Synergistic Effects of Multiple Metal Contaminants on Electrokinetic Remediation of Soils

This article presents a bench‐scale study performed to investigate the removal of heavy metals when they exist individually and in combination in soils. Electrokinetic experiments were conducted using two types of clayey soils, kaolin and glacial till. These soils were contaminated with Cr(VI) only, with Ni(II) only, and with Cr(VI), Ni(II), and Cd(II) combined. It was found that in kaolin, a significant pH variation occurred due to electric potential application, affecting the adsorption‐desorption and dissolution‐precipitation, as well as the extent of migration of the contaminants. In glacial till, however, pH changes were not affected significantly. In both kaolin and glacial till, the migration of Cr(VI) and Ni(II) was higher when they were present individually compared to when they existed together with Cd(II). Cr(VI) migration as single or combined contaminant was lower in kaolin as compared to that in glacial till. This result was due to the low pH conditions created near the anode region in kaolin that led to high Cr(VI) adsorption to the clay surfaces. In glacial till, however, nickel precipitated with or without the presence of co‐contaminants due to high pH conditions in the soil. Overall, this study demonstrates that adsorption, precipitation, and reduction are the significant hindering mechanisms for the removal of heavy metals using electrokinetic remediation. The direction of the contaminant migration and overall removal efficiency depend on the polarity of the contaminant, the presence of co‐contaminants, and the type of soil. © 2001 John Wiley & Sons.     

Removal of Cr(VI) from contaminated soil by electrokinetic remediation

A new process for the removal of hexavalent chromium [Cr(VI)] contaminated soil is described. The process provides for an efficient removal of anionic chemicals from contaminated soils. Chromate anions were removed from the soil to the anodic reservoir by the moving force of electromigration. In this process, the chromate anions that accumulate in the anodic reservoir are simultaneously eliminated by using a column packed adsorbent. The adsorbent (immobilized tannin) used was chemically incorporated into cellulose. Cr(VI) was found to be adsorbed to this adsorbent efficiently. In the electrokinetic process, the pH of the aqueous solution in the anodic reservoir was decreased by the electrolysis of water. In the present study, the pH of the solution in the anodic reservoir is maintained at pH 6 by the addition of an aqueous alkaline solution during the electrokinetic process. The advantage of pH control is that it promotes the release of Cr(VI) from the soil by electromigration, thus permitting the maximum adsorption of Cr(VI) on the immobilized tannin. Simultaneous collection of Cr(VI) from the anodic reservoir leads to the protection from secondary contamination with Cr(VI).     

Utilisation of Supernatants of Pure Cultures of Streptomyces thermocarboxydus NH50 to Reduce Chromium Toxicity and Mobility in Contaminated Soils

Chromium is a heavy metal used in various industrial sectors. Improper handling and storage of chromium-laden effluents or wastes can lead to the pollution of the environment. The most toxic form is the more mobile one: hexavalent chromium Cr(VI). The reduction of Cr(VI) results in the immobilisation of chromium into its less toxic trivalent form Cr(III). This phenomenon may prevent the contamination of groundwater when the soil in the vadose zone is contaminated. Many bacteria have been isolated from contaminated soils and described to reduce Cr(VI) into Cr(III). A new Cr(VI)-reducing strain, identified as a Streptomyces thermocarboxydus,has been isolated and studied in our laboratories for its ability to reduce Cr(VI). This aerobic bacterium, in contrast to other genera described which mediate reduction via enzymes, produces reducing agents into the culture supernatants. Cr(VI) reduction by these substances is accelerated by the presence of small concentration of cupric ions (Cu²⁺). The reducing agent(s) can be easily recovered from the bacterial cultures and used as cell-free solution to treat contaminated soils by an in situ or ex situ processes.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

Electrochemical remediation of heavy metal contaminated soils

Over the years, many soils have been contaminated with toxic heavy metals as a result of a variety of industrial and military activities. Electrokinetic soil treatment is an emerging technology that could prove to be very effective in the remediation of these sites. “Real-world” heavy metal contaminated (Pb(II), Cd(II), and Cr(III)) soils from three military sites with varying soil properties were subjected to electrokinetic treatment in the laboratory. Metal extractants (chelating agents and acids) were studied and found to be effective in enhancing the electrokinetic process. Results indicated that heavy metal removal efficiencies varied in the three soils tested. In one case, removal efficiencies of 90 percent and 60 percent were obtained for Cd and Cr, respectively, for the nitric acid amended experiments. For another case, over 60 percent of the total Pb in the system was deposited near the cathode for the non-amended and the citric-acid amended tests. Conversely, in the third case, the electrokinetic soil-washing treatment process failed to produce significant removal of any metal contaminant. The discrepancies that exist between the metal removal results of the three soils were attributed to the different physiochemical characteristics of each soil.     

Uptake of chromium by Aspergillus foetidus

Aspergillus foetidus has the ability to take up chromium during the stationary phase of growth and under growth-nonsupportive conditions. We observed a 97% decrease in hexavalent chromium (initial concentration 5 µg/g) at the end of 92 h of growth, which may be due to its reduction to Cr (III) and/or complexation with organic compounds released due to the metabolic activity of the fungus. Replacement culture studies under growth-nonsupportive conditions revealed that the maximum uptake of Cr (VI) at pH 7.0 is 2 mg/g of dry biomass. At low or high pH values, Cr (VI) uptake is significantly reduced. In addition, the initial rate of total chromium uptake is also enhanced by higher biomass concentrations and the presence of glucose. The results obtained through this investigation indicate the possibility of treating waste effluents containing hexavalent chromium using Aspergillus foetidus.     

Effect of microbial activity on the mobility of chromium in soils

The effect of microbial activity on the chemical state of chromium, in a contaminated soil located in the Rh?ne-Alpes region (France), has been investigated. This soil contained 4,700 mg kg(-1) Cr, with about 40% present in the soluble hexavalent form. Indigenous microbial activity was found to significantly reduce Cr(VI) to the less mobile form (III) when the soil was incubated at 30 degrees C in an aqueous medium containing glucose and nutrients. A Cr(VI)-reducing strain of Streptomyces thermocarboxydus was isolated from the contaminated soil. The strain was found to metabolize Cr(VI) in a similar manner as an exogenous inoculum of Pseudomonas fluorescens LB300, and to precipitate chromium as a Cr oxyhydroxide with a gammaCrOOH-like local structure. The Cr(VI)-reducing activity of S. thermocarboxydus was induced, or significantly accelerated, by the aggregation of bacterial cells or their adhesion to suspended solid particles, and was stimulated in pure culture by glycerol and chromate.     

Phosphogypsum chemistry under highly anoxic conditions

Phosphogypsum (PG), primary byproduct from phosphoric acid production, is accumulated in large stockpiles and occupies vast areas of land. Contaminants emanating from PG stacks can impact the environment including waterbodies. The major constraint for PG use in the environment is the presence of metals in high concentrations. Reduction of sulfate found in PG and significance of sulfide production in reducing aqueous concentrations of toxic metals were studied. Mississippi River alluvial sediment amended with PG was equilibrated under controlled redox (-250 mV) and pH (5.5, 6.5, and 7.5) conditions. Phosphogypsum addition resulted in a large increase in sulfide levels in sediment suspensions. As a result, the solubility of spiked heavy metals (Cd and Cr, 100 and 1000 mg kg(-1)) and natural trace elements (As, Ba, and Cd) was significantly reduced by precipitation as insoluble sulfides. Sediment pH also influenced sulfate reduction and sulfide formation in both PG-amended and control sediment. Low sediment pH (5.5) resulted in the highest release of all studied metals and sulfate into sediment solution. This study indicates that if PG or PG-products are placed in neutral to alkaline sediments/soils and/or reducing environments, metals released at toxic levels should be of little concern to the wetland environment.     

Removal of Cr6 + and Ni2+ from aqueous solution using bagasse and fly ash

Raw bagasse and fly ash, the waste generated in sugar mills and boilers respectively have been used as low-cost potential adsorbents. Raw bagasse was pretreated with 0.1N NaOH followed by 0.1N CH3COOH before its application. These low-cost adsorbents were used for the removal of chromium and nickel from an aqueous solution. The kinetics of adsorption and extent of adsorption at equilibrium are dependent on the physical and chemical characteristics of the adsorbent, adsorbate and experimental system. The effect of hydrogen ion concentration, contact time, sorbent dose, initial concentrations of adsorbate and adsorbent and particle size on the uptake of chromium and nickel were studied in batch experiments. The Sorption data has been correlated with Langmuir, Freundlich and Bhattacharya and Venkobachar adsorption models. The efficiencies of adsorbent materials for the removal of Cr(VI) and Ni(II) were found to be between 56.2 and 96.2% and 83.6 and 100%, respectively. These results were obtained at the optimized conditions of pH, contact time, sorbent dose, sorbate concentration of 100 mg/l and with the variation of adsorbent particles size between 0.075 and 4.75 mm. The order of selectivity is powdered activated carbon > bagasse > fly ash for Cr(VI) removal and powdered activated carbon > fly ash > bagasse for Ni(II) removal.     

Stabilization of As, Cr, Cu, Pb and Zn in soil using amendments--a review

The spread of contaminants in soil can be hindered by the soil stabilization technique. Contaminant immobilizing amendments decrease trace element leaching and their bioavailability by inducing various sorption processes: adsorption to mineral surfaces, formation of stable complexes with organic ligands, surface precipitation and ion exchange. Precipitation as salts and co-precipitation can also contribute to reducing contaminant mobility. The technique can be used in in situ and ex situ applications to reclaim and re-vegetate industrially devastated areas and mine-spoils, improve soil quality and reduce contaminant mobility by stabilizing agents and a beneficial use of industrial by-products. This study is an overview of data published during the last five years on the immobilization of one metalloid, As, and four heavy metals, Cr, Cu, Pb and Zn, in soils. The most extensively studied amendments for As immobilization are Fe containing materials. The immobilization of As occurs through adsorption on Fe oxides by replacing the surface hydroxyl groups with the As ions, as well as by the formation of amorphous Fe(III) arsenates and/or insoluble secondary oxidation minerals. Cr stabilization mainly deals with Cr reduction from its toxic and mobile hexavalent form Cr(VI) to stable in natural environments Cr(III). The reduction is accelerated in soil by the presence of organic matter and divalent iron. Clays, carbonates, phosphates and Fe oxides were the common amendments tested for Cu immobilization. The suggested mechanisms of Cu retention were precipitation of Cu carbonates and oxy-hydroxides, ion exchange and formation of ternary cation-anion complexes on the surface of Fe and Al oxy-hydroxides. Most of the studies on Pb stabilization were performed using various phosphorus-containing amendments, which reduce the Pb mobility by ionic exchange and precipitation of pyromorphite-type minerals. Zn can be successfully immobilized in soil by phosphorus amendments and clays.     

Metal fractionation in soil profiles at automobile mechanic waste dumps.

Soil profiles at five automobile mechanic waste dumps in Port-Harcourt, Nigeria were investigated to assess the spatial distribution, chemical speciation, and likely mobility of Cd, Cu, Pb, Zn, Cr and Ni in the soil as a function of the soil properties. A sequential fractionation protocol was used that generated six different fractions into which soil metal could partition. Cadmium was associated with non-residual fractions at surface horizons, but at lower depths it was in the residual fractions. Copper and Cr partitioned into organic and residual fractions, while Pb was associated with an Fe-Mn oxide fraction and the residual fractions. Zinc in surface horizons partitioned into an Fe-Mn oxide fraction and a fraction that captured carbonate-bound species, but in subsurface horizons, it was mainly in the residual fractions. Ni was predominantly found in the residual fractions. Mobility factors were calculated, and their values tended to decrease with increasing profile depth, indicating that these metals are relatively mobile in the surface horizons compared the subsurface except for chromium in the 15-30 cm depths. The mobility factors for the heavy metals follow the order: Cd > Zn > Pb > Cu > Cr > Ni. The results suggest that there is serious contamination hazard with Cd, Pb, and Zn in the soil profiles.     

Potential use of lateritic and marine clay soils as landfill liners to retain heavy metals

The potential of a lateritic soil and a marine clay, typical of those found in hot and humid climatic regions, was assessed for use as a landfill liner material. A series of tests were conducted - physical and chemical, batch adsorption, column, hydraulic conductivity, etc., - to evaluate the heavy metal sorption capacity, chemical compatibility of hydraulic conductivity, and transport parameters of the soils. Experimental results showed that the marine clay had better adsorption capacity than that of the lateritic soil and that its hydraulic conductivity was an order of magnitude lower. In addition, the hydraulic conductivities of both soils when permeated with low concentration heavy metal solutions were below 1x10(-7)cm/s. When permeated with Cr, Pb, Cd, Zn, and Ni solutions, the retardation factors of the lateritic soil and the marine clay ranged from 10 to 98 and 37 to 165, respectively, while the diffusion coefficients ranged from 1.0x10(-5) to 7.5x10(-6) and 3.0 to 9.14x10(-7)cm2/s, respectively. For both soils, Cr and Pb were retained relatively well, while Cd, Zn, and Ni were more mobile. The marine clay had higher retardation factors and lower diffusion coefficients, and its hydraulic conductivity was more compatible with Cr solution, than that of the lateritic soil. In general, the properties of the marine clay indicate that it has significant advantages over the lateritic soil as landfill liner material.     

Novel pilot-scale washing process and equipment for removing Cr(VI) from contaminated soil

In this study, a novel horizontal rotating soil washing process and equipment were developed and tested for pilot-scale remediation of soils from a site polluted by chromium ore process residue. Operating parameters, including cylinder rotational velocity, cylinder tilt angle, heating temperature and liquid/soil ratio, were investigated. The Taguchi method was used for the experiment design, and the standard L16 orthogonal array with four parameters and four levels was selected for optimising the operating parameters. Optimal removal efficiency was achieved at cylinder rotational velocity of 2.5 rpm, cylinder tilt angle of 2.6°, heating temperature of 200 °C and liquid/soil ratio of 8. The efficiency of citric acid as an extractant in the novel process was compared with that of water. The analysis of the residual Cr(VI) concentration of the soil shows that citric acid could efficiently remove 22.89 % more Cr(VI) than water in one-stage washing. The residual Cr(VI) concentration in the soil after the three-stage washing is as low as 26.16 mg/kg, which meets the screening levels for soil environmental risk assessment of sites in Beijing City (30 mg/kg). Further study is currently underway to optimise the novel process and equipment for commercial-scale use.     

复合重金属污染高岭土的电动修复

根据电子废弃物拆解场地的污染特征,以复合重金属(Cu,Cd,Pb)污染高岭土为研究对象,考察了电动技术对污染土壤的修复效果。实验结果表明:在电压梯度为1 V/cm、阳极液为自来水、阴极液为柠檬酸-柠檬酸钠缓冲液(pH=5)、靠近阴极设置活性炭渗透反应墙(PRB)的条件下电动修复96 h后,Cu,Cd,Pb的平均去除率分别可达79.93%,99.43%,39.36%;土壤的酸碱性对电动修复效果影响显著,通过在阴极添加缓冲液维持土壤偏酸性条件,有利于重金属污染物的电动去除;在靠近阴极设置活性炭PRB可富集重金属,减少阴极液的污染;迁移率大的酸可提取态重金属较易去除,残渣态重金属稳定性强,去除率较低。     

Bioremediation of Chromate by Sulfate-Reducing Bacteria, Cytochromes c3 and hydrogenases

The treatment of soils and ground waters polluted by heavy metals is of economical and environmental interest. Reduction of Cr(VI) to the less toxic Cr(III) associated to its precipitation is a potentially useful process for bioremediation. In order to develop ecological processes using micro-organisms, we have compared various sulfate-reducing bacteria for enzymatic reduction of chromate. The best Cr(VI) reductase activity was obtained with Desulfomicrobium norvegicum. Despite morphological changes induced by the presence of chromate, this strain can grow in the presence of up to 500 M Cr(VI) and can decontaminate waters polluted by Cr(VI) when seeded in bioreactors. We have demonstrated the ability of several metalloenzymes (cytochromes c ₃ and hydrogenases) to reduce chromate. Biophysical investigations of the chromate/protein interaction in order to get further informations on the mechanism of metal reduction by cytochromes c ₃ are under the way.     

Salinity, organic content, micronutrients and heavy metals in pig slurries from South-eastern Spain

The increase in commercial pig production is an opportunity to reuse animal manures in arid and semiarid soils as a source of nutrients and organic matter. However, there are components in pig slurry that are potentially dangerous for the environment. In this study, pig slurries of 36 pig farms in South-eastern Spain were evaluated for salt content (electrical conductivity, chloride and sodium), organic load (BOD5 and COD), micronutrients (Fe, Cu, Mn and Zn), and heavy metals (Cd, Co, Cr, Ni and Pb). Except for electrical conductivity, Cu and Zn, components in pig slurries did not vary considerably between animal production stages, indicating similar management of diverse animal types. Assuming an application rate based on the maximum input of nitrogen from animal manure (210 kg total N/ha/yr), the estimates for soil annual load of Cl and Na, 415 kg/ha, could be a significant salinisation risk. Cu and Zn seemed to be the metals that could be accumulated most in soils where application of pig slurries is common (4 and 15 kg/ha/yr, respectively). The estimated heavy metal (Cd, Co, Cr, Ni and Pb) input to soils would be 260 g/ha/yr, with a relative contribution of Cr>Ni>Pb>Co>Cd.     

Cr(VI) reduction in aqueous solutions by using copper smelter slag

The ability of Copper Smelter Slag (CSS) to reduce Cr(VI) in aqueous solutions has been investigated. The extent of reduction is dependent on the amounts of acid and reductant, contact time, Cr(VI) concentration, temperature of the solution and particle size of CSS. The amount of acid is the most important variable affecting the reduction process. When twice the amount of acid required with respect to Cr(VI) was used, Cr(VI) in 100 ml solution (100 mg/l) was completely reduced in a contact period less than 5 min by a 10 g/l dosage of CSS. Reduction efficiency increased with increase in temperature of solution, showing that the process is endothermic. Reduced chromium, and iron and other metals dissolved from CSS were effectively precipitated by using NaOH or calcinated carbonatation sludge from sugar plant.     

Recovery of Chromium(III) from Tannery Wastewater by Nanoparticles and Whiskers of Chitosan

Chitosan, its nanoparticles and whiskers present an excellent capacity to complex chromium ions. However, this phenomenon is influenced by different parameters. In our search, we determined the appropriate range of pH to form chitosan–Cr(III), nanoparticles Cr(III) and whiskers–Cr(III) complex. We studied also the influence of chromium concentration and nature of chitosan-based materials on complexation process. Our main aim is approximate the optimal conditions to remove chromium(III) from tanning bath, recuperated from tannery wastewater of Marrakech in Morocco. However, the results of adsorption kinetic in tannery wastewater revealed that chitosan, its nanoparticles, whiskers and biocomposites are good sorbent of chromium as well, even if the adsorbed quantity is less compared to chromium solution. Although, according to ICP-OES analysis in this real effluent, nanoparticles are the best complexing ligand, after 24 h of contact nanoparticles can remove 70% of chromium from this tannery wastewater.     

Recycling of ‘waste’ FE(III)/CR(III) hydroxide for the removal of nickel from wastewater: Adsorption and equilibrium studies

Effects of Ni(II) concentration, agitation time, temperature and pH on adsorption of Ni(II) on Fe(III)/Cr(III) hydroxide, a waste by-product from fertilizer industry, have been investigated. The percent adsorption increased from 55 to 69% with increase in temperature from 20 to 40°C and from 32 to 77% with increase in pH from 3.7 to 7.5 and from 38 to 79% with decrease in Ni(II) concentration from 100 to 25 mg/L. The equilibrium data fit well with the Langmuir isotherm and the adsorption capacity was found to be 21.0 mg/g at 30°C. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were evaluated. The adsorption rate constant was higher at lower concentration of Ni(II) and at higher temperature. Desorption studies show that 70% of Ni(II) can be desorbed from the adsorbent at pH 4.0. The adsorbent was tested using nickel plating industry wastewater and the maximum percent removal was 97.     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.