高岭土模拟铜污染土壤电动力学修复

采用电动力学方法修复重金属污染土壤。研究中采用高岭土模拟铜污染土壤,结合电动力学修复理论,考察了不同电压、添加络合剂条件下铜的修复效果。结果表明,当电压强度为0．5V／cm时,最靠近阴极部分的土壤中Cu^2＋的C／C。为1．596,当电压强度为1V／cm时,C／C0为2．245,说明适当提高电压强度能够有效的增加Cu^2＋的迁移效果;土壤中未加入络合剂时,Cu^2＋大部分集中在第5段土壤中,C／C0为1．339,在土壤中加入络合剂以后Cu^2＋大部分集中在靠近阴极部分的土壤中,C／C。为1．716,说明在污染土壤中加入一定量的络合剂可以与Cu^2＋结合生成螯合物,提高Cu^2＋的迁移效果。     

Electrokinetic enhancement of phenanthrene biodegradation in creosote-polluted clay soil

Given the difficulties caused by low-permeable soils in bioremediation, a new electrokinetic technology is proposed, based on laboratory results with phenanthrene, to afford bioremediation of polycyclic aromatic hydrocarbons (PAH) in clay soils. Microbial activity in a clay soil historically polluted with creosote was promoted using a specially designed electrokinetic cell with a permanent anode-to-cathode flow and controlled pH. The rates of phenanthrene losses during treatment were tenfold higher in soil treated with an electric field than in the control cells without current or microbial activity. Results from experiments with Tenax-assisted desorption and mineralization of 14C-labeled phenanthrene indicated that phenanthrene biodegradation was limited by mass-transfer of the chemical. We suggest that the enhancement effect of the applied electric field on phenanthrene biodegradation resulted from mobilization of the PAH and nutrients dissolved in the soil fluids.     

Pilot-scale electrokinetic treatment of a Cu contaminated red soil

A pilot-scale experiment for electrokinetic treatment of 700 kg of copper contaminated red soil was conducted using a constant voltage of 80 V. Dynamic removal percentages of Cu from the soil and energy consumption during the treatment were evaluated together with changes of soil pH, electrical conductivity and soil microbial functional diversity before and after the electrokinetic treatment. The results indicate that 76% of Cu was successfully removed from the soil after 140 d of treatment when lactic acid was used as enhancing reagent for adjusting the catholyte pH and dissolving soil Cu by complexation, and the pilot-scale electrokinetic experiment consumed electric energy of 224 kW h t-1 soil. The post-treatment soil pH values decreased about 0.1-1.6 units compared with the initial value (pH 4.8), and soil electrical conductivities in most of soil sections also significantly decreased. Soil microbial functional diversity varied after the electrokinetic treatment, particularly the increase of substrate richness index, which is possibly due to the stimulation of lactic acid that was introduced into the soil column during the experiment.     

Two-dimensional model for soil electrokinetic remediation of heavy metals. Application to a copper spiked kaolin

A two-dimensional numerical model has been developed to simulate the electrokinetic remediation of soils contaminated with heavy metals and has been validated using laboratory experiments performed with a copper spiked kaolin. The model divides the soil into compartments in a Cartesian grid and a non-conductivity barrier encloses the considered area. Basically, it consists in two main parts clearly distinguishable. The first part describes the electromigration phenomenon in the soil, which is represented by a set of electric resistors, following the Cartesian grid and using Kirchoff's laws of electricity to calculate the voltage drop distribution in the considered area. The second part describes the chemical equilibrium process between the heavy metal and the soil, assuming local equilibrium conditions within the compartments. A good agreement was obtained between the lab scale experimental assays and the model predictions. The model has also been used to examine the effect of the electrolyte neutralization within the scope of the acid-enhanced electrokinetic method. These simulations have foreseen problems related with the system evolution, which would not arise under one-dimensional geometries and are due to the changes of the potential distribution in the two-dimensional arrangement where some kind of short circuit arises, ultimately leading to a decrease of the system efficiency.     

Adsorption and desorption of Cu at high equilibrium concentrations by soil and clay samples from Bulgaria

Studies were carried out on the adsorption and desorption of added copper (from 100 to 600 microg g(-1)) to whole soils with contrasting properties: a Podzol (Godech A and Godech B) and a Chernozem (Gramada). Adsorption resulted in high Cu concentrations for the Podzol. The adsorbed copper, especially that in the B-horizon, is also potentially mobile, as judged by its ease of desorption on treatment with 0.01 m CaCl(2). A higher proportion of the added adsorbed copper is retained in Godech A soil (4% clay), than in Godech B soil (41% clay). Clay minerals are the principal adsorbent in the Podzol (Godech B), because of the high desorption observed at a low site coverage (7% CEC). The Godech B clay fraction (<0.001 mm) simulates the behaviour of the whole soil. The clay fraction from the Chernozem (Gramada) shows contrasting behaviour, as compared to the whole soil. Copper in the Chernozem is specifically (non-exchangeably) adsorbed, even at pH 2.7. A Langmuir model is appropriate for describing Cu-adsorption for the systems investigated at the acid pH values.     

鼠李糖脂协助下的土壤中镉电动修复

实验研究了重金属Cd在生物表面活性剂鼠李糖脂协助下的电动修复过程,通过不同方式、不同浓度、不同酸碱度的鼠李糖脂溶液的添加与空白处理对比,探讨了鼠李糖脂协助下电动修复过程中的Cd在土壤介质中的迁移转化和机理,分析了鼠李糖脂溶液作为电动修复添加剂的可行性。结果表明,中等浓度酸性的鼠李糖脂溶液(pH=4.78,浓度为0.5、1和2 g/L)能对土壤中的重金属Cd进行有效的富集,富集量均在初始值的4倍以上,且其可交换态比重均大于42.07%,非常有利于土壤进行二次修复。此外,以pH=4.78,浓度为0.5 g/L的鼠李糖脂溶液作为预处理剂的Ex-08中的重金属Cd并未出现富集现象,但其对重金属的Cd的总去除效率达到了49.27%。表明利用鼠李糖脂溶液作为电动修复添加剂进行土壤重金属修复是可行的。     

Remediating ethylbenzene-contaminated clayey soil by a surfactant-aided electrokinetic (SAEK) process

The objectives of this research are to investigate the remediation efficiency and electrokinetic behavior of ethylbenzene-contaminated clay by a surfactant-aided electrokinetic (SAEK) process under a potential gradient of 2 Vcm(-1). Experimental results indicated that the type of processing fluids played a key role in determining the removal performance of ethylbenzene from clay in the SAEK process. A mixed surfactant system consisted of 0.5% SDS and 2.0% PANNOX 110 showed the best performance of ethylbenzene removed in the SAEK system. The removal efficiency of ethylbenzene was determined to be 63-98% in SAEK system while only 40% was achieved in an electrokinetic system with tap water as processing fluid. It was found that ethylbenzene was accumulated in the vicinity of anode in an electrokinetic system with tap water as processing fluid. However, the concentration front of ethylbenzene was shifted toward cathode in the SAEK system. The electroosmotic permeability and power consumption were 0.17 x 10(-6)-3.01 x 10(-6) cm(2)V(-1)s(-1) and 52-123 kW h m(-3), respectively. The cost, including the expense of energy and surfactants, was estimated to be 5.15-12.65 USD m(-3) for SAEK systems, which was 2.0-4.9 times greater than that in the system of electrokinetic alone (2.6 USD m(-3)). Nevertheless, by taking the remediation efficiency of ethylbenzene and the energy expenditure into account for the overall process performance evaluation, the system SAEK was still a cost-effective alternative treatment method.     

Zinc, copper and nickel concentrations in soil extracts and crops grown on four soils treated with metalloaded sewage sludges

Sludges containing high concentrations of zinc, copper or nickel and an uncontaminated sludge were added to two sandy loams (pH 6.5 and 7.1), a heavy clay (pH 6.3) and a calcareous clay (pH 7.8) to give ten sludge treatments for each soil. The mixtures were incubated fallow, cropped continuously with clover, or cropped with barley and red beet in rotation for 21 months. The quantity of added metal either in the soil solution or extracted by 0.1m CaCl(2) depended on the metal loading, pH and soil cation exchange capacity, and changed with time after mixing soils and sludges. Crop metal concentrations, and the occurrence of metal-induced yield reductions, also depended on soil properties as well as metal loading. The best chemical extractant for predicting plant metal concentrations was 0.1m CaCl(2).     

The effects of pH and soil type on concentrations of zinc, copper and nickel extracted by calcium chloride from sewage sludge-treated soils

The effects of pH on concentrations of zinc, copper and nickel extracted by calcium chloride from a clay loam and two sandy loam soils that had been treated with sewage sludge were studied. Concentrations of all the metals increased rapidly as pH decreased below a threshold value ranging from 6.2 to 7.0 for Zn, 6.2 to 7.2 for Ni and 4.7 to 5.7 for Cu. Both the total concentrations and the threshold pH values were influenced by differences in soil texture and (between the two light-textured soils) by differences in soil cation exchange capacity. The amount of zinc and copper extracted from the mixtures was considerably less than that extracted from the same quantity of sludge alone.     

Removal of organic contaminants from soils by an electrokinetic process: the case of atrazine. Experimental and modeling

The atrazine behaviour in soils when submitted to an electric field was studied and the applicability of the electrokinetic process in atrazine soil remediation was evaluated. Two polluted soils were used, respectively with and without atrazine residues, being the last one spiked. Four electrokinetic experiments were carried out at a laboratory scale. Determination of atrazine residues were performed by enzyme-linked immunosorbent assay (ELISA). The results show that the electrokinetic process is able to remove efficiently atrazine in soil solution, mainly towards the anode compartment: Estimations show that 30-50% of its initial amount is removed from the soil within the first 24h. A one-dimensional model is developed for simulating the electrokinetic treatment of a saturated soil containing atrazine. The movement of atrazine is modelized taking into account the diffusion transport resulting from atrazine concentration gradients and the reversed electro-osmotic flow at acidic soil pH.     

Electrokinetic remediation of a Cu-Zn contaminated red soil by controlling the voltage and conditioning catholyte pH

Electrokinetics is an innovative technique for treating heavy metals contaminated soil, especially low pH soils such as the Chinese red soil (Udic Ferrisols). In this paper, a Cu-Zn contaminated red soil is treated by electrokinetics. When the Cu-Zn contaminated red soil was treated without control of catholyte pH during the electrokinetic treatment, the soil pH in the soil sections near cathode after the experiment was high above 6, which resulted in accumulation of large amounts of Cu and Zn in the soil sections with such high pH values. Compared to soil Cu, soil Zn was more efficiently removed from the soil by a controlled electrokinetic method. Application of lactic acid as catholyte pH conditioning solution caused an efficient removal of Cu and Zn from the soil. Increasing the electrolyte strength (salt concentration) of the conditioning solution further increased Cu removal, but did not cause a significant improvement for soil Zn. Soil Cu and Zn fractions after the electrokinetic treatments were analyzed using sequential extraction method, which indicated that Cu and Zn precipitation in the soil section closest to the cathode in the treatments without catholyte pH control limited their removal from the soil column. When the catholyte pH was controlled by lactic acid and CaCl(2), the soil Cu and Zn removal percentage after 554 h running reached 63% and 65%, respectively. Moreover, both the residual soil Cu and Zn concentrations were lower than 100 mg kg(-1), which is adequate and meets the requirement of the Chinese soil environmental quality standards.     

Improvement in electrokinetic remediation of heavy metal spiked kaolin with the polarity exchange technique

In the electrokinetic treatment of heavy metal polluted soil, an alkaline environment is generated at the cathode side. It provokes the precipitation of metal ions as hydroxides into the soil and diminishes the capability of the electroremediation to clean the polluted site. In this work the "polarity exchange" technique is presented as a simple way to avoid the negative effect of OH(-) on metal transportation. This technique lies in the operation during short time intervals at inverted polarity, so that the generation of H+ ions from the oxidation of water neutralize in the alkaline zone where the metal is precipitated, favouring its dissolution. Once the metals are redissolved, the polarity is set to the original position to transport them to the desired direction. Kaolin clay contaminated with Mn was used to test the feasibility of the polarity exchange technique. The application of the "conventional technique" dealt with a removal of 14% of the initial Mn in 7.6d. For a similar treatment time the polarity exchange technique resulted in 72% of removed Mn. Successive polarity exchanges will yield with a complete decontamination of the soil with a moderate increment in the electric power consumption.     

Experimental measurements and computer predictions of copper complex formation by soluble soil organic matter

Complexing of metals by organic matter can strongly influence their biological activity in the environment. The extent of copper complex formation by soluble organic matter extracted from an organic soil, a clay, and two sandy loams, was measured under identical conditions using two independent experimental methods. The results in every case fitted equations similar to Langmuir two-surface isotherms, but the values of complexing capacity and complexing strength were not the same for the organic matter from the four soils, and so were unsuitable for use in computer programs intended to predict concentrations of individual copper species in soil solutions. These concentrations can, however, be predicted by an empirical relationship between free and total copper at a constant pH and ionic strength.     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

Removal of fluorine from contaminated soil by electrokinetic treatment driven by solar energy

Instead of direct current power supply, a series of electrokinetic remediation experiments driven by solar energy on fluorine-contaminated soil were conducted in a self-made electrolyzer, in order to reduce energy expenditure of electrokinetic remediation. After the 12-day electrokinetic remediation driven by solar energy, the removal efficiency of fluorine was 22.3 %, and electrokinetic treatment had an impact on changes in partitioning of fluorine in soil. It proved that the combination of electrokinetics and solar energy was feasible and effective to some extent for the remediation of fluorine-contaminated soil. Meanwhile, the experimental results also indicated that the electromigration was a more dominant transport mechanism for the removal of fluorine from contaminated soil than electroosmosis, and the weather condition was the important factor in affecting the removal efficiency.     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

Solid/solution Cu fractionations/speciation of a Cu contaminated soil after pilot-scale electrokinetic remediation and their relationships with soil microbial and enzyme activities

The aim of this study was to investigate the detailed metal speciation/fractionations of a Cu contaminated soil before and after electrokinetic remediation as well as their relationships with the soil microbial and enzyme activities. Significant changes in the exchangeable and adsorbed-Cu fractionations occurred after electrokinetic treatment, while labile soil Cu in the solution had a tendency to decrease from the anode to the cathode, and the soil free Cu²⁺ ions were mainly accumulated in the sections close to the cathode. The results of regression analyses revealed that both the soil Cu speciation in solution phase and the Cu fractionations in solid phase could play important roles in the changes of the soil microbial and enzyme activities. Our findings suggest that the bioavailability of soil heavy metals and their ecotoxicological effects on the soil biota before and after electroremediation can be better understood in terms of their chemical speciation and fractionations.     

Long-Term Effects on Soil of the Disposal of Olive Mill Waste Waters (OMW)

Disposal of untreated olive mill waste waters (OMW) is a serious environmental problem in many Mediterranean countries. The aim of this work was to assess whether changes in soil properties have occurred due to direct disposal of raw OMW on soil and in evaporation ponds, and to investigate the potential fate and transport of pollutants after olive oil production had ceased. The results clearly showed that uncontrolled OMW disposal is a significant source of pollution to surface soil and waters. Disposal of OMW on soil greatly increased electrical conductivity (EC), available phosphorous (P), exchangeable potassium (K) and magnesium (Mg), organic matter, polyphenols, total and inorganic nitrogen (N), and available micronutrients mainly in surface soil layers. The presence of a high content of clay and carbonates in soil act as barriers and prevent downward transport of pollutants. Residual levels of total carbon (C), polyphenols, total and inorganic N, exchangeable K⁺, available P, iron (Fe), and copper (Cu) were also elevated even 8 years after mill closure. The long term disposal of OMW highlights the need to establish soil quality standards for soil parameters in order to identify soils affected by the disposal of OMW.     

Influence of soluble copper on the electrokinetic properties and transport of copper oxychloride-based fungicide particles

This article describes the influence of dissolved copper on the electrokinetic properties and transport of a copper oxychloride-based fungicide (COF) in porous media. The Zeta potential (ζ) of COF particles increases (viz. becomes less negative) with increasing concentration of Cu(2+) in the bulk solution. ζ decreases for COF when the electrolyte (NaNO(3)) concentration is raised from 1 to 10mM. This can be ascribed to ion correlation of Cu(2+) in the electrical double layer (EDL). COF transport tests in quartz sand columns showed the addition of Cu(2+) to the bulk solution to result in increased retention of the metal. Modelling particle deposition dynamics provided results consistent with kinetic attachment. Based on the effect of soluble Cu on colloid mobility, the transport of particulate and soluble forms of copper is coupled via the chemistry of pore water and colloid interactions. Mutual effects between cations and colloids should thus be considered when determining the environmental fate of particulate and soluble forms of copper in soil and groundwater (especially at copper-contaminated sites).     

A two-stage process using electrokinetic remediation and electrochemical degradation for treating benzo[a]pyrene spiked kaolin

An innovative process that combines soil electrokinetic remediation and liquid electrochemical oxidation for the degradation of organic compounds present in a polluted soil was developed and evaluated by using benzo[a]pyrene spiked kaolin. In order to increase benzo[a]pyrene solubility during electrokinetic treatment, the addition of a co-solvent or surfactant, such as ethanol or Brij 35, as flushing solution was tested. The research carried out demonstrated the influence of the desorption agent employed on benzo[a]pyrene remediation from the kaolin matrix. Thus, if the flushing solution was ethanol at 40%, there was no presence of contaminant in either chamber. On the contrary, when a solution of surfactant Brij 35 was used, benzo[a]pyrene was transported towards the cathode chamber, where it was collected. Moreover, the extent of this recovery depends on the pH profile on the soil. When no pH control was used, around 17% of initial contaminant was detected in the cathode chamber; however, when pH control was applied, the recovery of benzo[a]pyrene could be higher than 76%, when the pH control in the anode chamber was set at 7.0.In order to obtain the total degradation of mobilised benzo[a]pyrene from the contaminated soil, the liquid collected by electrokinetic remediation was oxidised by electrochemical treatment. This oxidation was accomplished via an electrochemical cell with a working volume of 0.4 L, and graphite as electrode material. The benzo[a]pyrene was almost totally degraded in 1 d, reaching a degradation of about 73% in 16 h.