Electrokinetic ion transport through unsaturated soil: 2. Application to a heterogeneous field site

Results of a field demonstration of electrokinetic transport of acetate through an unsaturated heterogeneous soil are compared to numerical modeling predictions. The numerical model was based on the groundwater flow and transport codes MODFLOW and MT3D modified to account for electrically induced ion transport. The 6-month field demonstration was conducted in an unsaturated layered soil profile where the soil moisture content ranged from 4% to 28% (m3 m(-3)). Specially designed ceramic-cased electrodes maintained a steady-state moisture content and electric potential field between the electrodes during the field demonstration. Acetate, a byproduct of acetic acid neutralization of the cathode electrolysis reaction, was transported from the cathode to the anode by electromigration. Field demonstration results indicated preferential transport of acetate through soil layers exhibiting higher moisture content/electrical conductivity. These field transport results agree with theoretical predictions that electromigration velocity is proportional to a power function of the effective moisture content. A numerical model using a homogeneous moisture content/electrical conductivity domain did not adequately predict the acetate field results. Numerical model predictions using a three-layer electrical conductivity/moisture content profile agreed qualitatively with the observed acetate distribution. These results suggest that field heterogeneities must be incorporated into electrokinetic models to predict ion transport at the field-scale.     

Simulation of carrier-facilitated transport of phenanthrene in a layered soil profile

The appropriate prediction of the fate of the contaminant is an essential step when evaluating the risk of severe groundwater pollutions-in particular in the context of natural attenuation. We numerically study the reactive transport of phenanthrene at the field scale in a multilayer soil profile based on experimental data. The effect of carrier facilitation by dissolved organic carbon is emphasized and incorporated in the model. Previously published simulations are restricted to the saturated zone and/or to homogeneous soil columns at the laboratory scale. A numerical flow and transport model is extended and applied to understand and quantify the relevant processes in the case of a strongly sorbing hydrophobic organic compound that is subject to carrier facilitation in the unsaturated zone. The contaminant migration is investigated on long- and short-term time scales and compared to predictions without carrier facilitation. The simulations demonstrate the importance of carrier facilitation and suggest strongly to take this aspect into account. By carrier facilitation breakthrough times at the groundwater level decreased from 500 to approximately 8 years and concentration peaks increased by two orders of magnitude in the long-term simulation assuming a temporary spill in an initially unpolluted soil with a non-sorbing carrier.     

Heavy metal contamination in water and sediments of an estuary in southeastern Turkey

The geochemical characteristics of some heavy metals (Cr, Cd, Pb, Zn and Ni) in the river and sea sediments, in the soil and in the river and groundwater of an estuary on the southeast coast of Turkey have been studied. In the sea sediments, the wastes from a chromium factory control these metal concentrations. The heavy metal contamination in the river sediments results from an existing chromite mine at the northern part of the area. These heavy metals are concentrated in the soil, but they do not penetrate into the groundwater because of the low permeability of the unsaturated zone in the region.     

A large-scale experiment on mass transfer of trichloroethylene from the unsaturated zone of a sandy aquifer to its interfaces

A large-scale experiment was conducted to investigate the transport of trichloroethylene (TCE) vapors in the unsaturated zone and to determine the mass transfer to the groundwater and the atmosphere. The experiment involved injection of 5 1 of TCE in the unsaturated zone under controlled conditions, with multidepth sampling of gas and water through the unsaturated zone and across the capillary zone into underlying groundwater. The mass transfer of TCE vapors from the vadose zone to the atmosphere was quantified using a vertical flux chamber. A special soil water sampler was used to monitor transport across the capillary fringe. Experimental data indicated that TCE in the unsaturated zone was mainly transported to the atmosphere and this exchange reduced significantly the potential for groundwater pollution. The maximum measured TCE flux to the atmosphere was about 3 g/m(2)/day. Observed and calculated fluxes based on vertical TCE vapor concentration gradients and Fick's law were in good agreement. This confirms that TCE vapor transport under the experimental conditions was governed essentially by molecular diffusion. TCE vapors also caused a lower, but significant contamination of the underlying groundwater by dispersion across the capillary fringe with a corresponding maximum flux of about 0.1 g/m(2)/day. This mass transfer to groundwater is partly uncertain due to an inadvertent entry of some nonaqueous phase liquid (NAPL) from the source area into the saturated zone. Application of an analytical solution to estimate the TCE flux from the unsaturated zone to the groundwater indicated that this phenomenon is not only influenced by molecular diffusion but also by vertical dispersion. The mass balance indicates that, under the given experimental conditions (e.g. proximity of the source emplacement relative to the soil surface, relatively high permeable porous medium), nearly 95% of the initial TCE mass was transferred to the atmosphere.     

A set of constitutive relationships accounting for residual NAPL in the unsaturated zone

Although laboratory experiments show that non-aqueous phase liquid (NAPL) is retained in the unsaturated zone, no existing multiphase flow model has been developed to account for residual NAPL after NAPL drainage in the unsaturated zone. We developed a static constitutive set of saturation-capillary pressure relationships for water, NAPL and air that accounts for both this residual NAPL and entrapped NAPL. The set of constitutive relationships is formulated similarly to the set of scaled relationships that is frequently applied in continuum models. The new set consists of three fluid-phase systems: a three-phase system and a two-phase system, that both comply with the original constitutive model, and a newly introduced residual NAPL system. The new system can be added relatively easily to the original two- and three-phase systems. Entrapment is included in the model. The constitutive relationships of the non-drainable residual NAPL system are based on qualitative fluid behavior derived from a pore scale model. The pore scale model reveals that the amount of residual NAPL depends on the spreading coefficient and the water saturation. Furthermore, residual NAPL is history-dependent. At the continuum scale, a critical NAPL pressure head defines the transition from free, mobile NAPL to residual NAPL. Although the Pc-S relationships for water and total liquid are not independent in case of residual NAPL, two two-phase Pc-S relations can represent a three-phase residual system of Pc-S relations. A newly introduced parameter, referred to as the residual oil pressure head, reflects the mutual dependency of water and oil. Example calculations show consistent behavior of the constitutive model. Entrapment and retention in the unsaturated zone cooperate to retain NAPL. Moreover, the results of our constitutive model are in agreement with experimental observations.     

Electrokinetic ion transport through unsaturated soil: 1. Theory, model development, and testing

An electromigration transport model for non-reactive ion transport in unsaturated soil was developed and tested against laboratory experiments. This model assumed the electric potential field was constant with respect to time, an assumption valid for highly buffered soil, or when the electrode electrolysis reactions are neutralized. The model also assumed constant moisture contents and temperature with respect to time, and that electroosmotic and hydraulic transport of water through the soil was negligible. A functional relationship between ionic mobility and the electrolyte concentration was estimated using the chemical activity coefficient. Tortuosity was calculated from a mathematical relationship fitted to the electrical conductivity of the bulk pore water and soil moisture data. The functional relationship between ionic mobility, pore-water concentration, and tortuosity as a function of moisture content allowed the model to predict ion transport in heterogeneous unsaturated soils. The model was tested against laboratory measurements assessing anionic electromigration as a function of moisture content. In the test cell, a strip of soil was spiked with red dye No 40 and monitored for a 24-h period while a 10-mA current was maintained between the electrodes. Electromigration velocities predicted by the electromigration transport model were in agreement with laboratory experimental results. Both laboratory-measured and model-predicted dye migration results indicated a maximum transport velocity at moisture contents less than saturation due to competing effects between current density and tortuosity as moisture content decreases.     

Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation

This paper presents the results of a detailed field investigation that was performed for studying groundwater recharge processes and solute downward migration mechanisms prevailing in the unsaturated zone overlying a chalk aquifer in Belgium. Various laboratory measurements were performed on core samples collected during the drilling of boreholes in the experimental site. In the field, experiments consisted of well logging, infiltration tests in the unsaturated zone, pumping tests in the saturated zone and tracer tests in both the saturated and unsaturated zones. Results show that gravitational flows govern groundwater recharge and solute migration mechanisms in the unsaturated zone. In the variably saturated chalk, the migration and retardation of solutes is strongly influenced by recharge conditions. Under intense injection conditions, solutes migrate at high speed along the partially saturated fissures, downward to the saturated zone. At the same time, they are temporarily retarded in the almost immobile water located in the chalk matrix. Under normal recharge conditions, fissures are inactive and solutes migrate slowly through the chalk matrix. Results also show that concentration dynamics in the saturated zone are related to fluctuations of groundwater levels in the aquifer. A conceptual model is proposed to explain the hydrodispersive behaviour of the variably saturated chalk. Finally, the vulnerability of the chalk to contamination issues occurring at the land surface is discussed.     

Pesticides and groundwater quality protection

A simple approach for ranking the leaching of pesticides from surface soil is presented and tentatively calibrated with field data from an agricultural area. The approach is based on the calculation of a leaching index indicating the proportion of active ingredient, with respect to the quantity applied, leaching from a soil model in a given time interval (one year). In the selected area, 85 wells tapping an unconfined aquifer were sampled for groundwater pesticide residue analysis, in order to explore the index region between leachers and nonleachers.     

Sorption of isoxaflutole diketonitrile degradate (DKN) and dicamba in unsaturated soil

When analyzing the sorption characteristics of weakly sorbing or labile pesticides, batch methods tend to yield a high margin of error attributable to errors in concentration measurement and to degradation, respectively. This study employs a recently developed unsaturated transient flow method to determine the sorption of isoxaflutole's herbicidally active diketonitrile degradate (DKN) and dicamba. A 20-cm acrylic column was packed with soils with varied texture that had been uniformly treated with 14C-labeled chemical.The antecedent solution herbicide in equilibrium with sorbed phase herbicide was displaced by herbicide-free water, which was infiltrated into the column. Sorption coefficients, Kd, were obtained from a plot of total herbicide concentration in the soil versus water content in the region where the antecedent solution accumulated. DKN Kd values were approximately 2-3 times (average Kd = 0.71 L kg-1) greater using the unsaturated transient flow method as compared to the batch equilibration method in clay loam (Kd = 0.33 L kg-1), but similar for the two methods in sand (0.12 vs 0.09 L kg-1) soils. Dicamba Kd values were 3 times greater using the unsaturated transient flow method as compared to the batch equilibration method in the clay loam soil (0.38 vs 0.13 L kg-1), however, the Kd values were the same for the two methods in the sand (approximately 0.06 L kg-1). This demonstrates that to determine sorption coefficients for labile hydrophilic pesticides, an unsaturated transient flow method may be a suitable alternative to the batch method. In fact, it may be better in cases where transport models have overpredicted herbicide leaching when batch sorption coefficients have been used.     

Modelling assessment of regional groundwater contamination due to historic smelter emissions of heavy metals

Historic emissions from ore smelters typically cause regional soil contamination. We developed a modelling approach to assess the impact of such contamination on groundwater and surface water load, coupling unsaturated zone leaching modelling with 3D groundwater transport modelling. Both historic and predictive modelling were performed, using a mass balance approach for three different catchments in the vicinity of three smelters. The catchments differ in their hydrology and geochemistry. The historic modelling results indicate that leaching to groundwater is spatially very heterogeneous due to variation in soil characteristics, in particular soil pH. In the saturated zone, cadmium is becoming strongly retarded due to strong sorption at neutral pH, even though the reactivity of the sandy sediments is low. A comparison between two datasets (from 1990 to 2002) on shallow groundwater and modelled concentrations provided a useful verification on the level of statistics of "homogeneous areas" (areas with comparable land use, soil type and geohydrological situation) instead of comparison at individual locations. While at individual locations observations and the model varies up to two orders of magnitude, for homogeneous areas, medians and ranges of measured concentrations and the model results are similar. A sensitivity analysis on metal input loads, groundwater composition and sediment geochemistry reveals that the best available information scenario based on the median value of input parameters for the model predicts the range in observed concentrations very well. However, the model results are sensitive to the sediment contents of the reactive components (organic matter, clay minerals and iron oxides). Uncertainty in metal input loads and groundwater chemistry are of lesser importance. Predictive modelling reveals a remarkable difference in geochemical and hydrological controls on subsurface metal transport at catchment-scale. Whether the surface water load will peak within a few decades or continue to increase until after 2050 depends on the dominant land use functions in the areas, their hydrology and geochemical build-up.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.     

Plant aided bioremediation in the vadose zone: model development and applications

Phytoremediation has the potential to enhance clean up of land contaminated by various pollutants. A mathematical model that includes a two-fluid phase flow model of water flow as well as a two-region soil model of contaminant reactions was developed and applied to various bioremediation scenarios in the unsaturated zone, especially to plant-aided bioremediation. To investigate model behavior and determine the main parameters and mechanisms that affect bioremediation in unplanted and planted soils, numerical simulations of theoretical scenarios were conducted before applying the model to field data. It is observed from the results that parameters affecting the contaminant concentration in the water phase, such as aqueous solubility, the octanol-water partition coefficient, and organic carbon content of the soil controlled the contaminant fate in the vadose zone. Simulation using the developed model also characterized the fate and transport of the contaminants both in planted and unplanted soils satisfactorily for field applications. Although phytoremediation has the potential for remediation of contaminated soils, results from both modeling and field studies suggested that plants may not always enhance the remediation efficiency when the soil already has a high microbial concentration, when the contaminant bioavailability is low, or when the overall reaction is mass transfer-limited. Therefore, other steps to increase contaminant bioavailability are needed in phytoremediation applications; natural purification mechanisms such as aging, volatilization, and natural bioremediation should be considered to maximize the plant effect and minimize the cost.     

Modelling the migration of contaminants through variably saturated dual-porosity, dual-permeability chalk

In the Hesbaye region in Belgium, tracer tests performed in variably saturated fissured chalk rocks presented very contrasting results in terms of transit times, according to artificially controlled water recharge conditions prevailing during the experiments. Under intense recharge conditions, tracers migrated across the partially or fully saturated fissure network, at high velocity in accordance with the high hydraulic conductivity and low effective porosity (fracture porosity). At the same time, a portion of the tracer was temporarily retarded in the almost immobile water located in the matrix. Under natural infiltration conditions, the fissure network remained inactive. Tracers migrated downward through the matrix, at low velocity in relation with the low hydraulic conductivity and the large porosity of the matrix. Based on these observations, Brouyère et al. (2004a) [Brouyère, S., Dassargues, A., Hallet, V., 2004a. Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation, J. Contam. Hydrol., 72 (1-4), 135-164, doi: 10.1016/j.conhyd.2003.10.009] proposed a conceptual model in order to explain the migration of solutes in variably saturated, dual-porosity, dual-permeability chalk. Here, mathematical and numerical modelling of tracer and contaminant migration in variably saturated fissured chalk is presented, considering the aforementioned conceptual model. A new mathematical formulation is proposed to represent the unsaturated properties of the fissured chalk in a more dynamic and appropriate way. At the same time, the rock water content is partitioned between mobile and immobile water phases, as a function of the water saturation of the chalk rock. The groundwater flow and contaminant transport in the variably saturated chalk is solved using the control volume finite element method. Modelling the field tracer experiments performed in the variably saturated chalk shows the adequacy and usefulness of the new conceptual, mathematical and numerical model.     

Redistribution of contaminants by a fluctuating water table in a micro-porous, double-porosity aquifer: field observations and model simulations

Large seasonal fluctuations of the water table are characteristic of aquifers with a low specific yield, including those fractured, double-porosity aquifers that have significant matrix porosity containing virtually immobile porewater, such as the Chalk of northern Europe. Where these aquifers are contaminated, a strong relationship between water table elevation and contaminant concentration in groundwater is commonly observed, of significance to the assessment, monitoring, and remediation of contaminated groundwater. To examine the processes governing contaminant redistribution by a fluctuating water table within the 'seasonally unsaturated zone', or SUZ, profiles of porewater solute concentrations have been established at a contaminated site in southern England. These profiles document the contaminant distribution in porewater of the Chalk matrix over the SUZ at a greater level of detail than recorded previously. A novel double-porosity solute transport code has been developed to simulate the evolution of the SUZ matrix porewater contaminant profiles, given a fluctuating water table, when the groundwater is initially contaminated and the SUZ is initially free of contamination. The model is simply characterised by: the matrix-fracture porosity ratio, the matrix block geometry, and a characteristic diffusion time. De-saturation and re-saturation of fractures is handled by a new approximation method. Contaminant accumulates in the upper levels of the SUZ, where it is less accessible to mobile groundwater, and acts as a persistent secondary source of contamination once the original source of contamination has been removed or has become depleted. The 'SUZ process' first attenuates the progress of contaminants in groundwater, and subsequently controls the slow release of contamination back to the mobile groundwater, thus prolonging the duration of groundwater contamination by many years. The SUZ process should operate in any fractured, micro-porous lithology e.g. fractured clays and mudstones, making this approach widely applicable.     

Metal ion and other key water quality constituent attenuation in soil columns

A set of soil columns was constructed to simulate discharge of disinfected tertiary treated wastewater to a river via nearby land application or indirect discharge. The system was primarily designed to observe the fate of metal ions and nutrients. The following three experiments were conducted: (1) flow through saturated soils only, which simulates indirect discharge where water is directly applied to groundwater; (2) flow through unsaturated soil followed by saturated flow, which simulates vadose then saturated zone transport; and (3) saturated flow only using ethylene diamine tetraacetic acid-metal chelates, which determined effects of metal organic complexes on metal mobility through the soil. Metal ion attenuation was substantial but not complete in experiments 1 and 2 (removal: 68% Cu2+, 43% Ni2+, 98% Pb2+, and 96% Hg2+), which was somewhat contrary to modeling results. Cyanide attenuation was also monitored (92% removal). In experiment 3, lead attenuation was somewhat reduced (92% removal) and delayed (requiring additional residence time); copper attenuation was significantly reduced (38% removal) and delayed; and nickel concentrations were higher in the 28-day sample (> 80 microg/L) than in the column feed water (58 microg/L). Near-complete denitrification and total phosphorus attenuation were observed. For the water quality constituents studied, unsaturated (vadose zone) transport did not appear to add additional benefit.     

地下水中轻质有机污染物(LNAPL)透镜体研究

在二维砂槽模型中模拟了轻质油在均匀多孔介质地下水非饱和区中的运移过程。模拟结果表明,地下水毛细区是轻质油污染的重点区,除了ＬＮＡＰＬ的残留以外,进入地下水饱和的ＬＮＡＰＬ终将被地下水顶托回到毛细区中,毛细区以上的约大多民将在重力作用下进入毛细区中,试验中观察到达稳定状态时ＬＮＡＰＬ透镜体的上边缘略微高出毛细区。利用多孔介质毛细管模型,建立了利用界面张力、接触角、介质特征孔隙直径等物理量估算不同位置     

A numerical model for transient-hysteretic flow and solute transport in unsaturated porous media

A two-dimensional flow and transport model was developed for simulating transient water flow and nonreactive solute transport in heterogeneous, unsaturated porous media containing air and water. The model is composed of a unique combination of robust and accurate numerical algorithms for solving the Richards', Darcy flux, and advection-dispersion equations. The mixed form of Richards' equation is solved using a finite-element formulation and a modified Picard iteration scheme. Mass lumping is employed to improve solution convergence and stability behavior. The flow algorithm accounts for hysteresis in the pressure head-water content relationship. Darcy fluxes are approximated with a Galerkin and Petrov-Galerkin finite-element method developed for random heterogeneous porous media. The transport equation is solved using an Eulerian-Lagrangian method. A multi-step, fourth-order Runge-Kutta, reverse particle tracking technique and a quadratic-linear interpolation scheme are shown to be superior for determining the advective concentration. A Galerkin finite-element method is used for approximating the dispersive flux. The unsaturated flow and transport model was applied to a variety of rigorous problems and was found to produce accurate, mass-conserving solutions when compared to analytical solutions and published numerical results.     

Transport and degradation of propyleneglycol and potassium acetate in the unsaturated zone

De-icing chemicals used during the winter season are potential pollutants for the groundwater underneath the new main airport of Norway. Several field experiments examining the transport and degradation of propyleneglycol (PG), potassium acetate (KAc) and non-reactive tracers were performed in a lysimeter trench under natural snowmelting conditions. Chemicals were applied underneath the snow cover and the transport in a heterogeneous coarse sandy soil was examined by extracting soil water from 30 or 40 suction cups placed at five depths between 0.4 and 2.4 m depth. Transport and degradation was analysed by spatial moment calculations. The de-icing chemicals showed the same basic displacement as chemically inactive tracers, an initial fast transport during the melting period followed by a period of stagnation throughout the summer season. PG seemed to be displaced to greater depths compared to non-reactive tracer after the first application. However, computer simulations of transport and degradation in a heterogeneous unsaturated soil showed that decreasing degradation constants with depth can generate a downward movement of the centre of mass without any flow occurring in the system. Potassium acetate showed some adsorption, with calculated retardation factors of approximately 1.3 and 1.2. The degradation rate constant for PG was calculated to be 0.015 day-1 in 1994 and increased to 0.047 day-1 in the second application made in 1995. The degradation rate constant for acetate was estimated to be 0.02 day-1. Increased manganese concentrations seem to be a good indicator of degradation of PG and Ac.     

The effect of surface-active solutes on water flow and contaminant transport in variably saturated porous media with capillary fringe effects

Organic contaminants that decrease the surface tension of water (surfactants) can have an effect on unsaturated flow through porous media due to the dependence of capillary pressure on surface tension. We used an intermediate-scale 2D flow cell (2.44 x 1.53 x 0.108 m) packed with a fine silica sand to investigate surfactant-induced flow perturbations. Surfactant solution (7% 1-butanol and dye tracer) was applied at a constant rate at a point source located on the soil surface above an unconfined synthetic aquifer with ambient groundwater flow and a capillary fringe of approximately 55 cm. A glass plate allowed for visual flow and transport observations. Thirty instrumentation stations consist of time domain reflectometry probes and tensiometers measured in-situ moisture content and pressure head, respectively. As surfactant solution was applied at the point source, a transient flow perturbation associated with the advance of the surfactant solution was observed. Above the top of the capillary fringe the advance of the surfactant solution caused a visible drainage front that radiated from the point source. Upon reaching the capillary fringe, the drainage front caused a localized depression of the capillary fringe below the point source because the air-entry pressure decreased in proportion to the decrease in surface tension caused by the surfactant. Eventually, a new capillary fringe height was established. The height of the depressed capillary fringe was proportional to height of the initial capillary fringe multiplied by the relative surface tension of the surfactant solution. The horizontal transport of surfactant in the depressed capillary fringe, driven primarily by the ambient groundwater flow, caused the propagation of a wedge-shaped drying front in the downgradient direction. Comparison of dye transport during the surfactant experiment to dye transport in an experiment without surfactant indicated that because surfactant-induced drainage decreased the storage capacity of the vadose zone, the dye breakthrough time to the water table was more than twice as fast when the contaminant solution contained surfactant. The extensive propagation of the drying front and the effect of vadose zone drainage on contaminant breakthrough time suggest the importance of considering surface tension effects on unsaturated flow and transport in systems containing surface-active organic contaminants or systems, where surfactants are used for remediation of the vadose zone or unconfined aquifers.