The effect of competition from other metal ions on the complexation of Ni with isosaccharinic acid, gluconic acid and picolinic acid, at high pH, is described. The competing metal ions used were divalent Co, trivalent Eu and tetravalent Th. In the majority of cases, competition from these metal ions followed the predicted pattern, with most anomalies seeming to be caused by sorption of Ni to the many different solid phases formed in presence of the competing ions. The Ni solid phase was shown to change with time during the course of the study. No major unexplained competition effects were found.

This paper provides a summary of the research programme undertaken in support of the Low Level Waste Repository's 2011 environmental safety case (ESC). The programme has been developed, based on an understanding of safety issues and the requirements of the ESC. The research requirements to underpin the safety case have been identified by means of an auditable process, and subjected to scrutiny by both the regulators and a peer review group. Key research priorities for the future are identified.

Mining is known to be a major source of metal contamination for fluvial systems worldwide. Monitoring and understanding the effects on downstream water and sediment quality is essential for its management and to mitigate against detrimental environmental impacts. This study aimed to examine the effects of the small-scale, abandoned, hydraulic Black Creek gold mine on the geochemical content of fine (<63 μm) stream bed and floodplain sediment in the Horsefly watershed (British Columbia, Canada), which is a part of the Quesnel River basin. Concentrations of As, Cd, Se and Zn were determined by aqua regia digestion and the modified BCR (European Community Bureau of Reference) sequential extraction procedure followed by inductively coupled plasma-optical emission spectroscopy or inductively coupled plasma-mass spectrometry. Age-depth models for the floodplain cores were constructed using excess Pb-210 and Cs-137 activity concentration profiles. The results show that the mine caused local As contamination of the Horsefly River floodplain sediment during the first years of operation, but at present the contamination is mainly contained in the Black Creek. Present-day and recent concentrations of Cd, Se and Zn in the Horsefly River are elevated and this is probably derived from other upstream mining activities. The spatial and temporal changes in heavymetal concentrations suggest a slight, but not particularly widespread, mining effect on the finesediment geochemistry in the Horsefly River system.

A range of potential concepts for the geological disposal of high level wastes and spent fuel are being studied and considered in the UK. These include concepts that use bentonite as a buffer material around the waste containers. The bentonite will be required to fulfil certain safety functions, the most important being (1) to protect the waste containers from detrimental thermal, hydraulic, mechanical and chemical processes; and (2) to retard the release of radionuclides from any waste container that fails. The bentonite should have a low permeability and a high sorption capacity.

These safety functions could be challenged by certain features, events and processes (FEPs) that may occur during the evolution of the disposal system. A consideration of how these FEPs may affect the safety functions can be used to identify and to prioritize the important areas for research on bentonite. We identify these important areas (which include hydration of compacted bentonite, illitization and erosion of bentonite), and describe how they are being investigated in current international research on bentonite.

The Äspö EBS Task Force is a collaborative international project designed to carry out research on bentonite. In 2011, the Nuclear Decommissioning Authority Radioactive Waste Management Directorate joined the EBS Task Force partly to benefit from its collective experience. The work of the EBS Task Force is split into two research subareas: (1) the THM subarea, which includes tasks to understand homogenization of bentonite as it resaturates, to investigate the hydraulic interaction between bentonite and fractured rock, and to model in situ experiments; and (2) the THC subarea, which includes tasks to investigate the issue of understanding transport through bentonite, and to model in situ experiments. In particular, the bentonite rock interaction experiment is a large-scale in situ experiment concerned with understanding groundwater exchange across bentonite rock interfaces, with the objective of establishing better understanding of bentonite wetting. In this paper, we describe our work to model the spatial and temporal resaturation of bentonite buffer in a fractured host rock.

In the Swedish KBS-3 repository concept, there is potential for gas to be generated from corrosion of ferrous materials under anoxic conditions, combined with the radioactive decay of the waste and radiolysis of water. A full understanding of the probable behaviour of this gas phase within the engineered barrier system (EBS) is therefore required for performance assessment. We demonstrate key features from gas transport experiments on pre-compacted Mx80 bentonite, under laboratory and field conditions, and discuss their implications in terms of a conceptual model for gas migration behaviour. On both scales, major gas entry is seen to occur close to the sum of the porewater and swelling pressures of the bentonite. In addition, gas pressure at breakthrough is profoundly sensitive to the number and location of available sinks for gas escape. Observations of breakthrough can be explained by the creation of dilatational pathways, resulting in localized changes in the monitored porewater pressures and total stresses. These pathways are highly unstable, evolving spatially and temporally, and must consequently influence the gas permeability as their distribution/geometry develops.

Such observations are poorly embodied by conventional concepts of two-phase flow, which do not fully represent the key processes involved. Although dilatancy based models provide a better description of these processes, the paucity of data limits further development and validation of these models at present.

A three-year European Commission project entitled performance assessment methodologies in application to guide the development of the safety case (PAMINA) was conducted in the period 2006–2009 and brought together 27 organizations from ten European countries, including the Nuclear Decommissioning Authority and Galson Sciences Ltd from the UK. The PAMINA project had the aim of improving and developing a common understanding of performance assessment (PA) methodologies for disposal concepts for spent fuel and other long-lived radioactive wastes in a range of geological environments.

Work undertaken within PAMINA focussed on four areas: (1) review of PA methodologies in participating organizations; (2) treatment of uncertainty in PA and the safety case; (3) other methodological advancements in PA; and (4) relevance of advanced PA approaches to practical cases.

The state of development of a radioactive waste disposal programme has a strong influence on the type of safety case and supporting PA that is produced. A range of PA methodologies has been developed by different waste management organizations. This paper presents a selection of conclusions from the PAMINA project, in the context of general understanding developed on what would constitute an acceptable safety case for a geological disposal facility, and outlines areas for further development.

The international long-term cement studies (LCS) project aims to increase the understanding of the behaviour of cement within a radioactive waste disposal system and how hyper-alkaline leachates may interact with host rock. Such an understanding enables confident, robust and safety-relevant statements to be made concerning future system behaviour, irrespective of host rock, engineered barrier system, or waste type. The LCS project involves laboratory experiments, in situ tests and numerical modelling to address these issues. The agencies participating are Nagra (Switzerland), JAEA (Japan), the Nuclear Decommissioning Authority, Radioactive Waste Mangement Directorate (UK), Posiva (Finland) and SKB (Sweden).

Project activities have included: the development of conceptual and theoretical models of cement–rock interaction; testing of numerical models against data from laboratory experiments and industrial and natural analogues of cement–rock reaction; and the synthesis and incorporation of performance assessment (PA) relevant data from analogue studies. Key threads running through these studies include an analysis of issues relating to upscaling of processes and data to the greater temporal and spatial scales relevant to PA, and investigations of modelling the changes in physical properties that accompany geochemical reaction. Here we present examples of the results from model test cases, highlighting the important issues that have arisen.

Pore-volume changes in porous media during water–rock interaction can be studied using hydrological tracers. The tracers used here were amino G acid, napthionic acid and fluorescein at pH 3 and 6.5 in contact with basaltic glass, quartz and rhyolite. The experimental setup mimicked that of a hydrological tracer test where a fixed volume of tracer was injected into a flow-through column and the breakthrough curve monitored. The measured breakthrough tracer curves were compared to theoretical 1-D reactive transport simulations calculated using the PHREEQC program. In some cases the tracers were observed to behave ideally, whereas in others they clearly reacted with the solid surfaces. This implies that some common hydrological tracers used in groundwater hydrology may not be suitable under all conditions as they may react with the surrounding rocks in the groundwater system.

Precipitation of amorphous silica (SiO2) in geothermal power plants, although a common factor limiting the efficiency of geothermal energy production, is poorly understood and no universally applicable mitigation strategy to prevent or reduce precipitation is available. This is primarily due to the lack of understanding of the precipitation mechanism of amorphous silica in geothermal systems.

In the present study data are presented about microstructures and compositions of precipitates formed on scaling plates inserted at five different locations in the pipelines at the Hellisheiði power station (SW-Iceland). Precipitates on these plates formed over 6 to 8 weeks of immersion in hot (120 or 60ºC), fast-flowing and silica-supersaturated geothermal fluids (~800 ppm of SiO2). Although the composition of the precipitates is fairly homogeneous, with silica being the dominant component and Fe sulfides as a less common phase, the microstructures of the precipitates are highly variable and dependent on the location within the geothermal pipelines. The silica precipitates have grown through aggregation and precipitation of silica particles that precipitated homogeneously in the geothermal fluid. Five main factors were identified that may control the precipitation of silica: (1) temperature, (2) fluid composition, (3) fluid-flow regime, (4) distance along the flow path, and (5) immersion time.

On all scaling plates, a corrosion layer was found underlying the silica precipitates indicating that, once formed, the presence of a silica layer probably protects the steel pipe surface against further corrosion. Yet silica precipitates influence the flow of the geothermal fluids and therefore can limit the efficiency of geothermal power stations.

Understanding flow along fractures and faults is of importance to the performance assessment (PA) of a geological disposal facility (GDF) for radioactive waste. Flow can occur along pre-existing fractures in the host-rock or along fractures created during the construction of the GDF within the excavation damage zone (EDZ). The complex fracture network will have a range of orientations and will exist within a complex stress regime. Critical stress theory suggests that fractures close to localized shear failure are critically stressed and therefore most conductive to fluid flow. Analysis of fault geometry and stress conditions at Sellafield has revealed that no features were found to be, or even close to being, classified as critically stressed, despite some being conductive. In order to understand the underlying reasons why non-critically stressed fractures were conductive a series of laboratory experiments were performed. A bespoke angled shear rig (ASR) was built in order to study the relationship between fluid flow (water and gas) through a fracture surface as a function of normal load. Fluid flow reduced with an increase in normal load, as expected. During unloading considerable hysteresis was seen in flow and shear stress. Fracture flow was only partially recovered for water injection, whereas gas flow increased remarkably during unloading. The ratio of shear stress to normal stress seems to control the fluid flow properties during the unloading stage of the experiment demonstrating its significance in fracture flow. The exhumation of the Sellafield area during the Palaeogene–Neogene resulted in considerable stress relaxation and in fractures becoming non-critically stressed. The hysteresis in shear stress during uplift has resulted in faults remaining, or becoming, conductive. The field and laboratory observations illustrate that understanding the stress-history of a fractured rock mass is essential, and a mere understanding of the current stress regime is insufficient to estimate the flow characteristics of present-day fractures.

Large volumes of depleted natural and low-enriched uranium exist in the UK waste inventory. This work reports on initial investigations of the leaching performance of candidate glass and cement encapsulation matrices containing UO3 powder as well as that of uranium oxide powders. The surface areas of UO3 powder and the monolith samples of UO3 conditioned in the glass and cement matrices were very different making leaching comparisons difficult. The results showed that for both types of monolith conditioned samples a steady increase of uranium concentration in solution with time was generally not observed. The wt.% of uranium leached from UO3 conditioned in the lead borosilicate glass wasteform was approximately five orders of magnitude less than that leached from UO3 powder. Similarly, the quantities of uranium leached from UO3 conditioned in composite cement made with ordinary Portland cement, and from magnesium phosphate cement, were approximately four and three orders of magnitude, respectively, less than that leached from UO3 powder. The performance of a mixed oxide borosilicate glass wasteform was only slightly better than that of UO3 powder. This work shows that wasteforms based on encapsulation in lead borosilicate glass and cement matrices have the greatest potential for further development.

Atomic force microscopy has been used to determine more precisely the mechanism of the initial stages of dolomite dissolution. Analysis of outflow solutions initially shows fluctuations of both Ca and Mg release with concentrations of Ca >> Mg. The dolomite surface dissolves congruently in the presence of slightly acidified water as confirmed by the regular spreading of characteristic rhombohedral etch pits. Direct in situ observations show that a new phase precipitates on the dissolving surface simultaneously. As the Ca and Mg release decreases with time, the precipitated phase can be seen to spread across the dolomite surface. These observations indicate that the apparent incongruent dissolution of dolomite is a two-step process involving stoichiometric dissolution with the release of Ca, Mg and CO3 ions to solution at the mineral–fluid interface coupled with precipitation of a new Mg-carbonate phase. The coupled element release confirms the interface-coupled dissolutionprecipitation mechanism.

The release and migration of gaseous carbon-14 has been identified as a key issue for geological disposal of intermediate-level radioactive wastes in the UK. A significant fraction of carbon-14 in the UK inventory is in irradiated graphite. This paper describes measurements of gaseous carbon-14 releases from irradiated graphite on immersion in alkaline solution. Apparatus has been developed to discriminate organic and inorganic (14CO/14CO2) species in the gas phase by means of selective oxidation and capture. In the initial experiment, small amounts of gaseous carbon-14 (∼4 Bq) were released from 9 g of crushed graphite within a two-week period. In a long-term experiment, cumulative releases were measured periodically from an intact specimen of graphite over a 14 month period. A small fraction of the graphite carbon-14 inventory was released to the gas phase (∼0.004% as CO/CO2 and ∼0.001% associated with organic compounds). A larger quantity of carbon-14, about 0.1%, was released to the solution phase and was thought to be mainly 14CO2, with some possible organic component. In general, the rate of gaseous carbon-14 release decreased with time. The results suggest a small initial release of relatively labile, accessible carbon-14, with longer term release occurring at a much slower rate. Tritium (T) releases were also measured.

Batch experiments have been used to assess the sorption properties of a potential cementitious repository backfill, NRVB (Nirex reference vault backfill), using Eu3+ as a model trivalent radionuclide and ethylenediaminetetraacetic acid (EDTA) as a competing ligand. The NRVB is an effective scavenger of Eu from solution, with most sorbed within minutes onto the crushed material and less than 1.5% remaining in solution after one day (R d values in the range 0.3–2.4 × 104 l kg−1). Ultrafiltration showed that nearly all of this remaining Eu (>94%) is attached to NRVB derived colloids or particulates that are mainly retained by a 100 kDa ultrafilter. High concentrations of EDTA (>0.01 M) reduced the extent of sorption at apparent equilibrium. The addition of EDTA to a pre-equilibrated system of Eu3+ and NRVB resulted in a temporary suspension of some Eu, but this very quickly returned to the solid phase. There is some irreversibility in these systems, with EDTA able to prevent removal of Eu(III) from solution, but unable to bring it back into solution under the same conditions.

The thermodynamic solubility product for baryte, determined at standard conditions, from data in commonly used compilations, was compared with published experimental solubility products for baryte and with the solubility products from databases used by the PHREEQC geochemical speciation code and MultiScale, which is often used by oil companies to predict or describe baryte scaling. The values in the various databases agree well with experimental data (10–10.05–10–9.96; Melcher, 1910; Neuman, 1933; Templeton, 1960; Davis and Collins, 1971; Blount, 1977; Felmy et al., 1990), which agree within uncertainty with the values presented in the compilations of Robie et al. (1979), Wagman et al. (1982), Lide (2005), Raju and Atkinson (1988), as well as Nordstrom and Munoz (1994), whose values have the least uncertainty. In solutions of 50% seawater mixed with 50% reservoir formation waters, the data predict baryte supersaturation, both at standard temperature and at the temperatures expected in the reservoir, completely consistent with field observations. This provides confidence that the Pitzer approach for activity correction and the database is valid for investigations of baryte precipitation rates in high ionic strength solutions.

The implementation of a geological disposal facility requires the demonstration of confidence that such a facility would be safe during both the operational period and in the long-term after the closure of such a facility. The generic environmental safety case described in this paper is the vehicle used to demonstrate an understanding of environmental safety. It will be used to prepare a site-specific environmental safety case in due course. The approach taken will be consistent with a staged development and approval process, as advocated by the environmental regulators.

The effects of the presence of ten organic ligands and common pH buffering agents – acetate, oxalate, tartrate, citrate, phthalate, EDTA, carbonate, TRIS, phosphate and borate – on aqueous Si concentration measurements made using the common molybdate blue method were quantified. The concentrations of these additives ranged from 0.01 to 0.1 mol/kg in the measured aqueous solutions. Whereas measured Si concentrations were not affected by the presence of up to 0.1 mol/kg acetate, hydrogen phthalate or TRIS, the presence of 0.1 mol/kg of all other selected additives altered substantially the measured Si concentrations using the molybdate blue method. For example the presence of 0.1 mol/kg of citrate, EDTA, and hydrogen phosphate decreased the ratio of measured to true Si concentrations to ~0.05. These variations are interpreted to stem from the formation of competing aqueous complexes in the aqueous phase limiting the formation of the characteristically blue SiMo12O404– complex.

This paper gives an overview of the geosphere research studies being undertaken by the Radioactive Waste Management Directorate (RWMD) of the Nuclear Decommissioning Authority. The approach of the RWMD in the current generic phase of the UK managing radioactive waste safely (MRWS) programme is to maintain an understanding of key processes and to carry out research and development into techniques so capability can be built. Although RWMD can demonstrate a general understanding of geosphere processes at this stage in the UK project, it is recognized that this will need to be made site-specific as the MRWS programme progresses. An understanding of the geosphere at the selected site(s) will be an important part of the future programme. Where possible, the RWMD will participate in international studies so that relevant site-based information can be accessed. In this way, the RWMD will be prepared for site-specific work in stage 5 of the MRWS process.