Conceptual and Numerical Modeling of Radionuclide Transport and Retention in Near-Surface Systems

Scenarios of barrier failure and radionuclide release to the near-surface environment are important to consider within performance and safety assessments of repositories for nuclear waste. A geological repository for spent nuclear fuel is planned at Forsmark, Sweden. Conceptual and numerical reactive transport models were developed in order to assess the retention capacity of the Quaternary till and clay deposits for selected radionuclides, in the event of an activity release from the repository. The elements considered were carbon (C), chlorine (Cl), cesium (Cs), iodine (I), molybdenum (Mo), niobium (Nb), nickel (Ni), radium (Ra), selenium (Se), strontium (Sr), technetium (Tc), thorium (Th), and uranium (U). According to the numerical predictions, the repository-derived nuclides that would be most significantly retained are Th, Ni, and Cs, mainly through sorption onto clays, followed by U, C, Sr, and Ra, trapped by sorption and/or incorporation into mineral phases.     

Comparative analysis of regional water quality in Canada using the Water Quality Index

The Canadian Council of Ministers for the Environment (CCME) has developed a Water Quality Index (WQI) to simplify the reporting of complex water quality data. This science-based communication tool tests multi-variable water data against numeric water quality guidelines and/or objectives to produce a single unit-less number that represents overall water quality. The CCME WQI has been used to rate overall water quality in spatial and temporal comparisons of site(s). However, it has not been used in a comparative-analysis of exposure sites to reference sites downstream of point source discharges. This study evaluated the ability of the CCME WQI to differentiate water quality from metal mines across Canada at exposure sites from reference sites using two different types of numeric water quality objectives: (1) the water quality guidelines (WQG) for the protection of freshwater aquatic life and (2) water quality objectives determined using regional reference data termed Region-Specific Objectives (RSO). The application of WQG to the CCME WQI was found to be a good tool to assess absolute water quality as it relates to national water quality guidelines for the protection of aquatic life, but had more limited use when evaluating spatial changes in water quality downstream of point source discharges. The application of the RSO to the CCME WQI resulted in assessment of spatial changes in water quality downstream of point source discharges relative to upstream reference conditions.     

Modelling of the migration of trace elements along groundwater flowpaths by using a steady state approach application to the site at El Berrocal (Spain)

The applications of geochemical modelling to natural water systems mostly rely upon the equilibrium assumption. This is in principle justified for deep groundwater systems with long water residence times.In addition, trace element behaviour in these natural systems has been normally modelled by taking into account the precipitation and dissolution of individual trace element phases.Recent geochemical modelling work related to natural analogue systems would indicate that: (1) the equilibrium condition is restricted to a limited number of components in long water residence times and (2) the behaviour of trace metals is very much connected to the major component cycling in the system.There is a need to develop our geochemical modelling capabilities to take these two facts into account in order to be able to predict the behaviour of trace components (radionuclides) in a geological repository.In this work we report on the successful application of steady-state kinetics in conjunction with co-dissolution/co-precipitation approaches to model trace element geochemistry in the natural analogue system at El Berrocal. The evolution of major components of the system (Ca (II), Al (III), CO₃²⁻ and Si) as well the trace elements investigated (U, Ba and Mn) is well reproduced by using the coupling between steady-state kinetics and co-dissolution/co-precipitation approaches.     

Review of the complexation of tetravalent actinides by ISA and gluconate under alkaline to hyperalkaline conditions

Isosaccharinic (ISA) and gluconic acids (GLU) are polyhydroxy carboxylic compounds showing a high affinity to metal complexation. Both organic ligands are expected in the cementitious environments usually considered for the disposal of low- and intermediate-level radioactive wastes. The hyperalkaline conditions imposed by cementitious materials contribute to the formation of ISA through cellulose degradation, whereas GLU is commonly used as a concrete additive. Despite the high stability attributed to ISA/GLU complexes of tetravalent actinides, the number and reliability of available experimental studies is still limited. This work aims at providing a general and comprehensive overview of the state of the art regarding Th, U(IV), Np(IV), and Pu(IV) complexes with ISA and GLU.In the presence of ISA/GLU concentrations in the range 10^− 5–10^− 2 M and absence of calcium, An(IV)(OH)_x(L)_y complexes (An(IV) = Th, U(IV), Np(IV), Pu(IV); L = ISA, GLU) are expected to dominate the aqueous speciation of tetravalent actinides in the alkaline pH range. There is a moderate agreement among their stability, although the stoichiometry of certain An(IV)-GLU complexes is still ill-defined. Under hyperalkaline conditions and presence of calcium, the species CaTh(OH)₄(L)₂(aq) has been described for both ISA and GLU, and similar complexes may be expected to form with other tetravalent actinides.In the present work, the available thermodynamic data for An(IV)–ISA/GLU complexes have been reviewed and re-calculated to ensure the internal consistency of the stability constants assessed. Further modelling exercises, estimations based on Linear Free-Energy Relationships (LFER) among tetravalent actinides, as well as direct analogies between ISA and GLU complexes have also been performed. This approach has led to the definition of a speciation scheme for the complexes of Th, U(IV), Np(IV) and Pu(IV) with ISA and GLU forming in alkaline to hyperalkaline pH conditions, both in the absence and presence of calcium.     

The use of a high-FeO olivine rock as a redox buffer in a nuclear waste repository

Due to the higher stability of the spent nuclear fuel (mainly composed of UO2) under reducing conditions, and in order to enhance the retention/retardation of some key radionuclides, the olivine rock from the Lovasj?rvi intrusion has been proposed as a potential redox-active backfill-additive in deep high-level nuclear waste (HLNW) repositories. In this work, two different approaches have been undertaken in order to establish the redox buffer capacity of olivine rock: (1) The capacity of the rock to respond to changes in pH or pe has been demonstrated and the final (pH, pe) coordinates agree with the control exerted by the system Fe(II)/Fe(III). (2) The rate of consumption of oxygen has been determined at different pH values. These rates are higher than the ones reported in the literature for other solids, what would point to the possibility of using this rock as an additive to the backfill material in a HLNW.     

Air quality biomonitoring through pollen viability of Fabaceae

In this study, pollen viability and germination of three plant species, Cercis siliquastrum L., Robinia pseudoacacia L., and Spartium junceum L., belonging to the Fabaceae family, was evaluated in sites with different intensity of road traffic, constantly monitored with continuous analysers for air pollutants (carbon monoxide (CO), sulphur dioxide (SO₂), and nitrogen dioxide (NO₂)) by the Municipality of Catania. Two sites, in which road traffic was absent, were selected, too. The percentages of viable pollen by 2,3,5-trypheniltetrazolium chloride (TTC) test ranged from 59.0 to 90.2 % in C. siliquastrum, from 61.5 to 83.5 % in S. junceum and from 67.5 to 84.3 % in R. pseudoacacia. The percentages of germination varied from 41.0 to 72.7 % in C. siliquastrum, from 42.0 to 64.7 % in S. junceum and from 38.3 to 66.3 % in R. pseudoacacia. The highest percentages of viable pollens were found in no-road traffic stations by either TTC or germination tests, while the lowest values were detected in a site characterised by heavy road traffic. In the monitored period (2007–2009), pollen viability, germinability and tube length of C. siliquastrum resulted in a significant negative correlation to CO, SO₂ and NO₂, whereas data from TTC and germination tests on S. junceum and R. pseudoacacia pollens were not well correlated to air pollutants. The results showed that pollen viability, germination and tube growth in C. siliquastrum were affected by air pollution. S. junceum and R. pseudoacacia were not very influenced by air pollutants, suggesting a different pollen sensitivity of these species.