Electrokinetic remediation of heavy metal-contaminated soils under reducing environments

This paper describes the migration of hexavalent chromium, Cr(VI), nickel, Ni(II), and cadmium, Cd(II), in clayey soils that contain different reducing agents under an induced electric potential. Bench-scale electrokinetic experiments were conducted using two different clays, kaolin and glacial till, both with and without a reducing agent. The reducing agent used was either humic acid, ferrous iron, or sulfide, in a concentration of 1000 mg/kg. These soils were then spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1000, 500 and 250 mg/kg, respectively, and tested under an induced electric potential of 1 VDC/cm for a duration of over 200 h. The reduction of chromium from Cr(VI) to Cr(III) occurred prior to electrokinetic treatment. The extent of this Cr(VI) reduction was found to be dependent on the type and amount of reducing agents present in the soil. The maximum reduction occurred in the presence of sulfides, while the minimum reduction occurred in the presence of humic acid. The concentration profiles in both soils following electrokinetic treatment showed that Cr(VI) migration was retarded significantly in the presence of sulfides due both to the reduction of Cr(VI) to Cr(III) as well as an increase in soil pH. This low migration of chromium is attributed to: (1) migration of Cr(VI) and the reduced Cr(III) fraction in opposite directions, (2) low Cr(III) migration due to adsorption and precipitation in high pH regions near the cathode in kaolin and throughout the glacial till, and (3) low Cr(VI) migration due to adsorption in low pH regions near the anode in both soils. Ni(II) and Cd(II) migrated towards the cathode in kaolin; however, the migration was significantly retarded in the presence of sulfides due to increased pH through most of the soil. Initial high pH conditions within the glacial till resulted in Ni(II) and Cd(II) precipitation, so the effects of reducing agenets were inconsequential. Overall, this study demonstrated that the reducing agents, particularly sulfides, in soils may affect redox chemistry and soil pH, ultimately affecting the electrokinetic remediation process.     

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.     

Optimizing Cr(VI) adsorption on activated carbon produced from heavy oil fly ash

In order to explore the beneficial utilization of heavy oil fly ash (HOFA) generated in the power plants, the present study is intended to optimize the chromium(VI) [Cr(VI)] adsorption on activated carbon produced from HOFA. The raw HOFA obtained from a power plant was washed by nitric/hydrochloric acid and activated at 800 °C with a holding time of 60 min to produce fly ash activated carbon (FAC). Phosphoric acid was used as a chemical agent to improve the surface characteristics of the HOFA during the activation process. Batch adsorption experiments were employed to evaluate the effects of different parameters such as initial Cr(VI) concentration, pH, and FAC dose on the removal of Cr(VI) from aqueous solution. A total of 17 adsorption experimental runs were carried out employing the detailed conditions followed the response surface methodology based on the Box–Behnken design. The results indicate that developed FAC has the potential for removing Cr(VI) from wastewater. Under the test conditions, a maximum of 91.51 % Cr(VI) removal efficiency was achieved.     

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.     

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).     

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.     

Removal of Cr(VI) Ions from Aqueous Solutions Using Poly 3-Methyl Thiophene Conducting Electroactive Polymers

This paper deals with a new application of poly 3-methyl thiophene synthesized chemically onto sawdust (termed as P3MTh/SD) as an effective adsorbent for removal of Cr(VI) ions from aqueous solutions using column system. Chemical synthesis of poly 3-methyl thiophene was performed by addition of ferric chloride (in chloroform) as oxidant to sawdust which had previously been soaked in monomer solution. All the sorption experiments were conducted using dynamic or column system at room temperature. The effect of important parameters such as pH and initial concentration on uptake of Cr(VI) was investigated. In order to find out the possibility of the regeneration and reuse of the exhausted adsorbent, desorption studies were also performed. The currently introduced adsorbent was found to be an efficient adsorbent for removal of highly toxic and hazardous Cr(VI) ions from aqueous solutions. As our breakthrough analysis has indicated, each gram of P3MTh/SD is able to remove more than 95% of Cr(VI)ions from 300 mL of Cr(VI) polluted solution with the initial concentration of 25 mg L⁻¹ in column system. Sorption/desorption of Cr(VI) ions was found to be a highly pH dependent processes.     

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.     

利用铬渣制备重铬酸钠

研究了采用焙烧—硫酸酸化法利用铬渣制备重铬酸钠的工艺.通过L16(44)正交实验得出铬渣焙烧—浸出的最佳工艺条件为:焙烧温度1 000℃,m(碳酸钠)∶m(铬渣)=0.18,液固比4,焙烧时间8h.在此条件下Cr(Ⅵ)回收率为99.3％.硫酸酸化制备重铬酸钠的最佳工艺条件为:浸出液pH为6.6,酸化液pH为3.5,浓缩液中重铬酸钠质量分数为83.1％.此条件下制备的产品重铬酸钠结晶率为44.5％,纯度为99.5％,符合GB1611-92《工业重铬酸钠》的一等品质量标准.处理1t铬渣可制备重铬酸钠约120 kg,增加收入660元.     

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.     

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.     

中孔活性炭对水溶液中Cr3+的吸附

采用模板法和氢氧化钾化学活化法制备出不同中孔率的中孔活性炭并用于水中Cr3+的静态吸附,探讨了中孔活性炭吸附Cr3+的影响因素.实验结果表明,当溶液pH为6.0、吸附温度为50℃、吸附时间为120min、活性炭加入量为2.0g/L以及活性炭中孔率为80.0％～90.0％时.中孔活性炭对溶液中Cr3+的去除率达到98.5％.分别采用Langmuir和Freundlich方程拟合活性炭对Cr3+吸附的等温线,发现Langmuir等温吸附模型对活性炭吸附Cr3+拟合程度更好.活性炭中孔率的增大有利于提高Cr3+的平衡吸附量,但同时还受到活性炭表面酸总量的影响.吸附Cr3+前、后活性炭的FTIR谱图表明,Cr3+与活性炭表面含氧官能团发生了离子交换反应.     

A study of Cr(VI) in ashes from fluidized bed combustion of municipal solid waste: leaching, secondary reactions and the applicability of some speciation methods

The use of the fluidized bed technique for the combustion of municipal solid waste is a rather new concept. This type of combustor produces ash residues with somewhat different properties than the residues generated from the traditional mass burn techniques. Therefore, chemical characterization and the investigation of toxic metals behavior during ash water reactions are necessary for the safe disposal of these residues. In the present work, the total elemental composition, mineralogy and leaching behavior of ashes from the combustion of municipal solid waste in a fluidized bed combustion boiler have been investigated. The cyclone ash and, in particular, the filter ash contained considerable amounts of soluble substances, thus giving leachates with high levels of Cl-, Na+, K+, Ca2 + and Al(IIl). On the other hand, the two ash fractions taken in the boiler, the bottom and hopper ashes, were much more stable with respect to the release of salts and heavy metals. Since Cr(VI) is mobile and toxic its release from combustion residues can pose environmental problem. Even though the total Cr contents were similar in all ashes studied, the bottom ash gave about a thousand times higher levels of Cr(VI) in test leachates than the hopper, cyclone and filter ashes. However, it was found that the leached amount of Cr(VI) from the bottom ash decreased significantly when bottom ash was mixed with the hopper ash. The most probable cause for this decrease is the coupled oxidation of Al(0) to Al(III) and reduction of dissolved Cr(VI) to Cr(III). This finding that the mixing of two ash streams from the same boiler could result in the immobilization of Cr may point at a simple stabilization method. Selective extraction of water soluble, exchangeable and sparingly soluble forms of Cr(VI) was also investigated. Extraction methods were evaluated for their suitability for ash matrixes. It was found that interferences due to the presence of reducing substances in some ash materials may occur.     

Magnetic Cr(VI) Ion Imprinted Polymer for the Fast Selective Adsorption of Cr(VI) from Aqueous Solution

In this study, a novel magnetic Cr(VI) ion imprinted polymer (Cr(VI)-MIIP) was successfully synthesized and used as a selective sorbent for the adsorption of Cr(VI) ions from aqueous solution. It can be synthesized through the combination of an imprinting polymer and magnetic nanoparticles. The high selectivity achieved using MIIP is due to the specific recognition cavities for Cr(VI) ions created in Cr(VI)-MIIP. Also, the magnetic properties that could be obtained using magnetic nanoparticles, helps to separate adsorbent with an external magnetic field without either additional centrifugation or filtration procedures. The magnetic Fe₃O₄ nanoparticles (MNPs) were synthesized using an improved co-precipitation method and modified with tetraethylorthosilicate (TEOS) before imprinting. The magnetic Cr(VI) ion imprinted polymer was prepared through precipitation copolymerization of 4-vinylpyridine as the complexing monomer, 2-hydroxyethyl methacrylate as a co-monomer, the Cr⁶⁺ anion as a template, and ethylene glycol dimethacrylate (EGDMA) as a cross-linker in the presence of modified magnetite nanoparticles. This novel synthesized sorbent was characterized using different techniques. Batch adsorption experiments were performed to evaluate the adsorption conditions, selectivity, and reusability. The results showed that the maximum adsorption capacity was 39.3 mg g^?1, which was observed at pH 3 and at 25?°C. The equilibrium time was 20 min, and the amount of adsorbent which gave the maximum adsorption capacity was 1.7 g L^?1. Isotherm studies showed that the adsorption equilibrium data were fitted well with the Langmuir adsorption isotherm model and the theoretical maximum adsorption capacity was 44.86 mg g^?1. The selectivity studies indicated that the synthesized sorbent had a high single selectivity sorption for the Cr(VI) ions in the presence of competing ions. Thermodynamic studies revealed that the adsorption process was exothermic (\(\Delta H\)?<?0) and spontaneous (\(\Delta G\)?<?0). In addition, the spent MIIP can be regenerated up to five cycles without a significant decrease in adsorption capacity.     

凹凸棒土/苯胺-邻氨基酚复合吸附剂的制备及其对Cr(Ⅵ)的吸附性能

采用原位聚合法制备了凹凸棒土/苯胺-邻氨基酚（ATP/PANOAP）复合吸附剂,对其进行了SEM和FTIR表征,并通过吸附实验考察了ATP/PANOAP对水中Cr（Ⅵ）的吸附性能。实验结果表明,ATP/PANOAP对水中Cr（Ⅵ）具有良好的去除效果,在Cr（Ⅵ）初始质量浓度为50 mg/L、溶液pH为6、吸附剂加入量为0.375 g/L、温度为298 K的条件下,Cr（Ⅵ）去除率达93.39%。ATP/PANOAP对Cr（Ⅵ）的吸附动力学过程符合准二级动力学模型,吸附热力学过程符合Langmuir单层吸附模型,该吸附过程以化学吸附为主,且为自发进行的吸热反应。     

Fabrication of Polypyrrole/Chitosan Nanocomposite Aerogel Monolith for Removal of Cr(VI)

Three-dimensional polypyrrole/chitosan nanocomposite monoliths are fabricated by polymerization of pyrrole in chitosan aqueous solution. The static polymerization of pyrrole monomer and the cross-linking of chitosan by glutaraldehyde occur simultaneously, resulting in the self-assembly of polypyrrole/chitosan nanocomposite aerogel monolith. The addition of methyl orange and glutaraldehyde and the static reaction play key roles in the formation of the self-standing aerogel monolith. The as-prepared monolith with larger specific surface area exhibits much better adsorption capability for Cr(VI) removal in comparison with that prepared without the addition of glutaraldehyde. The adsorption process and adsorption isotherms are found to well follow the pseudo-second-order and Langmuir models, respectively. Furthermore, this polypyrrole/chitosan nanocomposite monolith is stable and recyclable. About 73.5% of the initial adsorption capability is kept after eight adsorption–desorption cycles. The polypyrrole/chitosan nanocomposite monolith can be a promising candidate for the efficient removal of Cr(VI).     

多酚原位固化茶渣对水中Cr（Ⅵ）的吸附

通过甲醛与茶渣中多酚类组分的反应制备了多酚原位固化茶渣吸附材料,并将其用于对水中Cr（Ⅵ）的吸附。表征结果显示：茶渣多酚的原位固化提高了其热稳定性,同时对茶渣粒料起到了修补增强作用。固化茶渣对Cr（Ⅵ）的吸附量随溶液pH的减小而增大。在吸附温度303 K、初始Cr（Ⅵ）质量浓度60 mg/L、吸附剂投加量1.0 g/L、吸附时间300 min、溶液pH为2的条件下,固化茶渣对Cr（Ⅵ）的吸附量为56.56 mg/g,去除率达94.3%。固化茶渣对Cr（Ⅵ）的吸附符合Langmuir等温吸附模型和准二级动力学方程,吸附是一个自发的、吸热过程,303,318,333 K下的Langmuir饱和吸附量分别为83.26,107.64,129.20 mg/g。     

Electrochemical reduction of Cr(VI) in the decontamination process ELDECON

One of ABB Atom's methods, ELDECON, is an electrochemical process for decontamination of components used in nuclear power plants. ELDECON removes radioactive species while producing small amounts of waste. However, the waste sludge that is produced in the ELDECON process contains chrornate (Cr(VI)). According to the US Cod of Feguration, 40 CFR 261, if a process in any step creates chromate, the final waste has to be tested in a toxicity characteristic leachate procedure. In order to pass the test, the chromate has to be reduced to chromium (Cr(III)). Electrochemistry has proven to be a valuable tool. When incorporating indirect electrolysis into the ELDECON concept, the chromate ions are reduced. This is done by the use of an electrochemical cell (reactor bed). The method involves ferric nitrate as a reagent which, besides converting the chromate completely, also decreases the reaction time. The reaction time and the amount of solution treated in the cell have a close to linear relationship (i.e. the reaction time is proportional to the amount of solution). This makes the test cell feasible to scale up and use in the industry.     

铬渣资源化处理的零排放工艺

采用氧化—还原法对某钢厂的粗铬渣进行提纯回收，对各项工艺参数进行了优化，探讨了铬渣零排放处理工艺的可行性。实验结果表明：在氧化温度80 ℃、氧化时间1.5 h、双氧水加入量2.35 mL/g（以铬渣计），还原时间15 min、还原pH 1.5、NaHSO₃加入量0.445 g/g（以铬渣计），沉淀pH 8.0，煅烧温度1 050 ℃、煅烧时间1 h的条件下，所得废渣的w（Cr）为1.29%，回收铬绿产品的w（Cr₂O₃）为97.20%，铬回收率为94.40%;处理后废水的ρ（总铬）约为0.06 mg/L，低于GB 13456—2012《钢铁工业水污染物排放标准》中规定的1.50 mg/L，既可作为循环用水，也可排放;处理后废渣中含大量硅元素，可作为生产水泥发泡节能砖或砌块的原料;整个回收过程清洁无污染，零排放，且具备一定的盈利空间。     

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.