Swedish-German actinide migration experiment at ASPO hard rock laboratory

Within the scope of a bilateral cooperation between Svensk K?rnbr?nslehantering (SKB) and Forschungszentrum Karlsruhe, Institut für Nukleare Entsorgung (FZK-INE), an actinide migration experiment is currently being performed at the Asp? Hard Rock Laboratory (HRL) in Sweden. This paper covers laboratory and in situ investigations on actinide migration in single-fractured granite core samples. For the in situ experiment, the CHEMLAB 2 probe developed by SKB was used. The experimental setup as well as the breakthrough of inert tracers and of the actinides Am, Np and Pu are presented. The breakthrough curves of inert tracers were analyzed to determine hydraulic properties of the fractured samples. Postmortem analyses of the solid samples were performed to characterize the flow path and the sorbed actinides. After cutting the cores, the abraded material was analyzed with respect to sorbed actinides. The slices were scanned optically to visualize the flow path. Effective volumes and inner surface areas were measured. In the experiments, only breakthrough of Np(V) was observed. In each experiment, the recovery of Np(V) was < or = 40%. Breakthrough of Am(III) and Pu(IV) as well as of Np(IV) was not observed.     

Selectivity in the complexation of actinides by humic substances

The interactions of a range of actinide elements (Th, U, Np, Pu, Am) with humic substances from the Needle's Eye natural analogue site were studied by gel permeation chromatography. Bulk humic substances were isolated by ammonia extraction, followed by dialysis against distilled water and freeze-drying. The gel permeation results suggest that Needle's Eye humic substances can be fractionated into three incompletely resolved fractions with average molecular weights determined by analytical ultracentrifugation around 49 000 for Fraction 1, around 14 700 for Fraction 2 and around 8000 for Fraction 3. Although there are significant differences between the organic matter elution patterns in individual gel permeation experiments, presumably due to differences in column packing, these are much smaller than the differences between metal ions. The uranium that is naturally present in these humic substances is largely bound in the late-eluting fraction. Spikes of the early actinides, including Np and Pu in controlled valency states, have been added to the humic substances, and gel permeation of the spiked humic substances shows that the three humic fractions vary greatly in their effectiveness and selectivity as ligands for early actinides.     

Interpretation of actinide-distribution data obtained from non-destructive and destructive post-test analyses of an intact-core column of Culebra dolomite

The US Department of Energy (DOE), with technical assistance from Sandia National Laboratories, has successfully received EPA certification and opened the Waste Isolation Pilot Plant (WIPP), a nuclear waste disposal facility located approximately 42 km east of Carlsbad, NM. Performance assessment (PA) analyses indicate that human intrusions by inadvertent, intermittent drilling for resources provide the only credible mechanisms for significant releases of radionuclides from the disposal system. For long-term brine releases, migration pathways through the permeable layers of rock above the Salado formation are important. Major emphasis is placed on the Culebra Member of the Rustler Formation because this is the most transmissive geologic layer overlying the WIPP site. In order to help quantify parameters for the calculated releases, radionuclide transport experiments have been carried out using intact-core columns obtained from the Culebra dolomite member of the Rustler Formation within the WIPP site. This paper deals primarily with results of analyses for 241Pu and 241Am distributions developed during transport experiments in one of these cores. Transport experiments were done using a synthetic brine that simulates Culebra brine at the core recovery location (the WIPP air-intake shaft (AIS)). Hydraulic characteristics (i.e., apparent porosity and apparent dispersion coefficient) for intact-core columns were obtained via experiments using the conservative tracer 22Na. Elution experiments carried out over periods of a few days with tracers 232U and 239Np indicated that these tracers were weakly retarded as indicated by delayed elution of the species. Elution experiments with tracers 241Pu and 241Am were attempted but no elution of either species has been observed to date, including experiments of many months' duration. In order to quantify retardation of the non-eluted species 241Pu and 241Am after a period of brine flow, non-destructive and destructive analyses of one intact-core column were carried out to determine distribution of these actinides in the rock. Analytical results indicate that the majority of the 241Am remained very near the injection surface of the core (possibly as a precipitate), and that the majority of the 241Pu was dispersed with a very high apparent retardation value. The 241Pu distribution is interpreted using a single-porosity advection-dispersion model, and an approximate retardation value is reported.     

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.     

In situ tracer tests to determine retention properties of a block scale fracture network in granitic rock at the Aspö Hard Rock Laboratory, Sweden

Experiments were conducted at the Asp? Hard Rock Laboratory in order to improve the understanding of radionuclide retention properties of fractured crystalline bedrock in the 10-100 m scale (TRUE Block Scale Project, jointly funded by ANDRA, ENRESA, Nirex, JNC, Posiva and SKB). A series of tracer experiments were performed using sorbing tracers in three different flow paths. The different flow paths had Euclidian lengths of 14, 17 and 33 m, respectively, and one to three water conducting structures. Four tests were performed using different cocktails made up of radioactive sorbing tracers (22,24Na+, 42K+, 47Ca2+, 85Sr2+, 83,86Rb+, 131,133Ba2+ and 134,137Cs+). For each tracer injection, the breakthrough of sorbing tracers was compared to the breakthrough of a conservative tracer, 82Br-, 131I-, HTO and 186ReO4-, respectively. In the two longer flow paths, no breakthrough of 83Rb+ and 137Cs+ was observed after 8 months of pumping. Selected tracer tests were subject to basic modelling in which a one-dimensional (1D) advection-dispersion model, including surface sorption, and an unlimited matrix diffusion were used for the interpretation of the results. The results of the modelling indicated that there is a slightly higher mass transfer into a highly porous material in the block-scale experiment compared with in situ experiments performed over shorter distances and significantly higher than what would have been expected from laboratory data obtained from studies of the interactions in nonaltered intact rock.     

Actinide geochemistry: From the molecular level to the real system

Geochemical processes leading to either mobilization or retention of radionuclides in an aquifer system are significantly influenced by their interaction with rock, sediment and colloid surfaces. Therefore, a sound safety assessment of nuclear waste disposal requires the elucidation and quantification of those processes. State-of-the-art analytical techniques as e.g. laser- and X-ray spectroscopy are increasingly applied to study solid–liquid interface reactions to obtain molecular level speciation insight.We have studied the sorption of trivalent lanthanides and actinides onto aluminium oxides, hydroxides and purified clay minerals by the time-resolved laser fluorescence spectroscopy and X-ray-absorption spectroscopy. Chemical constitution and structure of surface bound actinides are proposed based on spectroscopic information. Open questions still remain with regard to the exact nature of mineral surface ligands and the mineral/water interface. Similarities of spectroscopic data obtained for M(III) sorbed onto γ-alumina, and clay minerals suggest the formation of very comparable inner-sphere surface complexes such as S–O–An(III)(OH)_x^(2 − x)(H₂O)_5 − x at pH > 5. Those speciation data are found consistent with those predicted by surface complexation modelling. The applicability of data obtained for pure mineral phases to actinide sorption onto heterogeneously composed natural clay rock is examined by experiments and by geochemical modelling. Good agreement of experiment and model calculations is found for U(VI) and trivalent actinide/lanthanide sorption to natural clay rock. The agreement of spectroscopy, geochemical modelling and batch experiments with natural rock samples and purified minerals increases the reliability in model predictions.The assessment of colloid borne actinide migration observed in various laboratory and field studies calls for detailed information on actinide–colloid interaction. Kinetic stabilization of colloid bound actinides can be due to inclusion into inorganic colloid matrix or by macromolecular rearrangement in case of organic, humic/fulvic like colloids. Only a combination of spectroscopy, microscopy and classical batch sorption experiments can help to elucidate the actinide–colloid interaction mechanisms and thus contribute to the assessment of colloids for radionuclide migration.     

Numerical modeling of humic colloid borne americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model

The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parmeters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.     

Uranium transport around the reactor zone at Bangombé and Okélobondo (Oklo): examples of hydrogeological and geochemical model integration and data evaluation

The sites at Bangombé and Okélobondo (Oklo) in Gabon provide a unique opportunity to study the behaviour of products from natural nuclear reactions in the vicinity of reactor zones which were active around two billion years ago. The Commission of the European Communities initiated the Oklo Natural Analogue Programme. One of the principal aims was to study indications of present time migration of elements from the reactor zones under ambient conditions. The hydrogeological and hydrochemical data from the Oklo sites were modelled in order to better understand the geochemical behaviour of radionuclides in the natural system, by using independent models and by comparing the modelling outcome. Two modelling approaches were used: M3 code (hydrochemical mixing and mass balance model), developed by the Swedish Nuclear Fuel and Waste Management Company (SKB) and HYTEC (reactive transport model) developed by Ecole des Mines de Paris.Two different reactor zones were studied: Bangombé, a shallow site, the reactor being at 11 m depth, and OK84 at Okélobondo, situated at about 450 m depth, more comparable with a real repository location. This allowed the validation of modelling tools in two different sedimentary environments: one shallow, with a more homogeneous layering situated in an area of meteoric alteration, and the other offering the opportunity to study radionuclide migration from the reaction zone over a distance of 450 m through very heterogeneous sedimentary layers.The modeling results indicate that the chemical reactions retarding radionuclide transport are very different at the two sites. At Bangombé, the decomposition of organic material consumes oxygen and at Okélobondo the oxygen is consumed by inorganic reactions resulting, in both cases, in uranium retardation. Both modelling approaches (statistic with M3 code and deterministic with HYTEC code) could describe this situation.The goal of this exercise is to test codes which can help to describe and understand the processes taking place at the sites, validate the models with in situ data, and thus build confidence in the tools used for future site characterization. Ultimately, this allows identifying and selecting processes and parameters that can be used as input into repository performance assessment calculations and modelling exercises.     

Migration of uranium(IV)/(VI) in the presence of humic acids in quartz sand: a laboratory column study

The migration behavior of U(IV) and U(VI) in the presence of humic acid was studied in a quartz sand system. Laboratory column experiments were performed using humic acid, U(VI) in humic acid absence, U(IV) and U(VI) in humic acid presence, and for comparison a conservative tracer. In experiments using humic acid, both redox species of U migrate nearly as fast as the conservative tracer. Humic acid accelerates the U(VI) breakthrough compared to the humic acid-free system. There are strong indications for a similar effect on the U(IV) transport. At the same time, a part of U(IV) and U(VI) associated with the humic acid is immobilized in the quartz sand due to humic colloid filtration thus producing a delaying effect. Tailing at a low concentration level was observed upon tracer elution. The experimental breakthrough curves were described by reactive transport modeling using equations for equilibrium and kinetic reactions. The present study demonstrates that humic acids can play an important role in the migration of actinides. As natural organic matter is ubiquitous in aquifer systems, the humic colloid-borne transport of actinides is of high relevance in performance assessment.     

Modelling of nonreactive tracer dipole tests in a shear zone at the Grimsel test site

The investigation of the migration of a high pH plume in a fractured shear zone is foreseen by a long-term experiment at the Grimsel rock laboratory. In order to characterise the initial conditions for the long-term experiment and to evaluate an optimal hydraulic in situ set-up, several dipole experiments with nonreacting tracers have been performed. The dipole experiments differ in geometry, pumping rates and orientation to the background water flow. Several single and double-porosity models have been applied to fit the results of these dipole tracer tests in order to extract values for some transport parameters and discriminate for certain transport processes. A two-dimensional porous medium approach was successfully used to fit tracer breakthrough curves measured for a dipole experiment. A model based on a one-dimensional dual porous medium approach was also successful, although the applied hydraulic dipole, with similar injection and extraction rates, suggests the existence of an extended two-dimensional flow field. For the two-dimensional porous medium approach, tracer breakthrough could only be fitted with a complex flow field geometry within the heterogeneous fractured shear zone. The heterogeneity was generated by heterogeneous porosity and hydraulic permeability distributions. Predictions for further dipole geometries and a sorbing tracer have been calculated by means of both models using the flow and transport parameters deduced from fits for a single dipole experiment. This allows for comparison with the measured breakthrough of sorbing tracers. The foreseen experiment with sorbing (radionuclide) tracers will help decide on the appropriate approach that should be used to describe such dipole experiments in this shear zone. Additionally, the migration and spreading of a solution with high pH has been calculated taking into account mineral dissolution and precipitation in a two-dimensional porous medium approach in order to estimate the amount and character of the mineral reactions induced by the interaction between the high pH solution and the rock.     

Plutonium in groundwater at the 100K-Area of the U.S. DOE Hanford Site

We examined the concentration, size distribution, redox state and isotopic composition of plutonium (Pu) in groundwater at the 100K-Area at the U.S. Department of Energy's (DOE) Hanford Site. Total concentrations of Pu isotopes were extremely low (10(-4) to 10(-6) pCi/kg, approximately 10(4) to 10(6) atoms/kg) but measurable for the first time in the 100K-Area wells using mass spectrometric analyses that are much more sensitive than alpha spectroscopy methods used previously. Size fractionation data from two wells suggest that 7-29% of the Pu is associated with colloids, operationally defined here as particles between 1 kDa-0.2 microm in size. These colloids were collected using a 1 kDa cross-flow ultrafiltration (CFF) system developed specifically for groundwater actinide studies to include careful controls both in the field and during processing to ensure in situ geochemical conditions are maintained and size separations can be well characterized. Pu in this colloidal fraction was exclusively in the more reduced Pu(III/IV) form, consistent with the higher affinity of Pu in the lower oxidation states for particle surfaces. While the overall concentrations of Pu were low, the Pu isotopic composition suggests at least two local sources of groundwater Pu, namely, local Hanford reactor operations at the 100K-Area and spent nuclear fuel from the N-reactor, which was stored in concrete pools at this site. Differences between this site and the Savannah River Site (SRS) are noted, since groundwater Pu at the F-Area seepage basin at SRS has been found using these same methods, to be characterized by lower colloidal abundances and higher oxidation states. This difference is not directly attributable to groundwater redox potential or geochemical conditions, but rather the physical-chemical difference in Pu sources, which at SRS appear to be dominated downstream from the seepage basins by decay of 244Cm, resulting in more oxidized forms of 240Pu. There is no clear evidence for colloid facilitated transport of Pu in groundwater at the Hanford Site, since downstream wells have both an order of magnitude lower concentrations of Pu and a lower fractional colloidal distribution.     

Laboratory migration experiments with radionuclides and natural colloids in a granite fracture

Natural colloids in groundwater could facilitate radionuclide transport, provided the colloids are mobile, are present in sufficient concentrations and can adsorb radionuclides. This paper describes the results of a laboratory migration study carried out with combinations of radionuclides and natural colloids within a fracture in a large granite block to experimentally determine the impact of colloids on radionuclide transport. The 85Sr used in this study is an example of a moderately sorbing radionuclide, while the 241Am is typical of a strongly sorbed radionuclide with very low solubility. The natural colloids used in this study were isolated from granite groundwater from Atomic Energy of Canada (AECL) Underground Research Laboratory (URL), and consisted of mostly 1-10 nm organic colloids, along with lesser amounts of 10-450 nm colloids (organics and aluminosilicates). The measured coefficients for radionuclide sorption onto these colloids were between 3 x 10(2) and 1 x 10(3) ml/g for 85Sr, and between 7 x 10(4) and 7 x 10(5) mg/l for 241Am. The 85Sr sorption on the natural colloids appeared to be reversible. Migration experiments in the granite block were carried out by establishing a flow field between two boreholes (out of a total of nine) intersecting a main horizontal fracture. These experiments showed that dissolved 85Sr behaved as a moderately sorbing tracer, while dissolved 241Am was completely adsorbed by the fracture surfaces and showed no evidence of transport. However, when natural colloids were injected together with dissolved 241Am, a small amount of 241Am transport was observed, demonstrating the ability of natural colloids to facilitate the transport of radionuclides with low solubility. Natural colloids had only a minor effect on the transport of 85Sr. In a separate experiment to test the effect of higher colloid concentrations on 85Sr migration, synthetic colloids were produced from Avonlea bentonite. The introduction of a relatively high concentration of bentonite colloids actually reduced 85Sr transport because, compared to natural colloids, the bentonite colloids were less mobile and they sorbed 85Sr more strongly.     

Comparison of two micro-analytical methods for detecting the spatial distribution of sorbed Pu on geologic materials

Subsurface transport of groundwater contaminants is greatly influenced by chemical speciation, precipitation and sorption processes at the mineral-water interface. The retardation of contaminants is often greatest at boundaries between minerals and in fractures and pore spaces. The investigation of the spatial distribution of sorbed contaminants along these boundaries requires micro-analytical techniques. The sorption of dissolved Pu(V) on a natural zeolitic tuff from Yucca Mountain (NV, USA) was examined using microautoradiography (MAR), X-ray diffraction (XRD), electron microprobe (EM) techniques, and synchrotron-based micro-X-ray fluorescence (micro-SXRF). The tuff contained a heterogeneous distribution of zeolites and trace quantities of smectites, Fe oxides (hematite), and Mn oxides (rancieite), which are present as fracture fill and pore space materials. Micro-SXRF studies showed that Pu is mostly associated with bodies of smectite plus Mn oxides, which were typically elevated in Ce, Ga, Nb, Pb, Y, Ca, Ti, and Zn. Sorbed Pu was not associated with Fe-rich bodies, which were enriched in Cl and Rb. Results of the MAR studies were complementary to that of the micro-SXRF studies in that Pu was associated with similar elements in the tuff. Indirect detection of Pu by EM or micro-SXRF (by analyzing Ag developed on the MAR photoemulsion) was a more sensitive method for detecting lower levels of sorbed Pu than the direct detection of sorbed Pu via micro-SXRF in the absence of the photoemulsion.     

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 Äspö 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 K_d 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 K_ds 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.     

Soil attenuation of As(III,V) and Se(IV,VI) seepage potential at ash disposal facilities

Leachate from ash landfills is frequently enriched with As and Se but their off-site movement is not well understood. The attenuation potential of As and Se by soils surrounding selected landfills during leachate seepage was investigated in laboratory column studies using simulated ash leachate. As(III, V) and Se(IV, VI) concentrations as well as pH, flow rate, and a tracer were monitored in influent and effluent for up to 800 pore volumes followed by sequential desorption, extraction, and digestion of column segments. Column breakthrough curves (BTCs) were compared to predictions based on previously measured sorption isotherms. Early As(V) breakthrough and retarded As(III) breakthrough relative to predicted BTCs are indicative of oxidative transformation during seepage. For Se(VI), which exhibits linear sorption and the lowest sorption propensity, measured BTCs were predicted fairly well by equilibrium sorption isotherms, except for the early arrival of Se(IV) in one site soil, which in part, may be due to higher column pH values compared to batch isotherms. Most of the As and Se retained by soils during leaching was found to be strongly sorbed (60–90%) or irreversibly bound (10–40%) with <5% readily desorbable. Redox potential favoring transformation to the more sorptive valence states of As(V) and Se(IV) will invoke additional attenuation beyond equilibrium sorption-based predictions. With the exception of Se(IV) on one site soil, results indicate that attenuation by down-gradient soils of As and Se in ash landfill seepage will often be no less than what is predicted by equilibrium sorption capacity with further attenuation expected due to favorable redox transformation processes, thus mitigating contaminant plumes and associated risks.     

Solute transport in crystalline rocks at Äspö — I: Geological basis and model calibration

Water-conducting faults and fractures were studied in the granite-hosted Äspö Hard Rock Laboratory (SE Sweden). On a scale of decametres and larger, steeply dipping faults dominate and contain a variety of different fault rocks (mylonites, cataclasites, fault gouges). On a smaller scale, somewhat less regular fracture patterns were found. Conceptual models of the fault and fracture geometries and of the properties of rock types adjacent to fractures were derived and used as input for the modelling of in situ dipole tracer tests that were conducted in the framework of the Tracer Retention Understanding Experiment (TRUE-1) on a scale of metres. After the identification of all relevant transport and retardation processes, blind predictions of the breakthroughs of conservative to moderately sorbing tracers were calculated and then compared with the experimental data. This paper provides the geological basis and model calibration, while the predictive and inverse modelling work is the topic of the companion paper [J. Contam. Hydrol. 61 (2003) 175].The TRUE-1 experimental volume is highly fractured and contains the same types of fault rocks and alterations as on the decametric scale. The experimental flow field was modelled on the basis of a 2D-streamtube formalism with an underlying homogeneous and isotropic transmissivity field. Tracer transport was modelled using the dual porosity medium approach, which is linked to the flow model by the flow porosity. Given the substantial pumping rates in the extraction borehole, the transport domain has a maximum width of a few centimetres only. It is concluded that both the uncertainty with regard to the length of individual fractures and the detailed geometry of the network along the flowpath between injection and extraction boreholes are not critical because flow is largely one-dimensional, whether through a single fracture or a network. Process identification and model calibration were based on a single uranine breakthrough (test PDT3), which clearly showed that matrix diffusion had to be included in the model even over the short experimental time scales, evidenced by a characteristic shape of the trailing edge of the breakthrough curve. Using the geological information and therefore considering limited matrix diffusion into a thin fault gouge horizon resulted in a good fit to the experiment. On the other hand, fresh granite was found not to interact noticeably with the tracers over the time scales of the experiments.While fracture-filling gouge materials are very efficient in retarding tracers over short periods of time (hours–days), their volume is very small and, with time progressing, retardation will be dominated by altered wall rock and, finally, by fresh granite. In such rocks, both porosity (and therefore the effective diffusion coefficient) and sorption K_ds are more than one order of magnitude smaller compared to fault gouge, thus indicating that long-term retardation is expected to occur but to be less pronounced.     

Mobile fission and activation products in nuclear waste disposal

When disposing nuclear waste in clay formations it is expected that the most radiotoxic elements like Pu, Np or Am move only a few centimetres to meters before they decay. Only a few radionuclides are able to reach the biosphere and contribute to their long-term exposure risks, mainly anionic species like I129, Cl36, Se79 and in some cases C14 and Tc99, whatever the scenario considered. The recent OECD/NEA cosponsored international MOFAP workshop focussed on transport and chemical behaviour of these less toxic radionuclides. New research themes have been addressed, such as how to make use of molecular level information for the understanding of the problem of migration at large distances. Diffusion studies need to face mineralogical heterogeneities over tens to hundreds of meters. Diffusion rates are very low since the clay rock pores are so small (few nm) that electrostatic repulsion limits the space available for anion diffusion (anion exclusion). The large volume of traversed rock will provide so many retention sites that despite weak retention, even certain of these “mobile” nuclides may show significant retardation. However, the question how to measure reliably very low retention parameters has been posed. An important issue is whether redox states or organic/inorganic speciation change from their initial state at the moment of release from the waste during long term contact with surfaces, hydrogen saturated environments, etc.     

Presence of plutonium contamination in soils from Palomares (Spain)

More than 30 years after the occurrence of an aircraft accident which involved the detonation of two nuclear weapons in the surrounding area of the village of Palomares (Spain), the affected terrestrial area has been investigated for remaining transuranic contamination. Evidence from the presence of this contamination was initially found through the analysis of the 241Am inventories in superficial soil samples collected in the region, and was confirmed through the analysis of the (239+240)Pu inventories and their associated 238Pu/(239+240)Pu activity ratios in the same samples. However, it was also observed that a considerable fraction of the remaining contamination in the area was present in particulate form, i.e. as "hot particles". The work performed in our laboratory for identification, isolation and characterisation of these "hot particles" as well as some conclusions obtained from these analyses are outlined in this paper.     

Transport of radionuclides in natural fractures: some aspects of laboratory migration experiments

Results are reported for a series of migration experiments performed in a hydraulically characterized, single, natural fracture in a block of granite with overall dimensions of 1 × 1 × 0.7 m (all approximate), using the conservative, poorly sorbing and strongly sorbing radionuclides ³H₂0, ¹³¹I, ²²Na, ⁸⁵Sr, ¹³⁷Cs, ⁶⁰Co, ^154,155Eu, ²³⁷Np, and ²³⁸Pu. The volumetric flow velocity of the transport solution was 3 ml h⁻¹, giving a residence time in the fracture of approximately 50 h. Elution profiles were obtained for ³H₂0, ¹³¹I, ²²Na, ⁸⁵Sr and ¹³⁷Cs but no evidence of the other radionuclides was observed in the eluent. Results from supporting static sorption measurements on crushed geological materials and granite coupons showed in general higher sorption on alteration minerals than on granite. Sorption was lowest for ²²Na and ⁸⁵Sr.The migration of ¹³¹I, ²²Na, ⁸⁵Sr through the fracture in real time was followed using end-window Geiger-Müller probes located in unused boreholes. Additional information, obtained by alpha and gamma scanning of the fracture surfaces after separating the block along the fracture, confirmed that transport had occurred along the flow path predicted from the hydraulic characterization of the fracture and that, over a 5.5 month period, the bulk of the injected ¹³⁷Cs had migrated only 75 cm along the flow path. The ⁶⁰Co, the rare earths and the actinides had not moved beyond the location of the injection borehole, suggesting that fracture infilling minerals played a major role in retarding radionuclide transport. Additional confirmation of the role of secondary minerals in radionuclide retardation was obtained using selective sequential extraction on the fracture surfaces. These observations support the inclusion of sorption data for fracture infilling minerals in the sorption database developed for the geosphere model for the Canadian Nuclear Fuel Waste Management Program.     

Measurement of plutonium isotopes, 239Pu and 240Pu,in air-filter samples from Seville (2001–2002)

Since the last nuclear atmospheric test carried out by the People Republic of China in 1980 and since the Chernobyl accident in 1986, the plutonium hasn't been directly released into the atmosphere. However, nowadays, it is still present in the troposphere. This is due to plutonium-bearing soil particles physical resuspension processes. In this work, we study for the first time the temporal variation of plutonium isotopes, ²³⁹Pu and ²⁴⁰Pu, baseline concentrations on a monthly basis in surface air from Seville (Spain), and their correlation with some tracers of mineral dust, during 2001 and 2002. The Pu analyses were performed by low-energy Accelerator Mass Spectrometry (AMS). The ²³⁹Pu plus ²⁴⁰Pu (^239+240Pu) activity levels achieved maximums during the summer period, characterized by the absence of rains, and minimums during the rainy seasons, laying in the range 1–20 nBq m^?3. The ²⁴⁰Pu/²³⁹Pu two-year average atomic ratio was 0.18 ± 0.03, in agreement with the fallout plutonium. A good correlation with Pu and Al and Ti levels is observed. They are crustal components usually used as tracers of African dust over European countries. The hypothesis of the influence of the Saharan dust intrusions is supported as well through the study of Total Ozone Mass Spectrometer (TOMS) daily images.