During electrochemical remediation of radionuclide, 235U, 238U, and 99Tc-contaminated aqueous solutions, pyroaurite-like phases, ideally [M(II)M(III)(OH)16CO3·4H2O] where M = Fe, were synthesized following coprecipitation with iron from metal iron electrodes. The effect of radionuclides on the transformation of amorphous precipitates to crystalline pyroaurite-like phases was investigated using X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray analysis, Fourier-transform infrared (FTIR) spectroscopy, and fluorescence spectroscopy. The synthetic iron carbonate hydroxide phases showed primary XRD peaks at 0.7 and 0.35 nm and FTIR spectra that indicated the presence of a brucite-like sheet structure with carbonate anions occupying the interlayer. Divalent and trivalent iron, eroded from the electrode, occupies the octahedral sites of the brucite-like sheets. The carbonate anions in the interlayer balance the excess positive charge from isomorphous substitution of the Fe2+ or Fe3+ by reduced uranium (U4+) and technetium (Tc4+). Because of the lower solubility associated with crystalline phases than amorphous phases, incorporation of radioactive contaminants into pyroaurite-like phases by electrochemical syntheses represents a more effective approach for removing U and Tc from contaminated aqueous solutions than traditional technologies.

In situ migration experiments using different radiotracers have been performed in the HADES Underground Research Facility (URF), built at a depth of 225 m in the Boom Clay formation below the SCK–CEN nuclear site at Mol (Belgium). Small-scale experiments, mimicking laboratory experiments, were carried out with strongly retarded tracers (strontium, caesium, europium, americium and technetium). Contrary to europium, americium and technetium which are subjected to colloid mediated transport, the transport of strontium and caesium can be described by the classic diffusion retardation formalism. For these last two tracers, the transport parameters derived from the in situ experiments can be compared with the laboratory-derived values. For both tracers, the apparent diffusion coefficients measured in the in situ experiments agree well with the laboratory-derived values.

In the large-scale experiments (of the order of metres) performed in the URF, non-retarded or slightly retarded tracers (HTO, iodide and H14CO3–) were used. The migration behaviour of these tracers was predicted based on models applied in performance assessment calculations (classic diffusion retardation) using migration parameter values measured in laboratory experiments. These blind predictions of large-scale experiments agree well in general with the experimental measurements. Fitting the experimental in situ data leads to apparent diffusion coefficients close to those determined by the laboratory experiments. The iodide and H14CO3– data were fitted with a simple analytical expression, and the HTO data were additionally fitted numerically with COMSOL multiphysics, leading to about the same optimal values.

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.

Understanding the environmental and biogeochemical behaviour of radionuclides is essential for managing our nuclear legacy safely. Remediation efforts and the concept of geological disposal of nuclear waste focus on immobilizing radionuclides within the subsurface. Here we review recent developments in the understanding of solid-phase capture processes of Cs, Sr, Tc, U, Pu and Np. Abiotic interactions between minerals and these radionuclides (including sorption, reductive precipitation and co-precipitation) have been studied in various conditions. Microbially driven processes are much less well characterized, for example the effects of microbial reduction on the structure and reactivity of existing minerals, or their role in the formation of new minerals. Metabolites released by bacteria can play a role in both mineral dissolution and formation, and better understanding their release and role in mineralization has great potential in the development of solid-phase capture processes for radionuclides.

With the aid of a map of the research landscape covered by this review (created using a cluster-analysis tool, a self-organizing map), we highlight the most promising sequestration processes for specific radionuclides. However, radionuclides exhibit highly species-specific behaviour in their interactions with minerals and microorganisms. More research is required to characterize the role mineral surfaces play in bioreductive immobilization of Pu and Np, the reduction products formed, and their relative stability. Further studies should concentrate on more environmentally relevant experiments that include bacteria, minerals and radionuclides.

One of the most important isotopes to be considered for disposal in the proposed UK Geological Disposal Facility (GDF) for higher-activity radioactive wastes will be 99Tc, due to its long half-life, high fission yield and ability to migrate through the geosphere as the pertechnetate ion. Much of the Tc is likely to be in the lower Tc(IV) oxidation state due to the low Eh in the near field. Batch Tc(IV) sorption experiments have been performed from pH 3–13, using 95mTc as a spike, in the presence of quartz, hematite, goethite, plagioclase feldspar, sand and shale. Solutions containing Tc(IV) were prepared at trace concentrations to avoid precipitation of TcO2. Values for the partition coefficient (Rd) were found to range from ∽4 up to ∽2 × 104 cm3 g–1. Rd was heavily dependent on pH in all cases, with the highest values being found in the circumneutral area. These data will inform the performance assessment for the near-field behaviour of technetium in the UK's planned higher-activity wastes GDF. Surface complexation modelling has been performed, fitting the data using both monodentate and bidentate binding models.

In the UK, technetium may be disposed of in a high pH, low Eh cementitious repository. In such a scenario, its chemistry would be dominated by TcO4 −, in aerobic conditions and the sparingly soluble TcO2(s) in anaerobic conditions. Repository heterogeneity could mean that both Tc(VII) and Tc(IV) are present simultaneously. The anthropogenic ligands EDTA and picolinic acid are commonly used as decontamination agents and are likely to be present in intermediate-level waste (ILW). They could complex with Tc(IV) increasing its aqueous concentration and mobility in the cement porewaters and beyond. The conditional stability constants (measured in 0.3 mol dm−3 NaOH) for the Tc(IV)–EDTA and Tc(IV)–picolinic acid complexes have been determined to be: βTc(IV)−EDTA = 1.6 × 1026, which corresponds to log β = 25.2±0.6; and βTc(IV)−PA = 8.65 × 1026, which corresponds to log β = 26.9±0.1, respectively.

Iron oxides resulting from the corrosion of large quantities of steel that are planned to be installed throughout a deep geological disposal facility (GDF) are expected to be one of the key surfaces of interest for controlling radionuclide behaviour under disposal conditions. Over the lengthy timescales associated with a GDF, the system is expected to become anoxic so that reduced Fe(II) phases will dominate. Batch experiments have therefore been completed in order to investigate how a model reduced Fe-oxide surface (wüstite, Fe1–xO) alters as a function of exposure to aqueous solutions with compositions representative of conditions expected within a GDF. Additional experiments were performed to constrain the effect that highly alkaline solutions (up to pH 13) have on the adsorption behaviour of the uranyl (UO22+) ion onto the surfaces of both wüstite and portlandite [Ca(OH)2; representative of the expected cementitious phases]. Surface co-ordination chemistry and speciation were determined by ex situ X-ray absorption spectroscopy measurements (both X-ray absorption near-edge structure analysis (XANES) and extended X-ray absorption fine structure analysis (EXAFS)). Diffraction, elemental analysis and XANES showed that the bulk solid composition and Fe oxidation state remained relatively unaltered over the time frame of these experiments (120 h), although under alkaline conditions possible surface hydroxylation is observed, due presumably to the formation of surface hydroxyl complexes. The surface morphology, however, is altered significantly with a large degree of roughening and an observed decrease in the average particle size. Reduction of U(VI) to U(IV) occurs during adsorption in almost all cases and this is interpreted to indicate that wüstite may be an effective reductant of U during surface adsorption. This work also shows that increasing the carbonate concentration in reactant solutions dramatically decreases the adsorption coefficients for U on both wüstite and portlandite, consistent with U speciation and surface reactivity determined in other studies. Finally, the EXAFS results include new details about exactly how U bonds to this metal oxide surface.

Introduction: Surgery for primary hyperparathyroidism has traditionally involved a bilateral neck exploration performed as an in-patient procedure. We present a feasibility study to demonstrate whether, with a focused surgical exploration, the procedure can be carried out as a day case.

Method: Eighty-seven patients had pre-operative sestamibi and ultrasound scans of the neck. When the results of these scans agreed, a unilateral neck exploration was carried out.

Results: Sixty-seven patients received a focused approach parathyroidectomy. Ninety-seven per cent of these patients were normocalcaemic after the first operation. All patients who fitted the day-case criteria left hospital the following morning.

Discussion: When pre-operative imaging results agree, a parathyroidectomy can be carried out using a unilateral neck exploration, avoiding the increased risks associated with a bilateral exploration.

Conclusion: Parathyroidectomy can be safely carried out as a day-case procedure in selected patients.