Influence of electroosmotic treatment on the hydro-mechanical behaviour of clayey silts: preliminary experimental results

Preliminary results of an investigation focused on the influence of electrokinetic treatment on the mechanical and hydraulic behaviour of clayey soils are presented. The experimental programme aims at providing a contribution to the sustainability of contaminant extraction or containment via electroosmosis. Changes in the hydraulic and mechanical properties of two illitic clayey soils, subjected to a DC electric field, were investigated. Samples of the two soils were subjected to electrokinetic filtration, for different periods of time, and under different constant loads. Afterwards, they were tested under one-dimensional compression to detect changes in stiffness and hydraulic conductivity due to the electrical treatment. After the application of a DC field for a few hours, a small reversible increment in the average soil stiffness was observed, with respect to the untreated soil, while the hydraulic conductivity was not affected substantially. Dramatic changes of the mechanical and hydraulic soil properties, correlated to changes of the soil pH, were observed following non-conditioned electrokinetic treatment with duration of the order of days.     

Electrokinetic remediation of copper mine tailings: Implementing bipolar electrodes

Important process parameters to optimize in electrokinetic soil remediation are those influencing remediation time and power consumption since these directly affect the cost of a remediation action. This work shows how the electrokinetic remediation (EKR) process could be improved by implementing bipolar electrodes in the porous material. The bipolar electrodes in EKR meant two improvements: (1) a shorter migration pathway for the contaminant, and (2) an increased electrical conductivity in the remediation system. All together the remediation proceeded faster with lower electrical resistance than in similar experiments but without the bipolar electrodes.The new electrokinetic remediation design was tested on copper mine tailings with different applied electric fields, remediation times and pre-treatment. The results showed that the copper removal was increased from 8% (applying 20 V for 8 days in sulphuric acidified tailings) without bipolar electrodes to 42% when bipolar electrodes were implemented.Furthermore, the results showed that in this system sulphuric acid addition prior to remediation was better than citric acid addition. In addition, applying a too strong electric field (even with bipolar electrodes) could cause a severe polarization (e.g. a high electrical resistance) in the remediation system.     

Experimental study and mathematical model on remediation of Cd spiked kaolinite by electrokinetics

An experimental study on electrokinetic removal of cadmium from kaolinitic clays is presented in this work, which is aimed to investigate the effect of surface reactions on the electrokinetic process. Enhanced electrokinetic tests were performed in which the pH of the compartments was controlled. Cadmium spiked kaolin was adopted in the experimental runs. On the basis of the experimental results, a numerical model was formulated to simulate the cadmium (Cd) transport under an electric field by combining a one-dimensional diffusion-advection model with a geochemical model: the combined model describes the contaminant transport driven by chemical and electrical gradients, as well as the effect of the surface reactions. The geochemical model utilized parameters derived from the literature, and it was validated by experimental data obtained by sorption and titration experiments. Electrokinetic tests were utilized to validate the results of the proposed model. A good prediction of the behaviour of the soil/cadmium ions system under electrical field was obtained: the differences between experimental and model predicted profiles for the species considered were less than 5% in all the examined conditions.     

Integrated electrokinetic-soil flushing to remove mixed organic and metal contaminants

The integrated use of hydraulic flushing and electrokinetic treatment was investigated for the remediation of silty sand contaminated by both PAHs and heavy metals. The soil was collected from a polluted former manufactured gas plant (MGP). Four bench-scale experiments were conducted to analyze the ability of the combined hydraulic flushing and the electrokinetic treatment for the simultaneous removal of PAHs and heavy metals. Sequential flushing with ethylenediaminetetraacetic acid (EDTA) or Igepal CA-720 were tested with or without the simultaneous application of a low intensity direct electric field (1 VDC cm⁻¹). The best results were obtained with 0.2 M EDTA flushing in two stages (without and with voltage gradient, 1 VDC cm⁻¹), followed by 5% Igepal flushing in two stages (without and with 1 VDC cm⁻¹). Heavy metals were removed mainly during the EDTA flushing, with removal efficiencies of about 60% for Zn, 80% for Pb, and 30% for Cu. During Igepal flushing, no heavy metals were removed, but PAHs were removed, including 40% phenanthrene, 30% pyrene, and 20% benzo[a]pyrene. Overall, this study showed that a carefully designed sequential hydraulic flushing scheme with selected chelant and surfactant is needed for the removal of both heavy metals and PAHs from MGP silty sands. Combining electrokinetics with hydraulic flushing may not necessarily improve contaminant removal from such soils.     

Evaluation of Transport Phenomena for Removing Vanadium from Petrochemical Industry Solid Waste

Transport phenomena are investigated which are involved in the electrokinetic remediation process used for removing vanadium from deactivated catalysts from oil catalytic cracking that are currently allotted to cement plants and class-I landfills. Variables such as the concentration of electrolyte, electric potential, and applied electric current were evaluated in order to determine the effects produced by electroosmosis, diffusion, hydraulic gradient, and electromigration on the removal of vanadium from the catalyst. It was observed that migration is the most relevant phenomenon in the remediation tests, and for the best remediation condition, the migratory flow accounted for about 87 % of the vanadium removal.     

Electrokinetic remediation of bottom ash from municipal solid waste incinerator

The electrokinetic remediation was studied to verify the possibility to reclaim the bottom ash from municipal solid waste incineration (MSWI). In Italy, a production of 1 million tons per year of this kind of residue has been estimated, 90% of which is still landfilled. This work shows the results of four electrokinetic remediation tests for the removal of Pb, Cu, Zn, Cd and chlorides, using an open cell with graphite electrodes and without enhancing agents. The four tests have, respectively, been performed at a constant current density of 0.89, 1.67, 2.04 and 2.48 mA cm⁻², with duration of 42, 68, 47 and 40 h. Heavy metals occur in ashes in various forms, such as exchangeable, adsorbed, precipitated, organically complexed and residual phases. In order to determine the nature of any given system, in terms of specific chemical species and pertaining mobilities, sequential extraction analyses have been performed. The release of pollutants was investigated for treated and untreated ash. After treatment, the concentration of pollutants in the leachate was reduced by 31-83%, better results being obtained for chlorides. Both the low amount of heavy metal extracted and the increase of ash pH during the electrokinetic tests, suggest to use enhancing agents or a cation exchange membrane at the cathode, to prevent the precipitation of metals as hydroxides.     

Electrokinetic flow velocity in charged slit-like microfluidic channels with linearized Poisson-Boltzmann field

In cases of the microfluidic channel, where the thickness of electric double layer is often comparable with the characteristic size of flow channels, the electrokinetic influence on the flow behavior can be found. The externally applied body force originating from the electrostatic interaction between the linearized Poisson-Boltzmann field and the flow-induced electrical field is applied in the equation of motion. An analytical solution to this Navier-Stokes equation of motion for well-defined geometry of slit-like microchannel is obtained by employing Green’s function. Also, an explicit analytical expression for the induced electrokinetic potential is successfully derived as functions of relevant physicochemical parameters. The effects of the ionic concentration of the fluid, the zeta potential of the solid surface, and the width of microchannels on the velocity profile as well as the streaming potential are examined. The electric double layer effect on the velocity profile becomes stronger as the channel width decreases, where the average fluid velocity is entirely reduced with the decrease in ionic concentration. The induced electrokinetic potential increases with an increase in pressure gradient, while it decreases as the ionic concentration increases.     

Testing pulsed electric fields in electroremediation of copper mine tailings

Mining processes, prior to pyrometallurgical copper production, generate large amounts of solid waste, which are and have been deposited in mine tailings impoundments. This work is based on three electrodialytic (EDR) and four electrokinetic (EKR) remediation experiments on fresh and aged copper mine tailings using pulsed electric fields. The EDR results are compared to conventional remediation with direct current (dc) electric field. Applying pulsed electric fields in EDR, it was found that the remediation time decreased compared to dc EDR. In the anode side of the cell, 72 h of remediation at 20 V with a frequency ≥28 cycles/day at a fixed time ratio (t_ON/t_OFF) of 20, in terms of copper removal would correspond to around 270 h of dc remediation time. With both EDR and EKR of 120 h, at 14 cycles/day, the copper removal is practically uniform in the whole cell. Increasing the frequency to ≥28 cycles/day, the copper removal in the anode side is improved, and in the cathode side an accumulation is observed. With an EKR of 240 h, a larger copper accumulation in the cathode side was observed due to precipitation of copper hydroxide. In EDR with a pulsed electric field, the transport across the cation exchange membrane becomes the rate determining step. This can be seen from: (a) accumulation in the cathode side when increasing the frequency and (b) similar total copper removal for the three frequencies studied. In EKR, free alkali diffusion into the cell occurred. This generated copper precipitation in the cathode side, and the effect of the pulsed electric field on total copper removal was reduced.     

Enhanced electrokinetic remediation of cadmium-contaminated natural clay using organophosphonates in comparison with EDTA

Soil contamination by metals is a worldwide environmental problem. Electrokinetic extraction is a promising technology for in-situ remediation of contaminated soils of low hydraulic permeability. However, the extraction of metals is usually hindered by the high buffer capacity of natural soils. Organophosphonates are strong metal chelates as ethylenediaminetetraacetic acid(EDTA) which has been widely studied in the enhancement of electrokinetic remediation. In this study, batch desorption experiments and bench-scale electrokinetic extraction experiments were carried out to study the effect of two organophosphonates, i.e.,(nitrilotrimethylene)triphosphonate(NTMP) (ethylenedinitrilo)-tetramethylenephosphonate(EDTMP), on the extraction of cadmium from a natural clay in comparison with EDTA. Results of the batch desorption experiments showed that more than 75% of the sorbed cadmium could be dissolved into solution using 0.1 mol·L~(-1) organophosphonates or EDTA in the wide p H range of 1–11. Results of the electrokinetic extraction experiments showed that the cadmium spiked in the specimen migrated towards the anode with the enhancement of NTMP,EDTMP, and EDTA under a constant voltage gradient of approximately 1.0 V·cm-1. Although cadmium mobilization enhanced by EDTA was more efficient than that by the organophosphonates, accumulation of cadmium was observed in the vicinity of the anode. The average removal efficiencies of cadmium from the soil after approximately 5 days of electrokinetic extraction enhanced by 0.1 mol·L-1 NTMP(22.8%) and EDTMP(22.4%) were higher than that by 0.1 mol·L~(-1) EDTA(15.1%).     

Generation of bipolar electric fields during industrial handling of powders

This paper presents the results of some field tests that were carried out to determine the electric fields generated due to bipolar charging that occurs during the filling of a container with conveyed powders in an industrial setting. Approximately 1000 kg of pneumatically conveyed powder was allowed to fall into a cubically shaped container made out of woven fibreglass cloth that was placed on a metallic base electrically connected to ground. During the filling operation, the electric fields at three points close to the outside surface of the container were measured with a calibrated electrostatic probe. The results show that as the container is being filled, the mass of powder that accumulates in the lower part generates outward directed positive electric fields. In contrast, the shrinking, unfilled, upper space in the container generates considerably stronger outward directed negative electric field at the surface. At the level of the powder filling the container, the outward directed electric field was approximately zero. As the container fills, the zero electric field level moves upwards and the negative electric field disappears leaving the entire surface with a positive electric field. The net charge to mass ratio of the conveyed powder was measured in the order of 1.5 E-10 C/g, while falling into the container. Some of the generated negative electric fields at the surface were as high as 30 kV/cm. These results confirm previous measurements with other powders that showed that in a poly-disperse mixture, fine particles tend to charge negatively whereas coarser particles charge positively.     

Electrokinetic extraction of surfactants and heavy metals from sewage sludge

Waste management represents a quite serious problem involving aspects of remediation technologies and potential re-utilization in different fields of human activities. Of course, wastes generated in industrial activities deserve more attention because of the nature and amount of xenobiotic components, often difficult to be eliminated. However, also ordinary wastes of urban origin are drawing more and more attention, depending on the concentration of noxious substances like surfactants and some heavy metal, which may eventually require expensive disposal. In the present paper, a research has been carried out on the application of electrokinetic treatments for the abatement of the above xenobiotic components from sewage sludge generated in urban wastewater treatment plants. Experiments were carried out on a laboratory scale, in a 250 mm × 50 mm × 100 mm cell, using 250-300 g of sludge for each test and current densities between 2.4 and 5.7 mA cm⁻². As a general result, quite significant abatements of heavy-metal ions and surfactants were achieved, with relatively low energy consumption.     

Enhanced electrokinetic remediation of polluted kaolinite with an azo dye

In this work, the feasibility of the combination of electrokinetic remediation and electrochemical oxidation for the remediation of polluted soil with organic compounds had been development and evaluated in kaolinite spiked with Reactive Black 5 (RB5) an azo dye. The process consists in the use of two combined phenomena to achieve a full remediation of RB5 spiked kaolinite and the degradation of the organic pollutant. Those phenomena were soil electrokinetic treatment combined to liquid electrochemical oxidation. Reactive Black 5 (0.39 g dye kg⁻¹) could be effectively removed from the kaolinite matrix by electrokinetics, however the removal results largely depended on the operating conditions. Complete removal of RB5 was achieved using K₂SO₄ as processing fluid (which enhanced the desorption of RB5 from the kaolinite matrix) and operating with pH control at 7 on the anode. This favoured the alkalinization of the system and, at high pH values, RB5 was ionized and migrated towards the anode chamber where it was collected and could be oxidized electrochemically. Also, it must be pointed out that in these optimized conditions the electric power consumption (56 kW/mg of removed dye) was ten times lower compared to the unenhanced electrokinetic process (with no pH-control in the electrode solutions). Separate electrochemical decolourization tests of RB5 showed the effectiveness of K₂SO₄ in the efficiency of the process. A linear relationship between K₂SO₄ concentration and the decolourization rate was found. Thus, nearly complete decolourization was achieved after 2 and 3 h of electrochemical treatment when the electrolyte concentration was 0.1 and 0.01 M of K₂SO₄, respectively.     

Bio-electro-remediation: electrokinetic transport of nitrate in a flow-through system for enhanced toluene biodegradation

The availability of electron acceptors and nutrients is often limiting the microbiological clean-up of polluted groundwater at contaminated sites. In this study, the feasibility of electrokinetic processes to improve mass transfer was demonstrated in a model system simulating laminar groundwater flow conditions. Electrokinetic nitrate transport and enhanced biodegradation of toluene under denitrifying conditions was studied as function of voltage gradient in a new flow-through system. The study was done in a three-dimensional anaerobic model aquifer system filled with coarse sand. The influent area was divided into seven chambers thus enabling a separate addition of toluene and nitrate. Mesh electrodes were inserted laterally in order to form an electric field perpendicular to the flow direction with voltage gradients of 0, 0.125 and 0.25 V cm⁻¹, respectively. Biodegradation was studied after inoculation with a denitrifying microbial mixed culture. Application of the electric field resulted in nitrate migration into areas containing toluene. In the presence of denitrifying bacteria, the availability of nitrate in toluene polluted areas resulted in toluene biodegradation, demonstrated by nitrite formation and decreased toluene concentration.     

电动力学辅助植物修复重金属污染土壤的特征机制与机遇

土壤重金属污染具有污染过程复杂、危害突出和修复困难等特点,修复刻不容缓。电动力学辅助植物修复（EKAPR）致力于弥补电动力学和植物修复各自劣势,协同发挥二者优势,解决电动力学无法彻底清除土壤重金属和植物修复缓慢、作用范围有限等突出问题。本文通过分层总结,归纳了电动力学辅助植物修复重金属的研究现状、影响类型与作用特征、相互作用关系及强化修复机制等。综述表明,EKAPR体系电动力学和植物相互作用,存在有利或不利于重金属清除的影响,在克服自身的局限方面两者也存在很多协同效应;EKAPR过程主要受电场类型、电场布置与强度、pH演变、添加剂等的控制。电动力学通过改善重金属的空间及形态分布,促进养分吸收及刺激根际分泌等作用机制,可有效提高重金属植物吸收富集及污染土壤修复效果。EKAPR被认为是新颖、绿色、可持续的原位重金属污染场地修复技术,在实现污染场地修复方面具有较大发展前景。分析表明,现有研究工作开展较少,若干技术问题和应用挑战仍然存在。加大关键变量影响特征分析及调控、电动力学辅助下植物营养与重金属分布变化机制、累积特征及强化机制研究是克服难点及推动EKAPR技术应用的关键。     

Effects of direct electric current and electrode reactions on vinyl chloride degrading microorganisms

The use of electro-bioremediation has gained increasing interest during recent years. In these hybrid technologies bioremediation is stimulated by electrochemical or electrokinetic techniques to increase pollutant biodegradation efficiency. It is a pre-requisite for successful application of the bio-electro-processes that the microorganisms are not negatively affected by the electric fields or electrode reactions.In this study, for the first time microbial activity of aerobic vinyl chloride (VC) degrading microorganisms was assessed after exposure to constant currents ranging from 0.04 to 14 mA cm⁻². Viability and degradation kinetics were monitored during electrolysis for 4 h using two different types of electrodes: stainless steel and dimensionally stable electrodes (DSA). When the mixed microbial culture was exposed in the electrode compartments, inhibiting effects were observed with stainless steel and DSA electrodes beyond doses of 100 and 50 kJ/L, respectively. Incubation of the VC degrading microorganisms in the mineral medium that was pretreated in the electrode compartments with similar doses, resulted in slower VC degradation kinetics thus demonstrating that the inhibition was due to electrochemical reaction products. When electrodes were separated from the microorganisms by bipolar membranes, no inhibition by the electric field was observed.     

Pulse-enhanced electrokinetic remediation of fluorine-contaminated soil

The presence of abundant fluorides in soil can pose potential threats to environment and human health. We investigated the effects of pulsed electric field on electrokinetic remediation of fluorine-contaminated soil by varying the pulse interval. Although the remediation time was increased, experimental results indicated pulse-enhanced electrokinetic remediation could improve the removal efficiency of fluorine better than the conventional electrokinetic remediation in the same intensity of electric field. The fluorine removal efficiency of the former (30 min, pulse interval) was 80.93% and that of normal electrokinetic remediation was 72.40%, because pulsed electric field could reduce the concentration polarization and increase the electrical current, electroosmotic flow and the electrical voltage part in soil cell. Therefore, in the later phase of electrokinetic remediation, when electrical current and the fluorine removal efficiency decreased obviously, at this time the pulse-enhanced method would be a considerable choice to eliminate fluorine in contaminated soils.     

微小三角形槽道内电渗流动特性分析

提出了微小三角形槽道内电渗流动理论计算方法,通过Galerkin法计算并分析了其内部的电势及速度分布,获得了温度、槽道尺寸、外加电势的电场强度、ζ电势以及电解质浓度对微小三角形槽道内电渗流动的影响规律。计算结果表明：微小三角形槽道内液体的质量流量随ζ电势、电场强度、流体温度及电解质浓度的增加而增加,随微小三角形槽道尺寸的增加先增加后减小。     

Electrochemically induced reactions in soils—a new approach to the in-situ remediation of contaminated soils?: Part 2: remediation experiments with a natural soil containing highly chlorinated hydrocarbons

An observed decay of immobile organic substances is not explained by the theory of electrokinetic soil remediation, when they are not transported by means of the electric field (electro-osmosis or -phoresis), as it is the case for chlorinated hydrocarbons like hexachlorobutadiene. It is assumed that the decrease of those substances is based on the presence of ‘microconductors’, particles with electronic conducting properties (e.g. metal oxides or others), inside the soil matrix. They are supposed to be able to induce electrochemical reactions in the vicinity of the contamination. Another possibility for the observed decay in their concentration are elimination reactions. Experiments and results with a natural soil containing chlorinated hydrocarbons with high boiling points coming from an industrial contamination site are presented. A decay of 80% and more for some of the substances could be observed. Degradation products (DP) with less chlorine in the molecule structure have been detected. Thus, redox- and elimination-reactions are possible. High pH-values seem to enhance the remediation.     

Cathodic Hydrogen as Electron Donor in Enhanced Reductive Dechlorination

In situ capping is an attractive and cost-effective method for remediation of contaminated sediments, but few studies on enhancing contaminant degradation in sediment caps have been reported, especially for chlorinated benzenes. Electrically enhanced bioactive barrier is a new process for in situ remediation for reducible compounds in soil or sediments. The primary objective of this study is to determine if electrodes in sediment could create a redox gradient and provide electron acceptor/donor to stimulate degradation of chlorinated contaminant. The results demonstrate that graphite electrodes lead to sustainable evolution of hydrogen, displaying zero-order kinetics in the initial stages with different voltages. The constant rates of hydrogen evolution at 3, 4, and 5 V are 1.05, 2.54, and 4.3 nmol·L 1·d 1, respectively. Even higher voltage can produce more hydrogen, but it could not keep long time because the over potentials on electrode surfaces prevent its function. The study shows that 4 V is more appropriate for hydrogen evolution. The measured and evaluated concentration of 1,2,3,5-tetrachlorobenzene in pore water of sediment and concentration of sulfate show that dechlorination is inhibited at higher concentration of sulfate.     

Nuclear decontamination of cementitious materials by electrokinetics: An experimental study

The objective of this paper is to evaluate the efficiency of an electrokinetic method of radionuclide removal from a cement-based material. This work is a two-part process. In the first part, a sample of mortar was uniformly contaminated for use as a reference. In order to ensure a uniform contamination, the ingress of the radioelement (cesium) was controlled by an external electrical field. The second part of this work concerns the removal of cesium from the contaminated mortar samples. This second, decontamination, phase was driven by the same electrical field. No electroosmosis was detected. Both phases were characterized by analyses of cesium and calcium concentrations in cathodic and anodic solutions, and by measurements of cesium content in the samples at the end of each phase. In addition to the electrical current, pH, and conductivity were measured during the experiments. Finally, the efficiency of the electrokinetic method was described in terms of decontamination factor, leading to promising results.