Intercomparison of reactive transport models applied to UO2 oxidative dissolution and uranium migration

Oxidative dissolution of uranium dioxide (UO(2)) and the subsequent migration of uranium in a subsurface environment and an underground waste disposal have been simulated with reactive transport models. In these systems, hydrogeological and chemical processes are closely entangled and their interdependency has been analyzed in detail, notably with respect to redox reactions, kinetics of mineralogical evolution and hydrodynamic migration of species of interest. Different codes, where among CASTEM, CHEMTRAP and HYTEC, have been used as an intercomparison and verification exercise. Although the agreement between codes is satisfactory, it is shown that the discretization method of the transport equation (i.e. finite elements (FE) versus mixed-hybrid FE and finite differences) and the sequential coupling scheme may lead to systematic discrepancies.     

Database uncertainty as a limiting factor in reactive transport prognosis

The effect of uncertainties in thermodynamic databases on prediction performances of reactive transport modeling of uranium (VI) is investigated with a Monte Carlo approach using the transport code TReaC. TReaC couples the transport model to the speciation code PHREEQC by a particle tracking method. A speciation example is given to illustrate the effect of uncertainty in thermodynamic data on the predicted solution composition. The transport calculations consequently show the prediction uncertainty resulting from uncertainty in thermodynamic data. A conceptually simple scenario of elution of uranium from a sand column is used as an illustrating example. Two different cases are investigated: a carbonate-enriched drinking water and an acid mine water associated with uranium mine remediation problems. Due to the uncertainty in the relative amount of positively charged and neutral solution species, the uncertainty in the thermodynamic data also infers uncertainty in the retardation behavior. The carbonated water system shows the largest uncertainties in speciation calculation. Therefore, the model predictions of total uranium solubility have a broad range. The effect of data uncertainty in transport prediction is further illustrated by a prediction of the time when eluted uranium from the column exceeds a threshold value. All of these Monte Carlo transport calculations consume large amounts of computing time.     

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.     

Intercomparison between TRIO-EF and IMPACT codes with reference to experimental strontium migration data

This work presents an intercomparison exercise between two geochemical migration codes, TRIO-EF (an object-oriented finite element code) and IMPACT (a chemical engineering code using mixing cells in series). The predictions of the two codes are compared with the reference experimental results obtained in a previous study of strontium transport in soil columns. This simulated geochemical system is well documented and includes ion exchange and dissolution-precipitation reactions. The solution transport is simulated by a one-dimensional advection-dispersion model. The predictions of TRIO-EF and IMPACT are both in good agreement with the experimental results. However, slight differences can be observed between the two codes, especially when concentration discontinuities are involved, such as precipitation fronts or changes in boundary conditions. These discrepancies between the two codes can mainly be attributed to the different discretisation approaches.     

Simulating bioremediation of uranium-contaminated aquifers; uncertainty assessment of model parameters

Bioremediation of trace metals and radionuclides in groundwater may require the manipulation of redox conditions via the injection of a carbon source. For example, after nitrate has been reduced, soluble U(VI) can be reduced simultaneously with other electron acceptors such as Fe(III) or sulfate to U(IV), which may precipitate as a solid (uraninite).To simulate the numerous biogeochemical processes that will occur during the bioremediation of trace-metal-contaminated aquifers, a time-dependent one-dimensional reactive transport model has been developed. The model consists of a set of coupled mass balance equations, accounting for advection, hydrodynamic dispersion, and a kinetic formulation of the biological or chemical transformations affecting an organic substrate, electron acceptors, corresponding reduced species, and trace metal contaminants of interest, uranium in this study. This set of equations is solved numerically, using a finite difference approximation. The redox conditions of the domain are characterized by estimating the pE, based on the concentration of the dominant terminal electron acceptor and its corresponding reduced species. This pE and the concentrations of relevant species are then used by a modified version of MINTEQA2, which calculates the speciation/sorption and precipitation/dissolution of the species of interest under equilibrium conditions. Kinetics of precipitation/dissolution processes are described as being proportional to the difference between the actual and calculated equilibrium concentration. A global uncertainty assessment, determined by Random Sampling High Dimensional Model Representation (RS-HDMR), was performed to attain a phenomenological understanding of the origins of output variability and to suggest input parameter refinements as well as to provide guidance for field experiments to improve the quality of the model predictions. By decomposing the model output variance into its different input contributions, RS-HDMR can identify the model inputs with the most influence on various model outputs, as well as their behavior pattern on the model output. Simulations are performed to illustrate the effect of biostimulation on the fate of uranium in a saturated aquifer, and to identify the key processes that need to be characterized with the highest accuracy prior to designing a uranium bioremediation scheme.     

Impact of hypoxia on hemolymph contamination by uranium in an aquatic animal, the freshwater clam Corbicula fluminea

Multi-stress situations are a major question and low-oxygenated waters (hypoxia) are a growing problem. Importantly, hypoxia stimulates the ventilatory flow rate in aquatic animals and this increases gill exposure to contaminants. Surprisingly, in the freshwater clam Corbicula fluminea, this is associated with increased bioaccumulation of uranium in gills but not in deep tissues. We searched for an explanation by analyzing hemolymph U-transport in Corbicula exposed to 0.36 μM dissolved uranium at various O₂-levels for 10 days. In hypoxia, one observed an increased U concentration in the arterial hemolymph flowing from gills to tissues but this was not associated with an increased U concentration in the venous hemolymph nor in the other tissues. We conclude that the cardiac flow rate must have decreased to explain this absence of over-accumulation. In addition to its already known deleterious effects, uranium can thus deeply impair cardiac flow rate in exposed aquatic animals during multi-stress exposures.     

Mineralogical compositions of aquifer matrix as necessary initial conditions in reactive contaminant transport models

Mineralogical compositions and their spatial distributions are important initial conditions for reactive transport modeling. However, popular Kd-based "reactive" transport models only require contaminant concentrations in the pore fluids as initial conditions, and minerals implicitly represent infinite sources and sinks in these models. That situation results in a general neglect of mineralogical characterization in site investigations. This study uses a coupled multi-component reactive mass transport model to predict the natural attenuation of a ground water plume at a uranium mill tailings site in western USA. Numerous ground water geochemistry data are available at this site, but mineralogical data are sketchy. Even given the well-defined pore fluid chemistry, variations of secondary mineral species and mineral abundances in the aquifer resulted in significantly different modeling outcomes. Results show that the amount of calcite in the aquifer determines the distances of plume migration. The possible presence of jurbanite, an aluminum sulfate phase, can store acidity temporarily but cause more severe contamination on a later date. The surfaces of iron oxyhydroxides can store significant amounts of sulfate and protons and serve as a second source for prolonged contamination. These simulations under field conditions illustrate that mineralogical compositions are an essential requirement for accurate prediction of contaminant fate and transport.     

Chemical reactions of uranium in ground water at a mill tailings site

We studied soil and ground water samples from the tailings disposal site near Tuba City, AZ, located on Navajo sandstone, in terms of uranium adsorption and precipitation. The uranium concentration is up to 1 mg/l, 20 times the maximum concentration for ground water protection in the United States. The concentration of bicarbonate (HCO₃⁻) in the ground water increased from ≤7×10⁻⁴ M, the background concentration, to 7×10⁻³ M. Negatively charged uranium carbonate complexes prevail at high carbonate concentrations and uranium is not adsorbed on the negatively charged mineral surfaces. Leaching experiments using contaminated and uncontaminated sandstone and 1 N HCl show that adsorption of uranium from the ground water is negligible. Batch adsorption experiments with the sandstone and ground water at 16°C, the in situ ground water temperature, show that uranium is not adsorbed, in agreement with the results of the leaching experiments. Adsorption of uranium at 16°C is observed when the contaminated ground water is diluted with carbonate-free water. The observed increase in pH from 6.7 to 7.3 after dilution is too small to affect adsorption of uranium on the sandstone. Storage of undiluted ground water to 24°C, the temperature in the laboratory, causes coprecipitation of uranium with aragonite and calcite. Our study provides knowledge of the on-site uranium chemistry that can be used to select the optimum ground water remediation strategy. We discuss our results in terms of ground water remediation strategies such as pump and treat, in situ bioremediation, steam injection, and natural flushing.     

Uranium uptake and depuration in the aquatic invertebrate Chironomus tentans

Evaluation of aqueous uranium (U) uptake and depuration in larvae of the midge Chironomus tentans were investigated in two separated experiments. First, a static-renewal experiment was performed with 10-d old C. tentans larvae exposed to 300 μg U/L. The animals steadily accumulated U (K_u = 20.3) approaching steady-state conditions (BAF = 56) in approximately 9-11 d. However, accumulated U was readily depurated (K_d = 0.36) with U tissue concentration decreasing rapidly within 3 d of the larvae being placed in clean water (t_1/2 = 1.9 d). Also, the growth of C. tentans larvae appeared to decrease after 6-11 d of U exposure, probably due to the reallocation of resources into U detoxification mechanisms. However, growth significantly increased once C. tentans were transferred to clean water. A separate short-term experiment was performed to evaluate the possible mechanism of U uptake in this invertebrate. Results suggested a passive mechanism of U uptake coupled with an active mechanism of U depuration but no details related to the type of mechanisms or pathway was investigated.     

Effective diffusivity of the uranyl ion in a granite from Inada, Ibaraki, Japan

The effective diffusivity of uranium(VI) in Inada granite has been determined by through-diffusion. Experiments were performed at room temperature (20–25°C) in a 0.1 mol 1⁻¹ KCl solution where uranium is present predominantly as the poorly sorbing UO₂²⁺. An effective diffusivity (D_e) of (3.6 ± 1.6) × 10⁻¹⁴ m² s⁻¹ was obtained, close to that for uranine (nonsorbing organic tracer), but one order of magnitude lower than those obtained for Sr²⁺ and NpO₂⁺, and two orders of magnitude lower than that obtained for I⁻. According to well established theory, a proportional relationship exists between D_e and the diffusivity in the bulk of the solution (D_v). The effective diffusivity obtained in granite was not proportional to D_v. This agrees with results obtained for effective diffusivity in a Swedish granite. The ratio D_e/D_v was found to be not constant but increased with D_e or D_v. This result suggests a limit to the application of the theory.     

Oxidative dissolution of uraninite precipitated on Navajo sandstone

Column and batch experiments were conducted with sandstone and ground water samples to investigate oxidation of uraninite precipitated by microbially mediated reduction of U(VI), a contaminant in ground water beneath a uranium mill tailings site near Tuba City, AZ, USA. Uraninite precipitated together with mackinawite (FeS_0.9) because Fe(III) from the sandstone and sulfate, another contaminant in the water were reduced together with U(VI). After completion of U(VI) reduction, experiments were conducted to find out whether uraninite is protected by mackinawite against reoxidation. Uncontaminated ground water from the same site, containing 7 mg/l of dissolved oxygen, was passed through the columns or mixed with sandstone in batch experiments. The results showed that small masses of uraninite, 0.1 μg/g of sandstone, are protected by mackinawite from reoxidation. Uraninite masses on the order of 0.1 μg/g correspond to U(VI) concentrations of 0.5 mg/l, typically encountered in uranium contaminated ground waters. Mackinawite is an effective buffer and is formed in sufficient quantity to provide long-term protection of uraninite. Uranium concentrations in ground water passed through the columns are too low (4 μg/l) to distinguish between dissolution and oxidative dissolution of uraninite. However, batch experiments showed that uraninite oxidation takes place.     

Uranium removal from groundwater via in situ biostimulation: Field-scale modeling of transport and biological processes

During 2002 and 2003, bioremediation experiments in the unconfined aquifer of the Old Rifle UMTRA field site in western Colorado provided evidence for the immobilization of hexavalent uranium in groundwater by iron-reducing Geobacter sp. stimulated by acetate amendment. As the bioavailable Fe(III) terminal electron acceptor was depleted in the zone just downgradient of the acetate injection gallery, sulfate-reducing organisms came to dominate the microbial community. In the present study, we use multicomponent reactive transport modeling to analyze data from the 2002 field experiment to identify the dominant transport and biological processes controlling uranium mobility during biostimulation, and determine field-scale parameters for these modeled processes. The coupled process simulation approach was able to establish a quantitative characterization of the principal flow, transport, and reaction processes based on the 2002 field experiment, that could be applied without modification to describe the 2003 field experiment. Insights gained from this analysis include field-scale estimates of the bioavailable Fe(III) mineral threshold for the onset of sulfate reduction, and rates for the Fe(III), U(VI), and sulfate terminal electron accepting processes.     

The migration of uranium into peat-rich soils at Broubster, Caithness, Scotland, U.K.

Uranium is being actively transported from uraniferous sedimentary rocks into a peat bog at the Broubster natural analogue site in Caithness, Scotland. Massive calcareous sandstone within the Caithness Flags sequence is the main source of uranium which resides primarily within diagenetic apatite and dispersed U---Si---Ti phases. Supergene weathering processes have decalcified the sandstone and are effective in mobilising uranium by groundwater leaching, primarily along a fault zone. Uranium transport in solution by means of groundwater and surface flows is effectively terminated by retardation within 4-kyr-old peat deposits laid down on boulder clay. This process of secondary fixation has resulted in a young uranium anomaly in the peat which comprises in excess of 0.1 wt% U. The site has been investigated comprehensively to define the geometry of the anomaly together with the hydrogeology, hydrochemistry, petrology, mineralogy and the nature of the peat sink-term. The main physical and geochemical properties of the system, including the uranium decay series radionuclide distributions in water and solid samples, are documented in this paper. From these data, the processes governing the distribution of uranium have been quantified using a three-dimensional groundwater flow package and an equilibrium speciation model incorporating a recently developed electrostatic surface complexation model to account for cation-organic interactions. The results described form part of a coordinated project on natural radionuclide migration undertaken to improve confidence in predictive methods used for radiological assessment.     

Study of the contaminant transport into granite microfractures using nuclear ion beam techniques

Hydrated bentonite is a very plastic material and it is expected to enter in the rock microfractures at the granite/bentonite boundary of a deep geological high-level waste repository. This process is enhanced by the high swelling pressure of the clay. Since bentonite has a very good sorption capability for many radionuclides, the displacement of the clay might lead to a "clay-mediated" contaminant transport into the rock. The aim of this work is to study the contaminant transport into granite microfractures using nuclear ion beam techniques, and to determine to what extent the clay can favour it. To do so, bentonite previously doped with uranium, cesium and europium was put in contact with the surface of granite sheets. Granite sheets contacted with non-doped bentonite and with radionuclide solutions were also prepared as references. This allowed analysing the differences in the diffusion behaviour of the three systems: clay, radionuclides and clay plus radionuclides. A combination of Rutherford backscattering spectrometry (RBS) and other nuclear ion-beam techniques such as particle-induced X-ray emission (PIXE) and microPIXE was used to study the depth and lateral distribution of clay and contaminants inside granite. It was also tried to evaluate not only the diffusion depth and diffusion coefficients but also the different areas of the granite where the diffusants have a preferential access.     

Kinetic modeling of microbially-driven redox chemistry of radionuclides in subsurface environments: coupling transport, microbial metabolism and geochemistry

Microbial reactions play an important role in regulating pore water chemistry as well as secondary mineral distribution in many subsurface systems and, therefore, may directly impact radionuclide migration in those systems. This paper presents a general modeling approach to couple microbial metabolism, redox chemistry, and radionuclide transport in a subsurface environment. To account for the likely achievement of quasi-steady state biomass accumulations in subsurface environments, a modification to the traditional microbial growth kinetic equation is proposed. The conditions for using biogeochemical models with or without an explicit representation of biomass growth are clarified. Based on the general approach proposed in this paper, the couplings of uranium reactions with biogeochemical processes are incorporated into computer code BIORXNTRN Version 2.0. The code is then used to simulate a subsurface contaminant migration scenario, in which a water flow containing both uranium and a complexing organic ligand is recharged into an oxic carbonate aquifer. The model simulation shows that Mn and Fe oxyhydroxides may vary significantly along a flow path. The simulation also shows that uranium(VI) can be reduced and therefore immobilized in the anoxic zone created by microbial degradation.     

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.     

Migration behavior of naturally occurring radionuclides at the Nopal I uranium deposit, Chihuahua, Mexico

Oxidation of pyrite at the Nopal I uranium deposit, Peña Blanca district, Chihuahua, Mexico has resulted in the formation of Fe-oxides/hydroxides. Anomalous U concentrations (i.e. several hundred to several thousand ppm) measured in goethite, hematite, and amorphous Fe-oxyhydroxides in a major fracture that crosscuts the deposit and the absence of U minerals in the fracture suggest that U was retained during secondary mineral growth or sorbed on mineral surfaces. Mobilization and transport of U away from the deposit is suggested by decreasing U concentrations in fracture-infilling materials and in goethite and hematite with distance from the deposit. Greater than unity ²³⁴U/²³⁸U activity ratios measured in fracture-infilling materials indicate relatively recent ( < 1 Ma) U uptake from fluids that carried excess ²³⁴U. Systematic decreases in ²³⁴U/²³⁸U activity ratios of fracture materials with distance from the deposit suggest a multistage mobilization process, such as remobilization of U from ²³⁴U-enriched infill minerals or differential or diminished transport of U-bearing solutions containing excess ²³⁴U.     

Uranium in Kosovo’s drinking water

The results of this paper are an initiation to capture the drinking water and/or groundwater elemental situation in the youngest European country, Kosovo. We aim to present a clear picture of the natural uranium concentration in drinking water and/or groundwater as it is distributed to the population of Kosovo. Nine hundred and fifty-one (951) drinking water samples were analyzed by inductively coupled plasma mass spectrometry (ICPMS). The results are the first countrywide interpretation of the uranium concentration in drinking water and/or groundwater, directly following the Kosovo war of 1999. More than 98% of the samples had uranium concentrations above 0.01 μg L⁻¹, which was also our limit of quantification. Concentrations up to 166 μg L⁻¹ were found with a mean of 5 μg L⁻¹ and median 1.6 μg L⁻¹ were found. Two point six percent (2.6%) of the analyzed samples exceeded the World Health Organization maximum acceptable concentration of 30 μg L⁻¹, and 44.2% of the samples exceeded the 2 μg L⁻¹ German maximum acceptable concentrations recommended for infant food preparations.     

Reduction of U(VI) by the deep subsurface bacterium, Thermus scotoductus SA-01, and the involvement of the ABC transporter protein

In this study we investigated the effect of uranium on the growth of the bacterium Thermus scotoductus strain SA-01 as well as the whole cell U(VI) reduction capabilities of the organism. Also, site-directed mutagenesis confirmed the identity of a protein capable of a possible alternative mechanism of U(VI) reduction. SA-01 can grow aerobically in up to 1.25 mM uranium and has the capability to reduce low levels of U(VI) in under 20 h. TEM analysis performed on cells exposed to uranium showed extracellular and membrane-bound accumulation of uranium. The reductase-like protein was surprisingly identified as a peptide ABC transporter, peptide-binding protein. This study showcases the concept of protein promiscuity, where this protein with a distinct function in situ can also have the unintended function of a reactant for the reduction of U(VI).