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.     

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.     

Numerical methods for describing chemical transport in the unsaturated zone of the subsurface

Finite-difference and finite-element methods of approximation have been extended to solve the one-dimensional nonlinear partial differential equations that describe the simultaneous transport of heat, moisture and chemical in the unsaturated zone. Especially for chemical transport, nodal spacing criteria are required to minimize numerical dispersion and oscillatory behavior in the solution vector for chemical concentration. Conservative criteria for nodal spacing for saturated flow can be used to set nodal spacing for unsaturated zone transport. When nodal spacing criteria are satisfied, for the same set of transport and boundary conditions, chemical concentration profiles calculated by the two numerical methods will be almost the same. A situation that is simulated very well with one-dimensional models, is the application of chemicals to land surfaces. To compare and contrast the characteristics of solutions given by the two numerical methods, moisture content, temperature and chemical concentration profiles for a 75-day period after application in the unsaturated zone are calculated for two representative types of organic chemicals. In the first, the chemical is very slowly degraded in the subsurface environment but strongly sorbed to soil surfaces. In the second, the chemical is rapidly degraded but weakly sorbed to soil surfaces. Because of differences in sorption coefficients and mechanisms of degradation, for the same set of hydrodynamic properties of the subsurface, the weakly sorbed chemical is more widely distributed throughout the unsaturated zone, whereas the strongly sorbed chemical stays very close to where it is put initially with little penetration into the subsurface. Satisfying nodal spacing criteria minimizes the impact of the method of approximation on the calculated solutions of the transport equations. For better model predictive performance, however, there are needs for more fundamental information on processes governing transport in the subsurface.     

Electrical resistivity tomography as monitoring tool for unsaturated zone transport: an example of preferential transport of deicing chemicals

Non-invasive spatially resolved monitoring techniques may hold the key to observe heterogeneous flow and transport behavior of contaminants in soils. In this study, time-lapse electrical resistivity tomography (ERT) was employed during an infiltration experiment with deicing chemical in a small field lysimeter. Deicing chemicals like potassium formate, which frequently impact soils on airport sites, were infiltrated during snow melt. Chemical composition of seepage water and the electrical response was recorded over the spring period 2010. Time-lapse electrical resistivity tomographs are able to show the infiltration of the melt water loaded with ionic constituents of deicing chemicals and their degradation product hydrogen carbonate. The tomographs indicate early breakthrough behavior in parts of the profile. Groundtruthing with pore fluid conductivity and water content variations shows disagreement between expected and observed bulk conductivity. This was attributed to the different sampling volume of traditional methods and ERT due to a considerable fraction of immobile water in the soil. The results show that ERT can be used as a soil monitoring tool on airport sites if assisted by common soil monitoring techniques.     

Pilot-scale electrokinetic treatment of a Cu contaminated red soil

A pilot-scale experiment for electrokinetic treatment of 700 kg of copper contaminated red soil was conducted using a constant voltage of 80 V. Dynamic removal percentages of Cu from the soil and energy consumption during the treatment were evaluated together with changes of soil pH, electrical conductivity and soil microbial functional diversity before and after the electrokinetic treatment. The results indicate that 76% of Cu was successfully removed from the soil after 140 d of treatment when lactic acid was used as enhancing reagent for adjusting the catholyte pH and dissolving soil Cu by complexation, and the pilot-scale electrokinetic experiment consumed electric energy of 224 kW h t-1 soil. The post-treatment soil pH values decreased about 0.1-1.6 units compared with the initial value (pH 4.8), and soil electrical conductivities in most of soil sections also significantly decreased. Soil microbial functional diversity varied after the electrokinetic treatment, particularly the increase of substrate richness index, which is possibly due to the stimulation of lactic acid that was introduced into the soil column during the experiment.     

Modeling assessment of air emission flux of mercury from soils in terrestrial landscape components: model tests and sensitivities

The abilities of a screening-level model to predict variations in elemental mercury (Hg0) air emissions from soils in terrestrial landscapes are examined by comparing simulation results to published observational data and by performing sensitivity analyses. Despite uncertainties and simplifications, the model results obtained offer some degree of confidence in the model's joint ability to relate readily available environmental parameters to airborne emissions of Hg predicted by coupling simple atmospheric and soil parameters with Hg cycling and transport algorithms. The model reasonably predicted the observational data in the considered data sets except for one site for which significant uncertainty was associated with model input data. Predictions are consistent with many trends observed in the field studies; better predictions were obtained for nonvegetated systems (relative errors between 0.4 and 9.7%) than for shaded-soil landscapes (relative errors between 2.3 and 27%). The model reflected field data showing that daily average emission rates of Hg0, formed by the reduction of Hg(II), are primarily controlled by changes in solar radiation, soil moisture, temperature, and, to a lesser extent, wind conditions. The model may have potential use in several preliminary studies to characterize trends of airborne Hg emitted from terrestrial sources to the atmosphere.     

Multicomponent simulation of wastewater-derived nitrogen and carbon in shallow unconfined aquifers. II. Model application to a field site

A multicomponent reactive transport model as presented by MacQuarrie and Sudicky [MacQuarrie, K.T.B., Sudicky, E.A., this volume. Multicomponent simulation of wastewater-derived nitrogen and carbon in shallow unconfined aquifers: I. Model formulation and performance, J. Contam. Hydrol.] is applied to a well-studied wastewater plume in a sandy aquifer near Cambridge, Ontario. Domestic wastewater is released into the unsaturated zone via a drain field at a depth of about 0.8 m. The physical transport parameters for the model are obtained by simulating a non-reactive solute, while kinetic input data for the nitrogen and carbon reaction network are obtained from the literature. The model shows that the wastewater-loading rate has little influence on the moisture content in the unsaturated zone, thus oxygen diffusion in the air phase is an important transport mechanism. The model results are in general agreement with the field-determined moisture and oxygen profiles near the drain field. The simulation results show that oxidation of ammonium and dissolved organic carbon (DOC) goes to completion in the 1.5-m distance between the drain field and the water table, and that calcite dissolution limits the pH reduction to about 0.2 units. The model-predicted nitrate concentrations in the core of the plume are in the range of 20-25 mg N/l and are in good agreement with the field data. Overall, the results for the major reactive species from the model simulation agree well with the geochemical data obtained below the drain field and it is concluded that the major physical and biochemical processes have been correctly captured in the current model formulation.     

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.     

In situ bioremediation of nitrate and perchlorate in vadose zone soil for groundwater protection using gaseous electron donor injection technology.

When present in the vadose zone, potentially toxic nitrate and perchlorate anions can be persistent sources of groundwater contamination. Gaseous electron donor injection technology (GEDIT), an anaerobic variation of petroleum hydrocarbon bioventing, involves injecting electron donor gases, such as hydrogen or ethyl acetate, into the vadose zone, to stimulate biodegradation of nitrate and perchlorate. Laboratory microcosm studies demonstrated that hydrogen and ethanol promoted nitrate and perchlorate reduction in vadose zone soil and that moisture content was an important factor. Column studies demonstrated that transport of particular electron donors varied significantly; ethyl acetate and butyraldehyde were transported more rapidly than butyl acetate and ethanol. Nitrate removal in the column studies, up to 100%, was best promoted by ethyl acetate. Up to 39% perchlorate removal was achieved with ethanol and was limited by insufficient incubation time. The results demonstrate that GEDIT is a promising remediation technology warranting further validation.     

可渗透反应复合电极法对土壤重金属的电动去除

将零价铁(Fe0)、沸石等活性材料附着在电极上形成可渗透反应层并构成可渗透反应复合电极,采用不同的复合电极对Cd2+、Ni 2+、Pb2+和Cu2+等4种阳离子型重金属污染土壤进行了电动力学修复。研究了不同可渗透反应复合电极对土壤pH的控制效果以及对重金属的去除作用,分析了迁移到复合电极中的重金属形态变化。结果表明,复合电极中添加酸、碱性沸石并适时更换,可有效中和、截留阴阳极电解产生的OH-和H+,避免或减缓土壤酸碱迁移带的形成,防止重金属离子的过早沉淀及土壤过度酸化,极大提高了重金属的去除率。复合电极中Fe0可将迁移进来的重金属离子进行还原稳定,实现重金属污染物的捕获与固定,与迁移到沸石复合电极中的4种重金属不稳定态相比,"Fe0+沸石"复合电极中重金属不稳定态分别下降了61.4、60.5、61.4、57.1百分点。结果还显示,阴极采用"Fe0+沸石"复合电极并适时进行更换,施加1.5V/cm的直流电压修复10d后,土壤中Cd、Ni、Pb、Cu的总去除率分别为44.5%、41.5%、33.5%和36.7%,且进一步延长修复时间和持续更换电极可获得更为理想的修复效果。     

Contaminant transport in a municipal drinking water supply: a steady-state approach to estimate rate and uncertainty

Contaminant transport is generally considered to be a key factor when assessing and classifying the environmental risk of polluted areas. In the study presented here, a steady-state approach was applied to obtain estimates of the transit time and concentration of the pesticide metabolite BAM (2,6-dichlorobenzoamide) at a site where it is contaminating a municipal drinking water supply. A Monte Carlo simulation technique was used to quantify the uncertainty of the results and to evaluate the sensitivity of the used parameters. The adopted approach yielded an estimated median transit time of 10 y for the BAM transport from the polluted site to the water supply. Soil organic carbon content in the unsaturated zone and the hydraulic conductivity in the saturated zone explained 44% and 23% of the uncertainty in the transit time estimate, respectively. The sensitivity analysis showed that the dilution factor due to regional groundwater flow and the soil organic carbon content at the polluted site explained 53% and 31% of the uncertainty of concentration estimates, respectively. In conclusion, the adopted steady-state approach can be used to obtain reliable first estimates of transit time and concentration, but to improve concentration predictions of degrading contaminants, a dynamic model is probably required.     

Investigation of hydrogeologic processes in a dipping layer structure: 2. Transport and biodegradation of organics

Numerical simulation tools have been used to study the dominating processes during transport of aromatic hydrocarbons in the unsaturated soil zone. Simulations were based on field observations at an experimental site located on a glacial delta plain with pronounced layered sedimentary structures. A numerical model for transport in the unsaturated zone, SWMS-3D, has been extended to incorporate coupled multispecies transport, microbial degradation following Monod kinetics and gas diffusive transport of oxygen and hydrocarbons. The flow field parameters were derived from previous work using nonreactive tracers. Breakthrough curves (BTC) from the hydrocarbon field experiment were used to determine sorption parameters and Monod kinetic parameters using a fitting procedure. The numerical simulations revealed that the assumption of homogeneous layers resulted in deviations from the field observations. The deviations were more pronounced with incorporation of reactive transport, compared with earlier work on nonreactive transport. To be able to model reasonable BTC, sorption had to be reduced compared to laboratory experiments. The initial biomass and the maximum utilisation rate could be adjusted to capture both the initial lag phase and the overall degradation rate. Nevertheless, local oxygen limitation is predicted by the model, which was not observed in the field experiment. Incorporation of evaporation and diffusive gas transport of the hydrocarbons did not significantly change the local oxygen demand. The main cause of the observed discrepancies between model and field are attributed to channelling as a result of small-scale heterogeneities such as biopores.     

Applicability of grid-net detection system for landfill leachate and diesel fuel release in the subsurface

The grid-net system estimating the electrical conductivity changes was evaluated as a potential detection system for the leakage of diesel fuel and landfill leachate. Aspects of electrical conductivity changes were varied upon the type of contaminant. The electrical conductivity in the homogeneous mixtures of soil and landfill leachate linearly increased with the ionic concentration of pore fluid, which became more significant at higher volumetric water contents. However, the electrical conductivity in soil/diesel fuel mixture decreased with diesel fuel content and it was more significant at lower water contents. The electrode spacing should be determined by considering the type of contaminant to enhance the electrode sensitivity especially when two-electrode sensors are to be used. The electrode sensitivity for landfill leachate was constantly maintained regardless of the electrode spacings while that for the diesel fuel significantly increased at smaller electrode spacings. This is possibly due to the fact that the insulating barrier effect of the diesel fuel in non-aqueous phase was less predominant at large electrode spacing because electrical current can form the round-about paths over the volume with relatively small diesel fuel content. The model test results showed that the grid-net detection system can be used to monitor the leakage from waste landfill and underground storage tank sites. However, for a successful application of the detection system in the field, data under various field conditions should be accumulated.     

Electro-migration of heavy metals in an aged electroplating contaminated soil affected by the coexisting hexavalent chromium

Cr(VI) was often reported to oxidize soil organic matter at acidic environments due to its high ORP, probably thus changing cationic metal species bound to soil organic matter, and influencing their electro-migration patterns. However, such an effect on the electro-migration was not confirmed in most previous studies. Therefore, this study applied a fixed voltage direct current field on an aged electroplating contaminated clayed soil, with a special interest in the direct or indirect influence of Cr(VI) on the electro-migration of other coexisting metals. After 353 h electrokinetic process, 81% of Zn, 53% of Ni and 22% of Cu in the original soil were electro-migrated into the electrolyte, and most of the remaining concentrated near the cathode. The Cr(VI) oxidized some soil organic matter along its migration pathway, with a pronounced reaction occurred near the anode at low pHs. The resulting Cr(III) reversed its original movement, and migrated towards the cathode, leading to the occurrence of a second Cr concentration peak in the soil. Metal species analyses showed that the amount of metals bound to soil organic matter significantly decreased, while a substantial increase in the Cr species bound to Fe/Mn (hydro-)oxides was observed, suggesting an enhancement of cationic metal electro-migration by the reduction of Cr(VI) into Cr(III). However, the Cr(VI) may form some stable lead chromate precipitates, and in turn demobilize Pb in the soil, as the results showed a low Pb removal and an increase in its acid-extractable and residual fractions after electrokinetic remediation.     

Fate of nitrogen for subsurface drip dispersal of effluent from small wastewater systems

Subsurface drip irrigation systems apply effluent from onsite wastewater systems in a more uniform manner at a lower rate than has been possible with other effluent dispersal methods. The effluent is dispersed in a biologically active part of the soil profile for optimal treatment and where the water and nutrients can be utilized by landscape plants. Container tests were performed to determine the fate of water and nitrogen compounds applied to packed loamy sand, sandy loam, and silt loam soils. Nitrogen removal rates measured in the container tests ranged from 63 to 95% despite relatively low levels of available carbon. A Hydrus 2D vadose zone model with nitrification and denitrification rate coefficients calculated as a function of soil moisture content fit the container test results reasonably well. Model results were sensitive to the denitrification rate moisture content function. Two-phase transport parameters were needed to model the preferential flow conditions in the finer soils. Applying the model to generic soil types, the greatest nitrogen losses (30 to 70%) were predicted for medium to fine texture soils and soils with restrictive layers or capillary breaks. The slow transport with subsurface drip irrigation enhanced total nitrogen losses and plant nitrogen uptake opportunity.     

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.     

Geostatistical analysis of soil hydrologic properties in a field plot

A 91-m transect was set up in an irrigated field near Las Cruces, New Mexico to obtain soil water tension and water content data to investigate their spatial variability. A total of 455 sampling points were monitored along a grid consisting of 91 stations placed 1 m apart by 5 depths per station (at 0.3, 0.6, 0.9, 1.2 and 1.5 m below the surface). Post-irrigation tension and wetness measurements were recorded over 45 days at 11 time periods. Soil water tension was measured with tensiometers using a hand-held pressure transducer. A neutron probe was used to obtain volumetric water content. Using the observed wetness and tension data, unsaturated hydraulic conductivity values were derived (using a cubic spline function to estimate the gradient), and an exponential model was used to fit the calculated conductivity-tension curves to obtain hydraulic conductivity parameter values. The spatial and temporal variability of wetness, tension, saturated hydraulic conductivity and pore-size distribution parameters, and texture at the 0.3-m depth were examined using geostatistical techniques.The exponential model was found to inadequately describe the hydraulic conductivity/tension relationship for the full range of tension, particularly in the tension range near saturation. The derived values of the saturated hydraulic conductivity parameter were much greater than expected and do not correspond to reasonable saturated hydraulic conductivity values.All of the soil parameters studied exhibited large spatial variability horizontally and vertically in the field. Ranges of dependence determined from semivariogram analysis over the 44-day drainage period are 3–32 m for wetness, 6–34 m for soil water tension, 5–35 m for natural log of saturated hydraulic conductivity parameters, 5–11 m for pore-size distribution parameter, and 8–24 m for percent sand, silt and clay at the 0.3 m depth. An alternate hole-effect model is suggested to describe the texture semivariograms.It was determined that the variance of volumetric water content generally increased at each depth over the measured time periods, which is consistent with certain past field studies and a stochastic analysis of unsaturated flow in heterogeneous soils. Future research is recommended relating soil texture to soil hydrologic parameters with the goal of predicting soil behavior with less extensive sampling schemes.     

Influence of electrical fields (AC and DC) on phytoremediation of metal polluted soils with rapeseed (Brassica napus) and tobacco (Nicotiana tabacum)

The combined use of electrokinetic remediation and phytoremediation to decontaminate soil polluted with heavy metals has been demonstrated in a laboratory-scale experiment. The plants species selected were rapeseed and tobacco. Three kinds of soil were used: un-contaminated soil from forest area (S1), artificially contaminated soil with 15 mg kg⁻¹ Cd (S2) and multi-contaminated soil with Cd, Zn and Pb from an industrial area (S3). Three treatment conditions were applied to the plants growing in the experimental vessels: control (no electrical field), alternating current electrical field (AC, 1 V cm⁻¹) and direct current electrical field (DC, 1 V cm⁻¹) with switching polarity every 3 h. The electrical fields were applied for 30 d for rapeseed and 90 d for tobacco, each experiment had three replicates. After a total of 90 d growth for rapeseed and of 180 d for tobacco, the plants were harvested. The pH variation from anode to cathode was eliminated by switching the polarity of the DC field. The plants reacted differently under the applied electrical field. Rapeseed biomass was enhanced under the AC field and no negative effect was found under DC field. However, no enhancement of the tobacco biomass under the AC treatment was found. The DC field had a negative influence on biomass production on tobacco plants. In general, Cd content was higher in both species growing in S2 treated with AC field compared to the control. Metal uptake (Cd, Cu, Zn and Pb) per rapeseed plant shoot was enhanced by the application of AC field in all soils.     

电动力学法修复土壤环境重金属污染的研究进展

介绍了电动力学法的基本原理和国外的一些电动力学修复重金属污染土壤的工艺,如Lasagna工艺、阴极区注导电性溶液工艺、阳离子选择性透过膜、CEHIXM工艺、Electro—Klean^TM电分离技术、电化学自然氧化技术、电化学离子交换技术、电吸附技术等,并指出了这些工艺的优缺点。评价了电动力学法处理地下土壤环境中重金属污染的优势及目前存在的问题。     

Mobilization of phenol and dichlorophenol in unsaturated soils by non-uniform electrokinetics

The poor mobility of organic pollutants in contaminated sites frequently results in slow remediation processes. Organics, especially hydrophobic compounds, are generally retained strongly in soil matrix as a result of sorption, sequestration, or even formation into non-aqueous-phase liquids and their mobility is thus greatly reduced. The objective of this study was to evaluate the feasibility of using non-uniform electrokinetic transport processes to enhance the mobility of organic pollutants in unsaturated soils with no injection reagents. Phenol and 2,4-dichlorophenol (2,4-DCP), and kaolin and a natural sandy loam soil were selected as model organics and soils, respectively. The results showed that non-uniform electrokinetics can accelerate the desorption and movement of phenol and 2,4-DCP in unsaturated soils. Electromigration and electroosmotic flow were the main driving forces, and their role in the mobilization of phenol and 2,4-DCP varied with soil pH. The movement of 2,4-DCP in the sandy loam towards the anode (about 1.0 cmd(-1)V(-1)) was 1.0-1.5 cmd(-1)V(-1) slower than that in the kaolin soil, but about 0.5 cmd(-1)V(-1) greater than that of phenol in the sandy loam. When the sandy loam was adjusted to pH 9.3, the movement of phenol and 2,4-DCP towards the anode was about twice and five times faster than that at pH 7.7, respectively. The results also demonstrated that the movement of phenol and 2,4-DCP in soils can be easily controlled by regulating the operational mode of electric field. It is believed that non-uniform electrokinetics has the potential for practical application to in situ remediation of organics-contaminated sites.