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Abstract
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−1 ) could be effectively
removed from the kaolinite matrix by electrokinetics, however the removal results largely depended on the operating conditions. Complete removal
of RB5 was achieved using K2 SO4 as processing fluid (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 K2 SO4 in the efficiency of the process.
A linear relationship between K2 SO4 concentration 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 K2 SO4 , respectively.
© 2006 Elsevier Ltd. All rights reserved.
0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.04.067
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transported towards the cathode and anode, respectively) and matrixes. During the consolidation process, a fraction of the
electroosmosis (the movement of a liquid containing ions initial water and dye was eliminated from the slurry. RB5 con-
relative to a stationary charged surface) [14,15]. Moreover, the centration in the soil matrix after the consolidation process was
oxidation/reduction of water at the anode/cathode generates H+ 0.39 g dye kg−1 of dry matter, and its pH was 4.2. The moisture
and OH− that move towards the cathode/anode creating an acid content was around 32%, expressed as the weight of water per
and basic front in the soil, respectively [16]. unit weight of wet kaolinite. In this sample, RB5 was adsorbed
During the electrokinetic treatment of a contaminated soil, on the kaolinite particles since no dye was released in extraction
charged dye is transported towards one of the electrode chambers tests with deionised water.
where it will be concentrated. Removal of contaminants of this Kaolinite was selected as model matrix since it shows much
concentrated solution may be accomplished by several means, lower buffering capacity, because of its lower cation exchange
among which liquid electrochemical oxidation is a promising capacity compared with other clay minerals. The kaolin used
technology. There are few reports that used the electrochemical has a particle size average of 3 m and a specific surface of
technology to degrade wastewater with high dye concentration. 13.5 m2 g−1 . The mineralogy analysis by X-ray diffraction indi-
Among them, Ciorba et al. [17], Gutierrez et al. [18], Donald- cated the presence of kaolinite clay 85%, mica 14% and quartz
son et al. [19], Kim et al. [20], Sanroman et al. [21,22] have 1%.
reported the enormous potential of the electrochemical technol-
ogy to decolourize wastewaters contaminated with several kinds 2.1.2. Electrokinetic cell
of dyes. They found that electrochemical oxidation is a versatile The experiments were performed in a cylindrical glass cell
alternative with a high potential to replace or improve existing depicted in Fig. 2. The sample, 80 g of RB5 spiked kaolinite
processes. (dry weight) was introduced in the central tube whose dimen-
In this work, an environment-friendly in situ integral method sions are 100 mm length and 32 mm inner diameter. The two
is presented. Hence, the method proposed in this paper consists electrode chambers (with 300 mL working volume) are placed
in two combined phenomena: soil electrokinetic treatment and at each end of the sample compartment isolated from this one by
liquid electrochemical oxidation on the electrode (anode). This a paper filter and porous stones. Graphite electrodes were used
coupling could permit the in situ total dye degradation. In order for both anode and cathode (P1, P2 and P3). Three auxiliary
to test the feasibility of the method purposed, the electrokinetic electrodes allow to measure the electric field distribution along
remediation of kaolin polluted with a representative dye of the the sample. Electrode chambers were filled with K2 SO4 (0.1 M)
azo group, Reactive Black 5 (RB5) and its degradation by elec- as processing fluid. Recirculation of liquid is applied by pumps
trochemical oxidation have been studied. to avoid concentration gradients. In some experiments pH on
the anode or the cathode chambers was controlled using NaOH
2. Materials and methods 0.1 M or H2 SO4 0.1 M, respectively.
A DC electric current with maximum values of 30 V or 10 mA
2.1. Electrokinetic treatment was applied in all experiments. Readings of the voltage drop,
current intensity and the pH in the electrode compartments were
2.1.1. Kaolinite sample preparation taken periodically.
Kaolinite samples were prepared mixing thoroughly 120 g of Analytical methods: upon completion of each experiment,
kaolinite clay with 120 mL of a solution of RB5 (0.5 g L−1 ). A samples were taken from cathode and anode solutions and the
slurry of 0.5 g dye kg−1 dry kaolinite clay was obtained. RB5 clay matrix for chemical analysis. The clay sample was divided
(Fig. 1) was purchased from Sigma. The mixture stood for 24 h in five sections of approximately 16 cm3 each, named S1–S5
to allow the possible sorption of dye to the surface of kaolinite from anode to cathode. They were analysed for moisture content,
particles. The pH of the mixture was 4. The resulting slurry was pH and RB5 concentration. The pH in the kaolinite sections after
compacted to a constant density and pressure in a consolidome- the experiment was measured adding KCl 1 M to dry kaolinite in
ter unit [23], which creates homogeneous, near-saturated soil a ratio 2.5 mL g−1 . 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 K2 SO4 0.1 M in a ratio
1 g of dry kaolinite: 8 mL. The extraction procedure was done
five times to assure a complete recovery of the dye. RB5 con-
centration was determined from the absorbance at the maximum
wavelength in the visible spectrum (597 nm) using a calibration
curve.
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Fig. 2. Schematic diagram of experimental set-up: (1) soil sample, (2) porous stones, (3) electrodes, (4) electrode chambers, (5) auxiliary electrodes, (6) gas valves,
(7) recirculation pumps and (8) power supply.
Magnetic stirring was used to avoid concentration gradients. A can be transported by electroosmosis and/or electromigration
constant potential difference (5 V) was applied with a power towards the electrode chambers. For this reason, in this experi-
supply (HP model 3662) and the process was monitored with ment potassium sulphate was selected as processing fluid, filling
multimeter (Fluke 175). The electrochemical decolourization the anode and cathode chamber with 0.1 M potassium sulphate.
of Reactive Black 5 (67 mg L−1 ) was studied using K2 SO4 as In this experiment, a pH jump between section S4 and S5
electrolyte (10–100 mM). (Fig. 3) was developed due to the electrolysis of water upon
the electrodes [24]. The formation of this pH jump was the
2.2.2. Decolourization responsible of the decreasing in the current intensity registered
Samples of reaction mixtures were taken from the electro- from the second day of treatment and the large increase
chemical cell to be analysed for pH and dye concentration. observed in the electrical resistance.
pH was measured with a Sentron pH meter (model 1001). As can be seen in Fig. 3, 14% of the initial RB5 was
The dye concentration was measured from the absorbance at removed from the soil and it is supposed to have reached the
the maximum wavelength in the visible spectrum (597 nm) electrode chambers by electromigration, electroosmosis and
using a calibration curve. Dye decolourization was associated diffusion. RB5 was almost complete removed from section
with the decrease in the concentration and expressed in terms S5, its concentration was reduced by 94%. There was also an
of percentage. The assays were done in duplicate, and the important decrease in dye concentration after the treatment
experimental error was less than 3%. in sections S1 (84%) and S2 (54%). However, RB5 was
accumulated in section S3 and especially in section S4, where
the final concentration was twice the initial one.
3. Results and discussion The electrokinetic treatment of the kaolinite sample polluted
with a coloured compound was followed visually. In the
3.1. Electrokinetic treatment of kaolinite polluted with RB5 beginning, the colour intensity was uniformly distributed along
the sample. The application of the electric field mobilized
A saturated kaolin clay sample polluted with RB5 was sub- the organic compound. The movement of RB5 results in the
jected to the electrokinetic process. The objective of this experi- appearance of white zones (or pale colour zones) on both sides
ment (exp. 1) was to determine the feasibility of the remediation of the kaolinite sample. The thickness of those white zones
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 fluid in the elec-
trode chambers, K+ and SO4 2− ions are transported through the
kaolinite sample from one electrode chamber to the other by
the effect of the electric field. The presence of the potassium
sulphate increases the electric conductivity and favours the des- Fig. 3. Electrokinetic treatment of RB5 spiked kaolinite (exp. 1). Normalized
orption of RB5 from the clay particles. Thus, the desorbed RB5 concentration (ⵦ) and pH ().
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was slowly widened during the first 5 days. However, no more with the initial concentration, and a slightly accumulation in
visual changes were observed during the rest of the experiment. sections S1 and S2 was observed. In these sections the final
So, it suggests that the reported results in RB5 removal were concentration was 20% higher than the initial concentration.
achieved in 5 days of treatment and the rest of the treatment do These results show that RB5 migrated towards the anode. In
not contribute significantly to the decontamination process. fact, during the experiment, the advance of the dye was followed
The electric power consumption registered at the end of by the change in colour of the soil (from blue to white). The
the experiment was 60 kWh (907 kWh mg−1 of removed dye), white layer appeared in the soil close to the cathode on the
but considering that the treatment was not effective from the second day and it moved towards the anode at a constant rate
fifth day on, the electric power consumption was only 37 kWh of 0.17 cm day−1 , until the day 15, when it reached a thickness
(592 kWh mg−1 of removed dye). of 4 cm. It corresponds with sections S4 and S5, which shows
In this experiment it is very clear that the pH jump limited the highest removal.
the current intensity and increased the electrical resistance of The mass balance showed that 26% of RB5 was removed from
the system. In other words, the transport of ions was limited the kaolinite and was collected on the anode chamber, where it
and therefore it affected the RB5 removal. On the other hand, was electrochemically decolourized. No RB5 was detected on
an important removal of RB5 was found on both sides of the the anode and cathode solution at the end of the experiment. The
kaolinite sample, where the pH values were complete different. electric power consumption was 338 kWh mg−1 of removed dye.
On the anode side, the pH of the kaolinite was very acid (pH
2.4), and pH was alkaline on the cathode side (pH 9.7). So, 3.3. Electrokinetic treatment with pH control on anode
it is proposed to study the behaviour of the system under pH- (exp. 3)
controlled conditions. It suppressed the pH jump and permitted
to study the removal of RB5 in alkaline or acid environment, with The pH control on the anode depolarized the oxidation of
the objective of revealing the optimum operating conditions for water avoiding the formation of H+ ions and the acid front.
RB5 removal. NaOH 0.1 M was used in the pH control to keep the pH value at
7.2 ± 0.2 in the anode. In this condition, the basic front generated
3.2. Electrokinetic treatment with pH control on cathode at the cathode penetrated into the kaolinite sample, increasing
(exp. 2) the pH of the interstitial fluid. At the end of the experiment, the
kaolinite sample reached a pH profile almost flat, from 9.7 to
In this experiment, pH value was controlled at 6.8 ± 0.2 on 9.9 (Fig. 5).
the cathode chamber with sulphuric acid 0.1 M. It avoided the The electrical resistance of the system was slightly higher
formation of an alkaline environment at the cathode side and than in experiment 2. It is probably due to the lower mobility
favoured the advance of the acid front. So, the kaolinite sample of the OH− ions (the predominant in experiment 3) than the H+
was acidified reaching an almost flat pH profile (from 2.9 to 3.2) ions (the predominant in experiment 2).
as shown in Fig. 4. The pH control at the cathode avoided the At the end of the experiment, 94% of RB5 was removed from
formation of the pH jump, and the electrical resistance of the the kaolinite sample demonstrating the high effectiveness of the
system was kept low compared to experiment 1. treatment. The removal degree in the different sections ranged
The distribution of RB5 in the kaolinite was very different from 91% in S1 to 96% in S5 (Fig. 5).
compared to experiment 1 (Fig. 4). A very important decrease During the experiment, it was observed that RB5 was trans-
in RB5 concentration was observed in section S4 (78%) and ported towards the anode side. In the first day of treatment, a
especially in section S5 (92%). The final concentration of RB5 white layer 1 cm width was detected on the cathode side. The
in section S3 (in the middle of the kaolinite sample) coincided rest of the kaolinite sample was blue. Both zones were separated
Fig. 4. Electrokinetic treatment of RB5 spiked kaolinite with pH control in the Fig. 5. Electrokinetic treatment of RB5 spiked kaolinite with pH control in the
cathode (exp. 2). Normalized concentration (ⵦ) and pH (). anode (exp. 3). Normalized concentration (ⵦ) and pH ().
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