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.     

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.     

Computational spectroscopic study of copper, cadmium, lead and zinc interactions in the environment

Molecular modelling has been used to investigate the interactions of various heavy metals, in order to understand and possibly to control the nature and behaviour of metals, especially in the aquatic environment. The interactions of copper, cadmium, lead and zinc with organic acids were studied using density functional theory (DFT) calculations. Carboxylic acid was used as a model molecule. The structure of each metal carboxylate was optimized and the vibrational spectrum calculated. The results indicate that there is a shift in the calculated v_S(C=O) of metal carboxylates compared with that of carboxylic acid. It was also found that hexaaqua structures of both cadmium and zinc are stable whereas those of copper and lead are not. Furthermore, dipole moment calculations indicate that cadmium carboxylate dihydrate is more representative of cadmium interactions in the aquatic environment. Moreover, hexaaquo cadmium could further interact with surrounding molecules in the aquatic environment.     

Column studies on transport of deicing additive benzotriazole in a sandy aquifer and a zerovalent iron barrier

Benzotriazole (BTA), a chemical with wide industrial applications, is a typical additive in deicer/anti-icer used at airport. To achieve a better understanding of the transport behaviour and environmental fate of BTA, laboratory column studies have been performed on subsoil samples from Oslo Airport, Gardermoen. To explore possibilities for aquifer remediation, BTA behaviour was also studied in a column of granular zerovalent iron (Fe(0)). The subsoil column study demonstrates a very limited retardation of BTA. Consecutive loadings of BTA of the subsoil column showed no change of the break-through curve (BTC) and complete desorption was observed. The sorption behaviour of BTA to metallic iron (Fe(0)) was rather complex. Considerable retardation was observed in the Fe(0) column and repeated BTA loading resulted in an earlier break-through. Between 20% and 50% of the input concentration was retained permanently in the iron (Fe(0)) column. The BTA sorption to metallic iron was found to be enhanced by chloride which lowered the break-through concentration (i.e the C/C(0) plateau). The fraction of BTA remaining in the iron column was found to vary with the flow rate, indicating a time dependant multilayer sorption mechanism. The steady increase in the amount of adsorbed BTA to the iron column during loading corresponds to a rather strong bonding of 4-15 BTA layers to the iron surface. A very slow desorption of BTA was observed; even after flushing with 753 pore volumes of BTA free water, 7.5% of the BTA remained in the column. A geochemical model was developed based on PHREEQC-2 to simulate the sorption and transport of BTA in the tested materials. The BTA sorption was modelled with Freundlich sorption isotherms, as earlier determined in batch experiments. A slight adjustment of the Freundlich parameters was required to fit the observed column break-through. However, our model was not able to simulate the long-term retainment of BTA in the granular iron columns. The simulations confirm the high mobility of BTA in groundwater aquifers and suggest that zerovalent iron could be used to retain a BTA plume, although oxidation of the sorbent might reduce the long-term performance of such a remediation scheme and slow desorption has been observed.     

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.     

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.     

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.     

Oxygenated fuel induced cosolvent effects on the dissolution of polynuclear aromatic hydrocarbons from contaminated soil

The cosolvent-induced dissolution of polynuclear aromatic hydrocarbons (PAHs) from contaminated soil caused by oxygenated fuel spills was studied. Oxygenated fuel induces a solvent flushing effect on the contaminated soil due to the high content of oxygenated compounds (i.e., methanol, ethanol, and methyl tert butyl ether (MTBE)). The miscible displacement techniques were applied to evaluate the increased potential for secondary contamination in an impacted site. Significant solubility enhancement of the 18 PAHs monitored during fuel spill simulation and cosolvent flushing is clearly evident when compared to normal water dissolution. The breakthrough concentration profile for each PAH constituent was integrated over the cumulative effluent volume (i.e., the zeroth moment) to determine the total PAH mass removed during the experiment. The removal efficiency of PAHs ranges from 46.6% to 99.9% in three oxygenated fuels (i.e., M85, E85, and oxygenated gasoline) during the fuel spill. Several factors including hydrophobicity of compounds, nonequilibrium dissolution due to nonuniform coal tar distribution, and heterogeneous media properties affect the oxygenated compound-induced dissolution process. This study provides a basis to predict the facilitated transport of hydrophobic organic compounds from subsurface environment due to the cosolvent effects of oxygenated fuels.     

Persulfate oxidation of trichloroethylene with and without iron activation in porous media

In situ chemical oxidation with persulfate anion (S2O82*) is a viable technique for remediation of groundwater contaminants such as trichloroethylene (TCE). An accelerated reaction using S2O82* to destroy TCE can be achieved via chemical activation with ferrous ion to generate sulfate radicals (SO4*)(E degrees =2.6 V). The column study presented here simulates persulfate oxidation of TCE in porous media (glass beads and a sandy soil). Initial experiments were conducted to investigate persulfate transport in the absence of TCE in the column. The persulfate flushing exhibited a longer residence time and revealed a moderate persulfate interaction with soils. In TCE treatment experiments, the results indicate that the water or persulfate solution would push dissolved TCE from the column. Therefore, the effluent TCE concentration gradually increased to a maximum when about one pore volume was replaced with the flushing solution in the column. The presence of Fe2+ concentration within the column caused a quick drop in effluent TCE concentration and more TCE degradation was observed. When a TCE solution was flushing through the soil column, breakthrough of TCE concentration in the effluent was relatively slow. In contrast, when the soil column was flushed with a mixed solution of persulfate and TCE, persulfate appeared to preferentially oxidize soil oxidizable matter rather than TCE during transport. Hence, persulfate oxidation of soil organics may possibly reduce the interaction between TCE and soil (e.g., adsorption) and facilitate the transport of TCE through soil columns resulting in faster breakthrough.     

Palygorskite as a feasible amendment to stabilize heavy metal polluted soils

The sorption behaviour of palygorskite has been studied with respect to lead, copper, zinc and cadmium in order to consider its application to remediate soils polluted with these metals. The Langmuir model was found to describe well the sorption processes offering maximum sorption values of 37.2 mg/g for lead, 17.4 mg/g for copper, 7.11 mg/g for zinc and 5.83 mg/g for cadmium at pH 5-6. In addition the effect of palygorskite amendment in a highly polluted mining soil has been studied by means batch extractions and leaching column studies. The soluble metal concentrations as well as the readily-extractable metal concentrations were substantially decreased at any concentration of palygorskite applied to soil (1, 2, 4%), although the highest decrease is obtained at the 4% dose. The column studies also showed a high reduction in the metal leaching (50% for lead, 59% for copper, 52% for zinc and 66% for cadmium) when a palygorskite dose of 4% was applied.     

Effect of cadmium and zinc on intestinal absorption of xylose and tryptophan in the fresh water teleost fish, Heteropneustesfossilis

The effect of cadmium and of zinc on the rate of uptake of a pentose sugar xylose and an aminoacid tryptophan by the intestine of a teleost fish, $\text{Heteropneustes}$$\text{fossilis}$ was studied under two experimental conditions. In the first, four concentrations of cadmium or zinc (1.0 mM, 0.1 mM, 0.01 mM and 0.001 mM) mixed with the nutrient solution were filled in the intestinal sacs, and the rate of absorption was recorded after 1 h at 23°C. In the second experiment fish were exposed by bath to a sublethal concentration of cadmium (0.26 mg/1) or zinc (4 mg/1) for 15 and 30 days and the rate of absorption of the two nutrients was measured. The activity of intestinal Na⁺, K⁺ activated adenosine triphosphatase was also assayed. The two heavy metals at all the four concentrations decreased the rate of intestinal transport of nutrients. Increase in the concentration of each of the heavy metals decreased the uptake of nutrients, but the decreases were not linear. The rate of intestinal absorption of the two nutrients was also reduced by exposure of fish to the heavy metals $\text{in}$$\text{vivo}$. The activity of Na⁺, K⁺ ATPase decreased $\text{in}$$\text{vitro}$ with all four concentrations of cadmium and zinc and was diminished in fish exposed for 15 and 30 days. Of the two heavy metals, cadmium was more effective in reducing the rate of transport of xylose and tryptophan.     

Influence of surfactant sorption on the removal of phenanthrene from contaminated soils

Laboratory column flushing experiments were conducted to remove phenanthrene from contaminated soils by Triton X-100 (TX100) with an aim to investigating the effect of surfactant sorption on the performance of surfactant-enhanced remediation process. The effluent concentration of phenanthrene from soil columns showed strong dependence on the sorption breakthrough curves of TX100. The removal of phenanthrene from contaminated soils was enhanced only when the sorption breakthrough of TX100 occurred and the influent concentration of TX100 was greater than the critical enhanced flushing concentration (CEFC). The sorption of surfactant onto soils and the subsequent partitioning of contaminants into soil-sorbed surfactant had a significant effect on the solute equilibrium distribution coefficient (KD) and thus the flushing efficiency for phenanthrene. A model was developed to predict KD and CEFC values for simulating the performance of surfactant-enhanced flushing for contaminated soils. These results are of practical interest in developing effective and safe surfactant-enhanced remediation technologies.     

Uptake of cadmium by Stichococcus bacillaris

The uptake of cadmium by the green alga $\text{Stichococcus bacillaris}$ was studied. It was found that about 80% of the uptake was due to adsorption, and about 20% to energy-dependent transport. Investigations on the relationship between the sorption of cadmium and the equilibrium concentration (Ce) revealed that the alga cells are saturated at Ce20mg Cd/1.     

Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).     

Removal of volatile and semivolatile organic contamination from soil by air and steam flushing

A soil core, obtained from a contaminated field site, contaminated with a mixture of volatile and semivolatile organic compounds (VOC and SVOC) was subjected to air and steam flushing. Removal rates of volatile and semivolatile organic compounds were monitored during flushing. Air flushing removed a significant portion of the VOC present in the soil, but a significant decline in removal rate occurred due to decreasing VOC concentrations in the soil gas phase. Application of steam flushing after air flushing produced a significant increase in contaminant removal rate for the first 4 to 5 pore volumes of steam condensate. Subsequently, contaminant concentrations decreased slowly with additional pore volumes of steam flushing. The passage of a steam volume corresponding to 11 pore volumes of steam condensate reduced the total VOC concentration in the soil gas (at 20 degrees C) by a factor of 20 to 0.07 mg/l. The corresponding total SVOC concentration in the condensate declined from 11 to 3 mg/l. Declines in contaminant removal rates during both air and steam flushing indicated rate-limited removal consistent with the persistence of a residual organic phase, rate-limited desorption, or channeling. Pressure gradients were much higher for steam flushing than for air flushing. The magnitude of the pressure gradients encountered during steam flushing for this soil indicates that, in addition to rate-limited contaminant removal, the soil permeability (2.1 x 10(-9) cm2) would be a limiting factor in the effectiveness of steam flushing.     

Removal of organic contaminants from soils by an electrokinetic process: the case of atrazine. Experimental and modeling

The atrazine behaviour in soils when submitted to an electric field was studied and the applicability of the electrokinetic process in atrazine soil remediation was evaluated. Two polluted soils were used, respectively with and without atrazine residues, being the last one spiked. Four electrokinetic experiments were carried out at a laboratory scale. Determination of atrazine residues were performed by enzyme-linked immunosorbent assay (ELISA). The results show that the electrokinetic process is able to remove efficiently atrazine in soil solution, mainly towards the anode compartment: Estimations show that 30-50% of its initial amount is removed from the soil within the first 24h. A one-dimensional model is developed for simulating the electrokinetic treatment of a saturated soil containing atrazine. The movement of atrazine is modelized taking into account the diffusion transport resulting from atrazine concentration gradients and the reversed electro-osmotic flow at acidic soil pH.     

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.     

电动与渗透反应格栅联合修复镉污染地下水实验

通过实验方法研究了地下水中镉污染的电动力学修复效果,并分析其迁移变化特征。实验结果表明,电动修复中由于阴阳两极的氧化还原反应造成电极附近pH值产生明显变化,其中阳极附近的pH值由开始时的7.0逐渐变小到6.8,而阴极附近则相反,由开始时6.9逐渐增大到9.1,表明土壤的酸碱条件变化明显。Cd浓度变化反映在自然渗透条件下含水层中重金属污染物的迁移能力较弱,阳极附近地下水中Cd的去除率仅8.4%,而在电场作用下地下水中重金属的浓度发生明显变化,使得重金属污染物能在电极附近富集而被去除,当实验电场强度为0.5 V/cm时,Cd在阴极的累积使得阳极附近地下水中去除率为72.9%,说明电动修复重金属Cd污染地下水的效果明显好于自然渗透状态。     

Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.