A laboratory experiment for determining both the hydraulic and diffusive properties and the initial pore-water composition of an argillaceous rock sample: a test with the Opalinus clay (Mont Terri, Switzerland)

Argillaceous formations are thought to be suitable natural barriers to the release of radionuclides from a radioactive waste repository. However, the safety assessment of a waste repository hosted by an argillaceous rock requires knowledge of several properties of the host rock such as the hydraulic conductivity, diffusion properties and the pore water composition. This paper presents an experimental design that allows the determination of these three types of parameters on the same cylindrical rock sample. The reliability of this method was evaluated using a core sample from a well-investigated indurated argillaceous formation, the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL) (Switzerland). In this test, deuterium- and oxygen-18-depleted water, bromide and caesium were injected as tracer pulses in a reservoir drilled in the centre of a cylindrical core sample. The evolution of these tracers was monitored by means of samplers included in a circulation circuit for a period of 204 days. Then, a hydraulic test (pulse-test type) was performed. Finally, the core sample was dismantled and analysed to determine tracer profiles. Diffusion parameters determined for the four tracers are consistent with those previously obtained from laboratory through-diffusion and in-situ diffusion experiments. The reconstructed initial pore-water composition (chloride and water stable-isotope concentrations) was also consistent with those previously reported. In addition, the hydraulic test led to an estimate of hydraulic conductivity in good agreement with that obtained from in-situ tests.     

Mobility of Cd and Cu in formulated sediments coated with iron hydroxides and/or humic acids: a DGT and DGT-PROFS modeling approach

The diffusive gradients technique in thin films (DGT) was used to investigate the kinetic resupply of Cd and Cu to pore water from the solid phase. For the sake of simplification, experiments were performed using formulated sediments that differed in the presence or absence of humic acids (HA) and/or of iron hydroxides (i.e., goethite and ferrihydrite). The effects of the time after the contamination of the solid phase (aging effect) on formulated sediments that were coated with goethite and HA and spiked with Cd were also evaluated. Kinetic DGT results were interpreted using the newly developed, multi-compartmental model DGT-PROFS.Due to Cu humate formation, the addition of HA slightly increased the Cu concentration in the pore water independent of the effect of the iron hydroxide coating on the formulated sediments and slightly decreased that of Cd. The impact of 8-190 d of aging resulted in a significant decrease in the Cd concentration of the pore water over an increasing incubation time.Modeling our results with DGT-PROFS led to the following conclusions concerning the impact of HA and iron hydroxides on Cd and Cu availability. First, in the presence of HA and absence of iron hydroxides, Cd is associated mainly with weak sites, while Cu is bound to strong sites. Similarly, in the presence of both iron hydroxides and HA, Cu appeared to be more heavily associated with the strong sites than did Cd. When the incubation time increased from 8 to 190 d, a proportion of Cd initially adsorbed onto weak sites transferred to the strong sites, suggesting that the adsorption of Cd on sediments is controlled partially by slow kinetic processes.     

Optimizing a recycling process of SMC composite waste

Investigations about the recycling of sheet moulding compounds (SMC) waste as incorporation material for thermoplastic polymer matrix are reported in this paper. A new efficient process is developed in order to strongly increase the reinforcement glass fraction of SMC leading to good mechanical performance of the new thermoplastic compounds. The overall process is composed of two main steps: mechanical and chemical. The second stage is characterised in terms of optimization and capability by means of experimental design and statistical process control techniques for finding the optimal chemical conditions and validating the process.     

Characterisation of HTO diffusion properties by an in situ tracer experiment in Opalinus clay at Mont Terri

A long-term single borehole diffusion experiment using tritiated water as tracer was carried out in Opalinus clay, an argillaceous rock formation that is accessible at the Mont Terri Underground Research Laboratory, situated in the Swiss Jura. The tracer was diluted in reconstituted formation water and introduced into a packed-off section of a borehole located in saturated rock. Pressure in this interval was maintained equal to the pore pressure of the surrounding rock in order to prevent any hydraulic gradient around the borehole and to avoid advective transport processes. The evolution of the tracer concentration in the injection system was monitored over time. After 1 year of diffusion, the claystone surrounding the interval was retrieved by overcoring the whole borehole and packer system, and by an adjacent oblique borehole. Compressed air was used as drilling fluid to reduce rock disturbances. The recovered overcore was sampled along profiles perpendicular to the borehole wall with a view to determining the tracer-concentration profiles in the rock. To avoid further evaporation of tritiated water, subsamples were immediately transferred into polyethylene bottles and disaggregated by adding a known amount of tracer-free water. Fifteen profiles were determined and showed a decreasing tracer concentration with distance into the rock. The pore-water contents were constant along those profiles, confirming that only very little water was lost during overcoring operations. The evolution of tritium-tracer concentration in the injection system over time and in situ profiles were interpreted with a 3-D numerical simulation of the experiment. That allowed for the identification of the transport parameters (orthotropic diffusion tensor and porosity) by minimising the relative quadratic error between the experimental and simulated data. The fitting is good and the results are consistent with data obtained on drill-core samples. The result of tritiated water is discussed regarding (1) the potential effect of mechanical and/or chemical disturbances around the injection borehole and (2) the specific behaviour of tritiated water.     

Equilibrium partitioning of (14)C-benzo(a)pyrene and (14)C-benazolin between fractionated phases from an arable topsoil

Equilibrium partitioning of hydrophobic (14)C-benzo(a)pyrene and hydrophilic (14)C-benazolin between fractionated phases from an arable topsoil of Merzenhausen (Germany) was investigated. Topsoil samples were collected from lysimeters which were incubated with different residual crops. A physical soil fractionation based on sedimentation and centrifugation steps was performed after water extraction. Four soil phases were obtained designated sediment (SED) phase (>20 microm), microaggregate (MA) phase (2 microm-20 microm), colloid (COL) phase (<2 microm) and electrolyte (EL) phase. The distribution of (14)C-benzo(a)pyrene, (14)C-benazolin and organic carbon between the soil phases was established. Enrichment factors for the two chemicals and organic carbon are higher in the COL and MA phases than in the SED phase. The distribution constant K(d) of chemicals for Merzenhausen topsoil was calculated according to two-phase or three-phase partitioning models. The three-phase partitioning model presumes the contribution of the organic carbon for the binding of chemicals. A log K(oc) of 5.55 can be calculated in the case of (14)C-benzo(a)pyrene, which is typical of the hydrophobic association with the soil organic carbon. In the case of (14)C-benazolin, much higher K(d) and K(oc) values were calculated than found with parent molecules after short-time experiments. Long-term aging processes must be considered. Specific effects on the chemical distribution due to the different crop residues were not detected.     

A weighted bootstrap method for the determination of probability density functions of freshwater distribution coefficients (Kds) of Co, Cs, Sr and I radioisotopes

The objective of the study was to provide global probability density functions (PDFs) representing the uncertainty of distribution coefficients (Kds) in freshwater for radioisotopes of Co, Cs, Sr and I. A comprehensive database containing Kd values referenced in 61 articles was first built and quality scores were affected to each data point according to various criteria (e.g. presentation of data, contact times, pH, solid-to-liquid ratio, expert judgement). A weighted bootstrapping procedure was then set up in order to build PDFs, in such a way that more importance is given to the most relevant data points (i.e. those corresponding to typical natural environments). However, it was also assessed that the relevance and the robustness of the PDFs determined by our procedure depended on the number of Kd values in the database. Owing to the large database, conditional PDFs were also proposed, for site studies where some parametric information is known (e.g. pH, contact time between radionuclides and particles, solid-to-liquid ratio). Such conditional PDFs reduce the uncertainty on the Kd values. These global and conditional PDFs are useful for end-users of dose models because the uncertainty and sensitivity of Kd values are taking into account.     

Use of tracer tests to evaluate the impact of enhanced-solubilization flushing on in-situ biodegradation

Tracer tests were conducted to evaluate the effect of a complexing sugar flush (CSF) on in-situ biodegradation potential at a site contaminated by jet fuel, solvents, and other organic compounds. Technical-grade hydroxypropyl-beta-cyclodextrin was used during the CSF study, which was conducted in a hydraulically isolated cell emplaced in a surficial aquifer. In-situ biodegradation potential was assessed with the use of tracer tests, which were conducted prior to and immediately following the CSF study. Ethanol, hexanol, and benzoate were used as the biodegradable tracers, while bromide was used as a nonreactive tracer. The results indicate that the biodegradation of benzoate was similar for both tracer tests. Conversely, the biodegradation of ethanol (23% increase) and hexanol (41% increase) was greater for the post-CSF tracer test. In addition, analysis of core samples collected from within the test cell indicates that the population density of aerobic jet-fuel degraders increased in the vicinity of the injection wells during the CSF. These results indicate that the cyclodextrin flush did not deleteriously affect the indigenous microbial community. This study illustrates that tracer tests can be used to evaluate the impact of remediation activities on in-situ biodegradation potential.     

Measurements of Traffic-Induced Turbulence within a Street Canyon during the Nantes'99 Experiment

A full scale experiment has been performed in a streetcanyon, the Rue de Strasbourg in Nantes (France). Thiscampaign, the Nantes'99 experiment, provided a detaileddata base documenting, amongst others, the production ofturbulent kinetic energy (TKE) by vehicles within thestreet. Airflow and CO concentration measurements have beenanalysed during days with low wind perpendicular to thestreet axis, i.e. for conditions expected to greatly favourthe enhancement of the turbulence produced by traffic onflow and dispersion within the street canyon. It is shownthat traffic is associated with an increase in turbulentkinetic energy at the lowest levels of the street,especially at the leeward side of the street. It issuggested that turbulent kinetic energy increases with thenumber of vehicles up to a threshold value and thendecreases when vehicles form a `block' shape that limitsthe additional production of turbulence. Moreover, it issuggested that traffic-produced turbulence affectspollutant dispersion reducing CO concentration at the lowerlevels of the leeward side of the street from a thresholdvalue of TKE equal to about 0.15 m² s^-2. On the other hand, high traffic density generates less turbulencewhich in turn leads to a lower pollutant dispersion.     

A field method using microcosms to evaluate transfer of Cd,Cu, Ni,Pb and Zn from sewage sludge amended forest soils to Helix aspersa snails

Juvenile Helix aspersa snails exposed in field microcosms were used to assess the transfer of Cd, Cu, Ni, Pb and Zn from forest soils amended with liquid and composted sewage sludge. Zn concentrations and contents were significantly higher in snails exposed to liquid and composted sludge after 5 and 7 weeks of exposure, when compared with control. Trends were less clear for the other metals. Present results show that Zn, among the cocktail of metallic trace elements (MTE) coming from sewage sludge disposal, represents the principal concern for food chain transfer and secondary poisoning risks. The microcosm design used in this experiment was well suited for relatively long-term (about 2 months) active biomonitoring with H. aspersa snails. The snails quickly indicated the variations of MTE concentrations in their immediate environment. Therefore, the present study provides a simple but efficient field tool to evaluate MTE bioavailability and transfer.