Recent developments in X-ray optics have allowed the development of a range of commercially available benchtop micro-XRF (μ-XRF) instruments that can produce X-ray spot sizes of 20–30 μm on the sample, allowing major- and trace-element analysis on a range of sample types and sizes with minimal sample preparation. Such instruments offer quantitative analysis using fundamental parameter based 'standardless' quantification algorithms. The accuracy and precision of this quantitative analysis on geological materials, and application of micro-XRF to wider geological problems is assessed using a single benchtop micro-XRF instrument. Quantitative analysis of internal reference materials and international standards shows that such instruments can provide highly reproducible data but that, for many silicate materials, standardless quantification is not accurate.Accuracy can be improved, however, by using a simple type-calibration against a reference material of similar matrix and composition. Qualitative analysis with micro-XRF can simplify and streamline sample characterization and processing for subsequent geochemical and isotopic analysis.

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.

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.

Calcium silicate hydrate (C-S-H) alteration was studied with flow-through experiments at 25°C and pH 9.2. Three materials with apparent Ca/Si ratios (C/S ratios) of 1.47, 1.38 and 0.86 were investigated. Physical (thermogravimetric analyses/differential thermal analysis), mineralogical (X-ray diffraction) and chemical (electron probe microanalysis, transmission electron microscopy/energy dispersive X-ray spectrometry) analyses were performed to characterize the reacting minerals. Initial stoichiometric C/S ratios were 1.22, 1.22 and 0.85, respectively. The excess of Ca is attributed mainly to the presence of calcium hydroxide intimately mixed in with C-S-H particles.

The C-S-H chemical compositions were monitored during flow-through experiments in order to determine the mineral stoichiometry needed for reaction kinetics. Under our experimental conditions the stoichiometric C/S ratios decreased continuously with time. A close to stoichiometric dissolution was observed after 2 days of experiments. Using an integrated approach, the kinetics was found to be a function of the C/S.

A decrease in layer-to-layer distance in the early stage of the alteration process is interpreted as interlayer Ca/Na exchange (Na being part of the pH buffering solution). A second dissolution step, marked by a close to stoichiometric release of Ca and Si, undoubtedly results from layer dissolution. The structural similarity of C-S-H and tobermorite was confirmed.

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.

The extended timescales involved in the decay of radioactive wastes to safe levels mean that geological disposal facilities must continue to function effectively long into the future. It is therefore essential to consider long-term climate evolution in post-closure performance assessments in order to evaluate a geological disposal system's response and robustness to a variety of potential environmental changes, driven by both natural and anthropogenic forcings. In this paper, we illustrate the multiple decay components that characterize the primary driver of climate change – atmospheric CO2 – in response to fossil fuel carbon emissions. We perform a multi-exponential analysis on a series of atmospheric CO2 decay curves predicted by an Earth system model and create an empirical response function that encapsulates the long-term (>1 kyr) removal of excess CO2 from the atmosphere. We present this response function as a simple tool for rapidly projecting the future atmospheric CO2 concentration resulting from any plausible cumulative release of CO2. We discuss the implications of the long 'tail' to this atmospheric CO2 decay curve, both in terms of future climate evolution as well as potential impacts on radioactive waste repositories.

In the deep geological disposal of nuclear waste in crystalline rock, erosion of the bentonite buffer may occur during periods of glaciation. Previous researchers have examined the mechanism and rates of extrusion and erosion for purified montmorillonite samples in smooth planar fractures. In this paper, we investigate the influence of using MX-80 material (as delivered, i.e. including accessory minerals) and a naturally varying aperture on bentonite erosion. A bespoke fracture flow cell was constructed for this purpose and flow through conducted with deionized water. Throughout the experiment, gravimetric analysis was undertaken on the effluent and the swelling pressure of the bentonite monitored. Quantitative image analysis of the extrusion process was also undertaken. When the swelling pressure data were analysed, alongside both the oscillations in erosion rate and the area of the accessory-mineral ring, a two-stage mechanism governing the erosion process became apparent. Once an accessory-mineral ring had formed at the edge of the extruded material, further increases in swelling pressure resulted in a breach in the accessory-mineral ring, triggering an erosive period during which, the mineral ring was supplemented with additional minerals. The cycle repeated until the ring was sufficiently strong that it remained intact. This observed process results in erosion rates one order of magnitude less than those currently used in long-term safetycase calculations.

The design of a novel MEMS (Micro-Electro-Mechanical System) sensor-based monitoring system is presented in this article for the in situ monitoring of the conditions (temperature, relative humidity) of an engineered bentonite barrier for the underground disposal of radioactive waste in a geological disposal facility (GDF). A first prototype of the monitoring system incorporating multiple state-of-the-art MEMS sensors has been developed on a PCB-based (Printed Circuit Board) structure, in order to measure the variation of temperature and relative humidity inside a cylindrical bentonite block during the hydration process. The monitoring system comprises separate sensor boards, the microcontroller-equipped interface board and the software user interface in the Labview environment. One of the main design priorities is to reduce the size of the embedded sensors in order to minimize their influence on the hydro-mechanical response of the bentonite block. The sensor boards are encapsulated in different manners to protect them from moisture, chemical corrosion and mechanical shocks. The sensor system has been tested and calibrated in the temperature range between –20°C and 120°C, and at different relative humidity levels implemented by saturated salt solutions in enclosed containers. Test results demonstrate that the sensors have shown good functionality and robustness in harsh test environments such as high temperature and high humidity. Both temperature and relative humidity sensors have shown satisfactory precision level and temporal stability, which are in good accordance with the design specification of these devices.

We have applied mechanical exfoliation for the preparation of ultra-thin samples of the phyllosilicate mineral biotite. We demonstrate that the 'scotch tape' approach, which was made famous as an early method for production of single-atom-thick graphene, can be used for production of sheet-silicate specimens that are sufficiently thin to allow high-resolution transmission electron microscope (HRTEM) imaging to be achieved successfully while also being free from the specimen preparation artefacts that are often caused by ion-beam milling techniques. Exfoliation of the biotite parallel to the (001) planes has produced layers as thin as two structural TOT units thick (∼2 nm). The minimal specimen thickness enabled not only HRTEM imaging but also the application of subsequent exit wavefunction restoration to reveal the pristine biotite lattice. Exit wavefunction restoration recovers the full complex electron wave from a focal series of HRTEM images, removing the effects of coherent lens aberrations. This combination of methods therefore produces images in which the observed features are readily interpreted to obtain atomic resolution structural information.

The existing capability and current development needs for implementing electroforming as a viable manufacturing process to produce copper cylinders with dimensions comparable to the Swedish KBS-3 design are discussed. Large freestanding copper cylinders can be produced readily, but there is a need to address challenges associated with controlling the electro-deposition process to conform to compositional and mechanical requirements of the copper layers produced. The methodology to optimize the manufacturing process, based on a study of key parameters, such as the effects of electrolyte additives on grain size and the chemical composition of electroformed layers, is described here. Possible ways to introduce a robust manufacturing route are also presented.

Carbon-14 is a key radionuclide in the assessment of the safety of a geological disposal facility because of the calculated assessment of the radiological consequences of gaseous carbon-14-bearing species. Radioactive Waste Management Limited has established an Integrated Project Team (IPT) in which partners are working together to develop an holistic approach to carbon-14 management in the disposal system. We have used an 'AND' approach to structure and prioritize our technical work. For a waste stream to be of concern, there has to be a significant inventory, AND carbon-14-bearing gas has to be generated, AND this gas has to be entrained by bulk gas, AND it has to migrate through the engineered barriers, AND it has to migrate through the overlying geological environment (either as gas or in solution), AND there have to be consequences in the biosphere. We are also using this approach to consider alternative treatment, packaging and design options.

Geological disposal (GD) of radioactive waste is close to becoming a reality for Finland, Sweden and France. High-technology development and advanced knowledge has made it possible to defend the feasibility and the safety of such facilities, making the European Union a leader in the field. Other European countries are closely behind, developing high competence through advanced research programmes, research infrastructures and public engagement.

At the other extreme, there are countries whose GD programmes are at an early stage and no systematic research programmes exist. These include several new Member States but not the Czech Republic and Hungary, both of which have already initiated a siting process.

There are several common reasons for this delay in schedule: small and relatively younger nuclear energy programmes, return of the spent fuel (especially from research reactors) to the countries of origin, open fuel cycle concept (requiring at least 50 years of wet and dry storage). In this context, there has been little pressure on setting up an early GD programme. Currently their disposal concepts are only generic and in most of these countries need updating, taking into account the current socio-economic context.

However, some of these new Member States still aim to have a GD in operation within several decades, e.g. 2055 in Romania and 2067 in Slovenia. Strategic planning based on the experience of more advanced programmes shows the GD process should start immediately in order to be able to achieve these deadlines.

In this context, the implementation of the EC Directive 70/2011 gives the opportunity to progress the advancement of the GD process in these countries.

Heat-generating waste provides a number of additional technical challenges over and above those associated with the disposal of ILW. A priority area of work for Radioactive Waste Management (RWM) concerns the effect of heat on the engineered barrier system, and how this may be mitigated through the management of heat (thermal dimensioning) in a UK Geological Disposal Facility (GDF). The objective of thermal dimensioning is to provide a strategy to enable acceptable waste package loading and spatial configurations of the packages to be determined in order to enable high-heat generating waste to be successfully disposed in a GDF. An early focus of the work has been to develop a thermal modelling tool to support analyses of different combinations of package assumptions and other GDF factors, such as spacing of those packages, to assess the compliance with thermal limits. The approach has a capability to investigate quickly and efficiently the implications of a wide range of disposal concepts for the storage of spent fuel/HLW and the dimensions of a GDF. This study describes the approach taken to undertaking this work, which has included a robust appraisal of the key data (and the associated uncertainty); recent thermal dimensioning analysis has been performed to identify constraints on those disposal concepts.

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.