The generation and migration of gas within and around proposed radioactive waste disposal facilities is potentially a safety critical process. A safety case for a facility that generates significant quantities of gas (e.g. through metal corrosion or radiolysis) will require demonstration that gas migration around and away from the waste is sufficiently understood and will not breach the safety case for the facility. Models can be used to understand the likely hydraulic evolution of such a disposal facility, but the models need to consider processes over a range of scales. A whole repository may extend over kilometres, with individual disposal cells at the scale of tens of metres and features which provide pathways for gas migration on a centimetre scale. All of these features may be significant from a safety perspective and capturing the impact of all of these features in a single model is a significant challenge.

This paper presents an approach to tackling this multi-scale problem, which allows the whole repository to be modelled in a computationally efficient manner. The approach involves identifying areas within the modelled domain that show very similar behaviour, and representing these areas with sub-models, so that small-scale features are retained, but computational overhead is decreased by using the results in more than one location in the model domain. The approach allowed a model of a whole repository to be run on a single processor core, whilst maintaining the small-scale features of the system. The model results were compared against more conventional upscaling techniques and show the advantage of a more detailed representation of small-scale features. The model results reflect the conceptual understanding of how gas would migrate in a repository.

Uranium incorporation into magnetite and its behaviour during subsequent oxidation has been investigated at high pH to determine the uranium retention mechanism(s) on formation and oxidative perturbation of magnetite in systems relevant to radioactive waste disposal. Ferrihydrite was exposed to U(VI)aq containing cement leachates (pH 10.5–13.1) and crystallization of magnetite was induced via addition of Fe(II)aq. A combination of XRD, chemical extraction and XAS techniques provided direct evidence that U(VI) was reduced and incorporated into the magnetite structure, possibly as U(V), with a significant fraction recalcitrant to oxidative remobilization. Immobilization of U(VI) by reduction and incorporation into magnetite at high pH, and with significant stability upon reoxidation, has clear and important implications for limiting uranium migration in geological disposal of radioactive wastes.

Carbon-14 is an important radionuclide in the inventory of radioactive waste and is considered to be a key radionuclide in performance assessment. In Switzerland, the 14C inventory in a cement-based repository for low- and intermediate-level radioactive waste is mainly associated with activated steel (∼85%). Anaerobic corrosion of the activated steel will determine the time-dependent release of 14C-bearing compounds from the cementitious near field into the host rock. The present study was carried out to provide an overview on the current state of the art knowledge regarding the carbon speciation during the anaerobic corrosion of activated and non-activated iron/steel and to critically assess the capability of thermodynamic modelling to predict 14C speciation in anoxic alkaline conditions. Previous experimental work showed the presence of oxidized and reduced hydrocarbons during corrosion in iron-water systems in anoxic (near neutral to alkaline) conditions which appears to be inconsistent with the negative redox potential of the system. The capability of thermodynamic modelling to predict the carbon speciation in these conditions was found to be limited due to uncertainties associated with the concept of metastability in the C–H–O system.

Neptunium-237 will be present in radioactive wastes over extended time periods due to its long half-life (2.13 × 106 years). 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.

Radial diffusion experiments have been carried out to assess the migration of 36Cl, as chloride, through a cementitious backfill material. Further experiments in the presence of cellulose degradation products were performed to assess the effect of organic ligands on the extent and rate of chloride diffusion. Results show that breakthrough of 36Cl is dependent on chloride concentration: as the carrier concentration increases, both breakthrough time and the quantity retained by the cement matrix decreases. Experiments in the presence of cellulose degradation products also show a decrease in time to initial breakthrough. However, uptake at various carrier concentrations in the presence of organic ligands converges at 45% of the initial concentration as equilibrium is reached. The results are consistent with organic ligands blocking sites on the cement that would otherwise be available for chloride binding, though further work is required to confirm that this is the case. Post-experimental digital autoradiographs of the cement cylinders, and elemental mapping showed evidence of increased 36Cl activity associated with black ash-like particles in the matrix, believed to correspond to partially hydrated glassy calcium-silicate-sulfate-rich clinker.

Ternary systems of 152Eu(III), bulk bentonite and ethylenediaminetetraacetic acid (EDTA) ([Eu] = 7.9 × 10–10 M; pH = 6.0–7.0) have been studied. Without EDTA, there was slow uptake in a two-stage process, with initial rapid sorption of Eu(III) (96%), followed by slower uptake of a much smaller fraction (3.0% over a period of one month). The reversibility of Eu(III) binding was tested by allowing Eu(III) to sorb to bentonite for 1–322 days. EDTA was added to the pre-equilibrated Eu bentonite systems at 0.01 M, a concentration that was sufficient to suppress sorption in a system where EDTA was present prior to the contact of Eu(III) with bentonite. A fraction of the Eu was released instantaneously (30–50%), but a significant amount remained bound. With time, the amount of Eu(III) retained by the bentonite reduced, with a slow fraction dissociation rate constant of approximately 4.3 × 10–8 s–1 (values in the range 2.2 × 10–8 – 1.0 × 10–7 s–1) for pre-equilibration times ≥7 days. Eventually, the amount of Eu(III) remaining bound to the bentonite was within error of that when EDTA was present prior to contact (4.5% ± 0.6), although in systems with pre-equilibration times >100 days, full release took up to 500 days. Europium interactions with colloidal bentonite were also studied, and the dissociation rate constant measured by a resin competition method. For the colloids, more Eu was found in the slowly dissociating fraction (60–70%), but the first-order dissociation rate constant was faster, with an average rate constant of 8.8 × 10–7 s–1 and a range of 7.7 × 10–7 –9.5 × 10–7 s–1. For both bulk and colloidal bentonite, although slow dissociation was observed for Eu(III), there was no convincing evidence for 'irreversible' binding.

Corrosion of steel canisters, disposed of in a repository for high-level waste (HLW), leads to generation of hydrogen gas for a long period after the repository's closure. The accumulation of hydrogen gas may lead to significant desaturation and unacceptable build-up of pressure in the backfilled disposal tunnels if the gas cannot escape through the low-permeability host rock. Consequently, the investigation of gas migration is of high relevance in the assessment of the repository's performance.

In this paper, the results of numerical investigations on gas migration performed using the computer code TOUGH2 (USA) are presented. The objective was to investigate migration of gas generated in a single disposal tunnel of a conceptual geological repository in a clay formation, which was suggested for benchmark studies in the European Commission project FORGE (Fate Of Repository GasEs). The analysis was focused on evaluation of the impact of an initial temperature in the repository and of different tortuosity models on gas migration. It was revealed that gas migration results were dependent on tortuosity model, while temperature variation in the repository had minor impact.

Large quantities of irradiated graphite will arise from the decommissioning of the UK's Magnox power stations. Irradiated graphite contains 14C as well as other longer lived radionuclides (e.g. 36Cl). The potential use of magnetic sector secondary ion mass spectrometry (MS-SIMS) to examine the distribution of the 14C within trepanned graphite samples from a Magnox nuclear power station has been investigated. This work indicates that the methodology proposed has the potential to be used to analyse irradiated graphite samples with preliminary results highlighting a possible 14C enrichment in the carbonaceous deposit found on a channel wall sample. 14C concentrations in samples without this deposit were below the limits of detection of the instrument. The methodology used for these determinations ensured that possible mass interferences between 14C species and oxygen-bearing or nitrogen-bearing species were eliminated from the analysis. Future work will utilize the methodology proposed in this work on a larger number of samples.

One of the most challenging aspects of understanding the flow of gas and water during testing in clay-rich low-permeability materials is the difficulty in visualizing localized flow. Whilst understanding has been increased using X-ray Computed-tomography (CT) scanning, synchrotron X-ray imaging and Nuclear Magnetic Resonance (NMR) imaging, real-time testing is problematic under realistic in situ conditions confining pressures, which require steel pressure vessels. These methods tend not to have the nano-metre scale resolution necessary for clay mineral visualization, and are generally not compatible with the long duration necessary to investigate flow in such materials. Therefore other methods are necessary to visualize flow paths during post-mortem analysis of test samples. Several methodologies have been established at the British Geological Survey (BGS), in order to visualize flow paths both directly and indirectly. These include: (1) the injection of fluorescein-stained water or deuterium oxide; (2) the introduction of nanoparticles that are transported by carrier gas; (3) the use of radiologically tagged gas; and (4) the development of apparatus for the direct visualization of clay. These methodologies have greatly increased our understanding of the transport of water and gas through intact and fractured clay-rich materials. The body of evidence for gas transport through the formation of dilatant pathways is now considerable. This study presents observations using a new apparatus to directly visualize the flow of gas in a kaolinite paste. The results presented provide an insight into the flow of gas in clay-rich rocks. The flow of gas through dilatant pathways has been shown in a number of argillaceous materials (Angeli et al., 2009; Autio et al., 2006; Cuss et al., 2014; Harrington et al., 2012). These pathways are pressure induced and an increase in gas pressure leads to the dilation of pathways. Once the gas breakthrough occurs, pressure decreases and pathways begin to close. This new approach is providing a unique insight into the complex processes involved during the onset, development and closure of these dilatant gas pathways.

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.

Geological disposal facilities (GDF) are intended to isolate and contain radioactive waste within multiple protective barriers, deep underground, to ensure that no harmful quantities of radioactivity reach the surface environment. The last line of defense in a multi-barrier GDF is the geosphere, where iron is present in the host rock mineralogy as either Fe(II) or Fe(III), and in groundwater as Fe(II) under reducing conditions. The mobility of risk-driving radionuclides, including uranium and technetium, in the environment is affected significantly by their valence state. Due to its low redox potential, Fe(II) can mediate reduction of these radionuclides from their oxidized, highly mobile, soluble state to their reduced, insoluble state, preventing them from reaching the biosphere. Here a study of five types of potential host rocks, two granitoids, an andesite, a mudstone and a clay-rich carbonate, is reported. The bulk rocks and their minerals were analysed for iron content, Fe(II/III) ratio, and for the speciation and fine-grained nature of alteration product minerals that might have important controls on groundwater interaction. Total iron content varies between 0.9% in clays to 5.6% in the andesite. X-ray absorption spectroscopy reveals that Fe in the granitoids and andesite is predominantly Fe(II), and in mudstones, argillaceous limestone and terrestrial sandstone is predominantly Fe(III). The redox reactivity of the potential host rocks both in the presence and absence of Fe(II)-containing 'model' groundwater was investigated using an azo dye as a probe molecule. Reduction rates as determined by reactivity with the azo dye were correlated with the ability of the rocks to uptake Fe(II) from groundwater rather than with initial Fe(II) content. Potential GDF host rocks must be characterized in terms of mineralogy, texture, grain size and bulk geochemistry to assess how they might interact with groundwater. This study highlights the importance of redox reactivity, not just total iron and Fe(II)/(III) ratio, when considering the host rock performance as a barrier material to limit transport of radionuclides from the GDF.

Opalinus clay has a high sealing capacity and is therefore considered as a viable candidate for hosting high-level radioactive waste. Assessment of the long-term containment function of clays requires understanding and modelling of mass transport through evolving pore systems. Development of pore network models for diffusion, which can be coupled to models for deformation and micro-cracking, is reported. Effects of clay texture and solid phase constitution are calculated and analysed. The results are in the range of, but slightly over-predicting, experimentally measured coefficients of diffusion in different clay directions. Further model improvements require better knowledge of micro-pore tortuosity, which awaits higher resolution experimental techniques.

The incorporation of pertechnetate (TcO4–) into feldspathoids produced by alkaline alteration of aluminosilicate clays may offer a potential treatment route for 99Tc-containing groundwater and liquors. Kaolinite was aged in NaOH to determine the effect of base concentration, temperature, and solution composition on mineral transformation and pertechnetate uptake. In all reactions, increased temperature and NaOH concentration increased the rate of kaolinite transformation to feldspathoid phases. In reactions containing only NaOH, sodalite was the dominant alteration product; however, small amounts (6–15%) of cancrinite also formed. In experiments containing NaOH/Cl and NaOH/NO3 mixtures, sodalite and nitrate cancrinite were crystallized (at 70°C), with no reaction intermediates. The addition of SO42– crystallized sulfatic sodalite at 40 and 50°C, but at higher temperatures (60 and 70°C) sulfatic sodalite transforms to vishnevite (sulfatic cancrinite). In experiments where a pertechnetate tracer was added (at ∼1.5 μmol l–1), only 3–5% of the 99Tc was incorporated into the feldspathoid phases. This suggests that the larger pertechnetate anion was unable to compete as favourably for the internal vacancies with the smaller OH–, NO3–, SO42– or Cl– anions in solution, making this method likely to be unsuitable for groundwater treatment.

DBE TECHNOLOGY, BGR and GRS are developing a methodology to demonstrate the safety of a repository for high-level waste and spent fuel (HLW/SF) in clays according to the requirements of the German regulating body. In particular, these requirements prescribe that the barrier effect of host rocks must not be compromised by a thermal impact resulting from HLW/SF emplacement. To substantiate and quantify this requirement, we carried out a literature survey of research on thermally-induced changes on clay properties. Effects thus compiled can be divided into thermo-hydro-mechanical and chemical-biological-mineralogical effects and were analysed with regard to their relevance to the integrity of clay host rocks. This analysis identified one effect of major influence within each group: thermal expansion and compaction as well as results of microbial activities. Importantly, it further revealed that a moderate temperature increase above 100°C cannot be expected to compromise the integrity of the geological barrier according to the current knowledge state. Evidence is presented in this paper that temperature increases up to 150°C can actually contribute to an improved performance of a radioactive waste repository by increasing the consolidation of the clay and sterilizing the repository's near-field to depress the deteriorative microbial effects. A quantitative temperature criterion for thermal impact of HLW/SF on clay host rocks is accordingly proposed.

Previously, it has been suggested that metal ions complexed to humic acid in the environment might show slower dissociation than those added to humic substances in the laboratory, which has serious implications for the transport of radionuclides in the environment. The dissociation of lanthanide and anthropogenic actinide ions from humic substance complexes has been studied as a function of humic concentration and metal ion:humic concentration ratio. The results suggest that the apparently slower kinetics observed for metal ions complexed in the environment are probably due to the large humic concentrations that are used in those studies. Further, there is no evidence that the dissociation rate constant varies at very low metal ion concentrations. Although humic samples size-fractionated by ultrafiltration showed that more metal may be bound non-exchangeably, there was no evidence for different rate constants. Ultrafiltration of Eu(III)/humic acid mixtures did show a shift in Eu from smaller to larger fractions over a period of two days. Therefore, the results suggest that dissociation rate constants determined in the laboratory at metal ion concentrations higher than those expected in the environment may be used in predicting radionuclide mobility, provided that the humic acid concentration is in the range expected at the site.

Cement in radioactive waste repositories will produce leachates of pH > 10 which may alter the host rock, affecting its ability to act as a barrier to radionuclide migration. To complement the many laboratory and modelling studies of rock alteration in cement leachates, analogue sites have been investigated to understand reactions at time scales relevant to geodisposal. However, analogue site histories may be poorly constrained and these systems may be influenced by site specific factors. Therefore increasing the number of sites studied is important to minimize uncertainty in the applicability of results. Herbert's Quarry has been characterized and assessed as a potential anthropogenic analogue. Streamwater sampling at the site identified Ca-rich fluids, ≤ pH 12, analogous to cement leachates. However, rock and sediment samples exhibited extensive CaCO3 precipitation in these fluids and no reaction of silicate rock. The streamwaters were also found to be oxidizing, unlike the reducing conditions expected at a repository, and temperatures were 15–25°C below those predicted for repositories. Therefore, Herbert's Quarry is believed to have limited applicability as an analogue in this context.

The generation and stability of inorganic colloids have been studied under hyperalkaline conditions. For the generation of colloids, intact cores of Bromsgrove Sandstone were flushed with simulated cement leachates, and the eluates were ultrafiltered sequentially (12 μm, 1 μm, 0.1 μm and 30 kDa) for the separation of any colloids found. No colloid formation was observed during the experiments; however the analysis by ICPMS of the eluates showed significant increases in Si and Al, indicating silicate mineral dissolution, as well as reduction of the concentration of Ca in the leachates indicating precipitation of secondary Ca-rich phases. Flow experiments with cement leachates spiked with tritiated water showed a noticeable reduction of the porosity of the sandstone as well as changes in the pore distribution. Additional stability experiments were carried out using model silica and Fe2O3 colloids. The experiments indicated that the stability of the colloids was mainly controlled by the concentration of Ca in solution and that both types were unstable under the chemical conditions in the alkaline disturbed zone. The presence of cement additives such as superplasticisers could enhance the stability of the colloids.

Under the alkaline conditions expected in an intermediate-level waste repository, cellulosic material will undergo chemical hydrolysis. This will produce hydrolysis products, some of which can form soluble complexes with some radionuclides. Analyses of samples containing autoclaved tissue and cotton wool incubated in a saturated solution of Ca(OH)2 ( pH > 12) confirmed previous reports that isosaccharinic acid (ISA) is produced from these cellulose polymers at high pH. However, when inoculated with a sediment sample from a hyperalkaline site contaminated with lime-kiln waste, microbial activity was implicated in the enzymatic hydrolysis of cellulose and the subsequent production of acetate. This in turn led to acidification of the microcosms and a marked decrease in ISA production from the abiotic alkali hydrolysis of cellulose. DNA analyses of microbial communities present in the microcosms further support the hypothesis that bacterial activities can have a controlling influence on the formation of organic acids, including ISA, via an interplay between direct and indirect mechanisms. These and previous results imply that microorganisms could have a role in attenuating the mobility of some radionuclides in and around a geological disposal facility, via either the direct biodegradation of ISA or by catalysing cellulose fermentation and therefore preventing the formation of ISA.

It is UK Government policy to dispose of higher activity radioactive waste through geological disposal into an engineered deep underground geological disposal facility (GDF; DECC, 2014). Those wastes include low-level (LLW) and intermediate-level (ILW) radioactive wastes that are very heterogeneous, containing a range of inorganic and organic materials, the latter including cellulosic items. After closure of the GDF, eventual resaturation with groundwater is expected, resulting in the development of a hyperalkaline environment due to the proposed use of a cementitious backfill. Under these high-pH conditions, cellulose is unstable and will be degraded chemically, forming a range of water-soluble, low molecular weight compounds, of which the most abundant is isosaccharinic acid (ISA). As ISA is known to form stable soluble complexes with a range of radionuclides, thereby increasing the chance of radionuclide transport, the impact of microbial metabolism on this organic substrate was investigated to help determine the role of microorganisms in moderating the transport of radionuclides from a cementitious GDF. Anaerobic biodegradation of ISA has been studied recently in high-pH cementitious ILW systems, but less work has been done under anaerobic conditions at circumneutral conditions, more representative of the geosphere surrounding a GDF. Here we report the fate of ISA in circumneutral microcosms poised under aerobic and anaerobic conditions; the latter with nitrate, Fe(III) or sulfate added as electron acceptors. Data are presented confirming the metabolism of ISA under these conditions, including the direct oxidation of ISA under aerobic and nitrate-reducing conditions and the fermentation of ISA to acetate, propionate and butyrate prior to utilization of these acids during Fe(III) and sulfate reduction. The microbial communities associated with these processes were characterized using 16S rRNA gene pyrosequencing. Methane production was also quantified in these experiments, and the added electron acceptors were shown to play a significant role in minimizing methanogenesis from ISA and its breakdown products.