Consideration of the biosphere is important in the post-closure safety assessment of a geological disposal facility (GDF) as the biosphere acts as the receptor for any contaminants that may be released from the geosphere. Considerable uncertainty exists in the characteristics of the biosphere at times in the far future when any contaminant releases from a GDF would reach the accessible environment. These uncertainties include human behaviour, affecting environmental change as well as exposure modes.

A number of critical scientific issues have been identified through the practical application of the International Atomic Energy Agency reference biosphere approach within both site generic and site specific repository assessment projects. These issues are being addressed through an international collaboration programme, BIOPROTA. The purpose of this paper is to describe the BIOPROTA programme, its objectives and typical working method. The approach is illustrated with examples from the recent work programme including model intercomparison studies for the radionuclides 36Cl and 79Se.

Cellulose degradation products (CDPs) can complex with radioelements causing solubility enhancement and sorption reduction, effects which are detrimental to the containment of radionuclides in the near field of a geological disposal facility and surrounding geosphere. Isosaccharinic acid (ISA) is the principal component of CDPs formed under the alkaline anaerobic conditions of a cement-based near field and appears to be largely responsible for the impact of CDPs on radionuclide solubility and sorption under near-field conditions. However, the situation appears to be more complicated under near-neutral pH geosphere conditions.

A combined experimental and modelling study was undertaken to compare the impact of a CDP leachate to ISA in a simple model ternary sorption system consisting of hematite as a single mineral substrate, thorium as the radioelement and ISA or a CDP leachate as the complexant. Thorium sorbs strongly to hematite. A triple layer model for thorium sorption to hematite was refined to fit to the experimental data in the absence of ISA or CDP leachate; the effect of ISA on thorium sorption was then predicted.

In the presence of CDP leachate, a significant reduction in thorium sorption was observed from pH 6 to 12 in good agreement with model predictions based on a high concentration of ISA. However, only a limited impact of ISA on thorium sorption was observed at pH 6 to 12, in contrast to predictions. The effects of ISA could be accounted for by assuming the formation of a ternary thorium–ISA–surface complex. The model has yet to be extended to the more complex CDP systems. Differences in the thorium speciation in solution due to the formation of a ternary calcium–thorium–ISA complex in the CDP leachate, which is absent from solutions with ISA only, provides the most likely explanation for the differences observed experimentally.

At the post-closure stage of a geological disposal facility for higher activity radioactive waste several species of gas are likely to be generated in the near-field environment. These could alter the sealing and chemical properties of the bentonite buffer and the local geochemical environment significantly. The authors' attempt to simulate multicomponent gas flow through variably saturated porous media is presented. Governing equations have been developed for a reactive gas-flow model to simulate the thermo-hydro-gas-chemical-mechanical behaviour, with specific reference to the performance of highly compacted bentonite buffer subjected to repository gas generation and migration. The developed equations have been included in the bespoke numerical model COMPASS and some generic simulations are also presented. The model presented extends current capability to assess buffer performance.

Fluid flow through a two-dimensional fracture network has been simulated using a discrete fracture model. The computed field-scale permeabilities were then compared to those obtained using an equivalent continuum approach in which the permeability of each grid block is first obtained by performing fine-scale simulations of flow through the fracture network within that region. In the equivalent continuum simulations, different grid-sizes were used, corresponding to N by N grids with N = 10, 40, 100 and 400. The field-scale permeabilities found from the equivalent continuum simulations were generally within 10% of the values found from the discrete fracture simulations. The discrepancies between the two approaches seemed to be randomly related to the grid size, as no convergence was observed as N increased. An interesting finding was that the equivalent continuum approach gave accurate results in cases where the grid block size was clearly smaller than the 'representative elementary volume'.

Understanding the behaviour of gas in a geological disposal facility (GDF) is an essential component of analysing the facility evolution and long-term (post-closure) safety performance. This includes the impacts of gas on the physico-chemical evolution of the GDF, and the release and migration of radionuclides in water and gas.

The Nuclear Decommissioning Authority Radioactive Waste Management Directorate is participating in the EC FORGE (fate of repository gases) project (www.forgeproject.org) and conducting independent research. Key research themes are modelling the impacts of different host rocks on facility evolution including coupled processes, and upscaling the effects of small scale features that can significantly influence the evolution of the whole facility.

Recent code developments have enabled coupled processes to be represented more realistically in models. This has significantly advanced understanding of facility evolution, as discussed in this paper, and will improve future assessment models. There is potential to further improve approaches to upscaling the effects of small scale features on strongly coupled processes, within the context of the EC FORGE project.

In the United Kingdom, disposal of radioactive waste may involve packages of grouted waste being placed in a geological disposal facility (GDF) and surrounded by a cementitious backfill. This paper describes modelling that has been carried out to develop an understanding of the possible spatial and temporal evolution within the GDF.

A single waste package is assumed to be filled with an encapsulation grout, placed in an underground vault and surrounded by a cementitious backfill. Groundwater from the host rock flows into the vault and through the backfill. A simplified model system examines the interactions between groundwater, cementitious backfill and grout.

In most cases the model predicts a reduction in the backfill porosity due to precipitation and dissolution reactions, particularly at the upstream edge of the vault. The degree to which this occurs depends on the groundwater composition. The model also predicts precipitation and dissolution reactions would occur in the grouts close to their interface with the backfill, reducing the local porosity significantly which may isolate the grouts from the backfill, so that the pH within the grouts would be unchanged over an extended period.

This paper gives an overview of the Nuclear Decommissioning Authority, Radioactive Waste Management Directorate approach to representing the biosphere in post-closure safety assessment studies. The assessments consider potential releases of radionuclides and chemically toxic substances from a geological disposal facility that may reach the biosphere by transport in groundwater and gas. It gives an outline of the key processes and understanding underpinning the representation of the biosphere and how the biosphere may evolve over the long timescales of relevance to post-closure safety. The current biosphere assessment approach and associated models are supported by research studies and collaboration that ensure they are consistent with international recommendations. Research studies are also commissioned to reduce uncertainty surrounding key contaminants and potential exposure pathways and to help ensure that the approach and models are adaptable and flexible enough to incorporate future developments, as the geological disposal programme moves towards site selection.

Results are reported here of an investigation into the effects of three carboxylic acid additives (tartaric, maleic and citric acids) on the precipitation of calcium sulfate phases. Precipitation reactions were followed at pH 7 in the pure CaSO4 system and in experiments with 0–20 ppm carboxylic acids added using in situ UV-VIS spectrophotometry (turbidity). The solid products were characterized in terms of their mineralogical composition, using X-ray diffraction, during and at the end of each reaction, and in terms of their morphological features, by scanning electron microscopy. All additives increased the time needed for turbidity to develop (induction time, start of precipitation) and the comparison between additive and additive-free experiments showed that, at equivalent concentrations, citric acid performed far better than the other two carboxylic acids. In all cases bassanite precipitated first and with time it transformed to gypsum. The addition of citrate stabilized bassanite and changed the final gypsum habit from typical needle-like crystals in the pure CaSO4 system to plates in the citrate-additive experiments.

The near field, together with the containment and isolation provided by the geosphere, contributes to the long-term safety provided by a geological disposal facility (GDF) after closure. The different engineered barriers can prevent or limit the release of radionuclides and their migration to the undisturbed host rock or geosphere and are expected to fulfil their post-closure safety functions for many thousands to hundreds of thousands of years. They will continue to contribute to containment after their eventual degradation when there would no longer be confidence that they would continue to fulfil all of their safety functions in their totality. By that time, significant radioactive decay will have occurred, substantially reducing the hazard associated with the wastes. Therefore, demonstration of long-term safety requires an understanding of the evolution of the engineered barriers and the consequences for the generic safety functions that the different barriers provide. This paper provides an overview of the research of the Nuclear Decommissioning Authority Radioactive Waste Management Directorate into the evolution of the near field of a GDF.

Microbial metabolism has the potential to control the biogeochemistry of redox-active radionuclides in a range of geodisposal scenarios. In this study, sediments from a high pH lime workings site were incubated under carefully controlled anaerobic conditions, at a range of alkali pH values with added electron donors and electron acceptors, to explore the limits and rates of bioreduction in a sediment system analogous to intermediate-level nuclear waste. There was a clear succession in the utilization of electron acceptors (in the order nitrate > Fe(III)-citrate > Fe(III) oxyhydroxide > sulfate), in accordance with calculated free energy yields and Eh values over the pH range 10–12. The rate and extent of bioreduction decreased at higher pH, with an upper limit for the processes studied at pH 12. The biochemical limits for such processes are discussed, alongside the potential impact of such forms of microbial metabolism on the solubility of a range of redox active radionuclides that will feature heavily in the safety case for the geological disposal of intermediate-level nuclear waste.

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.

The Nuclear Decommissioning Authority Radioactive Waste Management Directorate have been participating in the current DECOVALEX-2011 project (development of coupled models and their validation against experiments) one task of which has been examining the Mont Terri Ventilation Experiment (VE). This long-term (>9 years), field-scale experiment in the Opalinus Clay near the Swiss–French border, was designed to examine the coupled hydraulic–mechanical–chemical changes caused in the tunnel and in the surrounding geology, by the controlled ventilation of a 1.65 m diameter micro-tunnel.

In contrast to many conventional benchmarking and validation exercises, a key aspect of the VE as examined in DECOVALEX was that some data were held back and participants were required to make predictions of key metrics for the future evolution of the system. This paper presents an overview of the work conducted by the Quintessa and University of Edinburgh team including selected results. The coupled models developed include multiphase flow, elastic deformation and chemical processes in both detailed and upscaled geometries.

The models have been able to replicate the observed desaturation around the tunnel, tunnel deformation and localized failure, vapour migration in the tunnel, and the transition in redox conditions into the host rock.

Intermediate-level radioactive waste is normally encapsulated in cementitious grout. However, for some wastes, grout may not be suitable and polymeric encapsulants are being considered as an alternative. One concern with such encapsulants is their long-term chemical stability and the possibility that release of aggressive degradation products could cause corrosion.

This paper evaluates the potential for three polymeric encapsulants: two epoxy resins (the APS polymer system, (APS) and Alchemix 4760 (ALC)) and a vinyl-ester styrene (VES); to cause internal corrosion of stainless steel waste containers. The corrosion behaviour of stainless steel 316L in contact with each encapsulant was studied in saturated Ca(OH)2 solutions and deionized (DI) water, at 80°C, under non-irradiated and γ-irradiated conditions.

In aerated, alkaline conditions, 316L was resistant to corrosion in all the conditions tested. However, in DI water, the pH fell to values as low as three due to release of acidic species from the polymers. The two epoxy materials (particularly APS) also released significant levels of chloride; VES did not. Chloride release appeared to be increased by γ-irradiation. As a result of the low pH chloride-containing environment created by the APS encapsulant, 316L experienced localized corrosion, whereas coupons in Alchemix 4760 and VES did not. Weight loss measurements correlated with visual observations. γ-irradiation appeared to increase the degree of corrosion.

Few studies have sought to investigate the potential for dissolved organic matter (DOM) to bind (and thus potentially transport) radionuclides under the high pH regimes that are expected in cementitious disposal. We have used equilibrium dialysis to investigate uranyl binding to humic acid over a pH range of ∼10 to 13. The experimental results provide evidence that DOM can bind uranyl ions over this pH range, including in the presence of competing ions. There is a general decrease in binding with increasing pH, from ∼80% of total uranyl bound at pH 9.8 to ∼10% at pH 12.9. Modelling of the system with WHAM/Model VII can yield representative results up to pH ∼10.5.

In the UK, disposal of packaged intermediate-level radioactive waste may involve waste packages being placed in a geological disposal facility (GDF) and surrounded by a cementitious backfill. Cracking of the backfill could occur due to a number of mechanisms, and this could affect the post-closure performance of the GDF.

This work has assessed potential cracking in the backfill during the backfilling and early post-closure period of GDF vaults with an open crown space in a higher strength rock. From the comprehensive range of processes considered, three were identified as potentially causing cracking: (1) during backfilling, plastic settlement under solid horizontal surfaces could result in horizontal gaps beneath waste packages; (2) within days of backfilling, early-age thermal contraction of the backfill could result in primarily vertical cracks; (3) over a number of years, expansion of waste packages could result in large horizontal cracks.

A groundwater flow model incorporating a representation of the cracks was used to calculate flows through a backfilled GDF vault, and through the cracks themselves. Including cracks increased the flow rate significantly. A reactive transport model was used to estimate the evolution of the pore water chemistry as groundwater flows through the cracked backfill. Calcite and brucite were predicted to precipitate, with brucite subsequently dissolving. Calcite build-up could seal some cracks.

The concept of effective stress is one of the basic tenets of rock mechanics where the stress acting on a rock can be viewed as the total stress minus the pore water pressure. In many materials, including clay-rich rocks, this relationship has been seen to be imperfect and a coefficient (χ) is added to account for the mechanical properties of the clay matrix. Recent experimental results during the flow testing (both gas and water) of several rocks (Callovo-Oxfordian claystone, Opalinus Clay, Boom Clay) and geomaterials (bentonite, kaolinite) has given evidence for stable high pressure differentials. The design of the experiments allows multiple measurements of pore pressure, which commonly shows a complex distribution for several different experimental geometries. The observed stable high pressure differentials and heterogeneous pore pressure distribution makes the describing of stress states in terms of effective stress complex. Highly localized pore pressures can be sustained by argillaceous materials and concepts of evenly distributed pore pressures throughout the sample (i.e. conventional effective stress) do not fit many clay-rich rocks if the complexities observed on the micro-scale are not incorporated, especially when considering the case of gas flow.

Intermediate-level wastes (ILW) include substantial quantities of fissile material and controls are required to ensure that its storage, transport and disposal does not present a nuclear criticality hazard. This paper describes the Radioactive Waste Management Directorate's research to develop package fissile material limits (in the form of screening levels) for four different categories of ILW, defined according to uranium or plutonium composition: (1) irradiated natural and slightly enriched uranium (uranium containing up to 1.9 wt.% 235U); (2) low-enriched uranium (uranium containing up to 4 wt.% 235U); (3) high-enriched uranium (uranium containing up to 100 wt.% 235U); and (4) separated plutonium (plutonium containing up to 100 wt.% 239Pu).

The derivation of package screening levels was supported by neutron transport calculations that addressed conditions during waste package transport to a geological disposal facility (GDF), during the GDF operational phase and after GDF closure. The analysis included consideration of combinations of events and processes that could result in fissile material accumulation and concentration after GDF closure, when waste packages have deteriorated sufficiently for fissile material to be mobilized. The results of the calculations have provided input to Radioactive Waste Management Directorate's decision making on setting waste package screening levels.

Ultramafic rocks, such as the Semail Ophiolite in the Sultanate of Oman, are considered to be a potential storage site for CO2. This type of rock is rich in divalent cations that can react with dissolved CO2 and form carbonate minerals, which remain stable over geological periods of time. Dissolution of the ophiolite mobilizes heavy metals, which can threaten the safety of surface and groundwater supplies but secondary phases, such as iron oxides, clays and carbonate minerals, can take up significant quantities of trace elements both in their structure and adsorbed on their surfaces.

Hyperalkaline spring waters issuing from the Semail Ophiolites can have pH as high as 12. This water absorbs CO2 from air, forming carbonate mineral precipitates either as thin crusts on the surface of placid water pools or bottom precipitates in turbulent waters. We investigated the composition of the spring water and the precipitates to determine the extent of trace element uptake. We collected water and travertine samples from two alkaline springs of the Semail Ophiolite. Twenty seven elements were detected in the spring waters. The bulk of the precipitate was CaCO3 in aragonite, as needles, and rhombohedral calcite crystals. Traces of dypingite (Mg5(CO3)4(OH)2·5H2O) and antigorite ((Mg,Fe)3Si2O5(OH)4) were also detected. The bulk precipitate contained rare earth elements and toxic metals, such as As, Ba, Cd, Sr and Pb, which indicated scavenging by the carbonate minerals. Boron and mercury were detected in the spring water but not in the carbonate phases. The results provide confidence that many of the toxic metals released by ophiolite dissolution in an engineered CO2 injection project would be taken up by secondary phases, minimizing risk to water quality.

The formation of crystalline rare earth element (REE) (e.g. La, Ce, Pr, Nd) carbonates from aqueous solutions was examined at ambient temperature using UV-Vis spectrophotometry, combined with X-ray diffraction, high-resolution microscopy and infrared spectroscopy. In all experiments REE-lanthanites (REE2(CO3)3·8H2O) formed via a highly hydrated, nanoparticulate and poorlyordered REE-carbonate precursor. The lifetime of this precursor as well as the kinetics of crystallization of the various REE-lanthanites were dependent on the specific REE3+ ion involved in the reaction. The induction time and the time needed to fully form the crystalline REE-lanthanite end products increase linearly with the ionic potential. The authors show here that the differences in ion size and ionic potential as well as differences in dehydration energy of the REE3+ ions control the lifetime of the poorly ordered precursor and thus also the crystallization kinetics of the REE-lanthanites; furthermore, they also affect the structural characteristics (e.g. unit-cell dimensions and idiomorphism) of the final crystalline lanthanites.

Supersaturation-Nucleation-Time (S-N-T) diagrams are shown to be a useful tool to predict nucleation during reactive-transport processes in porous media. Such diagrams can be determined experimentally or estimated from theoretical calculations based on classical nucleation theory. With this aim, a ‘pragmatic’ understanding of the nucleation rate equation is adopted here and the meaning and magnitude of the interfacial tension and induction time discussed. Theoretical diagrams and experimental data are shown to match fairly well as long as there is an appropriate choice of the ‘relevant’ volume for induction-time calculations.