In this work, the feasibility of the combination of electrokinetic remediation and electrochemical oxidation for the remediation of polluted soil with organic compounds had been development and evaluated in kaolinite spiked with Reactive Black 5 (RB5) an azo dye. The process consists in the use of two combined phenomena to achieve a full remediation of RB5 spiked kaolinite and the degradation of the organic pollutant. Those phenomena were soil electrokinetic treatment combined to liquid electrochemical oxidation. Reactive Black 5 (0.39 g dye kg\u22121) could be effectively removed fromthe kaolinite matrix by electrokinetics, however the removal results largely depended on the operating conditions. Complete removal of RB5 was achieved using K2SO4as processing \ufb02uid (which enhanced the desorption of RB5 from the kaolinite matrix) and operating with pH control at 7 on the anode. This favoured the alkalinization of the system and, at high pH values, RB5 was ionized and migrated towards the anode chamber where it was collected and could be oxidized electrochemically. Also, it must be pointed out that in these optimized conditions the electric power consumption (56 kW/mg of removed dye) was ten times lower compared to the unenhanced electrokinetic process (with no pH-control in the electrode solutions). Separate electrochemical decolourization tests of RB5 showed the effectiveness of K2SO4in the ef\ufb01ciency of the process. A linear relationship between K2SO4concentration and the decolourization rate was found. Thus, nearly complete decolourization was achieved after 2 and 3 h of electrochemical treatment when the electrolyte concentration was 0.1 and 0.01 M of K2SO4, respectively.
Around 106 tonnes are produced annually world wide and used extensively in textile dyeing/\ufb01nishing and also in food, paper and cosmetic industries. It is estimated that about 15% of total world production of wastewater are lost in industrial ef\ufb02uents. The discharge of these highly coloured wastewaters into the ecosystem involves environmental problems. There are more than 10,000 of chemically different synthetic dyes and pigments. Among them, azo dyes are a major class of synthetic, coloured organic compounds and account for about half of the textile dyestuffs used today.
Several methods are using to decolourize wastewater (e.g., membrane technologies, coagulation and \ufb02occulation technolo- gies) with different colour removal capabilities, costs and might produce large amounts of solid wastes, which become pollu- tants on its own creating disposal problems[3\u201310]. Biological,
physical and chemical processes to remove organic pollutants have been considered for remediation of contaminated soils. However, few reports about dye removal from contaminated soils were found in the literature. Hence, there is a great interest for developing a soil remediation technology cost-effective and ecofriendly to this kind of organic pollutants.
The application of electrokinetic remediation for the decon- tamination of soil polluted with heavy metals has been very promising, and recently this technique has been employed for remediation of soil polluted with organic compounds[12,13]. The electrokinetic remediation is primarily a separation and removal technique for extracting contaminants from soils. It can be appliedin situ, which allows soil to be treated with- out being excavated and transported, resulting in potentially signi\ufb01cant cost savings and in a less destruction of the soil matrix.
The principle of electrokinetic remediation is based on the application of a low-intensity direct current through the soil, between two electrodes (anode and cathode). Pollutants are transported towards the electrodes by electromigration (positively and negatively charged organic compounds are
transported towards the cathode and anode, respectively) and electroosmosis (the movement of a liquid containing ions relative to a stationary charged surface)[14,15]. Moreover, the oxidation/reduction of water at the anode/cathode generates H+ and OH\u2212 that move towards the cathode/anode creating an acid and basic front in the soil, respectively.
During the electrokinetic treatment of a contaminated soil, charged dye is transported towards one of the electrode chambers where it will be concentrated. Removal of contaminants of this concentrated solution may be accomplished by several means, among which liquid electrochemical oxidation is a promising technology. There are few reports that used the electrochemical technology to degrade wastewater with high dye concentration. Among them, Ciorba et al., Gutierrez et al., Donald- son et al., Kim et al., Sanroman et al.[21,22] have reported the enormous potential of the electrochemical technol- ogy to decolourize wastewaters contaminated with several kinds of dyes. They found that electrochemical oxidation is a versatile alternative with a high potential to replace or improve existing processes.
In this work, an environment-friendlyin situ integral method is presented. Hence, the method proposed in this paper consists in two combined phenomena: soil electrokinetic treatment and liquid electrochemical oxidation on the electrode (anode). This coupling could permit thein situ total dye degradation. In order to test the feasibility of the method purposed, the electrokinetic remediation of kaolin polluted with a representative dye of the azo group, Reactive Black 5 (RB5) and its degradation by elec- trochemical oxidation have been studied.
Kaolinite samples were prepared mixing thoroughly 120 g of kaolinite clay with 120 mL of a solution of RB5 (0.5 g L\u22121). A slurry of 0.5 g dye kg\u22121dry kaolinite clay was obtained. RB5 (Fig. 1) was purchased from Sigma. The mixture stood for 24 h to allow the possible sorption of dye to the surface of kaolinite particles. The pH of the mixture was 4. The resulting slurry was compacted to a constant density and pressure in a consolidome- ter unit, which creates homogeneous, near-saturated soil
matrixes. During the consolidation process, a fraction of the initial water and dye was eliminated from the slurry. RB5 con- centration in the soil matrix after the consolidation process was 0.39 g dye kg\u22121 of dry matter, and its pH was 4.2. The moisture content was around 32%, expressed as the weight of water per unit weight of wet kaolinite. In this sample, RB5 was adsorbed on the kaolinite particles since no dye was released in extraction tests with deionised water.
Kaolinite was selected as model matrix since it shows much lower buffering capacity, because of its lower cation exchange capacity compared with other clay minerals. The kaolin used has a particle size average of 3\ue000m and a speci\ufb01c surface of 13.5 m2g\u22121. The mineralogy analysis by X-ray diffraction indi- cated the presence of kaolinite clay 85%, mica 14% and quartz 1%.
The experiments were performed in a cylindrical glass cell depicted inFig. 2. The sample, 80 g of RB5 spiked kaolinite (dry weight) was introduced in the central tube whose dimen- sions are 100 mm length and 32 mm inner diameter. The two electrode chambers (with 300 mL working volume) are placed at each end of the sample compartment isolated fromthis one by a paper \ufb01lter and porous stones. Graphite electrodes were used for both anode and cathode (P1, P2 and P3). Three auxiliary electrodes allow to measure the electric \ufb01eld distribution along the sample. Electrode chambers were \ufb01lled with K2SO4(0.1 M) as processing \ufb02uid. Recirculation of liquid is applied by pumps to avoid concentration gradients. In some experiments pH on the anode or the cathode chambers was controlled using NaOH 0.1 M or H2SO40.1 M, respectively.
A DC electric current with maximum values of 30 V or 10 mA was applied in all experiments. Readings of the voltage drop, current intensity and the pH in the electrode compartments were taken periodically.
Analytical methods: upon completion of each experiment, samples were taken from cathode and anode solutions and the clay matrix for chemical analysis. The clay sample was divided in \ufb01ve sections of approximately 16 cm3each, named S1\u2013S5 from anode to cathode. They were analysed for moisture content, pH and RB5 concentration. The pH in the kaolinite sections after the experiment was measured adding KCl 1 M to dry kaolinite in a ratio 2.5 mL g\u22121. After 1 h of contact time, pH was measured with a pH-meter Sentron model 1001. The RB5 was extracted from kaolinite sections with a solution of K2SO4 0.1 M in a ratio 1 g of dry kaolinite: 8 mL. The extraction procedure was done \ufb01ve times to assure a complete recovery of the dye. RB5 con- centration was determined fromthe absorbance at the maximum wavelength in the visible spectrum (597 nm) using a calibration curve.
Experiments were carried out in an electrochemical cell with a working volume of 300 mL. Electrodes were made of graphite, with an effective area of 38 cm2and the electrode gap was 8 cm.
Magnetic stirring was used to avoid concentration gradients. A constant potential difference (5 V) was applied with a power supply (HP model 3662) and the process was monitored with multimeter (Fluke 175). The electrochemical decolourization of Reactive Black 5 (67 mg L\u22121) was studied using K2SO4 as electrolyte (10\u2013100 mM).
Samples of reaction mixtures were taken from the electro- chemical cell to be analysed for pH and dye concentration. pH was measured with a Sentron pH meter (model 1001). The dye concentration was measured from the absorbance at the maximum wavelength in the visible spectrum (597 nm) using a calibration curve. Dye decolourization was associated with the decrease in the concentration and expressed in terms of percentage. The assays were done in duplicate, and the experimental error was less than 3%.
A saturated kaolin clay sample polluted with RB5 was sub- jected to the electrokinetic process. The objective of this experi- ment (exp. 1) was to determine the feasibility of the remediation of kaolin contaminated with RB5, using an electrokinetic tech- nique to mobilize the dye and collect it in the chamber of one of the electrodes.
In order to improve this electrokinetic process, it is necessary to add an electrolyte that increases the electric conductivity and favours the desorption of dye from the polluted clay sample. Potassium sulphate was found to have been very effective in the extraction of dye from the mineral matrix; in fact, potassium sulphate was used in the extraction of the residual RB5 from kaolinite in the analytical procedure. It is a strong electrolyte, which is completely dissociated in solution. When a solution of potassium sulphate is used as processing \ufb02uid in the elec- trode chambers, K+and SO4 2\u2212ions are transported through the kaolinite sample from one electrode chamber to the other by the effect of the electric \ufb01eld. The presence of the potassium sulphate increases the electric conductivity and favours the des- orption of RB5 from the clay particles. Thus, the desorbed RB5
can be transported by electroosmosis and/or electromigration towards the electrode chambers. For this reason, in this experi- ment potassium sulphate was selected as processing \ufb02uid, \ufb01lling the anode and cathode chamber with 0.1 M potassium sulphate.
In this experiment, a pH jump between section S4 and S5 (Fig. 3) was developed due to the electrolysis of water upon the electrodes. The formation of this pH jump was the responsible of the decreasing in the current intensity registered from the second day of treatment and the large increase observed in the electrical resistance.
As can be seen inFig. 3, 14% of the initial RB5 was removed from the soil and it is supposed to have reached the electrode chambers by electromigration, electroosmosis and diffusion. RB5 was almost complete removed from section S5, its concentration was reduced by 94%. There was also an important decrease in dye concentration after the treatment in sections S1 (84%) and S2 (54%). However, RB5 was accumulated in section S3 and especially in section S4, where the \ufb01nal concentration was twice the initial one.
The electrokinetic treatment of the kaolinite sample polluted with a coloured compound was followed visually. In the beginning, the colour intensity was uniformly distributed along the sample. The application of the electric \ufb01eld mobilized the organic compound. The movement of RB5 results in the appearance of white zones (or pale colour zones) on both sides of the kaolinite sample. The thickness of those white zones
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