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Fractured crystalline rocks have been chosen or are under consideration by several countries as host rock formations for deep geological repositories for spent nuclear fuel. In such geological formations, flow and solute transport are mostly controlled by a network of connected natural fractures, each of them being characterised by internal heterogeneity, also denoted as roughness. Fractures are, in turn, subject to variable load caused by various factors, such as the presence of thick ice sheets formed during glaciation periods. Understanding how coupled hydro-mechanical (HM) processes affect flow and transport at the scale of a single natural fracture is crucial for a robust parameterisation of large-scale discrete fracture network models, which are not only used for nuclear waste disposal applications but are also of interest to problems related to geothermics, oil and gas production or groundwater remediation. In this work, we analyse and model an HM experiment carried out in a single natural fracture and use the results of both, the experimental and the modelling work, to get insights into fundamental questions such as the applicability of local cubic law or the effect of normal load on channeling. The initial fracture aperture was obtained from laser scanning of the two fracture surfaces and an equivalent initial aperture was then defined by moving the two fracture surfaces together and comparing the results obtained using a Navier-Stokes based computational fluid dynamics (CFD) model with the experimental flowrate obtained for unloaded conditions. The mechanical effect of the different loading stages was simulated using a high-resolution contact model. The different computed fracture apertures were then used to run groundwater flow simulations using a modified Reynolds equation. The results show that, without correction, local cubic law largely overestimates flowrates. Instead, we show that by explicitly acknowledging the difference between the mechanical aperture and the hydraulic aperture and setting the latter equal to 1/5 of the former, cubic law provides a very reasonable approximation of the experimental flowrates over the entire loading cycle. A positive correlation between fluid flow channeling and normal load is also found., (© 2024. The Author(s).)

Industrial processes generate various quantities of waste that can be contaminated with radionuclides of natural origin (naturally occurring radioactive material ('NORM waste')). The efficient management of this waste is essential for any industries affected by NORM waste generation. To obtain an overview of current practices and approaches in Europe, the IRPA Task Group on NORM conducted a survey among task group members and other experts from European countries. The results revealed significant differences in methods and approaches in the European countries. In many countries, landfills are used to dispose of small- and medium-sized quantities of NORM waste with limited activity concentration. But our survey indicated that despite a uniform reference basis for national legislation in Europe, there are different framework conditions for the disposal of NORM waste in practice. In some countries, the disposal is hampered because the interface between the radiation protection system and the waste regime is not yet clearly regulated. Particular practical problems include the lack of acceptance of waste because of the 'radioactivity' stigma and only vague specifications by the legislators on acceptance obligations of the waste management sector., (© The Author(s) 2023. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

In large parts of Europe, the Chernobyl accident of 1986 caused fallout of Cs-137. This led to the uptake of Cs-137 in trees or other materials used for bioenergy production or as firewood for domestic purposes. This Cs-137 may concentrate in the ashes of the combustion process in such a way that the clearance level of 100 Bq per kg, defined in Directive 2013/59/Euratom (EU BSS), may consequently be exceeded. There is currently no clear consensus in Europe regarding the regulatory approach to this issue: should the import and use of Cs-137 contaminated biomass and its ashes be considered as a planned exposure situation or rather as an existing exposure situation? If considered as an existing exposure situation, which reference level should be applied? We compare the approaches in various European countries, such as Finland, Norway, Sweden, Belgium and the Netherlands. Results of a recent measurement campaign performed in Belgium on firewood imported from Belarus, Ukraine and other countries show a quite large range of Cs-137 activity concentration in firewood. Analysis of samples from biomass combustion confirms that the clearance level of 100 Bq per kg Cs-137 may be exceeded even when the activity concentration in the initial pellet is trivial. A review of dose-assessment studies performed by STUK and from the literature is presented. The general context of biomass energy production is sketched: for instance, in the Netherlands, 40 large biomass firing plants (capacity > 10 MW) are operational and some 20 more are already planned. The fly ashes from the biomass combustion may be a valuable resource for the construction industry, and the issue of Cs-137 contamination is connected with the requirements of the EU BSS regarding the natural radioactivity of building materials. Assessing the impact of Cs-137 contamination and clarifying regulations in the frame of a graded approach are important elements in this context., (© The Author(s) 2023. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Since 1952, liquid radioactive effluent containing 238-242 Pu, 241 Am, 237 Np, 137 Cs, and 99 Tc has been released with authorization from the Sellafield nuclear complex (UK) into the Irish Sea. This represents the largest source of plutonium (Pu) discharged in all western Europe, with 276 kg having been released. In the Eastern Irish Sea, the majority of the transuranic activity has settled into an area of sediments (Mudpatch) located off the Cumbrian coast. Radionuclides from the Mudpatch have been re-dispersed via particulate transport in fine-grained estuarine and intertidal sediments to the North-East Irish Sea, including the intertidal saltmarsh located at the mouth of the Esk Estuary. Saltmarshes are highly dynamic systems which are vulnerable to external agents (sea level change, erosion, sediment supply, and freshwater inputs), and their stability remains uncertain under current sea level rise projections and possible increases in storm activity. In this work, we examined factors affecting Pu mobility in contaminated sediments collected from the Esk Estuary by conducting leaching experiments under both anoxic and oxic conditions. Leaching experiments were conducted over a 9-month period and were periodically sampled to determine solution phase Pu via multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS), and to measure redox indicators (Eh, pH and extractable Fe(II)). Microbial community composition was also characterized in the sediments, and at the beginning and end of the anoxic/oxic experiments. Results show that: 1) Pu leaching is about three times greater in solutions leached under anoxic conditions compared to oxic conditions, 2) the sediment slurry microbial communities shift as conditions change from anoxic to oxic, 3) Pu leaching is enhanced in the shallow sediments (0-10 cm depth), and 4) the magnitude of Pu leached from sediments is not correlated with total Pu, indicating that the biogeochemistry of sediment-associated Pu is spatially heterogeneous. These findings provide constraints on the stability of redox sensitive Pu in biogeochemically dynamic/transient environments on a timescale of months and suggests that anoxic conditions can enhance Pu mobility in estuarine systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Ltd.)

Quantifying total well loss through well screens has been traditionally undertaken through experimentally based empirical equations or equations derived for water flow through (circular) orifices. Advances in computer capacity enables incorporation of CFD formulations at millimeter scale, coupling Darcy flow and Reynolds Averaged Navier Stokes (RANS) to better understand and quantify processes related to well loss for different screen types. This study provides a methodology of quantifying well screen head loss using numerical models, coupling Darcy flow (aquifer and filter/gravel pack) with turbulent flow (in-well and through screen) at a sub-millimeter scale. Results are used to compare performance of four different types of well screens (Louver, slotted, bridge and wire wrap) and their overall impact and contribution to total well head loss for different slot apertures, pumping rates and hydraulic conductivity of the filter/gravel pack providing a new empirical formulation to quantify screen head loss., (© 2022 National Ground Water Association.)

Drinking water provision has been a constant challenge in the Sahrawi refugee camps, located in the desert near Tindouf (Algeria). The drinking water supply system is itself divided in three zones which pump groundwater from different deep aquifers. It is equipped with reverse osmosis plants and chlorination systems for treating water. The allocation of water supplied to the Saharawi refugees for human consumption in 2016 has been estimated at between 14 and 17 L/person/day on average. This supplied water volume is below recommended standards, and also below the strategic objective of the Sahrawi government (20 L/person/day). Yet the local groundwater resources are huge in comparison with estimated consumption, and hence there is great potential for increasing the supplied volume through effecting improvements in the supply system. The physico-chemical quality of the raw and supplied water between 2006 and 2016 has been assessed according to Algerian standards for human consumption. The raw water of two zones of the supply system presents a very high conductivity and high concentrations of chloride, nitrate, fluoride, sulfate, sodium, calcium, potassium and iodide concentrations of natural origin, which may entail health risks. The treatment of water in a reverse osmosis plant greatly improves its quality and osmosed water met the standards. However, the supply of osmosed and raw water needs to be combined in Zone 1, to avoid an excessive reduction in water volume, and the supplied raw water poses a risk to the health of the refugees. The present study provides an example of a drinking water supply system under extreme drought conditions and in the political and social conditions of a refugee camp. Furthermore, it establishes a reference for supplied water allocation and quality in the Sahrawi refugee camps., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this work, water extracts from different bio-based products of plant origin were studied to evaluate their antioxidant capacity and their potential to form metal nanoparticles from aqueous solutions. Two traditional tests, the Folin-Ciocalteu assay and the DPPH radical scavenging capacity method were compared with a more recent one, SNPAC, based on the formation of silver nanoparticles. The silver nanoparticle antioxidant capacity method (SNPAC) was optimized for its application in the characterization of the extracts selected in this work; kinetic studies and extract concentration were also evaluated. The extracts were obtained from leaves of oak, eucalyptus, green tea, white and common thyme, white cedar, mint, rosemary, bay, lemon, and the seaweed Sargassum muticum . The results demonstrate that any of these three methods can be used as a quick test to identify an extract to be employed for nanoparticle formation. Additionally, we studied the synthesis of Cu, Fe, Pb, Ni, and Ag nanoparticles using eucalyptus extracts demonstrating the efficiency of this plant extract to form metallic nanoparticles from aqueous metal salt solutions. Metal nanoparticles were characterized by transmission electron microscopy and dynamic light scattering techniques.

In the present study, we investigated the possibilities and drawbacks of hollow fiber liquid phase microextraction (HF-LPME) combined with total reflection X-ray fluorescence (TXRF) spectrometry for the determination of low amounts of inorganic arsenic (As) species in water samples. The obtained results showed that a three-phase HF-LPME system was more suitable to be used in combination with TXRF than the two phase configuration, since lower detection limit and better precision for As determination can be attained. Relevant experimental parameters affecting As extraction (i.e. types of extractant, organic solvent, agitation speed, pH and extraction time) and TXRF analysis (deposition volume and drying mode) were systematically evaluated. It was found that As(III) was more efficiently extracted at pH 13, whereas, optimum pH for As(V) extraction was at pH 8.5. Limits of detection (LOD) achieved using the best analytical conditions meet the requirements of current legislation and allow the determination of inorganic As(V) and As(III) in water. The proposed method was also applied to different spiked environmental water samples for the preconcentration and subsequent determination of trace inorganic As species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Most of the highly radioactive spent nuclear fuel (SNF) around the world is destined for final disposal in deep-mined geological repositories. At the end of the fuel's useful life in a reactor, about 96% of the SNF is still UO 2 . Thus, the behaviour of UO 2 in SNF must be understood and evaluated under the weathering conditions of geologic disposal, which extend to periods of hundreds of thousands of years. There is ample evidence from nature that many uranium deposits have experienced conditions for which the formation of coffinite, USiO 4 , has been favoured over uraninite, UO 2+x , during subsequent alteration events. Thus, coffinite is an important alteration product of the UO 2 in SNF. Here, we present the first evidence of the formation of coffinite on the surface of UO 2 at the time scale of laboratory experiments in a solution saturated with respect to amorphous silica at pH = 9, room temperature and under anoxic conditions.

In the framework of the Life+ InSiTrate project, a pilot-plant was established to demonstrate the viability of inducing in-situ heterotrophic denitrification to remediate nitrate (NO 3 - )-polluted groundwater. Two injection wells supplied acetic acid by pulses to an alluvial aquifer for 22months. The monitoring was performed by regular sampling at three piezometers and two wells located downstream. In the present work, the pilot-plant monitoring samples were used to test the usefulness of the isotopic tools to evaluate the efficiency of the treatment. The laboratory microcosm experiments determined an isotopic fractionation (ε) for N-NO 3 - of -12.6‰ and for O-NO 3 - of -13.3‰. These ε 15 N NO3/N2 and ε 18 O NO3/N2 values were modelled by using a Rayleigh distillation equation to estimate the percentage of the induced denitrification at the pilot-plant while avoiding a possible interference from dilution due to non-polluted water inputs. In some of the field samples, the induced NO 3 - reduction was higher than 50% with respect to the background concentration. The field samples showed a reduced slope between δ 18 O-NO 3 - and δ 15 N-NO 3 - (0.7) compared to the laboratory experiments (1.1). This finding was attributed to the reoxidation of NO 2 - to NO 3 - during the treatment. The NO 3 - isotopic characterization also permitted the recognition of a mixture between the denitrified and partially or non-denitrified groundwater in one of the sampling points. Therefore, the isotopic tools demonstrated usefulness in assessing the implementation of the field-scale induced denitrification strategy., (Copyright © 2019. Published by Elsevier B.V.)

Flavins are ubiquitous redox-active compounds capable of producing reactive oxygen (O 2 •- , • OH, and H 2 O 2 ) and flavin radical species in natural environments, yet their roles in the redox transformations of environmental contaminants, such as arsenic (As), remain to be investigated. Here, we show that reduced flavins can be a source of effective oxidants for As(III) under both oxic and anoxic conditions. For instance, in the presence of 15 μM reduced riboflavin (RBFH 2 ), 22% of 30 μM As(III) is oxidized in aerated solution at pH 7.0. The co-oxidation of As(III) with RBFH 2 is pH-dependent, with a faster reaction rate under mildly acidic relative to alkaline conditions. Quencher tests with 2-propanol (for • OH) and catalase (for H 2 O 2 ) indicate that As(III) oxidation under oxic conditions is likely controlled by flavin-derived • OH at pH 5.2 and 7.0, and by H 2 O 2 at pH 9.0. Kinetic modeling further implies that flavin-derived reactive oxygen species are mainly responsible for As(III) oxidation under oxic conditions, whereas oxidation of As(III) under anoxic conditions at pH 9.0 is attributed to riboflavin radicals (RBFH • ) generated from co-existing oxidized and reduced riboflavin. The demonstrated ability of flavins to catalyze As(III) oxidation has potential implications for As redox cycling in the environment.

One of the major environmental concerns in the mining industry is the generation of acid leachates from tailings deposits, which are highly concentrated in potentially hazardous elements. The continuous processing of these leachates in treatment plant is unsustainable, so the in situ chemical improvement of the mine wastes and their leachates, mainly with another waste produced in the mining area, can reduce treatment and operational costs. This study aimed to evaluate the effect of two types of domestic wastewaters (DWW) on the improvement of the chemical characteristics of the leachates generated from mine wastes containing sulfides. A mesocosm assay was performed under greenhouse and controlled conditions with mine wastes collected in La Zanja mining area (Peru). Three irrigation treatments were tested: untreated DWW, treated DWW and water as control. Percolated leachates of each treatment were collected once per week, for a period of 10 weeks. Electrical conductivity, pH and multi-elemental concentration were analysed. During the assay, the mine wastes generated acid leachates (≈4) with significant concentrations of elements (mg/L; Al: 1.4-30.0; Cd: 0.05-0.19; Cu: 5.7-22.1; Fe: 1.6-19.4; Mn: 2.6-26.0; Zn: 1.2-9.2) and sulfates (204.3-997.8 mg/L), which exceed the thresholds established by Peruvian legislations. After DWW application, pH in the leachates increased to ≈7 and concentrations of several studied elements (e.g. Al, As, Fe, Cu, Zn, Cd, Pb, Ni, Mn) and sulfates decreased (>70% depending on DWW type, element and sampling) compared to the control. This fact allowed that the Environmental Quality standards from Peru (except for Cu and Mn) were reached. However, an enrichment of Na and K was obtained at the same leachates. At short term, the DWW application (especially untreated) on the mine wastes containing sulfides was effective in the improvement of the general chemical quality of their leachates. Moreover, the combined management of these two studied wastes (domestic wastewater and mine wastes) represents a promising cost-effective strategy during mining operation., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Currently, monitoring tools can be deployed in observation boreholes to better assess groundwater flow, flux of dissolved contaminants and their mass discharge in an aquifer. The relationship between horizontal water velocity in observation boreholes and Darcy fluxes in the surrounding aquifer has been studied for natural flow conditions (i.e., no pumping). Interpretation of measurements taken with dilution tests, the colloidal borescope, the Heat Pulse Flowmeter, and other techniques require the conversion of observed borehole velocity u to aquifer Darcy flux q ∞ . This conversion is typically done through a proportionality factor α = u/q ∞ . In experimental studies as well as in theoretical developments, reported values of α vary almost three orders of magnitude (from 0.5 to 10). This large variability in reported values of α could be explained by: (1) unclear distinction between Darcy flux and water seepage velocity, (2) unclear definition of water velocity in the borehole, (3) effects of well screen and the presence of the measurement device itself on the observable velocities, and (4) hydraulic conditions in the borehole annulus. We address (1), (2) from a conceptual/theoretical perspective, and (3) by means of numerical simulations. We show that issue (1) in low porosity aquifers can yield to order-of-magnitude discrepancies in estimates of q ∞ ; (2) may result in discrepancies of up to 50%, and (3) can cause differences up to 20% of water velocity in the borehole void space compared to the theoretical case of an open borehole., (© 2018, National Ground Water Association.)

The rock matrix of granites is expected to be an important buffer against the dispersion of contaminants, e.g. radionuclides, and against the ingress of oxygenated glacial meltwater. The influence of matrix heterogeneity on O 2 diffusive transport is assessed here by means of numerical experiments based on a micro-Discrete Fracture Network (micro-DFN) representation of the diffusion-available pore space along with random realisations of idealized biotite grains, to simulate the heterogeneous nature of granitic rocks. A homogeneous-based analytical solution is also presented and used to assess possible deviations of the numerical experiments from the assumption of homogeneity. The analytical solution is also used to test upscaled values of mineral surface area. The numerical experiments show that the matrix behaves as a composite system, with the coexistence of fast and slow diffusive pathways. This behavior is more evident at low Damköhler numbers. Our interpretation of the numerical experiments points out the importance to properly characterise the heterogeneity of the rock matrix., (Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.)

Field investigation studies, conducted in the context of safety analyses of deep geological repositories for nuclear waste, have pointed out that in fractured crystalline rocks sorbing radionuclides can diffuse surprisingly long distances deep into the intact rock matrix; i.e. much longer distances than those predicted by reactive transport models based on a homogeneous description of the properties of the rock matrix. Here, we focus on cesium diffusion and use detailed micro characterisation data, based on micro computed tomography, along with a grain-scale Inter-Granular Network model, to offer a plausible explanation for the anomalously long cesium penetration profiles observed in these in-situ experiments. The sparse distribution of chemically reactive grains (i.e. grains belonging to sorbing mineral phases) is shown to have a strong control on the diffusive patterns of sorbing radionuclides. The computed penetration profiles of cesium agree well with an analytical model based on two parallel diffusive pathways. This agreement, along with visual inspection of the spatial distribution of cesium concentration, indicates that for sorbing radionuclides the medium indeed behaves as a composite system, with most of the mass being retained close to the injection boundary and a non-negligible part diffusing faster along preferential diffusive pathways., (Copyright © 2017 Elsevier B.V. All rights reserved.)

We present an enhanced continuum-based approach for the modelling of groundwater flow coupled with reactive transport in crystalline fractured rocks. In the proposed formulation, flow, transport and geochemical parameters are represented onto a numerical grid using Discrete Fracture Network (DFN) derived parameters. The geochemical reactions are further constrained by field observations of mineral distribution. To illustrate how the approach can be used to include physical and geochemical complexities into reactive transport calculations, we have analysed the potential ingress of oxygenated glacial-meltwater in a heterogeneous fractured rock using the Forsmark site (Sweden) as an example. The results of high-performance reactive transport calculations show that, after a quick oxygen penetration, steady state conditions are attained where abiotic reactions (i.e. the dissolution of chlorite and the homogeneous oxidation of aqueous iron(II) ions) counterbalance advective oxygen fluxes. The results show that most of the chlorite becomes depleted in the highly conductive deformation zones where higher mineral surface areas are available for reactions., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this work, a multiscale modeling of the interaction of oxalate with clay mineral surfaces from macroscale thermodynamic equilibria simulations to atomistic calculations is presented. Previous results from macroscopic adsorption data of oxalate on montmorillonite in 0.01 M KNO3 media at 25 °C within the pH range from 2.5 to 9 have been used to develop a surface complexation model. The experimental adsorption edge data were fitted using the triple-layer model (TLM) with the aid of the FITEQL 4.0 computer program. Surface complexation of oxalate is described by two reactions: >AlOH + Ox(2-) + 2H(+) = >AlOxH + H2O (log K = 14.39) and >AlOH + Ox(2-) + H(+) = >AlOx(-) + H2O (log K = 10.39). The monodentate complex >AlOxH dominated adsorption below pH 4, and the bidentate complex >AlOx(-) was predominant at higher pH values. Both of the proposed inner-sphere oxalate species are qualitatively consistent with previously published diffuse reflectance FTIR spectroscopic results for oxalate on montmorillonite edge surface (Chem. Geol. 2014, 363, 283-292). Atomistic computational studies have been performed to understand the interactions at the molecular level between adsorbates and mineral surface, showing the atomic structures and IR frequency shifts of the adsorption complexes of oxalate with the edge surface of a periodic montmorillonite model.

Radionuclide retardation processes during transport are expected to play an important role in the safety assessment of subsurface disposal facilities for radioactive waste. The linear distribution coefficient (Kd) is often used to represent radionuclide retention, because analytical solutions to the classic advection-diffusion-retardation equation under simple boundary conditions are readily obtainable, and because numerical implementation of this approach is relatively straightforward. For these reasons, the Kd approach lends itself to probabilistic calculations required by Performance Assessment (PA) calculations. However, it is widely recognised that Kd values derived from laboratory experiments generally have a narrow field of validity, and that the uncertainty of the Kd outside this field increases significantly. Mechanistic multicomponent geochemical simulators can be used to calculate Kd values under a wide range of conditions. This approach is powerful and flexible, but requires expert knowledge on the part of the user. The work presented in this paper aims to develop a simplified approach of estimating Kd values whose level of accuracy would be comparable with those obtained by fully-fledged geochemical simulators. The proposed approach consists of deriving simplified algebraic expressions by combining relevant mass action equations. This approach was applied to three distinct geochemical systems involving surface complexation and ion-exchange processes. Within bounds imposed by model simplifications, the presented approach allows radionuclide Kd values to be estimated as a function of key system-controlling parameters, such as the pH and mineralogy. This approach could be used by PA professionals to assess the impact of key geochemical parameters on the variability of radionuclide Kd values. Moreover, the presented approach could be relatively easily implemented in existing codes to represent the influence of temporal and spatial changes in geochemistry on Kd values., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Granular activated carbon (GAC) is commonly used as adsorbent in water treatment plants given its high capacity for retaining organic pollutants in aqueous phase. The current knowledge on GAC behaviour is essentially empirical, and no quantitative description of the chemical relationships between GAC surface groups and pollutants has been proposed. In this paper, we describe a quantitative model for the adsorption of atrazine onto GAC surface. The model is based on results of potentiometric titrations and three types of adsorption experiments which have been carried out in order to determine the nature and distribution of the functional groups on the GAC surface, and evaluate the adsorption characteristics of GAC towards atrazine. Potentiometric titrations have indicated the existence of at least two different families of chemical groups on the GAC surface, including phenolic- and benzoic-type surface groups. Adsorption experiments with atrazine have been satisfactorily modelled with the geochemical code PhreeqC, assuming that atrazine is sorbed onto the GAC surface in equilibrium (log Ks = 5.1 ± 0.5). Independent thermodynamic calculations suggest a possible adsorption of atrazine on a benzoic derivative. The present work opens a new approach for improving the adsorption capabilities of GAC towards organic pollutants by modifying its chemical properties.

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept. In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution-precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.

Size dispersion effects during the migration of natural submicron bentonite colloids (<200 nm) through a ceramic column are observed for the first time by laser-induced breakdown detection (LIBD) at ppm (parts per million) mass concentration. Larger size fractions ( approximately 200 nm) arrive prior to smaller size fractions (<100 nm) at the column outlet in agreement with model predictions and earlier findings with carboxylated polystyrene spheres. By addition of trace amounts of americium(III) and plutonium(IV), colloid mediated transport of these radionuclides is studied. The peak arrival times of Pu-244 and Am-241, as measured by ICP-MS, match the bentonite colloid breakthrough and occur significantly prior to the conservative tracer (HTO) indicating the colloid-borne migration of tri- and tetravalent radionuclides.