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Treatment of Organics in Wastewater Using Electrogenerated

Gaseous Oxidants
Leticia Mirella da Silva, Ismael F. Mena, Cristina Saez, Artur J. Motheo, and Manuel A. Rodrigo*

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ABSTRACT: This work focuses on the comparison of the

performance of direct electrochemical oxidation with indirect
Downloaded via ESS INFLIBNET PCA 2 on December 31, 2024 at 14:25:20 (UTC).

electrolysis mediated by gaseous oxidants in the treatment of

diluted wastewater. To do this, energy consumptions of the
electrolysis using mixed metal oxide (MMO) electrodes are
compared with those required for the production and use of
chlorine dioxide in the degradation of methomyl contained in
aqueous solutions. Results demonstrate the feasibility of the
mediated oxidation process and that this process is competitive
with direct oxidation. The oxidants are produced under optimized
conditions using the same anodic material applied for the direct
degradation of organics, thus avoiding efficiency losses associated
with mass transfer limitations in the degradation of dilute organic
solutions. Thus, using the ClO2 gaseous oxidant, a concentration of 0.1 mM of methomyl from a solution containing 500 mL is
completely removed with an energy consumption as low as 50 Wh. The application of the same energy to a direct electrolytic
process for treating the same wastewater can only reach less than half of this removal. These findings may have a very important
application in the use of electrochemical technology to achieve the remediation of persistent pollutants in wastewater, where their
low concentrations typically make direct processes very inefficient.

1. INTRODUCTION the concentration of the organic pollutants that should be

The removal of pollutants from wastewater has been a topic of removed from wastewater.35 Typically, this technology is very
wide interest for decades.1−7 Many technologies have been efficient when treating wastewater with concentrations within
evaluated and, among them, electrochemical oxidation has the range of 1000−20,000 mg L−1 COD where, using diamond
been shown to be one of the most promising according to the electrodes and tailored cells, Coulombic efficiencies near 100%
scientific literature.8−17 In this context, once the viability of the can be reached.36 However, below this range, the efficiency
electrochemical technology for treating organic compounds decreases almost linearly with the concentration that needs to
contained in wastewater was demonstrated at the turn of the be removed. Thus, a typical efficiency when degrading
century, other challenges were faced looking for improving wastewater with a COD content of 100 mg L−1 is around
efficiency and sustainability, including the development of new 5−10% and, in treating waste with a COD of 10 mg L−1, it is
electrode materials,18−24 the synergistic effect and integration difficult to reach efficiencies over 2−3%, unless the bare
of electrolytic processes with other oxidation technolo- electrolytic process is combined with other processes (Fenton,
gies,25−30 and the powering of electrochemical processes ultraviolet (UV) irradiation, application of ultrasounds, etc.).37
with green energies.31 More recently, technological advance- This is explained because the efficiency of the direct
ment is focused on the development of more efficient electrochemical processes depends importantly on mass
electrochemical cells, with the final aim of increasing the transport within the electrochemical cell and below the range
technology readiness level (TRL) of these processes.32 In 1000−2000 mg L−1, this transport becomes the limiting stage
addition to this technological progress, fundamental studies
that demonstrate the important role of hydroxyl radicals were
considered extremely important to understand oxidation Received: September 14, 2023
mechanisms and optimize their performance. The key role of Revised: March 26, 2024
these radicals has contributed to classify electrochemical Accepted: March 27, 2024
oxidation as an advanced oxidation process (AOP).33,34 Published: April 9, 2024
One of the most important facts that must be evaluated
regarding the application of the electrochemical technology is
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(bottleneck), and it is necessary to change the primary state of chloride (−1) is raised to that of chlorate (+5)
oxidation mechanisms from direct transfer of electrons to a electrochemically, and then hydrogen peroxide decreases it
mediated process, to achieve a more efficient treatment. down to +4 (chlorine dioxide) (eq 5).60−6163
The combination of electrochemical technologies with other
2Cl Cl 2(aq) + 2e (1)
advanced oxidation processes (AOPs) is this objective. The
first works,38,39 made at a very low TRL of 2−3, aimed to Cl 2 + 2OH ClO + Cl + H 2O (2)
clarify the effect of the salts contained in wastewater on the
degradation of different pollutants (in fact, many of them were 3ClO ClO3 + 2Cl (3)
not real wastewater, but solutions containing the pollutant and
salts in nonrealistic concentrations). Many works demonstrate O2 (aq) + 2H+ + 2e H 2O2 (4)
the feasibility of removing the organic species in most cases,
but the resulting effluent was not suitable for use in any case 1 1
due to the difficulties in the separation of the oxidants and the ClO3 + H 2O2 + H+ ClO2 + O2 + H 2O
2 2 (5)
salts contained in the electrolyte, as cited by Sirés et al.40 Then,
the target of the research shifted from the evaluation of the The ease in the change of oxidation state of chlorine species
effect of salts to the clarification of the role of other species increases the difficulty of this process, which in addition needs
such as hydrogen peroxide that do not leave an unaffordable highly acidic media. However, the good prospects of chlorine
fingerprint in the treated waste. The main disadvantage dioxide made it interesting to go further in the development of
observed was the significant increase in cost when several this electrochemical production.
technologies are combined, possibly associated with the fact Considering this background, the main aim of this paper is
that those works were carried out at a low TRL.32 to make a preliminary comparison of the direct and mediated
Recently, interest has arisen in the electrochemical (using chlorine dioxide) degradation of pollutants at very low
production of oxidants off-site from the waste treatment concentrations, especially in terms of energy demand. To do
process, looking for higher efficiencies in this production, in this, the degradation of a diluted solution containing methomyl
which the electrolyte is not the waste but a special solution is evaluated when the pollutant is degraded by direct
made on purpose to produce the oxidant. electrolysis using mixed metal oxide (MMO) electrodes or
Once formed, this oxidant is applied to the waste and it is let when using for this degradation the oxidant chlorine dioxide,
to oxidize the organic pollutants chemically, either alone or produced from chlorate and hydrogen peroxide, formed
activated by chemical, photolytic, or ultrasound mecha- electrochemically with the same electrodes.
nisms.41−47 The main problem associated with this application
is that, along with the addition of the oxidant, other 2. MATERIALS AND METHODS
compounds contained in the electrolyte where the oxidant 2.1. Chemicals. For the generation of oxidants, deionized
was manufactured, are added to the water.48−50 Among these water (Millipore Mili-Q system, resistivity 18.2 MΩ·cm at 25
oxidant solutions, those containing peroxo species like °C, TOC:2 ppb) and the following analytical standard reagents
peroxocarbonates, peroxosulfates, peroxophosphates, and were used: sodium chloride, sodium perchlorate, 70%
hydrogen peroxide are worth to be mentioned. Also, and perchloric acid, and 1.9−2.1% of titanium(IV) oxysulfate
although used in much lower extension, hypochlorite solutions solution (CAS:13825−74−6/Sigma-Aldrich) as an indicator
are also included. Thus, the main limitation in their use is the for H2O2 measurement and oxidants analysis, and the samples
composition of the electrolyte used to manufacture them, were acidified with 20% sulfuric acid for subsequent reaction
because of the difficulties in the separation of the oxidants and with sodium thiosulfate. For the effluent preparation, 16.21 mg
the salts contained in the electrolyte in a cheap and efficient L−1 methomyl from its commercial compound was used,
way.40 whose composition is 215 g L−1 methomyl, 420 g L−1 ethanol,
This problem can be detached when the oxidant produced is and 324 g L−1 other ingredients.
a gas, like in the cases of chlorine, ozone51,52 and chlorine 2.2. Experimental Setup and Procedure. To generate
dioxide,53,54 because in those cases, the electrolyte used for the chlorate from a sodium chloride solution, an electrochemical
production is not added to the waste that is expected to be flow reactor (Figure 1A) manufactured with a three-dimen-
treated, but simply a gaseous stream containing the oxidant sional (3D) printer was used, and it was equipped with an
gas, because they can be easily stripped from the electrolyte MMO (based on RuO2/Ti and supplied by Ti anode) anode
solution by flowing air and this becomes a very important
advantage. This means that the fingerprint of this technology is
going to be less important than that obtained with other more
aggressively mediated processes. This approach is very new,
especially in the case of chlorine dioxide, which is an oxidant
whose electrochemical production has been the target of
research only very recently. Although there are several
approaches to produce this important oxidant,55−58 the most
interesting path seems to be the combination of the production
of chlorate (which is a well-known electrochemical process in
which the raw matter can be brine or a salty chloride solution)
(eqs 1−3) with the electrochemical production of hydrogen Figure 1. (A) Electrochemical flow reactor used for chlorate
peroxide (in which a great development is being reached generation with a plate of titanium as cathode and DSA as an
recently with the development of more and more efficient anode. (B) Gas diffusion cell used for hydrogen hydroxide generation
cells) (eq 4).48,59,60 In the combined process, the oxidation with DSA as anode and painted carbon paper as cathode.

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Figure 2. (A) Scheme of ClO2 production used for the treatment of methomyl in dissolution. (B) Electrochemical oxidation setup with MMO (Ti
anode) anode: (a) recirculation tank with Na2SO4 (0.05 mol L−1), (b) electrochemical flow reactor, and (c) power supply. japp = 79.5 mA cm−2,
and initial volume of 500 mL.

and a titanium cathode, both measuring 78.5 cm2. The Table 1. ClO2 Generation Conditions, Using 100 mL of
optimized conditions for production involved the use of a HClO4 (70%), and Vi = 500 mL
solution containing 5 g L−1 NaCl, applying 150 mA cm−2, at 15
ID airflow (mL h−1) ClO3− flow (mL h−1) H2O2 flow (mL h−1)
°C, using a titanium plate as cathode. From this, it was possible
to generate large amounts of ClO3− continuously at different (1) 50 62.5 92
flow rates. The same MMO electrodes were used to produce (2) 30 62.5 92
chlorates and the direct degradation of methomyl. (3) 10 62.5 92
To generate hydrogen peroxide (H2O2), an electrochemical (4) 30 67.9 187.5
gas diffusion cell (Figure 1B) printed on a 3D printer was used, (5) 30 180 64.3
using an MMO (based on RuO2/Ti and supplied by Ti anode)
as the anode (10.9 cm2) and a painted carbon paper 10.9 cm2 obtained are used to plot the main results of the methomyl
as the cathode. The optimized condition used for methomyl removal.
treatment in this work was a solution of 14.05 g L−1 NaClO4 t
acidified to pH 3.5, applying 4.6 mA cm−2, with a continuous W= I ·V ·dt
0 (6)
average flow of 100 mL h−1.
As demonstrated in Figure 2A, the experiments of ClO2 2.3. Analytical Techniques. The methomyl analysis was
generation were carried out in completely closed glass reactors performed using a high-performance liquid chromatography
of 1000 mL (Tank 1), adding different ratios of chlorate (4800 (HPLC) method. For this purpose, an Elipse Plus C18 column
mg L−1) and hydrogen peroxide (46−70 mg L−1) simulta- from Agilent (PN: 959961−902) was used, with a mobile
neously at different flow rates for ClO2 formation (eq 5). To phase of acetonitrile:water (20:80, v/v), a flow of 0.3 mL
maintain the strongly acidic pH, 100 mL of perchloric acid min−1, 25 °C, injection volume of 20 μL, and λmax = 233 nm.
70% were added in all cases as initial volume. Also, the H2O2 Chlorine dioxide (ClO2) in the liquid phase was monitored by
solution added was acid. Samples of the liquid and gas phases spectrophotometry using a Spectroquant Prove 300 from
were collected to quantify the evolution of ClO2. Merck KGaA, D-64293 Darmstadt, with a wavelength
Two initial experiments were carried out with the system absorbance of 360 nm. Previous experiments from our research
shown in Figure 2A. The first experiment (E1) used 2 L of KI group indicated the calibration curve of standard ClO2.60 For
(2 mol L−1) in TK2. The second experiment (E2) used 500 the gaseous phase determinations, samples of 5 mL of gas were
mL of a methomyl solution (0.1 × 10−3 mol L−1) in TK2. For taken and bubbled into 10 mL of water for measuring the
ClO2 generation (TK1) was applied a continuous flow of 4.0 spectra or into a solution containing potassium iodide,
and 0.18 mmol h−1 for ClO3− and H2O2, respectively, with an producing its transformation into iodine. In this latter case,
inlet airflow of 10 L h−1. Then, to evaluate the production of the iodine solution was titrated with sodium thiosulfate (0.001
chlorine dioxide, the airflow and dosages of ClO3− and H2O2 N) to quantify oxidants.
were varied as indicated in Table 1.
The degradation of methomyl by electrochemical oxidation 3. RESULTS AND DISCUSSION
using MMO (RuO2/Ti) as anode and Ti anode as cathode was 3.1. Degradation of Methomyl by the Mediated
carried out using the system shown in Figure 2B, using a Electrochemical Process. One of the main challenges in
recirculation tank of 500 mL (a) with Na2SO4 (0.05 mol L−1), the development of new processes to face the destruction of
electrochemical flow reactor (b), and power supply (c) to organics contained in wastewater is to evaluate their perform-
apply 79.5 mA cm−2. ance in continuous operation mode, which is the operation
To calculate energy consumption associated with electro- mode in which full-scale treatment should be applied. This is
chemical processes, eq 6 was applied using intensity and of great significance when the product is a gas, and it is
voltage data obtained during the electrolysis tests. Energy data especially important in the case of chlorine dioxide because its
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Figure 3. (a) H2O2 concentration (●) and H2O2 production (Δ) vs continuous flow rate (mL h−1). (b) Efficiency (×) and power (◊) calculated
for H2O2 production.

Figure 4. (a) Monitoring of chlorine species (mg Cl L−1), where the chlorine species are hypochlorite (□), chlorate (gray circle solid), and chloride
(▲). Chlorate production (+, mg h−1) vs continuous flow rate (mL h−1). (b) Efficiency (×) and power (◊) calculated for chlorate production.

Figure 5. (a) Monitoring of the liquid chlorine dioxide produced (mmol) in the tank of reaction (tank 1) and (b) gas chlorine dioxide (mmol)
diluted in the treatment tank with contaminated waste (tank 2). Conditions 1 (□), 2 (●), 3 (+), 4 (gray diamond solid), and 5 (▲) explained in
Table 1.

production implies the integration of two electrochemical with an electrode area of 9 cm2 was used (100 mL h−1) for the
processes (production of chlorate and hydrogen peroxide) and continuous production of H2O2. As seen, results are stable and
one chemical step (reaction between both electrogenerated with a tiny cell and extremely low energy consumption, it is
products). In previous works,60,63 it was shown how this possible to obtain a liquid stream of hydrogen peroxide with an
process yields good results, especially with the use of tailored average concentration over 60 mg L−1. Hence, as expected
cells and suitable values of the key operational parameters. In because of the dilution effect, the concentration of H2O2
this work, we start from the knowledge acquired in these decreases with the increase in the flow rate. This is not the
previous works and design the tests to operate under case with the production that it is maintained in values higher
conditions that were found to reach high efficiencies. than 6 mg h−1 regardless of the flow rate fed to the cell (with
It should be noted that Figure 3 shows the effect of the Faradaic efficiencies around 22.9%). In those conditions,
variability of the flow rate on the production of hydrogen power consumed is as low as 0.1 W, and thus, outstanding
peroxide using electrochemical technology within the nearness energy efficiencies are reached, in the nearness of 60 mg
of the design conditions selected in this work, in which a cell (Wh)−1.
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Figure 6. (a) Methomyl concentration decay (C0: 0.1 mmol L−1, Vi: 500 mL) due to the ClO2 reaction under different conditions. Inset: The
calculated constant rate vs airflow (mL h−1). (b) Chromatogram area of the sum of intermediates during the oxidation of methomyl using ClO2
produced. Conditions 1 (□), 2 (●), 3 (+), 4 (gray diamond solid), and 5 (▲) explained in Table 1. aint/aMet is the area of intermediates divided by
the area of Methomyl.

Figure 7. (a) Electrochemical removal of methomyl with the MMO (RuO2/Ti) anode (▲), using 0.1 mmol L−1 methomyl. (b) Chromatogram
area of the sum of intermediates (□) formed during the electrochemical oxidation reaction of methomyl using the MMO (RuO2/Ti) anode. The
supporting electrolyte was 0.05 mol L−1 Na2SO4, j = 79.5 mA cm−2, and Vi of 500 mL.

Figure 4 focuses on the continuous production of chlorate looked for. Hence, the most important parameter is not an
(in this case, at different flow rates in the nearness of 75 mL electrochemical parameter but the flow rate of stripping air
h−1, which was chosen as the design flow rate for an electrode used that prevents decomposition of chlorine dioxide in the
surface area of 78.5 cm2), and it also shows the key parameters reaction tank where it is produced.
to understand this electrochemical process. A mixture of This gas containing ClO2 is flowed into synthetic wastewater
chlorine oxoanions is produced during the process, although in polluted with methomyl. As seen in Figure 6a, the ClO2 stream
this case the effect of the flow rate is more relevant, and the rapidly produced a decay in the concentration of the pollutant,
higher the flow rate, the lower the concentration of chlorate in with a rate that is strongly dependent on the flow rate of gas
the resulting stream (same effect of that shown for hydrogen flows (as shown in the onset). Chlorine dioxide is a very good
peroxide, although in this case is more clearly observed). oxidant of organic matter and, opposite to chlorine and
Productions decrease with the flow rate, and values over 120 hypochlorite, it does not produce chlorinated organic
mg h−1 are obtained with power consumptions in the nearness intermediates because the main process responsible for the
of 110 W and energy efficiencies over 1.10 mg chlorate formation of these species is prevented, as the chlorine
(Wh)−1, values much higher than those required by hydrogen addition reaction to the double bonds of organics does not
peroxide production, making the energy required in that happen with this oxidant as previously reported elsewhere.64
process negligible. Results are plotted versus the energy applied for a later
Finally, the mixture of streams containing both species (in a comparison that will be made with a direct electrolytic process
strongly acidic perchlorate solution) yields chlorine dioxide (although as the production’s power is kept constant during
both in the liquid and, especially, in a gas stream, as shown in the experiments, this trend is the same as that obtained
Figure 5. Amounts of produced chloride dioxide largely concerning time). As seen in Figure 6a, energy consumption as
depend on the dosing between electrochemically manufactured low as 50 Wh allows for the total removal in the most efficient
products and the airflow rate used to strip chlorine dioxide conditions, and in the worse conditions, the energy
from the solution in which it is formed. The most significant consumption is below 100 Wh. An intermediate is formed
parameter is the airflow rate, which informs about the rapid during the treatment (Figure 6b) and, as expected, it is rapidly
degradation of the chlorine dioxide in the liquid reaction media depleted in the conditions in which more chlorine dioxide is
where it is produced, and of the necessity of exhausting it added to the reactor. Hence, chlorine dioxide produced
rapidly after being formed, especially if an efficient process is electrochemically can be used to degrade efficiently the
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Figure 8. (a) Voltage (V, □) and energy consumption (Wh, ×) of the electrochemical oxidation process using MMO (RuO2/Ti) anode (I = 6.24
A). (b) Electrochemical removal of methomyl with MMO (RuO2/Ti) anode, using 0.2 and 0.1 mmol L−1 methomyl represented by (●) and (▲),
respectively. The supporting electrolyte was 0.05 mol L−1 Na2SO4, j = 79.5 mA cm−2, and Vi = 500 mL.

methomyl contained in diluted solutions. TOC was measured this case, the energy efficiency of treating a solution with a
for all samples, but no significant changes were observed and, concentration of 0.2 mg L−1 is 0.60 mg (kW h)−1, while in
in fact, the small changes detected could be associated with treating a solution with an initial concentration of 0.1 mg L−1
measurement errors rather than with real variations in this the efficiency decreases down to 0.268 mg (kW h)−1, both
globalized parameter. This does not mean that no mineraliza- values much below the typically reported in studies in which
tion was obtained because it may be related to the complexity concentrations are much higher.67,68 Also, Coulombic
of the compounds contained in the commercial mixture used efficiencies considering an exchange of 26 electrons (nitrogen
and hence their different impact on the TOC value (many and sulfur as final products in the oxidation) lead to values of
different compounds for which the ratio TOCmeasured/ 1.81 and 0.78%, respectively, for the degradation of the
TOCtheoretical is not 1, because of the inefficiencies in the solutions containing 0.2 and 0.1 mg L−1, values which can be
oxidation made by the TOC analyzer). explained in terms of the dilution, as the kinetics of the
3.2. Degradation of Methomyl by the Direct Electro- oxidation processes typically fits to a pseudo-first-order
chemical Process. Using the same type of anodes that were kinetics.
used to produce chlorate (which was observed to be the These results confirm the good prospects of the mediated
bottleneck of the complete process), the electrolysis of the electrochemical technology proposed for the treatment of
same methomyl solution, evaluated in this work as synthetic dilute solutions and that they can become a real alternative to
waste, was made. Typical operation conditions for this type of anodic oxidation, being less sensitive to the effect of dilution
treatment were applied with a current density of 79.5 mA cm−2 than the commonly evaluated direct electrochemical processes.
and room temperature. The main results are summarized in
Figure 7, where the decay in the concentration of methomyl 4. CONCLUSIONS
and the total concentration of intermediates are shown in
terms of energy consumption. From this work, the following conclusions can be drawn:
As seen, the decay is much less efficient in terms of energy,
• Methomyl can be removed electrochemically either in
and more than 4 times more energy is required to complete the direct processes or from electrochemically produced
degradation of the methomyl solution as compared to the tests chlorine dioxide. Direct removal fits well to a first-order
in which chlorine dioxide produced electrochemically is used kinetic model, but decay kinetic constants depend on the
as an oxidant (200 vs 50−100 Wh, respectively). However, it initial concentration of methomyl in the wastes.
can be confirmed that anodic oxidation can also completely
deplete methomyl from the liquid solution. Opposite to what • Chlorine dioxide can be produced from the mixture of
was obtained when bubbling chlorine dioxide in the synthetic chlorate and hydrogen peroxide streams produced
solution, the intermediates detected in those tests did not electrochemically in continuous mode. The airflow rate
behave as intermediates here but as a final product, although it used to strip chlorine dioxide was found to be a very
was produced in the same range of concentrations that reached important parameter in reaching high efficiencies.
in the mediated oxidation tests, pointing out again the lower
efficiency of the direct electrochemical process. • The efficiency of the anodic oxidation of methomyl
Figure 8b compares the effect of the initial concentration in solutions depends almost linearly on the initial
a semilogarithmic plot, where it can be seen that the process concentration of pollutants in the treated wastewater.
fits well to a first-order kinetic and that the first-order decay Chlorine dioxide gaseous oxidants mediated electro-
constant depends on the initial concentration as reported in chemical technologies (GOMET) are more efficient
the literature,65,66 pointing out the inefficiency in the than anodic oxidation for the remediation of diluted
application of anodic oxidation processes when treating diluted wastewater. It is possible to degrade methomyl with the
waste. A negligible effect was observed in the resulting cell same anode material and concentration in the synthetic
voltage and energy applied to the system (Figure 8a), wastewater with 4 times less energy. This indicates that
confirming that the efficiency of direct anodic oxidation the development of GOMETs is a topic worthy of
processes increases linearly with the concentration. Thus, in further research.

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■ AUTHOR INFORMATION
Corresponding Author
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acquisition, project administration, supervision, validation,
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writing�review and editing. Anodes. J. Chem. Technol. Biotechnol. 2013, 89, 282−289,
Notes DOI: 10.1002/jctb.4118.
The authors declare no competing financial interest. (15) Aquino, J. M.; Pereira, G. F.; Rocha-Filho, R. C.; Bocchi, N.;

■ ACKNOWLEDGMENTS
This work comprises the research project TED2021-
Biaggio, S. R. Electrochemical Degradation of a Real Textile Effluent
Using Boron-Doped Diamond or β-PbO2 as Anode. J. Hazard. Mater.
2011, 192 (3), 1275−1282.
(16) Rocha, I. M. V.; Silva, K. N. O.; Silva, D. R.; Martínez-Huitle,
131630B−I00 granted by MCIN/AEI/10.13039/ C. A.; Santos, E. V. Coupling Electrokinetic Remediation with
501100011033/and “European Union Next Generation EU/ Phytoremediation for Depolluting Soil with Petroleum and the Use of
PRTR” and [2021/06908-0, 2018/26475-9 and 2017/10118- Electrochemical Technologies for Treating the Effluent Generated.
0] from the São Paulo Research Foundation (FAPESP, Brazil). Sep. Purif. Technol. 2019, 208, 194−200.

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