Alexandra B. Ribeiro

Electrokinetic remediation of organochlorines in soil: Enhancement techniques and integration with other remediation technologies

Electrokinetic remediation has been increasingly used in soils and other matrices for numerous contaminants such as inorganic, organic, radionuclides, explosives and their mixtures. Several strategies were tested to improve this technology effectiveness, namely techniques to solubilize contaminants, control soil pH and also couple electrokinetics with other remediation technologies. This review focus in the experimental work carried out in organochlorines soil electroremediation, aiming to systemize useful information to researchers in this field. It is not possible to clearly state what technique is the best, since experimental approaches and targeted contaminants are different. Further research is needed in the application of some of the reviewed techniques. Also a number of technical and environmental issues will require evaluation for full-scale application. Removal efficiencies reported in real contaminated soils are much lower than the ones obtained with spiked kaolinite, showing the influence of other factors like aging of the contamination and adsorption to soil particles, resulting in important challenges when transferring technologies into the field.

Removal of Cu, Pb and Zn in an applied electric field in calcareous and non-calcareous soils

The pH dependency of the removal of Cu, Zn and Pb by electrodialytic soil remediation from different industrially polluted soils was examined. From 18 experiments performed with five different soils, it was found that the order of mobilization due to a pH decrease was Zn>Cu>Pb. It was found, too, that each of the elements was removed at higher soil pH in calcareous soils (about 12% carbonates) than in soils with a carbonate content of less than 3.7%. In soils rich in carbonates, precipitation of heavy metal carbonates is an important retention mechanism and the heavy metal carbonates are dissolved at higher pH values than the pH at which heavy metals are desorbed in non-calcareous soils. Thus, the relation between the soil pH and the mobility of the heavy metal in the electric field is not only dependent on the heavy metal in focus, but also on the fraction of the heavy metal precipitated as carbonates.

A dynamic model for the electrokinetic removal of copper from a polluted soil

The electrokinetic process is a promising decontamination technique for removal of heavy metals from polluted sites. The authors have studied the removal of copper (Cu) from an industrially heavy-metal-contaminated soil, using the application of electric current. A sequential extraction procedure was used to monitor changes in the chemical associations of Cu during the electrokinetic treatment of the soil. A dynamic model is presented for the removal of Cu by electrokinetic decontamination. This model, based on a biregressional design, enables a joint analysis of the experiments which were carried out in a laboratory cell. The removal of Cu was found to be a local phenomenon, dependent on the release of metal by different soil fractions, cumulative and controlled by time as well as pH.

Phosphorus recovery from sewage sludge ash through an electrodialytic process

The electrodialytic separation process (ED) was applied to sewage sludge ash (SSA) aiming at phosphorus (P) recovery. As the SSA may have high heavy metals contents, their removal was also assessed. Two SSA were sampled, one immediately after incineration (SA) and the other from an open deposit (SB). Both samples were ED treated as stirred suspensions in sulphuric acid for 3, 7 and 14 days. After 14 days, phosphorus was mainly mobilized towards the anode end (approx. 60% in the SA and 70% in the SB), whereas heavy metals mainly electromigrated towards the cathode end. The anolyte presented a composition of 98% of P, mainly as orthophosphate, and 2% of heavy metals. The highest heavy metal removal was achieved for Cu (ca. 80%) and the lowest for Pb and Fe (between 4% and 6%). The ED showed to be a viable method for phosphorus recovery from SSA, as it promotes the separation of P from the heavy metals.

Electrodialytic Removal of Heavy Metals from Different Solid Waste Products

A variety of heavy metal polluted waste products must be handled today. Electrochemical methods have been developed for remediation of polluted soil. One of the methods is the electrodialytic remediation method that is based on electromigration of heavy metal ions and ionic species within the soil matrix, and a separation of the soil and the process solutions, where the heavy metals are concentrated, with ion exchange membranes. For remediation of some soils, such as calcareous soils, it is necessary to add an enhancement solution. It was shown in a laboratory experiment that ammonium citrate could be used when removing Cu and Cr from a soil with 25% carbonates. The final concentrations of the elements were below the target values after the remediation. A question of whether the electrodialytic remediation method can be used for other waste products arose. Preliminary experiments showed that the method could be used for removal of different heavy metals from impregnated wood waste, fly ash from straw combustion, and fly ash from municipal solid waste incineration. The best result was obtained with the wood waste where more than 80% of each of the polluting elements Cu, Cr and As was removed in a 7-day experiment in which oxalic acid was used as enhancement solution. From the straw ash, 66% of the Cd was removed, but 64% of the fly ash dry mass dissolved during the treatment. In this actual experiment, no enhancement solution was used but that will be necessary to avoid dissolution of the ash to such a high extent. For the fly ash from waste incineration, ammonium citrate was tested as enhancement solution and in 14 days 62% Cd, 53% Cu, 6% Pb, and 31% Zn were removed. The preliminary results were thus promising for developing the electrodialytic method to other products than soil, although more research is needed especially in finding the best enhancement solutions for each product.

Electrodialytic remediation of polychlorinated biphenyls contaminated soil with iron nanoparticles and two different surfactants

Polychlorinated biphenyls (PCB) are persistent organic pollutants (POP) that strongly adsorb in soils and sediments. There is a need to develop new and cost-effective solutions for the remediation of PCB contaminated soils. The suspended electrodialytic remediation combined with zero valent iron nanoparticles (nZVI) could be a competitive alternative to the commonly adapted solutions of incineration or landfilling. Surfactants can enhance the PCB desorption, dechlorination, and the contaminated soil cleanup. In this work, two different surfactants (saponin and Tween 80) were tested to enhance PCB desorption and removal from a soil sampled at a polluted site, in a two-compartment cell where the soil was stirred in a slurry with 1% surfactant, 10mL of nZVI commercial suspension, and a voltage gradient of 1Vcm(-1). The highest PCB removal was obtained with saponin. Higher chlorinated PCB congeners (penta, hexa, hepta and octachlorobiphenyl) showed removal percentages between 9% and 96%, and the congeners with highest removal were PCB138, PCB153 and PCB180. The use of low level direct current enhanced PCB removal, especially with saponin. Electrodechlorination of PCB with surfactants and nZVI showed encouraging tendencies and a base is thus formed for further optimization towards a new method for remediation of PCB polluted soils.

Assessing fly ash treatment: Remediation and stabilization of heavy metals

Fly ashes from Municipal Solid Waste (MSW), straw (ST) and co-combustion of wood (CW) are here analyzed with the intent of reusing them. Two techniques are assessed, a remediation technique and a solidification/stabilization one. The removal of heavy metals from fly ashes through the electrodialytic process (EDR) has been tried out before. The goal of removing heavy metals has always been the reuse of fly ash, for instance in agricultural fields (BEK). The best removal rates are here summarized and some new results have been added. MSW fly ashes are still too hazardous after treatment to even consider application to the soil. ST ash is the only residue that gets concentrations low enough to be reused, but its fertilizing value might be questioned. An alternative reuse for the three ashes is here preliminary tested, the combination of fly ash with mortar. Fly ashes have been substituted by cement fraction or aggregate fraction. Surprisingly, better compressive strengths were obtained by replacing the aggregate fraction. CW ashes presented promising results for the substitution of aggregate in mortar and possibly in concrete.

Electrokinetic remediation of six emerging organic contaminants from soil

Some organic contaminants can accumulate in organisms and cause irreversible damages in biological systems through direct or indirect toxic effects. In this study the feasibility of the electrokinetic (EK) process for the remediation of 17β-oestradiol (E2), 17α-ethinyloestradiol (EE2), bisphenol A (BPA), nonylphenol (NP), octylphenol (OP) and triclosan (TCS) in soils was studied in a stationary laboratory cell. The experiments were conducted using a silty loam soil (S2) at 0, 10 and 20mA and a sandy soil (S3) at 0 and 10 mA. A pH control in the anolyte reservoir (pH>13) at 10 mA was carried out using S2, too. Photo and electrodegradation experiments were also fulfilled. Results showed that EK is a viable method for the remediation of these contaminants, both through mobilization by electroosmotic flow (EOF) and electrodegradation. As EOF is very sensible to soil pH, the control in the anolyte increased EOF rate, consequently enhancing contaminants mobilization towards the cathode end. The extent of the mobilization towards the electrode end was mainly dependent on compounds solubility and octanol-water partition coefficient. In the last 24h of experiments, BPA presented the highest mobilization rate (ca. 4 μg min(-1)) with NP not being detected in the catholyte. At the end of all experiments the percentage of contaminants that remained in the soil ranged between 17 and 50 for S2, and between 27 and 48 for S3, with no statistical differences between treatments. The mass balance performed showed that the amount of contaminant not detected in the cell is similar to the quantity that potentially may suffer photo and electrodegradation.

Preliminary treatment of MSW fly ash as a way of improving electrodialytic remediation

In the current work electrodialytic remediation (EDR) was applied to remove heavy metals from municipal solid waste (MSW) fly ash, a hazardous waste collected during flue gas treatment. Tests were conducted to evaluate if EDR could be improved by introducing a preliminary treatment in which very soluble salts were removed. Three different preliminary treatments were conducted with different L:S ratios and pH. Treatment in which metal release and L/S ratio were lower was selected for EDR. Electrodialytic remediation was performed at a constant current of 38 mA, for 14 days, using gluconate as a solubilisation enhancement agent. Conductivity and pH were monitored and electrolyte samples were collected every 4 days to evaluate metal release over time. It was found that the preliminary treatment reduces fouling of the ion-exchange membranes used in EDR and drastically increases the removal of metals. Remediation time was also considerably reduced. Additionally, preliminary washing reduces energy consumption during EDR, since electric current is not wasted in the transport of soluble salts. Sequential extraction was performed in the untreated and treated samples to help identify how metals are bond to the fly ash. It was seen that at the end metals are mainly found in the strongly bonded and residual phases. This indicates that the combined treatment (washing + EDR) is successful in reducing the environmental risk posed by fly ash.

Electroremediation of PCB contaminated soil combined with iron nanoparticles: Effect of the soil type.

Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulate in soils and sediments. Currently, there is no cost-effective and sustainable remediation technology for these contaminants. In this work, a new combination of electrodialytic remediation and zero valent iron particles in a two-compartment cell is tested and compared to a more conventional combination of electrokinetic remediation and nZVI in a three-compartment cell. In the new two-compartment cell, the soil is suspended and stirred simultaneously with the addition of zero valent iron nanoparticles. Remediation experiments are made with two different historically PCB contaminated soils, which differ in both soil composition and contamination source. Soil 1 is a mix of soils with spills of transformer oils, while Soil 2 is a superficial soil from a decommissioned school where PCB were used as windows sealants. Saponin, a natural surfactant, was also tested to increase the PCB desorption from soils and enhance dechlorination. Remediation of Soil 1 (with highest pH, carbonate content, organic matter and PCB concentrations) obtained the maximum 83% and 60% PCB removal with the two-compartment and the three-compartment cell, respectively. The highest removal with Soil 2 were 58% and 45%, in the two-compartment and the three-compartment cell, respectively, in the experiments without direct current. The pH of the soil suspension in the two-compartment treatment appears to be a determining factor for the PCB dechlorination, and this cell allowed a uniform distribution of the nanoparticles in the soil, while there was iron accumulation in the injection reservoir in the three-compartment cell.