluorescence mapping, to gain a mechanistic understanding of the fate of U transported into an organic-rich soil from a pitchblende vein at the UK Needle's Eye Natural Analogue site. U is highly enriched in the Needle's Eye soils (similar to 1600 mg kg(-1)). We show that this enrichment is largely controlled by U(VI) complexation with soil organic matter and not U(VI) bioreduction. Instead, organic-associated U(VI) seems to remain stable under microbially-mediated Fe(III)-reducing conditions. U(IV) (as non-crystalline U(IV)) was only observed at greater depths at the site (>25 cm); the soil here was comparatively mineral-rich, organic-poor, and sulfate-reducing/methanogenic. Furthermore, nanocrystalline UO2, an alternative product of U(VI) reduction in soils, was not observed at the site, and U did not appear to be associated with Fe-bearing minerals. Organicrich soils appear to have the potential to impede U groundwater transport, irrespective of ambient redox conditions. (C) 2020 The Authors. Published by Elsevier Ltd.

Owing to the propensity for uranium(III) compounds to undergo disproportionation, uranium-element multiple bonds involving uranium(III) oxidation states remain rare. Here the authors report hexauranium-methanediide rings that formally contain uranium(III)- and uranium(IV)-methanediides supported by alternating halide and arene bridges.

Highly radioactive cesium-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) provide nano-scale chemical fingerprints of the 2011 tragedy. U, Cs, Ba, Rb, K, and Ca isotopic ratios were determined on three CsMPs (3.79–780 Bq) collected within ~10 km from the FDNPP to determine the CsMPs’ origin and mechanism of formation. Apart from crystalline Fe-pollucite, CsFeSi2O6 · nH2O, CsMPs are comprised mainly of Zn–Fe-oxide nanoparticles in a SiO2 glass matrix (up to ~30 wt% of Cs and ~1 wt% of U mainly associated with Zn–Fe-oxide). The 235U/238U values in two CsMPs: 0.030 (±0.005) and 0.029 (±0.003), are consistent with that of enriched nuclear fuel. The values are higher than the average burnup estimated by the ORIGEN code and lower than non-irradiated fuel, suggesting non-uniform volatilization of U from melted fuels with different levels of burnup, followed by sorption onto Zn–Fe-oxides. The nano-scale texture and isotopic analyses provide a partial record of the chemical reactions that occurred in the fuel during meltdown. Also, the CsMPs were an important medium of transport for the released radionuclides in a respirable form.

To understand the chemical durability of highly radioactive cesium-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant in March 2011, we have, for the first time, performed systematic dissolution experiments with CsMPs isolated from Fukushima soils (one sample with 108 Bq and one sample with 57.8 Bq of Cs-137) using three types of solutions: simulated lung fluid, ultrapure water, and artificial sea water, at 25 and 37 degrees C for 1-63 days. The Cs-137 was released rapidly within three days and then steady-state dissolution was achieved for each solution type. The steady-state Cs-137 release rate at 25 degrees C was determined to be 4.7 x 10(3), 1.3 x 10(3), and 1.3 x 10(3) Bq . m(-2)s(-1) for simulated lung fluid, ultrapure water, and artificial sea water, respectively. This indicates that the simulated lung fluid promotes the dissolution of CsMPs. The dissolution of CsMPs is similar to that of Si-based glass and is affected by the surface moisture conditions. In addition, the Cs release from the CsMPs is constrained by the rate-limiting dissolution of silicate matrix. Based on our results, CsMPs with similar to 2 Bq, which can be potentially inhaled and deposited in the alveolar region, are completely dissolved after >35 years. Further, CsMPs could remain in the environment for several decades; as such, CsMPs are important factors contributing to the long-term impacts of radioactive Cs in the environment. (C) 2019 Elsevier Ltd. All rights reserved.

Understanding interactions between iron (oxyhydr)oxide nanoparticles and plutonium is essential to underpin technology to treat radioactive effluents, in cleanup of land contaminated with radionuclides, and to ensure the safe disposal of radioactive wastes. These interactions include a range of adsorption, precipitation, and incorporation processes. Here, we explore the mechanisms of plutonium sequestration during ferrihydrite precipitation from an acidic solution. The initial 1 M HNO3 solution with Fe(III)((aq)) and Pu-242(IV)((aq)) underwent controlled hydrolysis via the addition of NaOH to pH 9. The majority of Fe(III)((aq)) and Pu(IV)((aq)) was removed from solution between pH 2 and 3 during ferrihydrite formation. Analysis of Pu-ferrihydrite by extended X-ray absorption fine structure (EXAFS) spectroscopy showed that Pu(IV) formed an inner-sphere tetradentate complex on the ferrihydrite surface, with minor amounts of PuO2 present. Best fits to the EXAFS data collected from Pu-ferrihydrite samples aged for 2 and 6 months showed no statistically significant change in the Pu(IV)-Fe oxyhydroxide surface complex despite the ferrihydrite undergoing extensive recrystallization to hematite. This suggests the Pu remains strongly sorbed to the iron (oxyhydr)oxide surface and could be retained over extended time periods.

Stainless steels can become contaminated with radionuclides at nuclear sites. Their disposal as radioactive waste would be costly. If the nature of steel contamination could be understood, effective decontamination strategies could be designed and implemented during nuclear site decommissioning in an effort to release the steels from regulatory control. Here, batch uptake experiments have been used to understand Sr and Cs (fission product radionuclides) uptake onto AISI Type 304 stainless steel under conditions representative of spent nuclear fuel storage (alkaline ponds) and PUREX nuclear fuel reprocessing (HNO3). Solution (ICP-MS) and surface measurements (GD-OES depth profiling, TOF-SIMS, and XPS) and kinetic modeling of Sr and Cs removal from solution were used to characterize their uptake onto the steel and define the chemical composition and structure of the passive layer formed on the steel surfaces. Under passivating conditions (when the steel was exposed to solutions representative of alkaline ponds and 3 and 6 M HNO3), Sr and Cs were maintained at the steel surface by sorption/selective incorporation into the Cr-rich passive film. In 12 M HNO3, corrosion and severe intergranular attack led to Sr diffusion into the passive layer and steel bulk. In HNO3, Sr and Cs accumulation was also commensurate with corrosion product (Fe and Cr) readsorption, and in the 12 M HNO3 system, XPS documented the presence of Sr and Cs chromates.

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 center dot nH(2)O) 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.

International audience; The abundance and distribution of highly radioactive cesium-rich microparticles (CsMPs) that were released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) during the first stage of the nuclear disaster in March 2011 are described for 20 surface soils collected around the FDNPP. Based on the spatial distribution of the numbers (particles/g) and radioactive fraction (RF) of the CsMPs in surface soil, which is defined as the sum of the CsMP radioactivity (in Bq) divided by the total radioactivity (in Bq) of the soil sample, three regions of particular interest have been identified: i.) near-northwest (N-NW), ii.) far-northwest (F-NW), and iii.) southwest (SW). In these areas, the number and RF of CsMPs were determined to be 22.1–101 particles/g and 15.4–34.0%, 24.3–64.8 particles/g and 36.7–37.4%, and 0.869–8.00 particles/g and 27.6–80.2%, respectively. These distributions are consistent with the plume trajectories of material released from the FDNPP on March 14, 2011, in the late afternoon through to the late afternoon of March 15, 2011, indicating that the CsMPs formed only during this short period. Unit 3 is the most plausible source of the CsMPs at the beginning of the release based on an analysis of the sequence of release events. The lower RF values in the N-NW region indicate a larger influence from subsequent plumes that mainly consisted of soluble Cs species formed simultaneously with precipitation. The quantitative map of the distribution of CsMPs provides an important understanding of CsMP dispersion dynamics and can be used to assess risks in inhabited regions.

One of the most challenging components of the UK nuclear legacy is Magnox sludge, arising from the corrosion of Mg alloy-clad irradiated metallic U fuel that has been stored in high pH ponds. The sludges mainly comprise Mg hydroxide and carbonate phases, contaminated with fission products and actinides, including Pu. Cementation and deep geological disposal is one option for the long-term management of this material, but there is a need to understand how Pu may be leached from the waste, if it is exposed to groundwater. Here, we show that cemented Mg(OH)2 powder prepared with Pu(IV)aq is altered on contact with water to produce a visibly altered &lsquo, leached zone&rsquo, which penetrates several hundred microns into the sample. In turn, this zone shows slow leaching of Pu, with long-term leaching rates between 1.8&ndash, 4.4 &times, 10&minus, 5% of total Pu per day. Synchrotron micro-focus X-ray fluorescence mapping identified decreased Pu concentration within the &lsquo, A comparison of micro-focus X-ray absorption spectroscopy (&micro, XAS) spectra collected across both leached and unleached samples showed little variation, and indicated that Pu was present in a similar oxidation state and coordination environment. Fitting of the XANES spectra between single oxidation state standards and EXAFS modeling showed that Pu was present as a mixture of Pu(IV) and Pu(V). The change in Pu oxidation from the stock solution suggests that partial Pu oxidation occurred during sample ageing. Similarity in the XAS spectra from all samples, with different local chemistries, indicated that the Pu oxidation state was not perturbed by macro-scale variations in cement chemistry, surface oxidation, sample aging, or the leaching treatment. These experiments have demonstrated the potential for leaching of Pu from cementitious waste forms, and its underlying significance requires further investigation.

Fe(II) bearing iron (oxyhydr)oxides were directly co-precipitated with Np(V)O2+ under anaerobic conditions to form Np doped magnetite and green rust. These environmentally relevant mineral phases were then characterised using geochemical and spectroscopic analyses. The Np doped mineral phases were then oxidised in air over 224 days with solution chemistry and end-point oxidation solid samples collected for further characterisation. Analysis using chemical extractions and X-ray absorption spectroscopy (XAS) techniques confirmed that Np(V) was initially reduced to Np(IV) during co-precipitation of both magnetite and green rust. Extended X-Ray Absorption Fine Structure (EXAFS) modelling suggested the Np(IV) formed a bidentate binuclear sorption complex to both minerals. Furthermore, following oxidation in air over several months, the sorbed Np(IV) was partially oxidised to Np(V), but very little remobilisation to solution occurred during oxidation. Here, linear combination fitting of the X-Ray Absorption Near Edge Structure (XANES) for the end-point oxidation samples for both mineral phases suggested approximately 50% oxidation to Np(V) had occurred over 7 months of oxidation in air. Both the reduction of Np(V) to Np(IV) and inner sphere sorption in association with iron (oxyhydr)oxides, and the strong retention of Np(IV) and Np(V) species with these phases under robust oxidation conditions, have important implications in understanding the mobility of neptunium in a range of engineered and natural environments.

Understanding the speciation and fate of radium during operational discharge from the offshore oil and gas industry into the marine environment is important in assessing its long term environmental impact. In the current work, 226Ra concentrations in marine sediments contaminated by produced water discharge from a site in the UK were analysed using gamma spectroscopy. Radium was present in field samples (0.1–0.3 Bq g−1) within International Atomic Energy Agency activity thresholds and was found to be primarily associated with micron sized radiobarite particles (≤2 μm). Experimental studies of synthetic/field produced water and seawater mixing under laboratory conditions showed that a significant proportion of radium (up to 97%) co-precipitated with barite confirming the radiobarite fate pathway. The results showed that produced water discharge into the marine environment results in the formation of radiobarite particles which incorporate a significant portion of radium and can be deposited in marine sediments.

International audience; A contaminated zone elongated toward Futaba Town, north-northwest of the Fukushima Daiichi Nuclear Power Plant (FDNPP), contains highly radioactive particles released from reactor Unit 1. There are uncertainties associated with the physio-chemical properties and environmental impacts of these particles. In this study, 31 radioactive particles were isolated from surface soils collected 3.9 km north-northwest of the FDNPP. Two of these particles have the highest particle-associated 134+137Cs activity ever reported for Fukushima (6.1 × 105 and 2.5 × 106 Bq per particle after decay-correction to March 2011). The new, highly-radioactive particle labeled FTB1 is an aggregate of flaky silicate nanoparticles with an amorphous structure containing ~0.8 wt% Cs, occasionally associated with SiO2 and TiO2 inclusions. FTB1 likely originates from the reactor building, which was damaged by a H2 explosion, after adsorbing volatilized Cs. The 134+137Cs activity in the other highly radioactive particle labeled FTB26 exceeded 106 Bq. FTB26 has a glassy carbon core and a surface that is embedded with numerous micro-particles: Pb–Sn alloy, fibrous Al-silicate, Ca-carbonate or hydroxide, and quartz. The isotopic signatures of the micro-particles indicate neutron capture by B, Cs volatilization, and adsorption of natural Ba. The composition of the micro-particles on FTB26 reflects the composition of airborne particles at the moment of the H2 explosion. Owing to their large size, the health effects of the highly radioactive particles are likely limited to external radiation during static contact with skin; the highly radioactive particles are thus expected to have negligible health impacts for humans. By investigating the mobility of the highly radioactive particles, we can better understand how the radiation dose transfers through environments impacted by Unit 1. The highly radioactive particles also provide insights into the atmospheric conditions at the time of the Unit 1 explosion and the physio-chemical phenomena that occurred during reactor meltdown.

International audience; Traces of Pu have been detected in material released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March of 2011; however, to date the physical and chemical form of the Pu have remained unknown. Here we report the discovery of particulate Pu associated with cesium-rich microparticles (CsMPs) that formed in and were released from the reactors during the FDNPP meltdowns. The Cs-pollucite-based CsMP contained discrete U(IV)O2 nanoparticles

Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages., Owing to the propensity for uranium(III) compounds to undergo disproportionation, uranium-element multiple bonds involving uranium(III) oxidation states remain rare. Here the authors report hexauranium-methanediide rings that formally contain uranium(III)- and uranium(IV)-methanediides supported by alternating halide and arene bridges.

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 nano-fragments of the nuclear fuels that were released from the FDNPP into the environment. Nano-fragments 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 nano-scale fuel fragments were either encapsulated by or attached to the 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. (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 gasses 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 the CsMPs are an important medium for the transport of debris fragments into the environment in a respirable form

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.

Neptunium-237 will be present in radioactive wastes over extended time periods due to its long half-life (2.13 × 106years). Understanding its behaviour under conditions relevant to radioactive waste disposal is therefore of particular importance. Here, microcosm experiments were established using sediments from a legacy lime workings with high-pH conditions as an analogue of cementitious intermediate-level radioactive waste disposal. To probe the influence of Fe biogeochemistry on Np(V) in these systems, additional Fe(III) (as ferrihydrite) was added to select experiments. Biogeochemical changes were tracked in experiments with low levels of Np(V) (20 Bq ml–1; 3.3 μM), whilst parallel higher concentration systems (2.5 KBq ml–1;414 μM) allowed X-ray absorption spectroscopy. As expected, microbial reduction processes developed in microbially-active systems with an initial pH of 10; however, during microbial incubations the pH dropped from 10 to ∼7, reflecting the high levels of microbial metabolism occurring in these systems. In microbially-active systems without added Fe(III), 90% sorption of Np(V) occurred within one hour with essentially complete removal by one day. In the ferrihydrite-amended systems, complete sorption of Np(V) to ferrihydrite occurred within one hour. For higher-activity sediments, X-ray absorption spectroscopy (XAS) at end points where Fe(II) ingrowth was observed confirmed that complete reductive precipitation of Np(V) to Np(IV) had occurred under similar conditions to low-level Np experiments. Finally, pre-reduced, Fe(III)-reducing sediments, with and without added Fe(III) and held at pH 10, were spiked with Np(V). These alkaline pre-reduced sediments showed significant removal of Np to sediments, and XAS confirmed partial reduction to Np(IV) with the no Fe system, and essentially complete reduction to Np(IV) in the Fe(III)-enriched systems. This suggested an indirect, Fe(II)-mediated pathway for Np(V) reduction under alkaline conditions. Microbial analyses using 16S rRNA gene pyrosequencing suggested a role for alkali-tolerant, Gram-positive Firmicutes in coupled Fe(III) reduction and Np immobilization in these experiments.

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 TcO

The high-yield fission products

Understanding interactions between radionuclides and mineral phases underpins site environmental clean-up and waste management in the nuclear industry. Transport and fate of radionuclides in many subsurface environments are controlled by adsorption, redox and mineral incorporation processes. Interactions of iron (oxyhydr)oxides with uranium have been extensively studied due to the abundance of uranium as an environmental contaminant and ubiquity of iron (oxyhydr)oxides in engineered and natural environments. Despite this, detailed mechanistic information regarding the incorporation of uranium into Fe(II) bearing magnetite and green rust is sparse. Here, we present a co-precipitation study where U(VI) was reacted with environmentally relevant iron(II/III) (oxyhydr)oxide mineral phases. Based on diffraction, microscopic, dissolution and spectroscopic evidence, we show the reduction of U(VI) to U(V) and stabilisation of the U(V) by incorporation within the near-surface and bulk of the particles during co-precipitation with iron (oxyhydr)oxides. U(V) was stable in both magnetite and green rust structures and incorporated via substitution for octahedrally coordinated Fe in a uranate-like coordination environment. As the Fe(II)/Fe(III) ratio increased, a proportion of U(IV) was also precipitated as surface associated UO2. These novel observations have significant implications for the behaviour of uranium within engineered and natural environments.

Laser Induced Breakdown Spectroscopy (LIBS) has the potential to allow direct, standoff measurement of contaminants on nuclear plant. Here, LIBS is evaluated as an analytical tool for measurement of Sr and Cs contamination on type 304 stainless steel surfaces. Samples were reacted in model acidic (PUREX reprocessing) and alkaline (spent fuel ponds) Sr and Cs bearing liquors, with LIBS multi-pulse ablation also explored to measure contaminant penetration. The Sr II (407.77nm) and Cs I (894.35nm) emission lines could be separated from the bulk emission spectra, though only Sr could be reliably detected at surface loadings0.5mgcm

The nuclear fuel reprocessing plants on the Sellafield site (UK) have released low-level effluents into the Irish Sea under authorisation since 1952. This has led to the labelling of nearby offshore sediments with a range of artificial radionuclides. In turn, these sediments act as a long-term secondary source of both soluble and particle-associated radionuclides to coastal areas. These radionuclides are of interest both in assessing possible environmental impacts and as tracers for marine processes. Here we present results from a study of the geochemistry of natural (234, 238U) and artificial (137Cs, 241Am, 238Pu, 239+240Pu, and 236U) radionuclides and their accumulation in sediments from Loch Etive, Scotland. The data are interpreted in the context of the historical radioactive discharges to the Irish Sea and biogeochemical processes in marine sediments. Loch Etive is divided into two basins; a lower, seaward basin where the sedimentation rate (∼0.6 cm/yr) is about twice that of the more isolated upper basin (∼0.3 cm/yr). These accumulation rates are consistent with the broad distribution of 137Cs in the sediment profiles which can be related to the maximum Sellafield discharges of 137Cs in the mid-1970s and suggest that 137Cs was mainly transported in solution to Loch Etive during that period. Enrichments of Mn, Fe, and Mo in sediment and porewater from both Loch Etive basins result from contemporary biogeochemical redox processes. Enrichments of 238U and 234U in the lower basin may be a result of the cycling of natural U. By contrast, the Sellafield-derived artificial isotope 236U does not seem to be affected by the redox-driven reactions in the lower basin. The 238Pu/239,240Pu ratios suggest contributions from both historical Sellafield discharges and global fallout Pu. The uniform sediment distributions of Pu and Am, which do not reflect Sellafield historical discharges, suggest the existence of a homogenous secondary source. This could be the offshore ‘mud patch’ in the vicinity of Sellafield from which the supply of radionuclides reflects time-integrated Sellafield discharges. This source could also account for the continuing supply of Cs to Loch Etive, even after substantial reductions in discharge from the Sellafield site.

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.

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. © 2014 American Chemical Society.

At nuclear contaminated sites, microbially-mediated Fe(III) reduction under alkaline conditions opens up the potential for co-treatment of the groundwater contaminants Tc-99, though reduction to less mobile Tc(IV) phases, and Sr-90, 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 Tc-99 and Sr (as stable Sr2+ at elevated concentrations and Sr-90(2+) 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 TcO4- added at 1.6 x 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 x 10 (10) M (as Sr-90(2+))) and at higher concentrations (1.15 x 10 (3) M (as stable Sr2+)). In ultra-trace experiments at pH 7, microbially active systems showed enhanced removal of Sr-90 compared to the sterile control. This was likely due to sorption of Sr-90(2+) to the Fe(II)-bearing biominerals that formed in situ. By contrast, at pH 9, the sterile control showed comparable removal of Sr-90 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, Sr-90 bioreduction experiments showed 60-70% removal of the added Sr-90 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 Sr-90 contamination. In systems with elevated Sr2+ concentrations and an initial pH of 7, microbially active systems showed

Iodine-129 is a high-yield fission product formed in nuclear reactors and is a risk-driving radionuclide in both contaminated land and radioactive waste disposal due to its high mobility and long half-life. Here, the bioreduction behaviour of iodate was investigated by tracking iodine speciation and concentration in solution during the development of progressive anoxia in sediment microcosm experiments incubated at neutral pH. Experiments with acetate added as an electron donor showed the expected cascade of terminal electron-accepting processes. Analysis of solution chemistry showed reduction of iodate to iodide during the early stages of metal (Mn(IV) and Fe(III)) reduction, but with no significant retention of iodine species on solids. There was, however, a net release of natural iodine associated with the sediments to solution when robust iron reduction / sulfate reduction had developed. In addition, over 210 days, the controls with no electron donor and the sterile controls showed no Mn(IV) or Fe(III) reduction but displayed modest sorption of iodate to the sediments in the absence of bioreduction. Overall these results show that under oxic conditions iodate may be partially sorbed to sediments over extended periods but that development of mildly reducing conditions leads to the reductive release of iodine to solution as iodide.

Uranium (as UO22+), technetium (as TcO4-) and neptunium (as NpO2+) are highly mobile radionuclides that can be reduced enzymatically by a range of anaerobic and facultatively anaerobic microorganisms, including Shewanella oneidensis MR-1, to poorly soluble analogues. The redox chemistry of Pu is more complicated, but the dominant oxidation state in most environments is poorly soluble Pu(IV), which can be reduced to the potentially more soluble Pu(III), which could enhance migration of Pu in the environment. Recently it was shown that flavins (riboflavin and flavin mononucleotide (FMN)) secreted by Shewanella oneidensis MR-1 can act as electron shuttles, promoting anoxic growth coupled to the accelerated reduction of poorly-crystalline Fe(III) oxides. Here we studied the role of riboflavin in mediating the reduction of radionuclides in cultures of Shewanella oneidensis MR-1. Our results demonstrate that the addition of 10 µM riboflavin enhances the reduction rate of Tc(VII) to Tc(IV) and Np(V) to Np(IV), but has no significant influence on the reduction rate of U(VI) by Shewanella oneidensis MR-1. The presence of riboflavin also accelerated Pu(IV) reduction, demonstrated by an increase in the percentage of Pu(IV) reduced to Pu(III), with and without riboflavin present (17 and 3%, respectively). Thus riboflavin can act as an extracellular electron shuttle to enhance rates of Tc(VII), Np(V) and Pu(IV) reduction, and may therefore play a role in controlling the oxidation state of key redox active actinides and fission products in natural and engineered environments. These results also suggest that the addition of riboflavin could be used to accelerate the bioremediation of radionuclide-contaminated environments.

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.

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.

The behavior of technetium at ultra-trace (

Around the world large quantities of sludge wastes derived from nuclear energy production are currently kept in storage facilities. In the UK, the British government has marked sludge removal as a top priority as these facilities are nearing the end of their operational lifetimes. Therefore chemical understanding of uranium uptake in Mg-rich sludge is critical for successful remediation strategies. Previous studies have explored uranium uptake by the calcium carbonate minerals, calcite and aragonite, under conditions applicable to both natural and anthropogenically perturbed systems. However, studies of the uptake by Mg-rich minerals such as brucite [Mg(OH)2], nesquehonite [MgCO3·3H2O] and hydromagnesite [Mg5(CO3)4(OH)2·4H2O], have not been previously conducted. Such experiments will improve our understanding of the mobility of uranium and other actinides in natural lithologies as well as provide key information applicable to nuclear waste repository strategies involving Mg-rich phases. Experiments with mineral powders were used to determine the partition coefficients (Kd) and coordination of UO22+ during adsorption and co-precipitation with brucite, nesquehonite and hydromagnesite. The Kd values for the selected Mg-rich minerals were comparable or greater than those published for calcium carbonates. Extended X-ray absorption fine structure analysis results showed that the structure of the uranyl-triscarbonato [UO2(CO3)3] species was maintained after surface attachment and that uptake of uranyl ions took place mainly via mineral surface reactions.

Groundwaters at nuclear sites are often characterised by low pH and high nitrate concentrations (10-100 mM). These conditions are challenging for bioremediation, often inhibiting microbial Fe(III)-reduction that can limit radionuclide migration. Here, sediment microcosms representative of the UK Sellafield site were used to study the influence of variable pH and nitrate concentrations on microbially-mediated TEAP (terminal electron accepting processes) progression. The rate of bioreduction at low pH (~ 5.5) was slower than that in bicarbonate-amended systems (pH ~ 7.0), but in the low pH systems, denitrification and associated pH buffering resulted in conditioning of the sediments for subsequent Fe(III) and sulfate reduction. Under very high nitrate conditions (100 mM), bicarbonate amendment (pH ~ 7.0) was necessary for TEAP progression beyond denitrification and the reduction of 100 mM nitrate created alkaline conditions (pH 9.5). 16S rRNA gene analysis showed that close relatives of known nitrate reducers Bacillus niacini and Ochrobactrum grignonense dominated the microbial communities. In the 100 mM nitrate system, close relatives of the Fe(III)-reducing species Alkaliphilus crotonatoxidans and Serratia liquifaciens were observed. These results highlight that denitrification can support bioreduction via pH conditioning for optimal metal reduction and immobilization.

Iron minerals influence the environmental redox behaviour and mobility of metals including the long-lived radionuclide technetium. Technetium is highly mobile in its oxidized form pertechnetate (Tc(VII)O4–), however, when it is reduced to Tc(IV) it immobilizes readily via precipitation or sorption. In low concentration tracer experiments, and in higher concentration XAS experiments, pertechnetate was added to samples of biogenic and abiotically synthesized Fe(II)-bearing minerals (bio-magnetite, bio-vivianite, bio-siderite and an abiotically precipitated Fe(II) gel). Each mineral scavenged different quantities of Tc(VII) from solution with essentially complete removal in Fe(II)-gel and bio-magnetite systems and with 84±4% removal onto bio-siderite and 68±5% removal onto bio-vivianite over 45 days. In select, higher concentration, Tc XAS experiments, XANES spectra showed reductive precipitation to Tc(IV) in all samples. Furthermore, EXAFS spectra for bio-siderite, bio-vivianite and Fe(II)-gel showed that Tc(IV) was present as short range ordered hydrous Tc(IV)O2-like phases in the minerals and for some systems suggested possible incorporation in an octahedral coordination environment. Low concentration reoxidation experiments with air-, and in the case of the Fe(II) gel, nitrate-oxidation of the Tc(IV)-labelled samples resulted in only partial remobilization of Tc. Upon exposure to air, the Tc bound to the Fe-minerals was resistant to oxidative remobilization with a maximum of ∼15% Tc remobilized in the bio-vivianite system after 45 days of air exposure. Nitrate mediated oxidation of Fe(II)-gel inoculated with a stable consortium of nitrate-reducing, Fe(II)-oxidizing bacteria showed only 3.8±0.4% remobilization of reduced Tc(IV), again highlighting the recalcitrance of Tc(IV) to oxidative remobilization in Fe-bearing systems. The resultant XANES spectra of the reoxidized minerals showed Tc(IV)-like spectra in the reoxidized Fe-phases. Overall, this study highlights the role that Fe-bearing biogenic mineral phases have in controlling reductive scavenging of Tc(VII) to hydrous TcO2-like phases onto a range of Fe(II)-bearing minerals. In addition, it suggests that on reoxidation of these phases, Fe-bound Tc(IV) may be octahedrally coordinated and is largely recalcitrant to reoxidation over medium-term timescales. This has implications when considering remediation approaches and in predictions of the long-term fate of Tc in the nuclear legacy.

Anoxic Tc(IV)-containing sediments representative of the UK Sellafield reprocessing facility were exposed to either air or NO3 − to investigate redox cycling of technetium and iron. With air, oxidation of Fe(II) in the reduced sediments was accompanied by ∼75% mobilization of Tc to solution, as soluble Tc(VII). Nitrate additions resulted in the bio-oxidation of Fe(II), coupled to microbially mediated NO− 3 reduction but was accompanied by only very limited (

Under anaerobic conditions, uranium solubility is significantly controlled by the microbially mediated reduction of relatively soluble U(VI) to poorly soluble U(IV). However, the reaction mechanism(s) for bioreduction are complex with prior sorption of U(VI) to sediments significant in many systems, and both enzymatic and abiotic U(VI) reduction pathways potentially possible. Here, we describe results from sediment microcosm and Fe(II)-bearing biomineral experiments designed to assess the relative importance of enzymatic vs. abiotic U(VI) reduction mechanisms and the long-term fate of U(IV). In oxic sediments representative of the UK Sellafield reprocessing site, U(VI) was rapidly and significantly sorbed to surfaces and during microbially-mediated bioreduction, XAS analysis showed that sorbed U(VI) was reduced to U(IV) commensurate with Fe(III)-reduction. Additional control experiments with Fe(III)-reducing sediments that were sterilized after bioreduction and then exposed to U(VI), indicated that U(VI) ...

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.

Technetium-99 is an important fission product in radioactive wastes. As Tc ( VII ) O 4 - , Tc is highly mobile in oxic environments but, under reducing conditions, Tc becomes strongly associated with sediments as hydrous Tc(IV)O2 like phases. In order to further examine the behaviour of Tc over a range of concentrations in estuarine sediments, anoxic incubation experiments were combined with a range of direct (transmission electron microscopy and gamma camera imaging) and indirect (incubation experiments and chemical extractions) experimental techniques. When TcO4− was incubated in sediment microcosms at micro-molar (10−6 mol L−1) concentrations, >99% Tc O 4 - was removed from solution over the course of 36 days in systems undergoing active microbial Fe(III)-reduction. By contrast, when spiked into pre-reduced estuarine sediments that were predominantly Fe(III)-reducing (incubated for 60 days) or SO 4 2 − -reducing (incubated for 270 days), >99% Tc O 4 - was removed from solution in under 10 min in both microbially active and heat sterilised systems. Chemical extraction techniques showed that 70 ± 3% of Tc bound to sediments was remobilised when sediments were exposed to the first strong oxidant (H2O2) in the extraction scheme. At higher Tc concentrations (∼0.05 mol kg−1 of sediment) scanning transmission electron microscopy, combined with energy dispersive X-ray mapping, was used to examine the associations of Tc in sediments. At these concentrations, Tc was localised and co-associated with nanometre size Fe(II)-rich particles, consistent with the hypothesis that removal of Tc may be controlled by reduction of Tc(VII) to Tc(IV) by biogenic Fe(II) in sediments. In addition, gamma camera imaging with the γ-emitting 99 m Tc O 4 - (half-life 6 h) at pico-molar (10−12 mol L−1) concentrations, was used to visualise the interaction of Tc in sediments at very low concentrations. Here, over the course of 24 h the scavenging of Tc to SO 4 2 − -reducing sediments was observed. As the Tc concentrations used in the 99mTc experiments were below the solubility limits for hydrous Tc(IV)O2 (ca. 10−9 mol L−1 at pH 7–9), sorption of Tc(IV) species is likely to be a significant control on Tc behaviour in these sediments even at very low concentrations. Overall, the results of this study show that multiple approaches are essential to understanding Tc speciation in complex heterogeneous sediments over the wide range of concentrations relevant to contaminated natural and engineered environments.

Porewater concentrations and benthic fluxes of phosphate, silicate, ammonia, nitrate and nitrite were measured at five sites spanning the Pakistan margin oxygen minimum zone (OMZ), in order to characterise the biogeochemical processes occurring, and to assess whether oxygen concentration and a seasonal pulse of organic matter are controlling factors. Typical concentrations of 1–70 μM, 50–250 μM, 0–270 μM, 30 cm) in the sediment. These processes are all redox-sensitive, and their intensities varied across the margin, suggesting that oxygen concentration exerts a strong influence over nutrient concentrations and cycling. Variation in nutrient concentrations and fluxes before and after the summer monsoon was limited to an oxygen-driven change to the PO43− profile at one site, indicating that either nutrient profiles do not generally alter on seasonal timescales, or that any impact of the monsoon had subsided before the post-monsoon sampling period. Porewater profile modelling tended to underestimate the magnitude of fluxes, but was in general agreement with the directions of measured fluxes, and in situ and shipboard flux measurements also generally agreed. Phosphate and H4SiO4 concentrations and benthic fluxes on the Pakistan margin were similar to those reported at abyssal sites from around the world, while NH4+ and NO3− concentrations and fluxes were comparable to shallower, more productive and/or hypoxic marine settings.

Biogeochemical processes and fluxes occurring across the sediment–water interface on continental margins impacted by oxygen minimum zones (OMZs) are important to bioelement cycles, ocean inventories, and productivity. The nature and magnitude of these processes depend heavily on spatial and temporal variability in dissolved O 2 concentrations in bottom waters and porewaters. In 2003, four research cruises to the Indus margin of the Arabian Sea (Pakistan) were undertaken to survey the benthic biogeochemical processes in the resident OMZ before and after the southwest monsoon. Sediment O 2 microdistribution and consumption rates were measured at five stations along a depth transect (140–1850 m) across the OMZ, during the spring intermonsoon and the late-to-post southwest monsoon periods, using in situ benthic research platforms (landers). Lander O 2 electrode data show that the intermonsoon and late-to-postmonsoon bottom-water O 2 levels had little to no variation (300 m, no change; 940 m, 1.7–2.8 μM; 1200 m, 10.2–12.6 μM; and 1850 m, 82–80 μM). In contrast, at the shallowest station (140 m), a large fluctuation occurred between the intermonsoon (O 2 =44.5 μM) and the late-to-postmonsoon (O 2 =1 μM), due to monsoon-forced shoaling of the upper OMZ boundary. Oxygen did not penetrate into the sediments at the 300-m site during either sampling season. During the intermonsoon season at the 140-m site, O 2 penetrated to a depth of ∼3 mm, but no measurable O 2 penetration occurred after the monsoon. At the 940 and 1200-m sites, O 2 penetration into the sediments was small (ca. 1–2 mm at both sites) and did not measurably change between the two sampling seasons. In contrast, at the 1850-m site, O 2 penetration decreased after the monsoon (18–12 mm). Calculated late-to-postmonsoon O 2 consumption rates were generally similar to or lower than intermonsoon values (0 vs. 2.22 mmol m −2 d −1 at 140 m, 0.37 vs. 0.31 mmol m −2 d −1 at 1200 m, and 0.73 vs. 1.01 mmol m −2 d −1 at 1850 m). The relatively small seasonal signal suggests that organic matter delivered during the monsoon period may have already been largely remineralized by the late-to-postmonsoon sampling period. Modelling of porewater O 2 profiles indicates that subsurface O 2 consumption associated oxidation of reduced inorganic species makes a significant contribution to total O 2 consumption at some sites. Similarly, differences in O 2 consumption rates determined by porewater profile modelling and whole-core incubations at some sites indicate significant contributions associated with bioturbation and bioirrigation.