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.     

Influence of season on the feeding habits of the common sole Solea solea

The object of the study was to determine whether the composition of the diet of sole Solea solea Linnaeus, 1758 throughout the year is influenced only by the presence and abundance of prey or whether in addition it is influenced by a selection procedure resulting from its energetic and nutritional needs. Feeding habits were established by examining the stomach contents of males and females throughout the year. We recorded the presence or absence of each prey item and identified dominant, occasional and accidental prey. Differences in the seasonal composition of the basic diet were analysed (chisquare). Throughout the year, the diet consisted mainly of crustaceans, except in autumn when polychaetes were the most abundant prey. Significant differences (chisquare) in feeding habits were established between seasons and between sexes in each season. Some of the dominant prey (Ampeliscidae and Callianassidae) live exclusively in estuaries and bays, and occur in highest abundance during winter, the season in which sole enter estuaries to spawn. These prey items were present in higher numbers in the stomach contents of the sole during this period, reflecting the dependence of its diet on prey availability.     

Study on the formation and transport of ozone in relation to the air quality management and vegetation protection in Tenerife (Canary Islands)

An experimental study on the formation and transport of ozone in ambient air was performed in Tenerife (Canary Islands) in order to investigate the processes affecting ozone levels and air quality. The special features of Tenerife (prevalence of the trade wind pattern (NE), orography and the specific location of the local ozone sources) permit to quantify the role of the ‘long-range transport from northern latitudes' versus the ‘formation and transport of ozone downwind of the main urban areas' of Tenerife. Levels of O₃, NO₂ and O_X were monitored in different types of environments to achieve this purpose. The results showed that: (1) upwind of the urban areas ozone is mainly transported from the ocean by trade winds, (2) local ozone titration (by NO) and ozone replenishment from the ocean are the main causes of ozone variations in urban and suburban areas, and (3) photochemical ozone production occurs downwind of the urban areas. Photochemical production causes daylight O₃ and O_X levels downwind of urban areas to be frequently (60% and 35% days/year, respectively) higher than upwind of the urban sites (O₃ and O_X excess frequently in the range 5–20 ppbv). Due to the above processes, different daily ozone cycles occur in short distances (<30 km), with maximum O₃ levels during daylight or night depending on the site. Ozone phytotoxicity was assessed by calculating the AOT40 index upwind and downwind of the main urban areas. The critical value for the 5-day-AOT40 index was simultaneously exceeded at the two sites (few times/year) during long-range transport events. During the additional exceedances of the critical value downwind of the urban area, relatively high 5-day-AOT40 values were recorded upwind of the urban site. Thus, long-range transport from northern latitudes may produce relatively high 5-days-AOT40 levels in the oceanic boundary layer. These results are important for the protection of the large number of endemic plants in the Canaries. The conceptual model discussed in this study may be qualitatively applied to other islands which possess features similar to those of Tenerife.     

Solute transport properties of compacted Ca-bentonite used in FEBEX project

The present Spanish concept of a deep geological high level waste repository includes an engineered clay barrier around the canister. The clay presents a very high sorption capability for radionuclides and a very small hydraulic conductivity, so that the migration process of solutes is limited by sorption and diffusion processes. Therefore, diffusion and distribution coefficients in compacted bentonite (i.e. in "realistic" liquid to solid ratio conditions) are the main parameters that have to be obtained in order to characterise solute transport that could be produced after the canister breakdown. Through-Diffusion (TD) and In-Diffusion (ID) experiments with HTO, Sr, Cs and Se were carried out using compacted FEBEX bentonite, which is the reference material for the Spanish concept of radioactive waste disposal. Experiments were interpreted by means of available analytical solutions that allow the estimation of diffusion coefficients and, in some cases, distribution coefficients. Analytical solutions are simple to use, but rely on hypotheses that do not hold in all the experiments. These experiments were interpreted also using an automatic parameter estimation code that overcomes the limitations of analytical solutions. Numerical interpretation allows the simultaneous estimation of porosity, diffusion and distribution coefficients, accounts for the role of porous sinters and time-varying boundary concentrations, and can use different types of raw concentration data.     

Influence of sex and age on the feeding habits of the common soleSolea solea

The lethal concentration of cadmium was determined for the mysidLeptomysis lingvura G.O. Sars, a Mediterranean species from surface coastal waters, and the effect of sublethal doses on respiration, ammonia excretion, and feeding efficiency at different temperatures, and on activities of 19 hydrolases was tested. Experiments were carried out on individuals collected in spring 1987 near Marseille. At 18°C, respiration rate was significantly affected only by concentrations >0.05 mg Cd l^–1. At 0.1 mg Cd l^–1, respiration rate was more significantly depressed at 20°C than at 10°C. There was a concomitant decrease in the Q₁₀ rate (by 23 to 59%, according to the particular experiment), indicating a strong synergistic effect of temperature. Ammonia excretion was likewise affected by cadmium, also with a concomitant decrease in the Q₁₀ rate (by 34%). Daily faecal pellet production was maximum at 18°C; it was inhibited by cadmium at temperatures between 14 and 20°C, and enhanced at extreme temperatures (10 and 22°C). The assimilation efficiency of contaminated individuals was reduced by 9%. These decreases in faecal pellet production and assimilation efficiency reflect a significant decrease in energy (by about 43%) which could rapidly lead to an unbalanced energy budget with a consecutive lowering of the reproductive potential. Generally, hydrolase activities usually increased initially in the presence of 0.2 mg Cd l^–1, but after 48 h they declined, reaching very low values at 72 h. Most physiological processes are therefore affected by exposure to cadmium and the unbalanced energy budget arises from the inability to utilize environmental food. These results are consistent with the literature data on cadmium contamination in marine organisms. Physiological and biochemical changes appear to be very informative in studies of in vitro sublethal effects of micropollutants and in situ environmental modifications.     

Large-scale modeling of reactive solute transport in fracture zones of granitic bedrocks

Final disposal of high-level radioactive waste in deep repositories located in fractured granite formations is being considered by several countries. The assessment of the safety of such repositories requires using numerical models of groundwater flow, solute transport and chemical processes. These models are being developed from data and knowledge gained from in situ experiments such as the Redox Zone Experiment carried out at the underground laboratory of Äspö in Sweden. This experiment aimed at evaluating the effects of the construction of the access tunnel on the hydrogeological and hydrochemical conditions of a fracture zone intersected by the tunnel. Most chemical species showed dilution trends except for bicarbonate and sulphate which unexpectedly increased with time. Molinero and Samper [Molinero, J. and Samper, J. Groundwater flow and solute transport in fracture zones: an improved model for a large-scale field experiment at Äspö (Sweden). J. Hydraul. Res., 42, Extra Issue, 157–172] presented a two-dimensional water flow and solute transport finite element model which reproduced measured drawdowns and dilution curves of conservative species. Here we extend their model by using a reactive transport which accounts for aqueous complexation, acid–base, redox processes, dissolution–precipitation of calcite, quartz, hematite and pyrite, and cation exchange between Na⁺ and Ca²⁺. The model provides field-scale estimates of cation exchange capacity of the fracture zone and redox potential of groundwater recharge. It serves also to identify the mineral phases controlling the solubility of iron. In addition, the model is useful to test the relevance of several geochemical processes. Model results rule out calcite dissolution as the process causing the increase in bicarbonate concentration and reject the following possible sources of sulphate: (1) pyrite dissolution, (2) leaching of alkaline sulphate-rich waters from a nearby rock landfill and (3) dissolution of iron monosulphides contained in Baltic seafloor sediments. Based on these results, microbially mediated processes are postulated as the most likely hypothesis to explain the measured increase of dissolved bicarbonates and sulphates after tunnel construction.     

Resolving CO2 and methane hydrate formation kinetics

We analyse the kinetics of CO₂ and methane hydrate formation. The characteristic formation times are associated with different steps of the formation process. Conditions for minimising these rate times are identified while maintaining a regime where CO₂ hydrate is formed and methane remains predominantly gaseous. This involves a rapid pressurisation routine and accesses points well above the phase boundary in order to enable faster kinetics. Conditions for optimising rates and times, to obtain maximum CO₂ uptake with respect to CH₄, were identified as (1) stirring faster than 1,000 rpm, (2) rapid pressurisation to a partial pressure of around 50 bar for CO₂ and (3) re-use of contaminated as opposed to fresh water.     

Vertical fluxes of aromatic and aliphatic hydrocarbons in the Northwestern Mediterranean Sea

Aliphatic and aromatic hydrocarbon fluxes were measured in time series sediment trap samples at 200 m and at 1000 m depths in the open Northwestern Mediterranean Sea, from December 2000 to July 2002. Averaged fluxes of n-alkanes, UCM and T-PAH₃₅ were 2.96 ± 2.60 μg m⁻² d⁻¹, 64 ± 60 μg m⁻² d⁻¹ and 0.68 ± 0.59 μg m⁻² d⁻¹, respectively. Molecular compositions of both hydrocarbon classes showed a contamination in petrogenic hydrocarbons well above the background levels of such an open site, whereas pyrolytic hydrocarbons stand in the range of other open Mediterranean locations. Fluxes displayed ample interannual and seasonal variabilities, mainly related to mass flux variation while concentration evolutions trigger secondary changes in pollutant fluxes. High lithogenic flux events exported particles with a larger pollutant load than biogenic particles formed during the spring bloom and during the summer. Sinking hydrocarbons were efficiently transported from 200 m to 1000 m.     

Modelling geochemical and microbial consumption of dissolved oxygen after backfilling a high level radiactive waste repository

Dissolved oxygen (DO) left in the voids of buffer and backfill materials of a deep geological high level radioactive waste (HLW) repository could cause canister corrosion. Available data from laboratory and in situ experiments indicate that microbes play a substantial role in controlling redox conditions near a HLW repository. This paper presents the application of a coupled hydro-bio-geochemical model to evaluate geochemical and microbial consumption of DO in bentonite porewater after backfilling of a HLW repository designed according to the Swedish reference concept. In addition to geochemical reactions, the model accounts for dissolved organic carbon (DOC) respiration and methane oxidation. Parameters for microbial processes were derived from calibration of the REX in situ experiment carried out at the Asp? underground laboratory. The role of geochemical and microbial processes in consuming DO is evaluated for several scenarios. Numerical results show that both geochemical and microbial processes are relevant for DO consumption. However, the time needed to consume the DO trapped in the bentonite buffer decreases dramatically from several hundreds of years when only geochemical processes are considered to a few weeks when both geochemical reactions and microbially-mediated DOC respiration and methane oxidation are taken into account simultaneously.