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.     

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.     

Electrokinetic Remediation Modeling Incorporating Geochemical Effects

Electrokinetic remediation technology is one of the developing technologies that offers great promise for the cleanup of soils contaminated with heavy metals. However, the performance of an electrokinetic remediation system depends on the interaction of a complex set of interrelated system variables and parameters. Many of these interactions were addressed in this study by incorporating geochemical reactions into electrokinetic remediation modeling. A one-dimensional transport model was developed to predict the transport and speciation of heavy metals (chromium, nickel, and cadmium) in soil during electrokinetic remediation as a function of time and space. The model incorporates: (1) pH-dependent adsorption of contaminants to the soil surface; (2) sensitivity of soil surface potential and electroosmotic flow to the pore water properties; and (3) synergistic effects of multiple chemical species on electrokinetic remediation. The model considers that: (1) Electrical potential in the soil is constant with time; (2) surface complexation reactions are applicable in the highly concentrated clay suspensions; (3) the effect of temperature is negligible; and (4) dissolution of soil constituents is negligible. The predicted pH profiles, electroosmotic flow, and transport of chromium, nickel, and cadmium in kaolin soil during electrokinetic remediation were found to reasonably agree with the bench-scale electrokinetic experimental results. The predicted contaminant speciation and distribution (aqueous, adsorbed, and precipitated) allow for an understanding of the transport processes and chemical reactions that control electrokinetic remediation.     

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.     

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.     

Heavy Metal Removal by Coagulation with Seawater Liquid Bittern

Soluble heavy metals present in water could be deleterious to health, and as a result, their discharge into surface waters has been regulated internationally. Many processes for the removal of heavy metals from water and wastewater have been investigated. Coagulation and precipitation are the processes that have been reported to be most effective in the removal of heavy metals. In this study, seawater liquid bittern (LB), as an inexpensive source of magnesium, added to wastewater alkalized with lime or caustic soda is investigated as a possible coagulant. The experiments covered tests on eight metals: arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc. The lime-LB process culminated in high removals (>90%) for cadmium, chromium, lead, mercury, and zinc and reasonably good removals (71, 82, and 75%) for arsenic, copper, and nickel, respectively. These results were superior to those obtained using the caustic-soda–LB process. The concurrent presence of different metals in solution has been shown to have a minor effect on removal efficiencies for most metals. However, in the case of nickel, removal was appreciably increased by 18.5%. Also, higher concentrations of a single metal showed higher removal efficiencies.     

Enhancement of Electrokinetic Extraction from Lead-Spiked Soils

An innovative system was developed to enhance electrokinetic extraction of heavy metals from contaminated soils. The system consists of a layer that was continuously flushed with nitric acid at pH 3 near the cathodic region and two reservoirs with 0.4 M NaOAc at pH 3.8 and acetic acid at pH 4 flushing the anode and cathode, respectively. Both pure kaolinite and carbonate-rich illitic soils were tested. With traditional electrokinetic systems, approximately 60% of lead was transported to the cathode for kaolinite, whereas there was little removal for carbonate-rich illitic soil. This result indicates that clay minerals have an important effect on the desorption process. The integrated electrokinetic system maximized contaminant extraction and minimized precipitation in the cathodic region. Over 80% of the lead was removed from carbonate-rich illitic soil, with 5,000-mg∕kg initial lead contaminated concentration, and leached out through the flushing layer. The system operated successfully in laboratory bench tests with carbonate-rich illitic soil.     

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).     

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.     

Electrochemical processing of the metallic wastes of ZhS32 nickel superalloys

Technological foundations are developed for the electrochemical oxidation of nickel superalloys containing alloying elements Re, Ta, Nb, Co, W, Cr, Mo, and Al. It is shown that nickel, cobalt, and aluminum pass to a sulfuric acid solution when an asymmetric sinusoidal industrial-frequency alternating current is applied and 70–75% tungsten, molybdenum, tantalum, niobium, and rhenium are concentrated in an anode cake. When a nitric acid electrolyte is used, rhenium, nickel, cobalt, aluminum, and chromium pass to a solution and tungsten, molybdenum, tantalum, and niobium are concentrated in an anode cake. Technological versions of the processing of the oxidation products with the formation of marketable products are discussed.     

Evaluating an Electrokinetically Driven Extraction Method for Measuring Heavy Metal Soil Contamination

Measuring the heavy metal burden of “old contamination” soils (soils with aged contamination) can be challenging. Many laboratory procedures are currently in use and these can yield a wide range of burden estimates for the same soil. The appropriate extraction method selection depends on the intended use of the information and on compatibility with the procedures used to generate the “reference” data to which results are compared. In this work, results for an extraction based on the electrokinetic mobilization of old contamination heavy metals were compared to the results of established single analyte and sequential extraction methods. Accomplishing extractions electrokinetically offers promise for simplifying processes and for evaluating the electrokinetic remediation potential of old contamination soils. On the brownfield soils tested, electrokinetic extraction identified an average of 82% of the soil’s Cr, Cu, Pb, and Zn burden relative to Environmental Protection Agency Method 3050B extractions. However, results also indicated that neither of these methods were successful at extracting all of the sequestered (residual) fraction of heavy metals and thus underestimated the total contamination burden of the soil.     

铬污染的微生物吸附技术研究进展

近年来,铬在工业生产中得到了广泛的应用,随之而来的含铬污染物对周围环境造成严重的污染和破坏,铬污染的修复已成为亟待解决的环境问题。微生物在铬污染的生物修复中发挥着重要的作用。它因铬污染修复过程中环保有效,安全可靠且无二次污染等优点,引起了相关学者们的广泛关注。首先简述了铬污染危害及传统处理技术,重点综述了微生物作为生物吸附剂的吸附机理及影响因素,并分别详述了典型细菌,真菌,酵母和藻类吸附Cr(VI)污染物的机理机制及相关研究进展,然后总结了微生物吸附Cr(VI)过程中铬浓度,赋存状态,微生物营养类型,培养条件及代谢产物等的主要影响因素,最后,分析了以微生物作为生物吸附剂所存在的问题并展望了未来的研究方向,结合基因工程和酶工程选育高效工程菌、开展多种技术联合应用等方法提高微生物对铬污染的去除能力。     

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.     

Comparative Evaluation of Low Nickel and Nickel Free Lean Duplex Stainless Steels with 316L in a Variety of Corrosive Media

For many applications duplex stainless steels with their superior strength coupled with lower raw material cost have emerged as an attractive alternative to austenitic stainless steels. With emphasis on conservation of scarce resources like nickel and molybdenum there is continuing endeavour to develop essentially molybdenum free lean duplex stainless steels with low nickel content such as 2304 (23Cr–4Ni), 2202 (22Cr–2Ni), 2101 (21Cr–1.5Ni). This paper compares the corrosion behaviour of a low nickel duplex (21Cr–1.5Ni) and a nickel free duplex (21Cr–1.5Cu) with 316L stainless steel in several corrosive media. All the three alloys exhibit similar excellent corrosion resistance under boiling conditions in less aggressive organic acids such as 20 % acetic acid, 25 % lactic acid, 25 % citric acid. However, in stronger organic acids such as 5 % formic acid, 5 % oxalic acid, and mixture of formic and acetic acid, the duplex grades exhibit superior corrosion resistance. This edge over 316L continues on addition of chloride ions in these acids. In boiling 50 % nitric acid solution, the corrosion resistance of these nickel free and low nickel duplex is slightly better than 316L grade. Since 304L grade is generally used in nitric acid plants, tests were also conducted on 304L and these duplex grades were found to be more resistant. Similarly in 50 % phosphoric acid also, the duplex grades exhibit superior corrosion resistance compared to 316L grade. Alloying with nickel and molybdenum is known to give rise to significant improvement in corrosion resistance in this acid. However, even in the absence of these elements, the beneficial effect of higher chromium content is evident. Of all the inorganic acids, sulfuric acid is used in largest volume in the industries. Boiling tests in dilute 1 and 5 % H₂SO₄ indicate that nickel free copper bearing duplex is more resistant than low nickel duplex grade and vastly superior to 316L Thus nickel-free and low-nickel duplex stainless steels offer a very attractive combination of high corrosion resistance coupled with cost effectiveness in a wide variety of corrosive media.     

能量色散X射线荧光光谱法对水溶液中多种重金属离子的检测方法探讨

使用小台式的能量色散X射线荧光光谱仪可以实现水溶液中多种痕量重金属离子的直接测试,不需要对溶液进行消解,且仪器简单,对环境要求低。通过对谱线能量不同的元素进行分组,对各组元素的滤光片进行选择:对于铬、锰、铁,使用0.2 mm Al滤光片;对于镍、铜、锌、铅、硒、砷、汞,使用0.5 mm Ti滤光片;对于锑,使用1.25 mm Mo滤光片。使用国家标准溶液配制铬、铁、锰、镍、铜、锌、铅、硒、砷、汞和锑的混合溶液,探讨仪器对水溶液中重金属的检测情况,各元素校准曲线的线性相关系数均达到0.99以上,检出限在0.04~0.39 μg/mL之间。对1 μg/mL的混合溶液进行多次测试,铬测定值的相对标准偏差(RSD)最大达到19.5%,锰、铜、铅、汞、锑的RSD在10%～15%之间,其余元素的RSD均小于10%。采用能量色散X射线荧光光谱法(EDXRF)可实现水溶液中多种重金属离子的快速检测,为水溶液中重金属离子的检测提供参考。     

Ex Situ Electroreclamation of Heavy Metals Contaminated Sludge: Pilot Scale Study

The ex situ remediation of heavy metals-contaminated industrial sludge (pH = 10.35, Zn = 3,500 mg∕kg) by electroreclamation (I = 2.5 A) was studied at pilot scale (42.5 kg of sludge). This research focused on acidification of sludge and electrochemically induced migration of metals, emphasizing their partitioning prior to electroreclamation. The sludge was preacidified to an initial pH of 4.5. After treatment, a very low anode reservoir pH (near 0) was reached, and the average sludge pH was 2. Addition of 1 M HNO3 to the cathode reservoir prevented basic conditions in the sludge. In accordance with selective sequential extraction results, a low migration of Zn and Cu was obtained. In the anode region, Zn and Cu concentrations decreased by 33 and 39%, respectively, and increased in the cathode region by 33 and 26%, respectively. These metals were concentrated in the cathode area but were not effectively transported onto the cathode. Mn appeared to be more mobile than other metals. After 10 days of current application, a layer mainly composed of Ca, Fe, and Mn appeared on the cathode surface.     

Effect of the Composition of Anodic Purging Solutions on Electroosmosis

The objective of this study is to investigate the effect of the composition of anodic purging solutions on electroosmosis in an electrokinetic (EK) system. The effect of buffering capacity of anodic purging solutions on electroosmosis was first studied. With the increase of buffering capacity, soil pH and electric current increased, but the maximal cumulative electroosmostic flow (EOF) was achieved with 0.010?mol/L Na2CO3/NaHCO3 buffer. Na2CO3/NaHCO3 containing NaCl and Na2SO4, respectively, were used as anodic purging solutions to investigate the effect of cation concentration and anion type on electroosmosis. The increase of cation concentration led to the increase of soil pH and electric current but the decrease of EOF. At the same cation concentration, Na2SO4 resulted in higher electric current and greater EOF than NaCl, but similar distribution of soil pH. The present study provides useful information for the selection of purging solution in the EK remediation of contaminated soils.     

Uptake, Selectivity, and Inhibition of Hydroponic Treatment of Contaminants

It is estimated that the Departments of Defense, Energy, and Agriculture will spend up to 300 billion federal dollars on environmental remediation during the next century. Phytoremediation, the use of vegetation for the remediation of contaminated sediments, soils, and ground water, is an emerging technology for treating several categories of persistent, toxic contaminants. Although effective, phytoremediation is still in a developmental stage and therefore is not a widely accepted technology by regulatory agencies and public groups. Research is currently being conducted to validate the process effectiveness as well as increase regulatory and community acceptance. This research will focus on the ability of plants to hydroponically treat water contaminated with cadmium, chromium, nickel, radionuclides (cesium and strontium), and∕or phthalates. Specifically, the effectiveness of dwarf sunflowers (Helianthus annuus) and two strains of mustard seed (Brassica juncea) were investigated. The selectivity, on a mass basis, for the sunflowers and Indian mustard was Cd > Ni > Cr and Cr > Ni > Cd, respectively. This selectivity order did not change when cesium was present. For the individual phthalate treatment, the selectivity was dibutyl phthalate > benzylbutyl phthalate > dioctyl phthalate. When metals were present, the uptake of phthalates was severely limited.     

The removal of heavy metals from aqueous solution using a recoverable poly [N-(dithiocarboxylate)-iminioethene] column

Poly [N-(dithiocarboxylate)-iminioethene] dispersed on kieselguhr provides a highly effective column packing for the removal of toxic heavy metals from aqueous solution. Metal ions removed include iron(II), cobalt(II), rhodium(III), nickel(II), palladium(II), platinum(II), copper(II), silver(I), zinc(II), cadmium(II) and mercury(II). The high metal ion uptakes previously observed in batch operation are maintained in column operation. Feed solutions with temperatures between ambient and 45°C are tolerated. pH values as low as 0.5 are not harmful to the column so long as the acid is hydrochloric acid. Nitric and sulphuric acids can be used down to pH 3.5 without harming the polymer. The column can be regenerated using cyanide solution for all metal ions except iron(II), cobalt(II) and zinc(II); disodium ethylenediaminetetraacetate can be used for these three metal ions.