D.J. Noy

Modelling the interaction of bentonite with hyperalkaline fluids

Many designs for geological disposal facilities for radioactive and toxic wastes envisage the use of cement together with bentonite clay as engineered barriers. However, there are concerns that the mineralogical composition of the bentonite will not be stable under the hyperalkaline pore fluid conditions (pH > 12) typical of cement and its properties will degrade over long time periods. The possible extent of reaction between bentonite and cement pore fluids was simulated using the reaction-transport model, PRECIP. Key minerals in the bentonite (Na-montmorillonite, analcite, chalcedony, quartz, calcite) were allowed to dissolve and precipitate using kinetic (time-dependent) reaction mechanisms. Simulations were carried out with different model variants investigating the effects of: temperature (25 and 70 � C); cement pore fluid composition; dissolution mechanism of montmorillonite; rates of growth of product minerals; solubilities of product minerals; and aqueous speciation of Si at high pH. Simulations were run for a maximum of 3.2ka. The results of all simulations showed complex fronts of mineral dissolution and growth, driven by the relative rates of these processes for different minerals. Calcium silicate hydrate (CSH) minerals formed closest to the cement-bentonite boundary, whereas zeolites and sheet silicates formed further away. Some growth of primary bentonite minerals (analcite, chalcedony, calcite and montmorillonite) was observed under certain conditions. Most alteration was associated with the fluid of highest pH, which showed total removal of primary bentonite minerals up to 60 cm from the contact with cement after � 1 ka. The maximum porosity increase observed was up to 80–90% over a narrow zone 1–2cm wide, close to the cement pore fluid- bentonite contact. All simulations (except that with alternative aqueous speciation data for Si) showed total filling of porosity a few cms beyond this interface with the cement, which occurred after a maximum of 3.2ka. Porosity occlusion was principally a function of the growth of CSH minerals such as tobermorite. There was very little difference in the alteration attained using different model variants, suggesting that bentonite alteration was not sensitive to the changes in parameters under the conditions studied, so that transport of pore fluid through the bentonite governed the amount of alteration predicted. Principal remaining uncertainties associated with the modelling relate to assumptions concerning the evolution of surface areas of minerals with time, and the synergy between changing porosity and fluid flow/diffusion. # 2002 Elsevier Science Ltd. All rights reserved.

The migration of uranium into peat-rich soils at Broubster, Caithness, Scotland, U.K.

Abstract Uranium is being actively transported from uraniferous sedimentary rocks into a peat bog at the Broubster natural analogue site in Caithness, Scotland. Massive calcareous sandstone within the Caithness Flags sequence is the main source of uranium which resides primarily within diagenetic apatite and dispersed USiTi phases. Supergene weathering processes have decalcified the sandstone and are effective in mobilising uranium by groundwater leaching, primarily along a fault zone. Uranium transport in solution by means of groundwater and surface flows is effectively terminated by retardation within 4-kyr-old peat deposits laid down on boulder clay. This process of secondary fixation has resulted in a young uranium anomaly in the peat which comprises in excess of 0.1 wt% U. The site has been investigated comprehensively to define the geometry of the anomaly together with the hydrogeology, hydrochemistry, petrology, mineralogy and the nature of the peat sink-term. The main physical and geochemical properties of the system, including the uranium decay series radionuclide distributions in water and solid samples, are documented in this paper. From these data, the processes governing the distribution of uranium have been quantified using a three-dimensional groundwater flow package and an equilibrium speciation model incorporating a recently developed electrostatic surface complexation model to account for cation-organic interactions. The results described form part of a coordinated project on natural radionuclide migration undertaken to improve confidence in predictive methods used for radiological assessment.

Gas flow in Callovo-Oxfordian claystone (COx): results from laboratory and field-scale measurements

Abstract To understand the fate and impact of gas produced within a repository for radioactive waste, a series of laboratory and field scale experiments have been performed on the Callovo-Oxfordian claystone (COx), the proposed host rock for the French repository. Results show the movement of gas is through a localized network of pathways, whose properties vary temporarily and spatially within the claystone. Significant evidence exists from detailed laboratory studies for the movement of gas along highly unstable pathways, whose aperture and geometry vary as a function of local stress, gas and porewater pressures. The coupling of these parameters results in the development of significant time-dependent effects, impacting on all aspects of COx behaviour, from gas breakthrough time, to the control of deformation processes. Variations in gas entry, breakthrough and steady-state pressures are indicative of microstructural heterogeneity which exerts an important control on the movement of gas. The localization of gas flow is also evident in preliminary results from the large scale gas injection test (PGZ) where gas flow is initially focussed within the excavation damaged zone (EDZ), which acts as a preferential pathway for gas. Numerical models based on conventional two-phase flow theory are unable to adequately describe the detailed observations from laboratory tests.

The role of biofilms in subsurface transport processes

Abstract Landfill and radioactive waste disposal risk assessments focus on contaminant transport and are principally concerned with understanding the movement of gas, water and solutes through engineered barriers and natural groundwater systems. However, microbiological activity can affect transport processes, changing the chemical and physical characteristics of the subsurface environment. Such effects are generally caused by biofilms attached to rock surfaces. Currently most existing transport models have to introduce additional assumptions about the relationships between the microbial growth and changes to the porosity and permeability. These relationships are particularly poorly understood. This paper reviews recent experimental work directed at the development of biofilms and their influence on subsurface flow and the transport of contaminants in intergranular and fracture porosity flow systems. The results are then discussed in terms of a more complex conceptual model.

Experimental simulation of the alkaline disturbed zone around a cementitious radioactive waste repository: numerical modelling and column experiments

Abstract One approach to describe the migration of an alkaline plume from the cementitious engineered barriers of a geological disposal facility for radioactive wastes is to employ coupled chemistry and flow computer models. Although evidence from natural systems is useful to constrain reaction mechanisms and minerals to be incorporated into such models, time-dependent information is generally lacking. A series of laboratory column experiments has been conducted in order to test the capabilities of two of the currently available, coupled models to predict product solids and output fluid compositions with time. The coupled models PRECIP and CHEQMATE were used to provide predictive calculations based upon known experimental parameters and data available from the literature. The predictions did not replicate all the variations in mineralogy observed in the experiments, primarily due to restrictions in the availability of kinetic and thermdynamic data for the range of secondary phases of interest. However, the model predictions did reproduce the general variation of secondary phases with time and distance along the columns.

Microcosm studies of microbial degradation in a coal tar distillate plume

Investigation of a groundwater plume containing up to 24 g l(-1) phenolic compounds suggested that over a period of nearly 50 years, little degradation had occurred despite the presence of a microbial community and electron acceptors within the core of the plume. In order to study the effect of contaminant concentration on degradation behaviour, laboratory microcosm experiments were performed under aerobic and anaerobic conditions at four different concentrations obtained by diluting contaminated with uncontaminated groundwater. The microcosms contained groundwater with total phenols at ca. 200, 250, 660 and 5000 mg l(-1), and aquifer sediment that had been acclimatised within the plume for several months. The microcosms were operated for a period of 390-400 days along with sterile controls to ascertain whether degradation was microbially mediated or abiotic. Under aerobic conditions, degradation only occurred at concentrations up to 660 mg l(-1) total phenols. At phenol concentrations below 250 mg l(-1) a benzoquinone intermediate, thought to originate from the degradation of 2,5-dimethylphenol, was isolated and identified. This suggested an unusual degradative pathway for this compound; its aerobic degradation more commonly proceeding via catecholic intermediates. Under anaerobic conditions, degradation only occurred in the most dilute microcosm (total phenols 195 mg l(-1)) with a loss of p-cresol accompanied by a nonstoichiometric decrease in nitrate and sulphate. By inference, iron(III) from the sediment may also have been used as a terminal electron acceptor, in which case the amount of biologically available iron released was calculated as 1.07 mg Fe(III)/g of sediment. The study shows that natural attenuation is likely to be stimulated by dilution of the plume.

Release of contaminants from a heterogeneously fractured low permeability unit underlying a DNAPL source zone.

The invasion of DNAPL into fractured low permeability deposits results in the formation of secondary source zones that represent a long-term source of VOCs to adjacent aquifers. We present data from a site underlain by a fractured mudstone contaminated with TCE DNAPL that was poised for release following remediation of the overlying aquifer. Observations of contaminant distributions and fracture networks from the site and a nearby mudstone exposure respectively, enabled prediction of the imminent aquifer recontamination. The fractures, likely formed by gypsum dissolution, were characterised by fracture apertures and spacings that ranged from 0.01 to 49 mm and 0.047 to 3.37 m (10th and 90th percentile values) respectively. Numerical model results show that prediction of outward mass flux in the first year was highly variable (8 to 32 g/m²/d for an initial constant concentration with depth profile) and dependent on both the fracture spacing and aperture and the contaminant distribution. However after 1 year, assuming a heterogeneous distribution of fractures, mass flux was predictable within a narrow range of values (at 20 years; 0.04-0.08 g/m²/d). Similar results were obtained from more typical fracture networks with spacings of 0.1 to 0.5 m and apertures of 10 to 100 μm. These results suggest that when considering potential recontamination in a bounding aquifer, fracture characterisation may not be necessary and instead the focus should be on determining the surface area contributing contaminant mass to an aquifer, the contaminant concentration depth profiles, the hydraulic properties of the receiving aquifer and the elapsed time since aquifer remediation.

Microbiological influences on fracture surfaces of intact mudstone and the implications for geological disposal of radioactive waste

Abstract The significance of the potential impacts of microbial activity on the transport properties of host rocks for geological repositories is an area of active research. Most recent work has focused on granitic environments. This paper describes pilot studies investigating changes in transport properties that are produced by microbial activity in sedimentary rock environments in northern Japan. For the first time, these short experiments (39 days maximum) have shown that the denitrifying bacteria, Pseudomonas denitrificans, can survive and thrive when injected into flow-through column experiments containing fractured diatomaceous mudstone and synthetic groundwater under pressurized conditions. Although there were few significant changes in the fluid chemistry, changes in the permeability of the biotic column, which can be explained by the observed biofilm formation, were quantitatively monitored. These same methodologies could also be adapted to obtain information from cores originating from a variety of geological environments including oil reservoirs, aquifers and toxic waste disposal sites to provide an understanding of the impact of microbial activity on the transport of a range of solutes, such as groundwater contaminants and gases (e.g. injected carbon dioxide).

A biogeochemical assessment of the Tono site, Japan

Abstract When designing investigations of microbial populations in the subsurface, it is extremely valuable to undertake scoping calculations to estimate the likely microbial abundances and evaluate the effects of contamination during sampling. A biogeochemical assessment of the groundwater and lithologies of the Tono mine, Japan, has been made using the BGS/NAGRA computer code BGSE (Bacterial Growth in Subsurface Environments). This code enables an assessment to be made of the maximum microbial growth rates that may be achieved in ideal circumstances, based on availability of nutrients and energy calculated from mineralogical and groundwater analyses. The effect of drilling fluid/groundwater mixing on biomass was assessed using a hypothetical drilling fluid composition. The results of modelling the mixing between groundwater and drilling fluid shows that the addition of only small concentrations of drilling fluid (

Influence of biofilms on transport of fluids in subsurface granitic environments – some mineralogical and petrographical observations of materials from column experiments

Abstract Landfill and radioactive waste disposal risk assessments focus on contaminant transport and are principally concerned with understanding the movement of gas, water and solutes through engineered barriers and natural groundwater systems. However, microbiological activity can impact on transport processes changing the chemical and physical characteristics of the subsurface environment. Such effects are generally caused by biofilms attached to rock surfaces. This paper will present some mineralogical and petrographical observations of materials extracted at the completion of an experimental column study which examined the influences of biofilm growth on groundwater flow through crushed diorite from the Äspö Hard Rock Underground Research Laboratory, Sweden.