Mechanisms of electron acceptor utilization: implications for simulating anaerobic biodegradation

Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum-contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and methanogenic conditions. Using this transport model, we had limited success in simulating overlap of redox products using reasonable ranges of parameters within a strictly sequential electron acceptor utilization framework. Simulation results indicate that overlap of redox products cannot be accurately simulated using the constructed model, suggesting either that Fe(III) reduction and methanogenesis are occurring simultaneously in the source area, or that heterogeneities in Fe(III) concentration and/or mineral type cause the observed overlap. Additional field, experimental, and modeling studies will be needed to address these questions.     

Biogeochemistry and isotope geochemistry of a landfill leachate plume

The biogeochemical processes were identified which improved the leachate composition in the flow direction of a landfill leachate plume (Banisveld, The Netherlands). Groundwater observation wells were placed at specific locations after delineating the leachate plume using geophysical tests to map subsurface conductivity. Redox processes were determined using the distribution of solid and soluble redox species, hydrogen concentrations, concentration of dissolved gases (N(2), Ar, and CH(4)), and stable isotopes (delta15N-NO(3), delta34S-SO(4), delta13C-CH(4), delta2H-CH(4), and delta13C of dissolved organic and inorganic carbon (DOC and DIC, respectively)). The combined application of these techniques improved the redox interpretation considerably. Dissolved organic carbon (DOC) decreased downstream in association with increasing delta13C-DOC values confirming the occurrence of degradation. Degradation of DOC was coupled to iron reduction inside the plume, while denitrification could be an important redox process at the top fringe of the plume. Stable carbon and hydrogen isotope signatures of methane indicated that methane was formed inside the landfill and not in the plume. Total gas pressure exceeded hydrostatic pressure in the plume, and methane seems subject to degassing. Quantitative proof for DOC degradation under iron-reducing conditions could only be obtained if the geochemical processes cation exchange and precipitation of carbonate minerals (siderite and calcite) were considered and incorporated in an inverse geochemical model of the plume. Simulation of delta13C-DIC confirmed that precipitation of carbonate minerals happened.     

Effect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers

Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26 per thousand), which is consistent with field observations. At most sampling points, the delta(13)C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a (13)C enrichment of up to 2.4 per thousand was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with (12)C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the delta(13)C values varied substantially from -24.3 per thousand to -33.6 per thousand. Comparison of the delta(13)C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in delta(13)C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network.     

Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume

The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.     

Assessing the impacts of partial mass depletion in DNAPL source zones I. Analytical modeling of source strength functions and plume response

Analytical solutions are developed for approximating the time-dependent contaminant discharge from DNAPL source zones undergoing dissolution and other decay processes. The source functions assume a power relationship between source mass and chemical discharge and can consider partial DNAPL source remediation (depletion) at any time after the initial DNAPL release. The source functions are used as a time-dependent boundary condition in an idealized chemical transport model to develop leading order approximations of the plume response to DNAPL source removal. The results suggest that partial DNAPL remediation does not tend to have a dramatic impact on the maximum extent of the plume if very low concentration values are used to define the plume boundaries. However, the solutions show that partial DNAPL removal from the source zone is likely to lead to large reductions in plume concentrations and mass, and it reduces the longevity of the plume. When the mass discharge from the source zone is linearly related to the DNAPL mass, it is shown that partial DNAPL depletion leads to linearly proportional reductions in the plume mass and concentrations.     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.     

A coupled THC model of the FEBEX in situ test with bentonite swelling and chemical and thermal osmosis

The performance assessment of a geological repository for radioactive waste requires quantifying the geochemical evolution of the bentonite engineered barrier. This barrier will be exposed to coupled thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes. This paper presents a coupled THC model of the FEBEX (Full-scale Engineered Barrier EXperiment) in situ test which accounts for bentonite swelling and chemical and thermal osmosis. Model results attest the relevance of thermal osmosis and bentonite swelling for the geochemical evolution of the bentonite barrier while chemical osmosis is found to be almost irrelevant. The model has been tested with data collected after the dismantling of heater 1 of the in situ test. The model reproduces reasonably well the measured temperature, relative humidity, water content and inferred geochemical data. However, it fails to mimic the solute concentrations at the heater-bentonite and bentonite-granite interfaces because the model does not account for the volume change of bentonite, the CO(2)(g) degassing and the transport of vapor from the bentonite into the granite. The inferred HCO(3)(-) and pH data cannot be explained solely by solute transport, calcite dissolution and protonation/deprotonation by surface complexation, suggesting that such data may be affected also by other reactions.     

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O(2) to waters otherwise depleted in O(2). Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH(4) partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.     

Establishing the propensity for dioxin formation using a plume temperature model for medical waste incinerator emissions in developing countries

Air pollution control devices (APCDs) are not compulsory for medical waste incinerators (MWIs) in developing countries. In South Africa, combustion gases are usually vented directly to the atmosphere at temperatures greater than the formation temperature of dioxin. The possibility of dioxin formation outside the incinerator stack has been hypothesized. A plume model has been developed and tested in the wind tunnel with a scale model of an incinerator stack. The plume temperature and trajectory predictions of the plume model were verified within a +/- 3% experimental accuracy. Using South African data, the plume model predicts that the residence time of gases in the temperature range of 150-450 degrees C in a plume is 1.3 sec on average for 5% of a year (18 days) at meteorological conditions resulting in wind speeds of less than 1 m/sec. Two published dioxin formation models were used to assess the probability of dioxin formation in the plume. The formation models predict that the average polychlorinated dibenzodioxins/furans (PCDD/Fs) formed in the plume will exceed the stack emission regulations in South Africa of 0.2 ng/Nm3 toxic equivalent quotient (TEQ) by between 2 and 40 times. The calculated concentrations do not include additional gaseous PCDD/F compounds that may be formed at high-temperature post-combustion zones through pyrosynthesis mechanisms.     

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.     

Assessing the natural attenuation of organic contaminants in aquifers using plume-scale electron and carbon balances: model development with analysis of uncertainty and parameter sensitivity

A quantitative methodology is described for the field-scale performance assessment of natural attenuation using plume-scale electron and carbon balances. This provides a practical framework for the calculation of global mass balances for contaminant plumes, using mass inputs from the plume source, background groundwater and plume residuals in a simplified box model. Biodegradation processes and reactions included in the analysis are identified from electron acceptors, electron donors and degradation products present in these inputs. Parameter values used in the model are obtained from data acquired during typical site investigation and groundwater monitoring studies for natural attenuation schemes. The approach is evaluated for a UK Permo-Triassic Sandstone aquifer contaminated with a plume of phenolic compounds. Uncertainty in the model predictions and sensitivity to parameter values was assessed by probabilistic modelling using Monte Carlo methods. Sensitivity analyses were compared for different input parameter probability distributions and a base case using fixed parameter values, using an identical conceptual model and data set. Results show that consumption of oxidants by biodegradation is approximately balanced by the production of CH4 and total dissolved inorganic carbon (TDIC) which is conserved in the plume. Under this condition, either the plume electron or carbon balance can be used to determine contaminant mass loss, which is equivalent to only 4% of the estimated source term. This corresponds to a first order, plume-averaged, half-life of > 800 years. The electron balance is particularly sensitive to uncertainty in the source term and dispersive inputs. Reliable historical information on contaminant spillages and detailed site investigation are necessary to accurately characterise the source term. The dispersive influx is sensitive to variability in the plume mixing zone width. Consumption of aqueous oxidants greatly exceeds that of mineral oxidants in the plume, but electron acceptor supply is insufficient to meet the electron donor demand and the plume will grow. The aquifer potential for degradation of these contaminants is limited by high contaminant concentrations and the supply of bioavailable electron acceptors. Natural attenuation will increase only after increased transport and dilution.     

Assessing impacts of partial mass depletion in DNAPL source zones: II. Coupling source strength functions to plume evolution

Analytical solutions, describing the time-dependent DNAPL source-zone mass and contaminant discharge rate, derived previously in Part I [Falta, R.W., Rao, P.S., Basu, N., this issue. Assessing the impacts of partial mass depletion in DNAPL source zones: I. Analytical modeling of source strength functions and plume response. J. Contam. Hydrol.] are used as a flux-boundary condition in a semi-analytical contaminant transport model. These analytical solutions assume a power relationship between the flow-averaged source concentration, and the source DNAPL mass; the empirical exponent (gamma) is a function of the flow field heterogeneity, DNAPL architecture, and the correlation between them. The DNAPL source strength terms can account for partial source remediation, either at time zero, or at some later time after the DNAPL release. The transport model considers advection, retardation, three-dimensional dispersion, and sequential first-order decay/production of several species. A separate solution is used to compute the time-dependent mass of each contaminant in the plume. A series of examples using different values of gamma shows how the benefits of partial DNAPL source remediation can vary with site conditions. In general, when gamma>1, relatively large short-term reductions in the plume concentrations and mass occur, but the source longevity is not strongly affected. Conversely, when gamma<1, the short-term reductions in the plume concentrations and mass are smaller, but the source longevity can be greatly reduced. In either case, the source remediation effort is much more effective if it is undertaken at an early time, before much contaminant mass has entered the plume. If the remediation effort is significantly delayed, the leading parts of the plume are not affected by the source remediation, and additional control or remediation of the plume itself is required.     

Modeling porosity reductions caused by mineral fouling in continuous-wall permeable reactive barriers

A study was conducted to assess key factors to include when modeling porosity reductions caused by mineral fouling in permeable reactive barriers (PRBs) containing granular zero valent iron. The public domain codes MODFLOW and RT3D were used and a geochemical algorithm was developed for RT3D to simulate geochemical reactions occurring in PRBs. Results of simulations conducted with the model show that the largest porosity reductions occur between the entrance and mid-plane of the PRB as a result of precipitation of carbonate minerals and that smaller porosity reductions occur between the mid-plane and exit face due to precipitation of ferrous hydroxide. These findings are consistent with field and laboratory observations, as well as modeling predictions made by others. Parametric studies were conducted to identify the most important variables to include in a model evaluating porosity reduction. These studies showed that three minerals (CaCO3, FeCO3, and Fe(OH)2 (am)) account for more than 99% of the porosity reductions that were predicted. The porosity reduction is sensitive to influent concentrations of HCO3-, Ca2+, CO3(2-), and dissolved oxygen, the anaerobic iron corrosion rate, and the rates of CaCO3 and FeCO3 formation. The predictions also show that porosity reductions in PRBs can be spatially variable and mineral forming ions penetrate deeper into the PRB as a result of flow heterogeneities, which reflects the balance between the rate of mass transport and geochemical reaction rates. Level of aquifer heterogeneity and the contrast in hydraulic conductivity between the aquifer and PRB are the most important hydraulic variables affecting porosity reduction. Spatial continuity of aquifer hydraulic conductivity is less significant.     

A field experiment on cation exchange-affected multicomponent solute transport in a sandy aquifer

A field experiment was performed in an aquifer in order to study multicomponent cation-exchange processes under natural flow conditions. The aquifer is a glacial outwash plain with sandy aquifer material having a cation-exchange capacity (CEC) of 1.0 meg/100 g. A continuous injection of groundwater spiked with sodium and potassium as chlorides was accomplished over 37 days to resemble leachate contamination from landfills. The plume was monitored by sampling in a dense spatial network (length 100 m, width 20 m) over a period of 2.5 years in order to obtain breakthrough curves and spatial contour maps of the chemical compounds. Na and especially K showed a substantial retardation caused by cation-exchange processes despite the low CEC of the aquifer material. The average velocity of K⁺ was only 10% of the velocity of chloride (0.7 m day⁻¹). The relative migration velocity of Na⁺ was not a constant in the plume, but apparently influenced by dilution. Ca²⁺ and Mg²⁺ were expelled from the cation-exchange sites of the aquifer material and subsequently transported with the same velocity as chloride. The breakthrough curves of the various compounds showed multiple peaks and low concentration zones. It was concluded by calculations with PHREEQE that changes in calcite equilibrium may occur in the lower part of the aquifer, while complexation processes seem to be of no importance. Cation exchange is then the most important process in this field experiment, and further evaluation of the data by a geochemical transport model including cation exchange is recommended.     

Assessment of intrinsic bioremediation of a coal-tar-affected aquifer using Two-dimensional reactive transport and Biogeochemical mass balance approaches.

Expedited site characterization and groundwater monitoring using direct-push technology and conventional monitoring wells were conducted at a former manufactured gas plant site. Biogeochemical data and heterotrophic plate counts support the presence of microbially mediated remediation. By superimposing solutions of a two-dimensional reactive transport analytical model, first-order degradation rate coefficients ((day-1) ) of various compounds for the dissolved-phase plume were estimated (i.e., benzene [0.0084], naphthalene [0.0058], and acenaphthene [0.0011]). The total mass transformed by aerobic respiration, nitrate reduction, and sulfate reduction around the free-phase coal-tar dense-nonaqueous-phase-liquid region and in the plume was estimated to be approximately 4.5 kg/y using a biogeochemical mass-balance approach. The total mass transformed using the degradation rate coefficients was estimated to be approximately 3.6 kg/y. Results showed that a simple two-dimensional analytical model and a biochemical mass balance with geochemical data from expedited site characterization can be useful for rapid estimation of mass-transformation rates.     

Demonstration of a global modeling methodology to determine the relative importance of local and long-distance sources

A global three-dimensional (3D) transport–dispersion model was used to simulate Krypton-85 (⁸⁵Kr) background concentrations at five sampling locations along the US east coast during 1982–1983. The samplers were established to monitor the ⁸⁵Kr plume downwind of the Savannah river plant (SRP), a nuclear fuel reprocessing facility. The samplers were located 300–1000 km downwind of the SRP. In the original analyses of the measurements, a constant background concentration, representing an upper-limit and different for each sampling station, was subtracted from the measurements to obtain the part of the measurement representing the SRP plume. The use of a 3D global model, which includes all major ⁸⁵Kr sources worldwide, was able to reproduce the day-to-day concentration background variations at the sampling locations with correlation coefficients of 0.36–0.46. These 3D model background predictions, without including the nearby SRP source, were then subtracted from the measured concentrations at each sampler, the result representing the portion of the measurement that can be attributed to emissions from the SRP. The revised plume estimates were a factor of 1.3–2.4 times higher than from the old method using a constant background subtraction. The greatest differences in the SRP plume estimates occurred at the most distant sampling stations.     

Microbiological analysis of multi-level borehole samples from a contaminated groundwater system

A range of bacteriological, geochemical process-related and molecular techniques have been used to assess the microbial biodegradative potential in groundwater contaminated with phenol and other tar acids. The contaminant plume has travelled 500 m from the pollutant source over several decades. Samples were obtained from the plume using a multi-level sampler (MLS) positioned in two boreholes (boreholes 59 and 60) which vertically transected two areas of the plume. Activity of the microbial community, as represented by phenol degradation potential and ability to utilise a range of substrates, was found to be influenced by the plume. Phenol degradation potential appeared to be influenced more by the concentration of the contaminants than the total bacterial cell numbers. However, in the areas of highest phenol concentration, the depression of cell numbers clearly had an effect. The types of bacteria present were assessed by culture and DNA amplification by polymerase chain reaction (PCR). Bacterial groups or processes associated with major geochemical processes, such as methanogenesis, sulphate reduction and denitrification, that have the potential to drive contaminant degradation, were detected at various borehole levels. A comparative molecular analysis of the microbial community between samples obtained from the MLS revealed the microbial community was diverse. The examination of microbial activity complemented those results obtained through chemical analysis, and when combined with hydrological data, showed that MLS samples provided a realistic profile of plume effects and could be related to the potential for natural attenuation of the site.     

Multicomponent simulation of wastewater-derived nitrogen and carbon in shallow unconfined aquifers. I. Model formulation and performance

One of the most common methods to dispose of domestic wastewater involves the release of septic effluent from drains located in the unsaturated zone. Nitrogen from such systems is currently of concern because of nitrate contamination of drinking water supplies and eutrophication of coastal waters. The objectives of this study are to develop and assess the performance of a mechanistic flow and reactive transport model which couples the most relevant physical, geochemical and biochemical processes involved in wastewater plume evolution in sandy aquifers. The numerical model solves for variably saturated groundwater flow and reactive transport of multiple carbon- and nitrogen-containing species in a three-dimensional porous medium. The reactive transport equations are solved using the Strang splitting method which is shown to be accurate for Monod and first- and second-order kinetic reactions, and two to four times more efficient than sequential iterative splitting. The reaction system is formulated as a fully kinetic chemistry problem, which allows for the use of several special-purpose ordinary differential equation (ODE) solvers. For reaction systems containing both fast and slow kinetic reactions, such as the combined nitrogen-carbon system, it is found that a specialized stiff explicit solver fails to obtain a solution. An implicit solver is more robust and its computational performance is improved by scaling of the fastest reaction rates. The model is used to simulate wastewater migration in a 1-m-long unsaturated column and the results show significant oxidation of dissolved organic carbon (DOC), the generation of nitrate by nitrification, and a slight decrease in pH.     

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.     

In situ modification of an aquifer material by a cationic surfactant to enhance retardation of organic contaminants

Sorption of hexadecyltrimethylammonium chloride (HDTMA), a cationic surfactant, on aquifer material from Columbus AFB, Mississippi, U.S.A., was examined. Transport studies using flow-through columns and a box model aquifer showed that an almost stationary zone of HDTMA-modified aquifer material could be produced in situ without a significant decrease in hydraulic conductivity.Perchloroethylene (PCE) and naphthalene sorption isotherms on the HDTMA-modified aquifer material were linear, and sorption coefficients were increased by over two orders of magnitude relative to the unmodified material. The retardation of PCE by insitu emplaced HDTMA zones within a column was examined. Agreement between batch- and column-derived sorption coefficients and breakthrough curve symmetry indicates that local equilibrium was attained. Significant retardation of a naphthalene plume by an in situ emplaced surfactant zone was demonstrated in the box model aquifer system.The experimental results indicate that it is feasible to create in situ a sorbent zone within an aquifer using cationic surfactants. In most situations, the sorbent zone concept needs to be coupled with contaminant degradation processes for sorbent emplacement to be a practical tool in the remediation of groundwater contamination sites. Sorbent zones may be of benefit in the engineering of suitable environments for microbial or abiotic degradation reactions and by providing time slow reactions to occur.