Identifiability of diffusion and sorption parameters from in situ diffusion experiments by using simultaneously tracer dilution and claystone data

In situ diffusion experiments are performed in geological formations at underground research laboratories to overcome the limitations of laboratory diffusion experiments and investigate scale effects. Tracer concentrations are monitored at the injection interval during the experiment (dilution data) and measured from host rock samples around the injection interval at the end of the experiment (overcoring data). Diffusion and sorption parameters are derived from the inverse numerical modeling of the measured tracer data. The identifiability and the uncertainties of tritium and Na-22(+) diffusion and sorption parameters are studied here by synthetic experiments having the same characteristics as the in situ diffusion and retention (DR) experiment performed on Opalinus Clay. Contrary to previous identifiability analyses of in situ diffusion experiments, which used either dilution or overcoring data at approximate locations, our analysis of the parameter identifiability relies simultaneously on dilution and overcoring data, accounts for the actual position of the overcoring samples in the claystone, uses realistic values of the standard deviation of the measurement errors, relies on model identification criteria to select the most appropriate hypothesis about the existence of a borehole disturbed zone and addresses the effect of errors in the location of the sampling profiles. The simultaneous use of dilution and overcoring data provides accurate parameter estimates in the presence of measurement errors, allows the identification of the right hypothesis about the borehole disturbed zone and diminishes other model uncertainties such as those caused by errors in the volume of the circulation system and the effective diffusion coefficient of the filter. The proper interpretation of the experiment requires the right hypothesis about the borehole disturbed zone. A wrong assumption leads to large estimation errors. The use of model identification criteria helps in the selection of the best model. Small errors in the depth of the overcoring samples lead to large parameter estimation errors. Therefore, attention should be paid to minimize the errors in positioning the depth of the samples. The results of the identifiability analysis do not depend on the particular realization of random numbers. (C) 2012 Elsevier B.V. All rights reserved.

Diffusion-driven transport in clayrock formations

Clay mineral-rich sedimentary formations are currently under investigation to evaluate their potential use as host formations for installation of deep underground disposal facilities for radioactive waste (e.g. Boom Clay (BE), Opalinus Clay (CH), Callovo-Oxfordian argillite (FR)). The ultimate safety of the corresponding repository concepts depends largely on the capacity of the host formation to limit the flux towards the biosphere of radionuclides (RN) contained in the waste to acceptably low levels. Data for diffusion-driven transfer in these formations shows extreme differences in the measured or modelled behaviour for various radionuclides, e. g. between halogen RN (Cl-36, I-129) and actinides (U-238,U-235, Np-237, Th-232, etc.), which result from major differences between RN of the effects on transport of two phenomena: diffusion and sorption. This paper describes recent research aimed at improving understanding of these two phenomena, focusing on the results of studies carried out during the EC Funmig IP on clayrocks from the above three formations and from the Boda formation (HU). Project results regarding phenomena governing water, cation and anion distribution and mobility in the pore volumes influenced by the negatively-charged surfaces of clay minerals show a convergence of the modelling results for behaviour at the molecular scale and descriptions based on electrical double layer models. Transport models exist which couple ion distribution relative to the clay-solution interface and differentiated diffusive characteristics. These codes are able to reproduce the main trends in behaviour observed experimentally, e.g. D-e(anion) < D-e(HTO) < D-e(cation) and D-e(anion) variations as a function of ionic strength and material density. These trends are also well-explained by models of transport through ideal porous matrices made up of a charged surface material. Experimental validation of these models is good as regards monovalent alkaline cations, in progress for divalent electrostatically-interacting cations (e.g. Sr2+) and still relatively poor for 'strongly sorbing', high K-d cations. Funmig results have clarified understanding of how clayrock mineral composition, and the corresponding organisation of mineral grain assemblages and their associated porosity, can affect mobile solute (anions, HTO) diffusion at different scales (mm to geological formation). In particular, advances made in the capacity to map clayrock mineral grain-porosity organisation at high resolution provide additional elements for understanding diffusion anisotropy and for relating diffusion characteristics measured at different scales. On the other hand, the results of studies focusing on evaluating the potential effects of heterogeneity on mobile species diffusion at the formation scale tend to show that there is a minimal effect when compared to a homogeneous property model. Finally, the results of a natural tracer-based study carried out on the Opalinus Clay formation increase confidence in the use of diffusion parameters measured on laboratory scale samples for predicting diffusion over geological time-space scales. Much effort was placed on improving understanding of coupled sorption-diffusion phenomena for sorbing cations in clayrocks. Results regarding sorption equilibrium in dispersed and compacted materials for weakly to moderately sorbing cations (Sr2+, Cs+, Co2+) tend to show that the same sorption model probably holds in both systems. It was not possible to demonstrate this for highly sorbing elements such as Eu(III) because of the extremely long times needed to reach equilibrium conditions, but there does not seem to be any clear reason why such elements should not have similar behaviour. Diffusion experiments carried out with Sr2+, Cs+ and Eu(III) on all of the clayrocks gave mixed results and tend to show that coupled diffusion-sorption migration is much more complex than expected, leading generally to greater mobility than that predicted by coupling a batch-determined K-d and Ficks law based on the diffusion behaviour of HTO. If the K-d measured on equivalent dispersed systems holds as was shown to be the case for Sr, Cs (and probably Co) for Opalinus Clay, these results indicate that these cations have a D-e value higher than HTO (up to a factor of 10 for Cs+). Results are as yet very limited for very moderate to strongly sorbing species (e.g. Co(II), Eu(III), Cu(II)) because of their very slow transfer characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

Anisotropic diffusion at the field scale in a 4-year multi-tracer diffusion and retention experiment – I: Insights from the experimental data

Abstract Claystones are considered worldwide as barrier materials for nuclear waste repositories. In the Mont Terri underground research laboratory (URL), a nearly 4-year diffusion and retention (DR) experiment has been performed in Opalinus Clay. It aimed at (1) obtaining data at larger space and time scales than in laboratory experiments and (2) under relevant in situ conditions with respect to pore water chemistry and mechanical stress, (3) quantifying the anisotropy of in situ diffusion, and (4) exploring possible effects of a borehole-disturbed zone. The experiment included two tracer injection intervals in a borehole perpendicular to bedding, through which traced artificial pore water (APW) was circulated, and a pressure monitoring interval. The APW was spiked with neutral tracers (HTO, HDO, H2O-18), anions (Br, I, SeO4), and cations (Na-22, Ba-133, Sr-85, Cs-137, Co-60, Eu-152, stable Cs, and stable Eu). Most tracers were added at the beginning, some were added at a later stage. The hydraulic pressure in the injection intervals was adjusted according to the measured value in the pressure monitoring interval to ensure transport by diffusion only. Concentration time-series in the APW within the borehole intervals were obtained, as well as 2D concentration distributions in the rock at the end of the experiment after overcoring and subsampling which resulted in �250 samples and �1300 analyses. As expected, HTO diffused the furthest into the rock, followed by the anions (Br, I, SeO4) and by the cationic sorbing tracers (Na-22, Ba-133, Cs, Cs-137, Co-60, Eu-152). The diffusion of SeO4 was slower than that of Br or I, approximately proportional to the ratio of their diffusion coefficients in water. Ba-133 diffused only into �0.1 m during the �4 a. Stable Cs, added at a higher concentration than Cs-137, diffused further into the rock than Cs-137, consistent with a non-linear sorption behavior. The rock properties (e.g., water contents) were rather homogeneous at the centimeter scale, with no evidence of a borehole-disturbed zone. In situ anisotropy ratios for diffusion, derived for the first time directly from field data, are larger for HTO and Na-22 (�5) than for anions (�3�4 for Br and I). The lower ionic strength of the pore water at this location (�0.22 M) as compared to locations of earlier experiments in the Mont Terri URL (�0.39 M) had no notable effect on the anion accessible pore fraction for Cl, Br, and I: the value of 0.55 is within the range of earlier data. Detailed transport simulations involving different codes will be presented in a companion paper.

Long-term diffusion experiment at Mont Terri: first results from field and laboratory data

The diffusion of radionuclides is an important safety aspect for nuclear waste disposal in argillaceous host rocks. A long-term diffusion experiment, termed DI-A, is being carried out at the Mont Terri Rock Laboratory in the Opalinus Clay formation. The aim of this experiment is the understanding of the migration and sorption behaviour of cationic and anionic species in consolidated clays. This study reports on the experimental layout and the first results obtained from the DI-A experiment, which include the investigation of HTO, Na-22(+), Cs+, and I- migration during a period of 1 year by analysing these tracers in the water circulating in the borehole. In addition, results obtained from through-diffusion experiments on small-sized samples with HTO, I-, and Cl-36(-) are presented. The decrease of tracer concentrations in the borehole is fastest for Cs+, followed by Na-22(+), HTO, and finally I-. The chemical composition of the artificial pore water in the borehole shows very little variation with time, thus indicating almost no chemical disturbance around the borehole. Through-diffusion experiments in the laboratory that were performed parallel to the bedding plane with two different methods yielded effective diffusion coefficients for HTO of 4-5 X 10(-11) m(2) s(-1) and significantly lower ones for anions Cl- and I- (0.7-1.6 X 10(-11) m(2) s(-1)). The results indicate the importance of anion exclusion effects arising from the negatively charged clay surfaces. Furthermore, they demonstrate the anisotropic diffusion properties of the clay formation with significantly increased diffusion rates parallel to bedding relative to the perpendicular direction. The tracer data of the in situ experiment were successfully described with 2D diffusion models using diffusion and sorption parameters obtained from the above mentioned and other laboratory studies. The modelling results indicate that HTO and I- diffused with no retardation. The retardation of Na+ and Cs+ could be described by empirical sorption expressions from previously derived batch sorption (Cs+) or diffusion (Na+) experiments. Overall, the obtained results demonstrate the feasibility of the technical concept to study the diffusion of nonsorbing and sorbing tracers in consolidated clays. (C) 2004 Elsevier B.V. All rights reserved.

Biogeochemical processes in a clay formation in situ experiment: Part F - Reactive transport modelling

Reactive transport modelling was used to simulate solute transport, thermodynamic reactions, ion exchange and biodegradation in the Porewater Chemistry (PC) experiment at the Mont Terri Rock Laboratory. Simulations show that the most important chemical processes controlling the fluid composition within the borehole and the surrounding formation during the experiment are ion exchange, biodegradation and dissolution/precipitation reactions involving pyrite and carbonate minerals. In contrast, thermodynamic mineral dissolution/precipitation reactions involving alumo-silicate minerals have little impact on the fluid composition on the time-scale of the experiment. With the accurate description of the initial chemical condition in the formation in combination with kinetic formulations describing the different stages of bacterial activities, it has been possible to reproduce the evolution of important system parameters, such as the pH, redox potential, total organic C. dissolved inorganic C and SO(4) concentration. Leaching of glycerol from the pH-electrode may be the primary source of organic material that initiated bacterial growth, which caused the chemical perturbation in the borehole. Results from these simulations are consistent with data from the over-coring and demonstrate that the Opalinus Clay has a high buffering capacity in terms of chemical perturbations caused by bacterial activity. This buffering capacity can be attributed to the carbonate system as well as to the reactivity of clay surfaces.

Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen

The Effingen Member is a low-permeability rock unit of Oxfordian age (ca. 160 Ma) that occurs across northern Switzerland. It comprises sandy calcareous marls and (argillaceous) limestones. This report describes the hydrogeochemistry, mineralogy and supporting physical properties of the Effingen Member in three boreholes in the Jura-Südfuss area: Oftringen, Gösgen and Küttigen, where it is 220–240 m thick. The top of the Effingen Member is at 420, 66 and 32 m depths at the three sites. Core materials are available from Oftringen and Gösgen, whereas information from Küttigen is limited to cuttings, in-situ hydrogeological testing and geophysical logging. Hydrogeological boundaries of the Effingen Member vary between locations. Ground-water flows were identified during drilling at the top (Geissberg Member), but not at the base, of the Effingen Member at Oftringen, at the base (Hauptrogenstein Formation) of the Effingen Member at Gösgen, and in a limestone layer (Gerstenhübel unit) within the Effingen Member at Küttigen. The marls and limestones of the Effingen Member have carbonate contents of 46–91 wt.-% and clay-mineral contents of 5–37 wt.-%. Pyrite contents are up to 1.6 wt.-%, but no sulphate minerals were detected by routine analyses. Clay minerals are predominantly mixed-layer illite-smectite, illite and kaolinite, with sporadic traces of chlorite and smectite. Veins filled with calcite ± celestite occur through the Effingen Member at Oftringen but not at Gösgen or Küttigen. They formed at 50–70 ºC from externally derived fluids, probably of Miocene age. Water contents are 0.7–4.2 wt.-%, corresponding to a water-loss porosity range of 1.9–10.8 vol.-%. Specific surface areas, measured by the BET method, are 2–30 m2/g, correlating with clay-mineral contents. Water activity has been measured and yielded surprisingly low values down to 0.8. These cannot be explained by pore-water salinity alone and include other effects, such as changes in the fabric due to stress release or partial saturation. Observed variations in measurements are not fully understood. Cation exchange capacity (CEC) and exchangeable cation populations have been studied by the Ni-en method. CEC, derived from the consumption of the index cation Ni, is 9–99 meq/kgrock at a solid:liquid ratio of 1, correlating with the clay-mineral content. Cation concentrations in Ni-en extract solutions are in the order Na+≥Ca2+>Mg2+>K+>Sr2+. However, the analytical results from the Ni-en extractions have additional contributions from cations originating from pore water and from mineral dissolution reactions that occurred during extraction, and it was not possible to reliably quantify these contributions. Therefore, in-situ cation populations and selectivity coefficients could not be derived. A suite of methods have been used for characterising the chemical compositions of pore waters in the Effingen Member. Advective displacement was used on one sample from each Oftringen and Gösgen and is the only method that produces results that approach complete hydrochemical compositions. Aqueous extraction was used on core samples from these two boreholes and gives data only for Cl- and, in some cases, Br-. Out-diffusion was used on core samples from Oftringen and similarly gives data for Cl- and Br- only. For both aqueous extraction and out-diffusion, reaction of the experimental water with rock affected concentrations of cations, SO42 and alkalinity in experimental solutions. Another method, centrifugation, failed to extract pore water. Stable isotope ratios (δ18O and δ2H) of pore waters in core samples from Oftringen were analysed by the diffusive exchange method and helium contents of pore water in Oftringen samples were extracted for mass spectrometric analysis by quantitative outgassing of preserved core samples. Several lines of evidence indicate that drillcore samples might not have been fully saturated when opened and subsampled in the laboratory. These include comparisons of water-loss porosities with physical porosities, water-activity measurements, and high contents of dissolved gas as inferred from ground-water samples. There is no clear proof of partial saturation and it is unclear whether this might represent in-situ conditions or is due to exsolution of gas due to the pressure release since drilling. Partial saturation would have no impact on the recalculation of pore-water compositions from aqueous extraction experiments using water-loss porosity data. The largest uncertainty in the pore-water Cl- concentrations recalculated from aqueous extraction and out-diffusion experiments is the magnitude of the anion-accessible fraction of water-loss porosity. General experience of clay-mineral rich formations suggests that the anion-accessible porosity fraction is very often about 0.5 and generally in a range of 0.3 to 0.6 and tends to be inversely correlated with clay-mineral contents. Comparisons of the Cl- concentration in pore water obtained by advective displacement with that recalculated from aqueous extraction of an adjacent core sample suggests a fraction of 0.27 for an Oftringen sample, whereas the same procedure for a Gösgen sample suggests a value of 0.64. The former value for anion-accessible porosity fraction is presumed to be unrepresentative given the local mineralogical heterogeneity at that depth. Through-diffusion experiments with HTO and 36Cl- suggest that the anion-accessible porosity fraction in the Effingen Member at Oftringen and Gösgen is around 0.5. This value is proposed as a typical average for rocks of the Effingen Member, bearing in mind that it varies on a local scale in response to the heterogeneity of lithology and pore-space architecture. The substantial uncertainties associated with the approaches to estimating anion-accessible porosity propagate into the calculated values of in-situ pore-water Cl- concentrations. On the basis of aqueous extraction experiments, and using an anion-accessible porosity fraction of 0.5, Cl- concentrations in the Effingen Member at Oftringen reach a maximum of about 14 g/L in the centre. Cl- decreases upwards and downwards from that, forming a curved depth profile. Cl- contents in the Effingen Member at Gösgen increase with depth from about 3.5 g/L to about 14 g/L at the base of the cored profile (which corresponds to the centre of the formation). Out-diffusion experiments were carried out on four samples from Oftringen, distributed through the Effingen Member. Recalculated Cl- concentrations are similar to those from aqueous extraction for 3 out of the 4 samples, and somewhat lower for one sample. Concentrations of other components, i.e. Na+, K+, Ca2+, Mg2+, Sr2+, SO42- and HCO3- cannot be obtained from the aqueous extraction and out-diffusion experimental data because of mineral dissolution and cation exchange reactions during the experiments. Pore-water pH also is not constrained by those extraction experiments. The only experimental approach to obtain complete pore-water compositions for samples from Oftringen and Gösgen is advective displacement of pore water. The sample from Oftringen used for this experiment is from 445 m depth in the upper part of the Effingen Member and gave eluate with 16.5 g/L Cl- whereas aqueous extraction from a nearby sample indicated about 9 g/L Cl-. The sample from Gösgen used for advective displacement is from 123 m depth in the centre of the Effingen Member sequence and gave eluate with about 9 g/L Cl- whereas aqueous extraction gave 11.5 g/L Cl-. In both cases the pore waters have Na-(Ca)-Cl compositions and SO42- concentrations of about 1.1 g/L. The Gösgen sample has a Br/Cl ratio similar to that of sea water, whereas this ratio is lower for the Oftringen sample. Taking account of uncertainties in the applied experimental approaches, it is reasonable to place an upper limit of ca. 20 g/L on Cl- concentration for pore water in the Effingen Member in this area. There are major discrepancies between pore-water SO42- concentrations inferred from aqueous extraction or out-diffusion experiments and those obtained from advective displacement in both the Oftringen and Gösgen cases. A general conclusion is that all or at least part of the discrepancies are attributable to perturbation of the sulphur system and enhancement of SO42- by sulphate mineral dissolution and possibly minor pyrite oxidation during aqueous extraction and out-diffusion. Therefore, data for SO42- calculated from those pore-water sampling methods are considered not to be representative of in-situ conditions. A reference pore-water composition was defined for the Effingen Member in the Jura Südfuss area. It represents the probable upper limits of Cl- contents and corresponding anion and cation concentrations that are reasonably constrained by experimental data. Except for Cl- and possibly Na+ concentrations, this composition is poorly constrained especially with respect to SO42- and Ca2+ concentrations, and pH and alkalinity. Stable isotope compositions, δ18O and δ2H, of pore waters in the Effingen Member at Oftringen plot to the right of the meteoric water line, suggesting that 18O has been enriched by water-rock exchange, which indicates that the pore waters have a long residence time. A long residence time of pore water is supported by the level of dissolved 4He that has accumulated in pore water of the Effingen Member at Oftringen. This is comparable with, or slightly higher than, the amounts of 4He in the Opalinus Clay at Benken. Ground waters were sampled from flowing zones intersected by boreholes at the three locations. The general interpretation is that pore waters and ground-water solutes may have similar origins in Mesozoic and Cenozoic brackish-marine formations waters, but ground-water solutes have been diluted rather more than pore waters by ingress of Tertiary and Quaternary meteoric waters. The available hydrochemical data for pore waters from the Effingen Member at these three locations in the Jura-Südfuss area suggest that the geochemical system evolved slowly over geological periods of time, in which diffusion was an important mechanism of solute transport. The irregularity of Cl- and δ18O profiles and spatial variability of advective ground-water flows in the Malm-Dogger system suggests that palaeohydrogeological and hydrochemical responses to changing tectonic and surface environmental conditions were complex.

Constraining porewater chemistry in a 250m thick argillaceous rock sequence

The geochemistry of an argillaceous rock sequence from a deep borehole in NE-Switzerland was investigated. The focus was to constrain the porewater chemistry in low permeability Jurassic rocks comprising the Liassic, the Opalinus Clay formation, the 'Brown Dogger' unit and the Effingen Member (Malm). A multi-method approach including mineralogical analysis, aqueous and Ni-ethylenediamine extraction, squeezing tests and pCO(2) measurements as well as geochemical modelling was applied for this purpose. A consistent dataset was obtained with regard to the main solutes in the porewaters. A fairly constant anion-accessible porosity of similar to 50% of the total porosity was deduced for all analysed samples which displayed variable clay-mineral contents. Sulphate concentrations were shown to be constrained by a sulphate-bearing phase, presumably by celestite or a Sr-Ba sulphate. Application of a simple equilibrium model, including cation exchange reactions, calcite and celestite equilibrium showed good agreement with squeezing data, indicating the suitability of the modelling approach to simulate porewater chemistry in the studied argillaceous rocks. The modelling highlighted the importance of correct determination of the exchangeable cation population. The analysis corroborates that squeezing of the studied rocks is a viable and efficient way to sample porewater.

Translational diffusion of water in compacted clay systems

The translational diffusion of water in compacted clays at a high hydration level has been investigated by quasielastic neutron scattering at a time-of-flight spectrometer FOCUS (SINQ). Four compacted clays with systematic structural differences have been studied: Na-montmorillonite, Na-illite, kaolinite and pyrophyllite. The QENS experiments were performed using two different incident wavelengths in order to access a larger Q range and verify the data analysis. The translational diffusion coefficient for water in Na-montmorillonite and Na-illite are lower than those for bulk water, whereas the preliminary results for kaolinite and pyrophyllite show larger diffusion coefficient.

Resolving diffusion in clay minerals at different time scales: Combination of experimental and modeling approaches

Since no single experimental or modeling technique provides data that allow a description of transport processes in clays and clay minerals at all relevant scales, several complementary approaches have to be combined to understand and explain the interplay between transport relevant phenomena. In this paper molecular dynamics simulations (MD) were used to investigate the mobility of water in the interlayer of montmorillonite (Mt), and to estimate the influence of mineral surfaces and interlayer ions on the water diffusion. Random Walk (RW) simulations based on a simplified representation of pore space in Mt were used to estimate and understand the effect of the arrangement of Mt particles on the meso- to macroscopic diffusivity of water. These theoretical calculations were complemented with quasielastic neutron scattering (QENS) measurements of aqueous diffusion in Mt with two pseudo-layers of water performed at four significantly different energy resolutions (i.e. observation times). The size of the interlayer and the size of Mt particles are two characteristic dimensions which determine the time dependent behavior of water diffusion in Mt. MD simulations show that at very short time scales water dynamics has the characteristic features of an oscillatory motion in the cage formed by neighbors in the first coordination shell. At longer time scales, the interaction of water with the surface determines the water dynamics, and the effect of confinement on the overall water mobility within the interlayer becomes evident. At time scales corresponding to an average water displacement equivalent to the average size of Mt particles, the effects of tortuosity are observed in the meso- to macroscopic pore scale simulations. Consistent with the picture obtained in the simulations, the QENS data can be described using a (local) 3D diffusion at short observation times, whereas at sufficiently long observation times a 2D diffusive motion is clearly observed. The effects of tortuosity measured in macroscopic tracer diffusion experiments are in qualitative agreement with RW simulations. By using experimental data to calibrate molecular and mesoscopic theoretical models, a consistent description of water mobility in clay minerals from the molecular to the macroscopic scale can be achieved. In turn, simulations help in choosing optimal conditions for the experimental measurements and the data interpretation. (C) 2014 Elsevier B.V. All rights reserved.

Solute transport in crystalline rocks at Äspö — II: Blind predictions, inverse modelling and lessons learnt from test STT1

Based on the results from detailed structural and petrological characterisation and on up-scaled laboratory values for sorption and diffusion, blind predictions were made for the STT1 dipole tracer test performed in the Swedish A¨ spo¨ Hard Rock Laboratory. The tracers used were nonsorbing, such as uranine and tritiated water, weakly sorbing 22Na+, 85Sr2 +, 47Ca2 +and more strongly sorbing 86Rb+, 133Ba2 +, 137Cs+. Our model consists of two parts: (1) a flow part based on a 2D-streamtube formalism accounting for the natural background flow field and with an underlying homogeneous and isotropic transmissivity field and (2) a transport part in terms of the dual porosity medium approach which is linked to the flow part by the flow porosity. The calibration of the model was done using the data from one single uranine breakthrough (PDT3). The study clearly showed that matrix diffusion into a highly porous material, fault gouge, had to be included in our model evidenced by the characteristic shape of the breakthrough curve and in line with geological observations. After the disclosure of the measurements, it turned out that, in spite of the simplicity of our model, the prediction for the nonsorbing and weakly sorbing tracers was fairly good. The blind prediction for the more strongly sorbing tracers was in general less accurate. The reason for the good predictions is deemed to be the result of the choice of a model structure strongly based on geological observation. The breakthrough curves were inversely modelled to determine in situ values for the transport parameters and to draw consequences on the model structure applied. For good fits, only one additional fracture family in contact with cataclasite had to be taken into account, but no new transport mechanisms had to be invoked. The in situ values for the effective diffusion coefficient for fault gouge are a factor of 2–15 larger than the laboratory data. For cataclasite, both data sets have values comparable to laboratory data. The extracted Kd values for the weakly sorbing tracers are larger than Swedish laboratory data by a factor of 25–60, but agree within a factor of 3–5 for the more strongly sorbing nuclides. The reason for the inconsistency concerning Kds is the use of fresh granite in the laboratory studies, whereas tracers in the field experiments interact only with fracture fault gouge and to a lesser extent with cataclasite both being mineralogically very different (e.g. clay-bearing) from the intact wall rock.

Quantification of water content across a cement-clay interface using high resolution neutron radiography

In many designs for radioactive waste repositories, cement and clay will come into direct contact. The geochemical contrast between cement and clay will lead to mass fluxes across the interface, which consequently results in alteration of structural and transport properties of both materials that may affect the performance of the multi-barrier system. We present an experimental approach to study cement-clay interactions with a cell to accommodate small samples of cement and clay. The cell design allows both in situ measurement of water content across the sample using neutron radiography and measurement of transport parameters using through-diffusion tracer experiments. The aim of the high- resolution neutron radiography experiments was to monitor changes in water content (porosity) and their spatial extent. Neutron radiographs of several evolving cement-clay interfaces delivered quantitative data which allow resolving local water contents within the sample domain. In the present work we explored the uncertainties of the derived water contents with regard to various input parameters and with regard to the applied image correction procedures. Temporal variation of measurement conditions created absolute uncertainty of the water content in the order of ±0.1 (m3/m3), which could not be fully accounted for by correction procedures. Smaller relative changes in water content between two images can be derived by specific calibrations to two sample regions with different, invariant water contents.