Iodide-Enhanced Electrokinetic Remediation of Mercury-Contaminated Soils

This study investigates using an iodide-enhanced solution at the cathode during electrokinetic treatment to optimize the removal of mercury from soils. The experimental program consisted of testing two types of clayey soils, kaolin, and glacial till, that were initially spiked with 500 mg/kg of Hg(II). Experiments were conducted on each soil type at two voltage gradients (1.0 or 1.5 VDC/cm) to evaluate the effect of the voltage gradient when employing a 0.1 M KI solution. Additional experiments were performed on each soil type to assess the effect of using a higher iodide concentration (0.5 M KI) when using a 1.5 VDC/cm voltage gradient. The tests conducted on the kaolin soil showed that when the 0.1 M KI concentration was employed with the 1.0 VDC/cm voltage gradient, approximately 97% of the mercury was removed, leaving a residual concentration of 16 mg/kg in the soil after treatment. The tests conducted on glacial till indicated that it was beneficial to use the higher (0.5 M KI) iodide concentration and the higher (1.5 VDC/cm) voltage gradient to enhance mercury removal, because, under these conditions, a maximum of 77% of the mercury was removed from the glacial till, leaving a residual concentration of 116 mg/kg in soil after electrokinetic treatment. Compared to kaolin, the lower mercury removal from the glacial till soil is attributed to the more complicated soil composition, such as the presence of carbonates and organic matter, which caused Hg(II) to adsorb to the soil and/or exist as an immobile chemical species.     

Sequentially Enhanced Electrokinetic Remediation of Heavy Metals in Low Buffering Clayey Soils

This paper presents the results of an experimental investigation undertaken to evaluate different purging solutions to enhance the removal of multiple heavy metals, particularly chromium, nickel, and cadmium, from a low buffering clay, specifically kaolin, during electrokinetic remediation. Experiments were conducted on kaolin spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1,000, 500, and 250 mg/kg, respectively, which simulate typical electroplating waste contamination. A total of five different tests were performed to investigate the effect of different electrode purging solutions on the electrokinetic remedial efficiency. A constant DC voltage gradient of 1 V/cm was applied for all the tests. The removal of heavy metals from the soil using tap water as the purging solution was very low. When 1 M acetic acid was used as the purging solution in the cathode, the removal of chromium, nickel, and cadmium was increased to 20, 19, and 13%, respectively. Using 0.1 M ethylene diamine tetraacetic acid as the purging solution in the cathode, 83% of the initial Cr was removed; however, the nickel and cadmium removal was very low. A sequentially enhanced electrokinetic remediation approach involving the use of water as a purging solution at both the anode and cathode initially, followed by the use of acetic acid as the cathode purging solution and a NaOH alkaline solution as the anode purging solution was tested. This sequential approach resulted in a maximum removal of chromium, nickel, and cadmium of 68–71, 71–73, and 87–94%, respectively. This study shows that the sequential use of appropriate electrode purging solutions, rather than a single electrode purging solution, is necessary to remediate multiple heavy metals in soils using electrokinetics.     

Enhanced Electrokinetic Remediation of Heavy Metals in Glacial Till Soils Using Different Electrolyte Solutions

Previous electrokinetic remediation studies involving the geochemical characterization of heavy metals in high acid buffering soils, such as glacial till soil, revealed significant hexavalent chromium migration towards the anode. The migration of cationic contaminants, such as nickel and cadmium, towards the cathode was insignificant due to their precipitation under the high pH conditions that result when the soil has a high acid buffering capacity. Therefore the present laboratory study was undertaken to investigate the performance of different electrolyte (or purging) solutions, which were introduced to either dissolve the metal precipitates and/or form soluble metal complexes. Tests were conducted on a glacial till soil that was spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1,000, 500, and 250 mg/kg, respectively, under the application of a 1.0 VDC/cm voltage gradient. The electrolyte solutions tested were 0.1M EDTA (ethylenediaminetetraacetic acid), 1.0M acetic acid, 1.0M citric acid, 0.1M NaCl/0.1M EDTA, and 0.05M sulfuric acid/0.5M sulfuric acid. The results showed that 46–82% of the Cr(VI) was removed from the soil, depending on the purging solution used. The highest removal of Ni(II) and Cd(II) was 48 and 26%, respectively, and this removal was achieved using 1.0M acetic acid. Although cationic contaminant removal was low, the use of 0.1M NaCl as an anode purging solution and 0.1M EDTA as a cathode purging solution resulted in significant contaminant migration towards the soil regions adjacent to the electrodes. Compared to low buffering capacity soils, such as kaolin, the removal of heavy metals from the glacial till soil was low, and this was attributed to the more complex composition of glacial till. Overall, this study showed that the selection of the purging solutions for the enhanced removal of heavy metals from soils should be primarily based upon the contaminant characteristics and the soil composition.     

Sequential Electrokinetic Remediation of Mixed Contaminants in Low Permeability Soils

The coexistence of heavy metals and polycyclic aromatic hydrocarbons (PAHs) at many of the contaminated sites poses a severe threat to public health and the environment. Very few technologies, such as soil washing/flushing and stabilization/solidification, are available to remediate such sites; however, these technologies are ineffective and expensive to treat contaminants in low permeability clayey soils. Previous studies have shown that electrokinetic remediation has potential to remove heavy metals and organic compounds when they exist individually in clayey soils. In the present study, the feasibility of using surfactants and organic acids sequentially and vice versa during electrokinetic remediation was evaluated for the removal of both heavy metals and PAHs from clayey soils. Kaolin was selected as a model clayey soil and it was spiked with phenanthrene and nickel at concentrations of 500 mg/kg dry each to simulate typical field mixed contamination. Bench-scale electrokinetic experiments were performed with the sequential anode conditioning with: (1) 1 M citric acid followed by 5% Igepal CA-720; (2) 1 M citric acid followed by 5% Tween 80; and (3) 5% Igepal CA-720 followed by 1 M citric acid. A periodic voltage gradient of 2 V/cm (with 5 days on and 2 days off cycles) was applied in all the tests. A removal of about 96% of phenanthrene was observed in the test with 5% Igepal CA-720 followed by 1 M citric acid sequence. Most of the nickel (>90%) migrated from anode to cathode in this test; however, it precipitated in the section very close to the cathode due to the high pH conditions. Conversely, the removal efficiency of nickel was about 96 and 88% in the tests with 1 M citric acid followed by 5% Igepal CA-720 sequence and 1?M citric acid followed by 5% Tween 80 sequence, respectively. However, the migration and removal efficiency of phenanthrene in both of these tests were very low. Overall, it can be concluded that the sequential use of 5% Igepal CA-720 followed by 1 M citric acid may be an effective remedial strategy to remove coexisting heavy metals and PAHs from clayey soils.     

Cyclodextrin-Enhanced Electrokinetic Remediation of Soils Contaminated with 2,4-Dinitrotoluene

The removal of 2,4-dinitrotoluene (2,4-DNT), a munitions waste constituent and an industrial intermediate, from contaminated soils was evaluated using enhanced electrokinetic (EK) remediation. Two model soils were spiked with 480?mg of 2,4-DNT/kg of dry soil for the EK experiments. The spiked soils were kaolin, a low-buffering clayey soil, and glacial till, a high-buffering silty soil. The glacial till was obtained from a field site and contained 2.8% organic matter. Deionized (DI) water and cyclodextrin solutions were used as the EK purging solutions. Cyclodextrin was selected as a nonhazardous solubility enhancer for enhancing the desorption and removal of 2,4-DNT from soils in EK remediation. Two aqueous solutions of hydroxypropyl β-cyclodextrin (HPCD) at concentrations of 1 and 2% were selected for kaolin and glacial till, respectively, based on results for batch extraction of 2,4-DNT from the same soils. During the EK experiments, greater current and electro-osmotic flow were observed for HPCD solutions than for DI water. After the completion of the EK experiments, the soils in the EK cell were extruded and the residual 2,4-DNT in the soils was determined. Less 2,4-DNT remained in the kaolin soil (up to 94% transformed) than in the glacial till soil (20% transformed) due to strong retention of 2,4-DNT by the soil organic matter in glacial till. For kaolin, less 2,4-DNT remained in the soil using HPCD solutions than using DI water. For glacial till, comparable levels of 2,4-DNT remained in the soil for both EK solutions. Since no 2,4-DNT was detected in the effluents from the EK cells, the decrease in 2,4-DNT concentration in the kaolin and glacial till soils was attributed to electrochemical transformation of 2,4-DNT to other species.     

Electrokinetic Remediation of Cadmium-Contaminated Clay

Electrokinetic extraction has been demonstrated to be very effective in removing heavy metals from Georgia kaolinite. The relatively high removal efficiency depends on the extremely acidic soil environment generated by the electrokinetic process. However, the efficiency observed in Georgia kaolinite cannot be achieved in soils of high acid/base buffer capacity without enhancement. In this study, the effect of ethylenediaminetetraacetic acid (EDTA) to enhance electrokinetic extraction of cadmium from Milwhite kaolinite was examined. The influence of electro-osmotic flow direction on the migration of cadmium, EDTA, and their complexes were also investigated. It was observed that injection of EDTA from the cathode reservoir by a reverse electro-osmotic flow could mobilize the cadmium in the specimen effectively. A less significant mobilization of cadmium was observed when the electro-osmotic flow was directed toward the cathode. However, accumulation of cadmium near the anode was observed regardless of the electro-osmotic flow direction.     

Complicating Factors of Using Ethylenediamine Tetraacetic Acid to Enhance Electrokinetic Remediation of Multiple Heavy Metals in Clayey Soils

Batch and electrokinetic experiments were conducted to investigate the removal of three different heavy metals, chromium(VI), nickel(II), and cadmium(II), from a clayey soil by using ethylenediamine tetraacetic acid (EDTA) as a complexing agent. The batch experiments revealed that high removal of these heavy metals (62–100%) was possible by using either a 0.1?M or 0.2?M EDTA concentration over a wide range of pH conditions (2–10). However, the results of the electrokinetic experiments using EDTA at the cathode showed low heavy metal removal efficiency. Using EDTA at the cathode along with the pH control at the anode with NaOH increased the pH throughout the soil and achieved high (95%) Cr(VI) removal, but the removal of Ni(II) and Cd(II) was limited due to the precipitation of these metals near the cathode. Apparently, the low mobility of EDTA and its migration direction, which opposed electroosmotic flow, prevented EDTA complexation from occurring. Overall, this study found that many complicating factors affect EDTA-enhanced electrokinetic remediation, and further research is necessary to optimize this process to achieve high contaminant removal efficiency.     

Experimental Studies on Heavy Metal Extraction from Contaminated Soil Using Ammonium Citrate as Alkaline Chelate during the Electrokinetic Process

Researchers have performed experimental studies using ammonium citrate (AC) during the electrokinetic (EK) remediation process for the extraction of cadmium (Cd) and copper (Cu) from the contaminated soil. They evaluated the efficiency of ammonium citrate by considering it as a washing solution and a purging solution at the anode electrode compartment. The efficiency of electrokinetic extraction was observed to be significantly influenced by the pH and buffering nature of the soil medium. The experimental studies indicate that the removal of cadmium and copper was 48.9% and 30.0%, respectively, when ammonium citrate was used both washing and purging solution. The solubility of both cadmium (Cd++) and copper (Cu++) in EK-treated soils has also been estimated by sequential extraction studies with deionized (DI) water. The analytical techniques, X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscope (SEM) provide the evidence of migration of cations during treatment of contaminated soil by process of electroosmosis (EO). The SEM images of both cadmium- and copper-contaminated soils show that these soils have a fluffier and more porous structure. This might be caused by the change in surface charges of the clay particles as a result of introduction of heavy metals. The mineralogical compositions of soil are not altered significantly by electrokinetic process.     

Evaluation of Electrokinetic Removal of Heavy Metals from Tailing Soils

Electrokinetic remediation was studied for the removal of toxic heavy metals from tailing soils. The study emphasized the dependency of removal efficiencies upon their speciations, as demonstrated by the different extraction methods used, which included sequential extraction, total digestion, and 0.1 N HCl extraction. The tailing soils examined showed different physicochemical characteristics, such as initial pH, particle size distribution, and major mineral constituents, and they contained high concentrations of target metal contaminants in various forms. The electrokinetic removal efficiencies of heavy metals were significantly influenced by their partitioning prior to treatment, and the pHs of the tailing soils. The mobile and weakly bound fractions of heavy metals, such as the exchangeable fraction, were easily removed by electrokinetic treatment (more than 90% removal efficiency), but immobile and strongly bound fractions, such as the organically bound species and residual fractions, were not significantly removed (less than 20% removal efficiencies).     

Mercury-Contaminated Soil Remediation by Iodide and Electroreclamation

Mercury was removed from a field-contaminated soil by a combination of redox and complexation processes with iodide/iodine and electrokinetic mobilization. Iodide added to the cathode compartment was transported into the soil and oxidized to iodine near the anode. Mercury was mobilized and transported to the anode as a mercury–iodide complex. After 5 days, some 50% of the total mercury content had migrated to the anode compartment, and another 25% was recovered from the soil water in the vicinity of the anode. No volatile mercury was formed. Electromigration is the dominant transport process for the (charged) mercury–iodide complex, since electro-osmosis would have moved the mercury toward the cathode. The combination of iodide as complexing agent and an electric field for physical mobilization could be developed to a new method for in situ remediation of mercury contaminated soil.     

Enhancement of Remediation of NAPL Contaminated Fractured Permeable Formations—Modeling Study

This study has been originated and motivated by a series of discussions, concerning the containment and use of polluted groundwater of a comparatively wide part of the Coastal Plain Aquifer (CPA) in Israel that has been polluted by kerosene [light nonaqueous phase liquid (LNAPL)]. A variety of types of information have indicated that hydraulic barriers should be employed. However, such an operation should be subject to optimize the aquifer remediation, which is also obtained due to the hydraulic barrier operation. The particular part of the CPA is comprised of “fractured permeable formation” namely sandstone interbedded with sandy clay lenses. Therefore, in this study a simplified conceptual model is applied to represent the formation and implement the pump-and-treat remediation procedure, whose major objective is cost effective containment of the polluted area. Three physical measures, aimed at the remediation process enhancement, have been analyzed: (1) changing the pumping-injection discharge, (2) use of surfactant additives (or other types of solubilizing agents), and (3) use of controlled means to increase the aperture size and density of fracture segments. Possibly, an appropriate combination of such means is most feasible and should be determined. However, the present study evaluates the separate possible effects of each one of such measures on major parameters of the remediation process (time and volume of water that should be treated). It is shown that a particular set of parameters can be applied to evaluate the optimal design and adequate combination of such physical measures aimed at remediation enhancement.     

Modeling Elution Histories of Copper and Lead from Contaminated Soil Treated by Poly(amidoamine) Dendrimers

A dynamic “two-site” model was formulated and tested for simulating the elution histories of copper (Cu2+) and lead (Pb2+) from a contaminated soil treated by poly(amidoamine) dendrimers. In the model, the metal sorption sites of the soil were divided into two compartments: one with a fast desorption rate and the other with a slow desorption rate. The model was tested for simulating and predicting Cu2+ and Pb2+ elution histories obtained from column experiments. Compared to the classical “one-site” model and the modified “gamma distribution” model, the “two-site” model not only provides much improved power for simulating the observed metal elution data, but also can more accurately predict the metal elution histories under various experimental conditions including initial metal concentration in soil, dendrimer concentration, and pH.     

Development of an Apparatus for pH-Isolated Electrokinetic In Situ Chemical Oxidation

An apparatus was designed, manufactured, and implemented to isolate pH during electrokinetic in situ chemical oxidation (EK-ISCO). H+ and OH- electromigration were used to determine the adequacy of the designed apparatus for pH isolation. A series of pH-isolation and normal-mode (no pH-isolation) experiments were undertaken and compared. It was found that pH isolation was achieved when the electrode reservoirs were separated by porous media combined with the purging of the electrode reservoir fluid. The electromigration retardation factor of H+ and OH- was calculated for the porous media using the observed pH breakthrough times. The retardation factor for H+ was also calculated by considering mass flux data. The retardation factors for H+ and OH- were found to be 28.3 and 95, respectively, when using the breakthrough time. The retardation factor for H+ was calculated to be 36.7 using the mass flux data.     

Mercury Geochemistry in Wetland and its Implications for In Situ Remediation

The objective of this study was to characterize the nature of Hg sorption to a wetland sediment with the intent of providing guidance for the selection of an appropriate in situ remediation strategy. Total Hg concentrations in the sediments were as high as 10 mg/kg, whereas associated pore water Hg concentrations were below detection, <0.010 mg/L. Sediment Hg was not in an exchangeable form, and <8% of it was associated with organic matter. The remainder of the Hg was strongly associated with Fe oxides and/or with a precipitated phase, presumably a sulfide. Sediment Hg concentrations were significantly correlated (r = 0.94) with Fe oxide concentrations. Thermodynamic calculations based on field Eh/pH measurements and laboratory results suggest that under present field conditions metacinnabar (HgS) would not be stable due to the relatively low pH (～4.2) and sulfate concentrations (0.14 mM) and high Eh levels at the study site. However, these calculations indicate that metacinnabar may have formed when the Hg first entered the wetland at elevated concentrations (～5 mg/L). Given the ecologically sensitive nature of the wetland and the fact that the Hg is strongly bound to the sediment, it was concluded that a monitored natural attenuation approach for site remediation may be appropriate.     

Nodal Failure Index Approach to Groundwater Remediation Design

Computer simulations often are used to design and to optimize groundwater remediation systems. We present a new computationally efficient approach that calculates the reliability of remedial design at every location in a model domain with a single simulation. The estimated reliability and other model information are used to select a best remedial option for given site conditions, conceptual model, and available data. To evaluate design performance, we introduce the nodal failure index (NFI) to determine the number of nodal locations at which the probability of success is below the design requirement. The strength of the NFI approach is that selected areas of interest can be specified for analysis and the best remedial design determined for this target region. An example application of the NFI approach using a hypothetical model shows how the spatial distribution of reliability can be used for a decision support system in groundwater remediation design.     

Remediation of RDX-Contaminated Water Using Alkaline Hydrolysis

The objective of this study was to assess the effectiveness of alkaline hydrolysis as an alternative ex situ technology for remediating groundwater contaminated with hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Treatment in both batch reactor and continuous stirred tank reactor (CSTR) was investigated. RDX reactivity was strongly dependent on the reaction pH investigated (11–13). The batch system achieved pseudo-first-order RDX reaction rates in the range of (0.8–27.7)×10?3?min?1, corresponding to half-life periods of 17.9?to?0.5?h, respectively. In the CSTR system operated at the initial RDX concentration of 4.5×10?3?mM, 99% RDX removal was achieved with the hydraulic retention time of 2?days and the reaction pH of 11.9. Formate and nitrite were produced as the major hydrolysates in the CSTR system, indicating a simultaneous reaction mechanism involving RDX ring cleavage and elimination of the ring nitrogen. The net OH? demand used only for RDX removal in the CSTR was found to be 1.5, 390, and 130?M OH?/M RDXremoved at pH values of 11.9, 11.5, and 11.0, respectively. A conceptual cost analysis indicated that the expense of alkaline treatment may be comparable to the expense of granular activated carbon treatment for long treatment periods (30?years or more), due to the potentially lower annual operational cost of alkali treatment.     

Case Study of Subsidence in Interstratified Sedimentary Bedrock: Parking Garage Distress Investigation and Remediation

This case study illustrates the investigation and remediation of distress and subsidence on a multilevel, posttension, cast-in-place concrete parking garage that was constructed at the crest and over the side of a gentle sloping hillside. A comprehensive exploration program was conducted to determine the cause of the subsidence. The investigation included core borings through the distressed caissons and the underlying bedrock and the use of a downhole camera to determine the rock conditions. Based on the investigation, it was concluded that the caisson subsidence was caused by the collapse of a large cavity underlying the sandstone. A grouting program was performed to reduce the potential of further settlement. This paper summarizes the findings and conclusions derived from this investigation and the remedial measures undertaken to reduce the potential of further distress to the structure.     

Fully Coupled Analysis of Failure and Remediation of Lower San Fernando Dam

The extent of flow deformation in an embankment dam is determined by the driving forces and the residual strength of the soil, as well as by the kinematic constraints. The soil conditions of berm and buttress, as well as of foundation, are also critical factors affecting seismic performance of an embankment dam. A careful examination of these factors is necessary when proposing remedial measures to a seismically deficient dam. This paper presents a set of fully coupled finite element analyses of the response of the well-known lower San Fernando Dam during the 1971 earthquake. A critical state model incorporating the concept of state-dependent dilatancy was employed to describe soil behavior over the full range of loading conditions encountered. The results show clearly that a flow slide occurred on the upstream side, and indicate that a downstream flow slide would occur, too, if the downstream berm had not been constructed before the event. The analyses show also that the addition of an upstream berm could effectively prevent the upstream flow slide.     

Chemical-Enhanced Washing for Remediation of Soils Contaminated with Marine Diesel Fuel in the Presence/Absence of Pb

The effects of the operating conditions, the initial concentrations of marine diesel fuel (MDF) and the coexisting Pb in the soil, and the ethylene diamine tetra acetic salt (EDTA) in solution on MDF removal by sodium dodecyl sulfate (SDS) washing were extensively investigated with the aim of optimizing the process parameters and determining the MDF removal efficiency by SDS under different contamination conditions. The experimental results from batch tests indicated that the majority of MDF was removed by SDS in the first 2?h, and its optimal pH was nearly neutral. Increasing the SDS concentration linearly increased the MDF removal efficiency. At a given SDS concentration, the removal efficiency was dependent on the existing forms of MDF in soils, and the free phase of MDF was found to be more easily removed than the adsorbed phase. MDF removal by SDS was significantly reduced by the coexisting Pb in soils, which likely forms a complexation with SDS and thereby enhances the partitioning of MDF in the soil by the re-adsorption of released MDF onto the hydrophobic tails of the adsorbed SDS. EDTA alone, or with SDS, could remove MDF, but the remaining MDF in the contaminated soil after EDTA washing became more difficult to be removed by SDS. Therefore, the EDTA washing followed by SDS washing is not recommended for MDF removal.     

Using Continuum Approach to Quantify the Remediation of Nonaqueous Phase Liquid Contaminated Fractured Permeable Formations

This study addresses the feasibility of using a continuum modeling approach to simulate pump-and-treat remediation of nonaqueous phase liquid (NAPL) contaminated fractured permeable formations. A simplified discrete fracture model, which incorporates permeable blocks with embedded parallel equidistant constant aperture fractures, was used to simulate the NAPL dissolution in an idealized fractured permeable formation. The applicability of this model is defined by the ranges of a dimensionless mobility number and interphase mass transfer coefficient. A continuum based model able to simulate phenomena predicted by the discrete fracture model has also been used. Three dimensionless parameters referring to organic solute advection and dispersion, and the continuum interphase mass transfer coefficient govern the performance of the continuum model. The nonlinear relationships between the discrete fracture and continuum model have been identified and formulated. However, the simplified conceptual models of this study may be inapplicable to many types of fractured formations. Ranges of possible use of the continuum modeling were determined in terms of dimensionless parameters. The discrete fracture and continuum approaches of this study can be useful for the preliminary evaluation of ideas concerning optimization of the remediation of NAPL contaminated fractured permeable formations.