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.

ENTRAP comprises a pan-European cooperation of leading scientific institutions and regulatory bodies in the field of nuclear-waste characterization and its quality assurance for the safe disposal of radioactive waste. Here, the scope of this cooperation is presented and explained and links or interfaces for a potential collaboration with partners fulfilling tasks of IDG-TP are pursued.

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.

A geological disposal facility (GDF) will include fissile materials that could, under certain conditions, lead to criticality. Demonstration of criticality safety therefore forms an important part of a GDF's safety case.

Containment provided by the waste package will contribute to criticality safety during package transport and the GDF operational phase. The GDF multiple-barrier system will ensure that criticality is prevented for some time after facility closure. However, on longer post-closure timescales, conditions in the GDF will evolve and it is necessary to demonstrate: an understanding of the conditions under which criticality could occur; the likelihood of such conditions occurring; and the consequences of criticality should it occur.

Work has addressed disposal of all of the UK's higher-activity wastes in three illustrative geologies. This paper, however, focuses on presenting results to support safe disposal of spent fuel, plutonium and highlyenriched uranium in higher-strength rock.

The results support a safety case assertion that post-closure criticality is of low likelihood and, if it was to occur, the consequences would be tolerable.

The first comprehensive assessment of the dissolution kinetics of simulant Magnox–ThORP blended UK high-level waste glass, obtained by performing a range of single-pass flow-through experiments, is reported here. Inherent forward rates of glass dissolution were determined over a temperature range of 23 to 70°C and an alkaline pH range of 8.0 to 12.0. Linear regression techniques were applied to the TST kinetic rate law to obtain fundamental parameters necessary to model the dissolution kinetics of UK high-level waste glass (the activation energy (Ea), pH power law coefficient (η) and the intrinsic rate constant (k0)), which is of importance to the post-closure safety case for the geological disposal of vitreous products. The activation energies based on B release ranged from 55 ± 3 to 83 ± 9 kJ mol–1, indicating that Magnox–THORP blend glass dissolution has a surface-controlled mechanism, similar to that of other high-level waste simulant glass compositions such as the French SON68 and LAW in the US. Forward dissolution rates, based on Si, B and Na release, suggested that the dissolution mechanism under dilute conditions, and pH and temperature ranges of this study, was not sensitive to composition as defined by HLW-incorporation rate.

Carbon-14 (C-14) is a key radionuclide in the assessment of a geological disposal facility (GDF) for radioactive waste. In the UK a significant proportion of the national C-14 inventory is associated with reactor-core graphite generated by the decommissioning of the UK's Magnox and AGR reactors.

There are a number of uncertainties associated with the fate and transport of C-14 in a post-closure disposal environment that need to be considered when calculating the radiological impacts of C-14-containing wastes. Some of these uncertainties are associated with the distribution of C-14-containing gaseous species such as 14CH4 and 14CO2 between the groundwater and gaseous release pathways. As part of the C14-BIG programme, a modelling framework has been developed to investigate these uncertainties. This framework consists of a biogeochemical near-field evolution model, incorporating a graphite carbon-14 release model, which interfaces with a geosphere/biosphere model. The model highlights the potential impact of the microbial reduction of 14CO2 to 14CH4, through the oxidation of H2, on C-14 transport. The modelling results could be used to inform the possible segregation of reactor graphite from other gasgenerating wastes.

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.

Pb-lawsonite, PbAl2[(OH)2|Si2O7]·H2O, space group Pbnm, was synthesized as crystals up to 15 μm × 5 μm × 5 μm in size by a piston cylinder technique at a pressure of ∼4 GPa and a temperature of 873 ± 10 K. Temperature-dependent powder and single-crystal X-ray diffraction (XRD) analyses partly using synchrotron radiation as well as Raman spectroscopic investigations reveal a phase transition around 445 K resulting in the Cmcm high-temperature structure. The transformation temperature is considerably higher than that of lawsonite around 273 K, which is characterized predominantly by proton order/disorder. The transition is confirmed using principal component analysis and subsequent hierarchical cluster analysis on both the powder XRD patterns and the Raman spectra. Furthermore, a non-uniform change is observed around 355 K, which is not as pronounced as the 445 K transition and apparently comes from enhanced hydrogen bonding, which stops the atom shifts in Pb-lawsonite. These are the same bonds that mainly characterize the phase transition in lawsonite around 273 K. In contrast, the structural transition of Pblawsonite at 445 K seems to originate from the interaction of the SiO4 tetrahedra and AlO6 octahedra framework with the Pb2+ cation. The structural environment of Pb2+ can be described by a 12-fold coordination above 445 K, which changes towards irregular ten-fold coordination below this temperature. An assignment of the O–H stretching Raman bands confirms moderately strong H bonds in Pb-lawsonite, whereas both strong and weak H bonds exist in lawsonite. Therefore, a further phase transition of Pblawsonite, similar to that of lawsonite around 273 K, is not expected.

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.

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.

The Implementing Geological Disposal of Radioactive Waste Technology Platform (IGD-TP) was launched in November 2009 to facilitate international cooperation in common areas of research, development and demonstration (RD&D) with a view to advancing the implementation of geological disposal facilities for spent fuel, high-level and other long-lived waste in Europe.

The IGD-TP's Vision is that “by 2025, the first geological disposal facilities for spent fuel, high-level waste and other long-lived radioactive waste will be operating safely in Europe”. Aside from most European waste management organisations, the IGD-TP currently has 124 members covering most of the RD&D actors in the field of implementing geological disposal of radioactive waste in Europe.

Five years after its inception, the IGD-TP has been shown to play a leading role in coordinating joint actions for RD&D in radioactive waste geological disposal programmes. The work of the platform takes into account differences between the timing and challenges for the respective waste management programmes. Following implementation of Posiva's geological disposal facility in Finland it is expected that within the next 5 years the construction of the Swedish and French geological disposal facilities will commence. Within IGD-TP, the SecIGD2 project whose remit is “Coordination and Support Action under the 7th Framework programme” aims at supporting, at the European level, the networking and structuring of RD&D programmes and competences in countries with less advanced geological disposal programmes, including those in the new European Union Member States. Furthermore, the SecIGD2 supports the development and coordination of the necessary competences to meet the Vision 2025 as a part of the platform's Competence Maintenance, Education and Training (CMET) working group.

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.

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.

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.

In support of the Radioactive Waste Management (RWM) safety case for a geological disposal facility (GDF) in the UK, there is a regulatory requirement to consider the likelihood and consequences of nuclear criticality. Waste packages are designed to ensure that criticality is not possible during the transport and operational phases of a GDF and for a significant period post-closure. However, over longer post-closure timescales, conditions in the GDF will evolve.

For waste packages containing spent fuel, it can be shown that, under certain conditions, package flooding could result in a type of criticality event referred to as 'quasi-steady-state' (QSS). Although unlikely, this defines a 'what-if' scenario for understanding the potential consequences of post-closure criticality. This paper provides an overview of a methodology to understand QSS criticality and its application to a spent fuel waste package.

The power of such a hypothetical criticality event is typically estimated to be a few kilowatts: comparable with international studies of similar systems and the decay heat for which waste packages are designed. This work has built confidence in the methodology and supports RWM's demonstration that post-closure criticality is not a significant concern.

The use of underground geological repositories, such as in radioactive waste disposal (RWD) and in carbon capture (widely known as Carbon Capture and Storage; CCS), constitutes a key environmental priority for the 21st century. Based on the identification of key scientific questions relating to the geophysics, geochemistry and geobiology of geodisposal of wastes, this paper describes the possibility of technology transfer from high-technology areas of the space exploration sector, including astrobiology, planetary sciences, astronomy, and also particle and nuclear physics, into geodisposal. Synergies exist between high technology used in the space sector and in the characterization of underground environments such as repositories, because of common objectives with respect to instrument miniaturization, low power requirements, durability under extreme conditions (in temperature and mechanical loads) and operation in remote or otherwise difficult to access environments.

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.

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.

Many countries encourage national forums for transparency, dialogue and participation with regards to radioactive waste disposal. However, the local actors (authorities, non-government organisations and the public) often note a lack of public participation in the decision making process. Civil society is often frustrated with its limited involvement in the consultative process. Participation is regulated by national laws and rules and the right to participate in environmental decision-making is covered by the Aarhus Convention. Continuous dialogue amongst stakeholders is seen as important in building sustainable solutions in radioactive waste management. In addition, understanding public concerns and needs can increase the trust between the partners and build confidence in the process.

Different national and local contexts have contributed to the development of quite a broad set of approaches and tools for stakeholder engagement. This paper describes the use of such tools in the engagement with the Saligny community in the siting process of a repository for low- and intermediate-level wastes in Romania. Some specific issues are highlighted such as: the low level of interest amongst the public in relation to long-term projects; over-estimation of benefits in comparison to the negative aspects of hosting a repository; lack of a coherent public voice; and a perceived lack of information on the project from the authorities and the implementer. The present study describes the setting up of the participatory approach to engage with the public and the different methods employed (including citizen juries, workshops, open days, etc.). A number of criteria were developed for evaluating the effectiveness of these methods particularly with regards to their adaptability to a local context such as Saligny. The paper then focuses on the results of one of these methods – the use of focus groups covering a cross-section of civil society – including members of the general public, a group of professionals and a group of local councillors. The study has resulted in a number of recommendations to the implementer on how to build a new programme for public participation.

It is common practice to estimate a mean diameter for spherical or sub-spherical particles or vesicles in a rock by multiplying the average diameter of the approximately circular cross-sections visible in thin section by a factor of 1.273. This number-weighted average may be dominatedby the hard-to-measure fine tail of the size distribution, and is unlikely to be representative of the average particle diameter of greatest interest for a wide range of geological problems or processes. Average particle size can be quantified in a variety of ways, based on the mass or surfacearea of the particles, and here we provide exact relations of these different average measures to straightforward measurements possible in thin section, including an analysis of how many particles to measure to achieve a desired level of uncertainty. The use of average particle diameter isillustrated firstly with a consideration of the accumulation of olivine phenocrysts on the floor of the 135 m thick picrodolerite/crinanite unit of the Shiant Isles Main Sill. We show that the 45 m thick crystal pile on the sill floor could have formed by crystal settling within about a year.The second geological example is provided by an analysis of the sizes of exsolved Fe-rich droplets during unmixing of a basaltic melt in a suite of experimental charges. We show that the size distribution cannot be explained by sudden nucleation, followed by either Ostwald ripening or Browniancoalescence. We deduce that a continuous process of droplet nucleation during cooling is likely to have occurred.