Sustainable Environment Research xxx (2016) 1e9

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Original Research Article

Comparative study of electrochemical oxidation of herbicide 2,4,5-T:

Kinetics, parametric optimization and mineralization pathway
Hicham Zazou a, b, Nihal Oturan a, Hui Zhang c, Mohamed Hamdani b,
Mehmet A. Oturan a, *
a
Laboratoire G

eomat
eriaux et Environnement (EA 4508), Universit
e Paris-Est, Marne-la-Vall

ee 77454, France
b
Electrochemical, Catalysis and Environment Lab, Science Faculty, Ibn-Zohr University, Agadir BO 8106, Morocco
c
Department of Environmental Engineering, Wuhan University, Wuhan 430079, China

a r t i c l e i n f o a b s t r a c t

Article history: Oxidative degradation of herbicide 2,4,5-T was studied by electrochemical advanced oxidation processes
Received 1 August 2016 anodic oxidation and electro-Fenton (EF) using Pt/carbon felt and BDD/carbon felt cells. The effect of
Received in revised form main operating parameters on oxidation of 2,4,5-T and mineralization of its aqueous solution were
6 October 2016
investigated. The rate constant for oxidation of 2,4,5-T by
OH was determined as
Accepted 2 November 2016
Available online xxx
(3.7 ± 0.2)  109 M¡1 s¡1 using competition kinetics method. The EF process with BDD anode was shown
to be very efficient reaching 94% mineralization in 3 h treatment. Based on identified aromatic in-
termediates, short-chain carboxylic acids, released inorganic ions and total organic carbon removal
Keywords:
2,4,5-T
measurements, a plausible oxidation pathway for mineralization of 2,4,5-T by hydroxyl radical was
Electro-Fenton proposed. In addition, the evolution of solution toxicity during treatment was monitored by Microtox
Anodic oxidation method showing the formation of toxic aromatic/cyclic intermediates. The results showed also that EF
Mineralization process was able to remove efficiently toxic intermediates and consequently solution toxicity.
Hydroxyl radical © 2016 Chinese Institute of Environmental Engineering, Taiwan. Production and hosting by Elsevier B.V.
TOC removal This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).

1. Introduction high concentration levels in the United States and European

Pesticides are chemicals used against weeds, diseases and pest
to improve crop yield. Among them, herbicides are used as weed
killers in agriculture. However, the accumulation of these chemicals
in natural water stream constitutes a serious issue because of their
adverse effects on human and animal health. The herbicide 2,4,5-
trichlorophenoxyacetic acid (2,4,5-T), developed in the late 1940s,
was used mainly in agriculture for control of perennial broad-
leaved weed species and for improving crop yields. Its main char-
acteristics are given in Table 1. This is a toxic and poorly biode-
gradable pollutant [1].
Because of its toxicity problems towards human and animal
beings [2e4], the use of 2,4,5-T acid was banned in some developed
countries but is still widely used nowadays in most countries. As it
is soluble in water, its occurrence and accumulation at relatively
* Corresponding author.
E-mail address: Mehmet.Oturan@univ-paris-est.fr (M.A. Oturan).
Peer review under responsibility of Chinese Institute of Environmental
Engineering.
groundwater [5] has been reported. For this reason and due to its
persistence and non-biodegradability character in water and soil,
development of efficient and environment friendly techniques is of
great importance for elimination of this pollutant to avoid its
release to the water stream. Thereby, a great attention has been
paid to application of advanced oxidation processes (AOPs) [6e9].
These processes promote in situ generation of strong oxidizing
agents such as hydroxyl radical (
OH) able to react rapidly and non-
selectively on organic pollutants leading to their mineralization
[10e12].
Several studies have been carried out on the elimination of
2,4,5-T from water using chemical, photochemical and electro-
chemical processes such as Fe(II)/oxone and electrochemical
treatment (electro-Fe(II)/oxone) or photocatalysis (Fe(II)/oxone-
UV) with high degradation efficiency [11,13]. Besides, a high
degradation efficiency of 2,4,5-T was also obtained by electro-
chemical oxidation using metal-oxide-coated Ti electrode Ti/
SnO2eSb/CeePbO2 as anode [12]. The gamma radiolysis was also
performed for degradation of 2,4,5-T in water [14]. The photo-
catalytic degradation of 2,4,5-T using irradiated TiO2 is also well

http://dx.doi.org/10.1016/j.serj.2016.11.008
2468-2039/© 2016 Chinese Institute of Environmental Engineering, Taiwan. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: Zazou H, et al., Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric
optimization and mineralization pathway, Sustainable Environment Research (2016), http://dx.doi.org/10.1016/j.serj.2016.11.008
2 H. Zazou et al. / Sustainable Environment Research xxx (2016) 1e9
Table 1
Physicochemical properties of 2,4,5-T.
Structural formula
Physical state White powder
Molecular weight 255.5 g mol1
Solubility 275 at 20  C
Density 1.80 at 20  C
Vapor pressure 105 Pa at 20  C
Dissociation constants pKa 2.88 at 25  C
Octanol/water partition coefficient log Kow ¼ 4
documented in the literature [15,16]. Finally, electro-Fenton (EF)
and anodic oxidation (AO) processes using a Pt anode and an O2-
diffusion cathode were reported by Boye et al. [3] with high
degradation efficiency. As considering the above discussion, we
focused in this study on the oxidative degradation of 2,4,5-T and
effective mineralization of its aqueous solution using two electro-
chemical advanced oxidation processes (AOPs); AO and EF due to
their high oxidation/mineralization capacities [17e22].
In the AO process, highly reactive and strongly oxidant hetero-
geneous hydroxyl radicals M(
OH) are produced on the anode (M)
surface by electrochemical oxidation of water, according to reaction
(1), using high O2-overvoltage anodes such as boron-doped dia-
mond (BDD) [20e26]:
M þ H2 O/Mð
OHÞads þ Hþ þ e
The EF process is based on in situ generation of homogeneous


OH_ in the bulk of solution from Fenton's reaction (2). H2O2 is
generated from 2  e reduction of O2 according to the reaction (3)
using a suitable cathode [27,28]. The externally added catalyst
(Fe2þ) is then regenerated electrocatalytically by reaction (4) from
Fe3þ formed by Fenton's reaction [23e37]:
Fe2þ þ H2 O2 /Fe3þ þ
OH þ OH
O2 þ 2Hþ þ 2e /H2 O2
Fe3þ þ e /Fe2þ



The M( OH)/ OH obtained from reactions (1) and (2) are non-
selective, very powerful oxidizing agents that oxidize 2,4,5-T to
aromatic/aliphatic intermediates or to CO2 in the case of prolonged
electrolysis times [18,38,39].
In the present study we investigated the oxidative degradation
of 2,4,5-T and mineralization of its aqueous solution by EF and AO
processes using Pt-carbon felt and BDD-carbon felt electrode con-
figurations. Oxidative degradation of this herbicide has been
already studied by Brillas et al. [40], but the identification of aro-
matic intermediates formed during the treatment and toxicity
assessment were not performed. In addition our study was per-
formed at different conditions such as the use of a very small
catalyst concentration (0.1 mM instead of 1 mM). In addition, we
have performed a detailed kinetics study.
The influence of operating parameters, such as the nature of the
anode and the applied current on degradation of 2,4,5-T and
mineralization of its solution were studied. The effect of catalyst
(Fe2þ) concentration was also investigated in the case of EF process.
The kinetics of oxidation and mineralization by hydroxyl radicals
was carried out and the rate constant of the reaction between 2,4,5-
T and
OH was determined by competition kinetics method. Results
Please cite this article in press as: Zazou H, et al., Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric
optimization and mineralization pathway, Sustainable Environment Research (2016), http://dx.doi.org/10.1016/j.serj.2016.11.008
showed that EF process was able to mineralize efficiently 2,4,5-T
solutions with complete removal of acute toxicity. Finally, a plau-
sible mineralization pathway of 2,4,5-T by
OH/M(
OH) was
proposed.
2. Materials and methods
2.1. Chemicals
All chemicals used in the present study were analytical grade
and used without further purification. 2,4,5-T acid (2,4,5-T,
C8H5Cl3O3) was obtained from sigma-Aldrich. Acetic, malefic,
oxalic, fumaric, formic, succinic and malonic acids (as standard
acids) and Iron(II) sulfate heptahydrate used as Fe2þ (catalyst)
source were supplied by Fluka. p-hydroxybenzoic acid (used as
competitor in determination of absolute constant) was obtained
from Merck. Anhydrous sodium sulfate (supporting electrolyte) and
methanol (mobile phase for HPLC (High performance liquid chro-
matography)) were ACS reagent grade and purchased from Across.
The pH values were adjusted with analytical grade sulfuric acid
from Across. Sodium nitrate (Merck), ammonium nitrate and so-
dium phosphate (SigmaeAldrich) were used as standards for ionic
chromatography analysis. Organic solvents and other chemicals
used were either of HPLC or analytical grade purchased from Merck
and Fluka. All the solutions were prepared with ultrapure water
produced by a Millipore Milli-Q (simplicity 185) system with re-
sistivity of >18 MU cm.
2.1.1. Experimental protocol
(1) All experiments were carried out in an open, undivided elec-
trochemical cell. The cathode consists of a piece of carbon felt
(14  5  0.6 cm) from Carbone Lorraine, France. A cylindrical Pt
grid of 3 cm in diameter and 5 cm in height and a BDD thin film
deposited on niobium substrate (from Condias GmbH, Germany) of
24 cm2 were used as anode. The current applied to the electro-
chemical cell was set by a stabilized current supply model
HM8040-30. A volume of 230 mL of 2,4,5-T solution containing
ferrous ion (0.1 mM, otherwise stated) and 50 mM Na2SO4 as
(2) supporting electrolyte was introduced into the cell and then the pH
of the solution was adjusted to 3 (optimal value for the EF process)
(3) with 1 M analytical grade sulfuric acid using the pH meter
(CyberScan pH 1500, Eutech Instruments). The solution was aerated
with compressed air at a flow of 0.2 L min1 for 10 min before
(4)
starting the electrolysis so as to saturate the solution with oxygen.
AO experiments were carried out without adding ferrous ions
(catalyst).
2.1.2. Analysis procedure
To follow the decay kinetics of 2,4,5-T and the extent of miner-
alization of treated solutions as well as to determine and analyze
degradation products (aromatic and aliphatic intermediates) dur-
ing the electrolysis and to follow inorganic ion formation, several
analytical techniques were employed:
2.1.3. HPLC
The degradation kinetic study of 2,4,5-T was monitored by HPLC
using a Merck-Hitachi Lachrom chromatograph equipped with a
diode array UVeVis detector (model L-7455) fitted with a reverse
phase purospher RP-18, 5 mm, 4.6  250 mm column (Merck,
France). This column was eluted isocratically in all experiments
with a mobile phase consisting of a mixture of methanol/
(water þ 0.1% H3PO4 acid) 70:30 (v/v) at a flow rate of 0.7 mL min1.
The column temperature was adjusted to 35  C, the detection was
performed at 234 nm and pressure value 16.7 MPa 2,4,5-T exhibited
a well-defined chromatographic peak at retention time of 11.23 min
 H. Zazou et al. / Sustainable Environment Research xxx (2016) 1e9
under above experimental conditions. The short-chain carboxylic
acids were identified and quantified with ion-exclusion chroma-
tography using Supelcogel H column (ɸ ¼ 7.8  300 mm) with a
mobile phase of H2SO4 (0.1%) at 220 nm.
2.1.4. Gas chromatography coupled with mass spectrometry
(GCeMS)
This technique was used for identification of intermediates from
2,4,5-T degradation, using an ISQ Single Quadrupole MS coupled
with Trace 1300 Series GC equipped with a Trace Gold TG-5MS
(30 m  0.25 mm; 0.25 mm) column. The mobile phase was heli-
um gas. This system was connected to a data acquisition and pro-
cessing unit using the Thermo Xcalibur analysis software. The
liquideliquid extraction was carried out using ethyl acetate as
solvent. Retention time for 2,4,5-T was determined at
20.28 ± 0.5 min.
2.1.5. Total organic carbon (TOC)
The TOC of treated solution during mineralization experiments
was measured using a Shimadzu VCSH analyzer equipped with a
manual injector. The maximum injection volumes were 50 mL. The
TOC was measured by combustion with catalytic oxidation at
680  C using high-purity oxygen gas. Calibration curves of the
analyzer were attained with standard potassium hydrogen phtha-
late solution (99.5%).
2.1.6. Ion chromatography
Ion chromatography was used to monitor the release and evo-
lution of chloride ion during mineralization of 2,4,5-T solution.
25 mL of samples was injected into a Dionex ICS-1000 Basic Ion
Chromatography system. The system was fitted with an IonPac
AS4A-SC column and eluted with a mixture of 1.8 mM Na2CO3 and
1.7 mM NaHCO3 at 2.0 mL min1 flow rate. The system was
equipped with a DS6 conductivity detector containing a cell heated
at 35  C and was controlled through Chromeleon SE software.
2.1.7. Toxicity assessment
The evolution of acute toxicity of treated 2,4,5-T solutions dur-
ing mineralization experiments was assessed by Microtox® method
according to the international standard process (OIN 11348-3) us-
ing a Microtox® model 500. The measurements were performed
with the bio-luminescence marine bacteria Vibrio fischeri provided
by Hach Lange France SAS [41]. Solution toxicity was measured as
inhibition of the luminescence (%) calculated after 5 min of expo-
sure of samples at 15  C.
3. Results and discussion
The optimization of some experimental parameters, such as the
nature of the anode, the applied current, the concentration of
catalyst (Fe2þ) and the pH of the solution are essential for efficient
degradation of persistent organic pollutants such as 2,4,5-T by
electrochemical AOPs. The optimal value of pH has been studied
and determined, it was proven to be definitely around the value of 3
[24,35e39]. Therefore, the influence of other parameters was
studied to determine operating conditions for an optimal removal
of the 2,4,5-T from aqueous solution.
3.1. Parameters influencing kinetics of degradation of 2,4,5-T acid
3.1.1. Effect of catalyst concentration
Effect of Fe2þ ions (catalyst) on the degradation of 2,4,5-T was
studied during EF process with Pt and BDD anodes. A series of ex-
periments were performed with different concentration of Fe2þ at
100 mA current and pH 3 and decay of 2,4,5-T was followed by HPLC.
Please cite this article in press as: Zazou H, et al., Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric
optimization and mineralization pathway, Sustainable Environment Research (2016), http://dx.doi.org/10.1016/j.serj.2016.11.008
3
The electrolysis time required to achieve complete degradation of
2,4,5-T was found to be a function of catalyst concentration as
depicted in Fig. 1. Indeed, in both cases (BDD or Pt anode), the con-
centration of 0.1 mM appears as optimal value for effective degrada-
tion of the pesticide: electrolysis time for total disappearance of 2,4,5-
T is reached in 15 and 20 min on Pt and BDD anodes, respectively. The
disappearance kinetics is relatively slow below this concentration;
this can be explained by the small amount of hydroxyl radicals pro-
duced from the reaction (2), because Fe2þ acts as the limiting reagent
in EF treatment. On the other hand, degradation kinetics is hindered
at high catalyst concentration due to the enhancement of reaction (5)
that competes with 2,4,5-T for
OH [18,26].
Fe2þ þ
OH/Fe3þ þ OH (5)
3.1.2. Effect of the current intensity
The effect of the applied current on the degradation kinetics of
2,4,5-T was studied at current intensities ranging from 100 to
1000 mA For EF with Pt (EF-Pt) or BDD (EF-BDD) and AO with Pt
(AO-Pt) and BDD(AO-BDD) anodes. Results obtained are shown in
Fig. 2. It appears from Fig. 2a and b that the nature of the anode
influences significantly degradation kinetics of 2,4,5-T: EF-Pt de-
grades 2,4,5-T more efficiently than EF-BDD. Indeed, 2,4,5-T
completely disappeared in 10 min with the Pt anode at 300 mA
current intensity, while its complete disappearance required
20 min with BDD anode under same conditions. 2,4,5-T is mainly
oxidized to its intermediates in EF-Pt while it is also mineralized
simultaneously in the latter case: this fact is evident during
mineralization experiments. Therefore, current of 300 mA can be
considered as optimal current for EF-Pt, while degradation kinetics
increases with current in the range of 100e1000 mA for EF-BDD. On
the other hand, AO experiments requires longer electrolysis times
to oxidize all of the 2,4,5-T as can be seen in Fig. 2c and d. In fact, at
1000 mA, total disappearance of 2,4,5-T takes 50 min and 40 min
for AO-Pt and AO-BDD, respectively. These results are expected,
because in the case of AO, oxidation of organics is carried out only
by M(
OH) (reaction 1) without contribution of homogeneous
OH
[2,42,43]. Oxidation kinetics is relatively more rapid in the case of
AO-BDD due to its high oxidation power [18,25,33].
3.1.3. Determination of the apparent and absolute rate constants
The apparent rate constants (kapp) are calculated considering
pseudo-first order reaction kinetics, based on the assumption of
steady state concentration for
OH since it cannot accumulate in the
solution. Considering these conditions, ln (C0/C) ¼ f (t) curve allows
determination of the apparent rate constant for oxidation of 2,4,5-T
by hydroxyl radicals using EF-Pt and EF-BDD cells (Fig. 3). The kapp
values determined for EF as well as AO treatments with Pt and BDD
anodes are summarized in Table 2. These values are in agreement
with the trend explained above: For EF-Pt maximum value is
attained at 300 mA while they increase with current in the case of
EF-BDD. In the case of AO, kapp values rise with current until
1000 mA for both anodes.
The absolute rate constant for oxidation of 2,4,5-T by hydroxyl
radicals was determined by the competitive kinetic method using
4-hydroxybenzoic acid (pHB) as a reference competitor and whose
absolute rate constant of the reaction with
OH is well-known (kabs
1 1
(pHB) ¼ 2.19  10 M
9
s at 25  C) [44]. Thus, an equimolar
mixture (0.1 mM) of pHB and 2,4,5-T was electrolyzed by applying
the EF-Pt at 50 mA. The evolution of this mixture was monitored by
HPLC at the beginning of electrolysis, in order to neglect the
intervention of the intermediates formed during treatment.
Disappearance rate of these two products in competition are given
by Eqs. (6) and (7), with, kapp ¼ kabs  [
OH]. Finally Eq. (8) for
4 H. Zazou et al. / Sustainable Environment Research xxx (2016) 1e9

0.1 0.1

0.08 0.08

Concentration (mM)

Concentration (mM)
0.06 0.06

0.04 0.04

0.02 0.02

0 0
0 20 40 60 0 20 40 60
Time (min) Time (min)

Fig. 1. Influence of catalyst (Fe2þ) concentration on the oxidative degradation of 2,4,5-T in aqueous solution by EF process at 100 mA with (a): Pt and (b): BDD anode. [Fe2þ] ¼ (◊):
0.0 mM, (:): 0.05 mM, (C): 0.1 mM, (): 0.2 mM, (A): 0.5 mM.

0.12 0.12
(a) (b)
0.1 0.1
Concentration (mM)
Concentration (mM)

0.08 0.08

0.06 0.06

0.04 0.04

0.02 0.02

0 0
0 4 8 12 16 20 24 28 0 4 8 12 16 20 24
Time (min) Time (min)

0.12 0.12

0.1 (c) 0.1 (d)

Concentration (mM)
Concentration (mM)

0.08 0.08

0.06 0.06

0.04 0.04

0.02 0.02

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Time (min) Time (min)

Fig. 2. Influence of applied current intensity on degradation kinetics of 2,4,5-T (C0 ¼ 0.1 mM) during treatment with: (a): EF-Pt, (b): EF-BDD, (c): AO-Pt, (d): AO-BDD. I ¼ (A):
100 mA, (:): 300 mA, (C): 500 mA, (): 1000 mA.

determination of kabs(2,4,5-T) is obtained by combination of Eqs. (6) Therefore the absolute rate constant of oxidation reaction of
and (7) [45]. 2,4,5-T by hydroxyl radicals was then determined as kabs(2,4,5-T) ¼
(3.7 ± 0.2)  109 M1 s1. This value is close to the value
d½2; 4; 5  T 6.4  109 M1 s1, determined by Zona et al. [14] using pulse
 ¼ kabsð2;4;5TÞ ½
OH ½2; 4; 5  T
dt radiolysis method. The difference can be related to the rate constant
¼ kappð2;4;5TÞ ½2; 4; 5  T (6) value of pHB.

d½pHB 3.1.4. Study of the mineralization

 ¼ kabsðpHBÞ ½
OH ½pHB ¼ kappðpHBÞ ½pHB (7)
dt The electrolysis by the EF was carried out under the same
kappð2;4;5TÞ operating conditions as in the previous section in order to optimize
kabsð2;4;5TÞ ¼ kabsðpHBÞ  (8)
kappðpHBÞ and confirm the optimal values. For this, we used the initial solution
of 2,4,5-T acid (0.1 mM) with initial TOC0 ¼ 9.6 mg L1.

Please cite this article in press as: Zazou H, et al., Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric
optimization and mineralization pathway, Sustainable Environment Research (2016), http://dx.doi.org/10.1016/j.serj.2016.11.008
 H. Zazou et al. / Sustainable Environment Research xxx (2016) 1e9 5

6 3.5
y = 0.32x
y = 0.6065x (a) 3 (b) R² = 0.9963 y = 0.2609x
5 R² = 0.9802 R² = 0.9922
y = 0.4393x
R² = 0.9866
2.5 y = 0.234x
4 R² = 0.9913
y = 0.3105x 2

ln(C0/C)
ln(C0/C)
R² = 0.9827
3 y = 0.2024x
1.5 R² = 0.9828

2 y = 0.2392x
R² = 0.9948 1

1 0.5

0 0
0 5 10 15 0 5 10 15
Time (min) Time (min)

Fig. 3. Determination of apparent rate constants during treatment with: (a): EF-Pt, (b): EF-BDD cells using pseudo-first order reaction kinetics law as a function of applied current
intensity. (A): 100 mA, (:): 300 mA, (C): 500 mA, (): 1000 mA.

Table 2 12
Apparent rate constants (kapp) for oxidation of 0.1 mM 2,4,5-T in 0.05 M Na2SO4
solution as a function of applied current intensity.
10
Process Anode I (mA) kapp (s1) R2

TOC (mg L-1)

EF Pt 100 0.23 0.99 8
300 0.61 0.98
500 0.44 0.98 6
1000 0.31 0.98
BDD 100 0.20 0.98
300 0.23 0.99 4
500 0.26 0.99
1000 0.32 0.99 2
OA Pt 300 0.03 0.99
500 0.04 0.98
1000 0.08 0.99
0
BDD 300 0.04 0.99 0 100 200 300 400
500 0.06 0.99
1000 0.13 0.99
Time (min)

Fig. 4. Influence of concentration of Fe2þ (catalyst) on the mineralization of 2,4,5-T

aqueous solution with EF-Pt at 100 mA [Fe2þ] ¼ (◊): 0.0 mM, (:): 0.05 mM, (C):
0.1 mM, (): 0.2 mM, (A): 0.5 mM.

3.1.4.1. Effect of catalyst concentration. The catalyst (Fe2þ) concen-

tration has a great effect on the mineralization kinetics of 2,4,5-T. It
was observed that the mineralization rate increases with the in-
crease in Fe2þ concentration up to 0.1 mM and decreases steadily 2 H2 O þ 2 e /H2 þ 2 OH (9)
thereafter during the electrolysis, as shown in Fig. 4. The percent-
age of TOC removal is about 88% with 0.1 mM against 82% with
0.2 mM after 360 min of treatment. This result can be explained by 2 H2 O/O2 þ 4 Hþ þ 4 e (10)
the enhancement of the rate of reaction (5) for high Fe2þ concen-
tration in detriment of oxidation of 2,4,5-T.
2 Mð
OHÞ/2 M þ O2 þ 2 Hþ þ 2 e (11)

3.1.4.2. Effect of the current intensity. The TOC removal curves ob-
tained during mineralization of 0.1 mM 2,4,5-T aqueous solution by
EF and AO with Pt and BDD anodes at different current values are
depicted in Fig. 5. The TOC abatement rate increases up to 92% after
6 h treatment at 300 mA in EF-Pt with no significant effect of
further increase observed beyond this value (TOC removal effi-
ciency is only 90% at 500 mA, Fig. 5a). An almost complete miner-
alization (>96% TOC removal) was attained with EF-BDD at 500 mA
after 6 h treatment (Fig. 5b). The decrease in mineralization effi-
ciency at high current values is related to intensification of side
reactions, such as evolution of H2 on the carbon felt cathode (Eq.
(9)) and evolution of O2 in the case of Pt anode (due to its lower O2
overpotential value) (Eq. (10)) and M(
OH) oxidation to O2 (Eq. (11))
or dimerization (Eq. (12)) of M(
OH) at the anode in the case of BDD
anode at high current intensities [18,25,26,33]:
2 Mð
OHÞ/2 M þ H2 O2 (12)
Regarding AO experiments, a poor mineralization degree (45%)
was observed in AO-Pt (Fig. 5c) while a significantly better miner-
alization efficiency (90%) (Fig. 5d) was reached with AO-BDD. These
results can be explained by the fact that chemisorbed hydroxyl
radicals are generated when using Pt instead of physisorbed radi-
cals at the BDD surface. Furthermore, the mineralization rate is high
for all cases at the beginning of the electrolysis and then it starts to
decrease with longer treatment times. Indeed, at the first stage of
treatment, 2,4,5-T and its aromatic intermediates are more readily
oxidized by hydroxyl radicals leading to the formation of short-
chain carboxylic acids that are resistant to mineralization in addi-
tion to the weak organic matter concentration, at longer treatment
times.

Please cite this article in press as: Zazou H, et al., Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric
optimization and mineralization pathway, Sustainable Environment Research (2016), http://dx.doi.org/10.1016/j.serj.2016.11.008
6 H. Zazou et al. / Sustainable Environment Research xxx (2016) 1e9

12 12
(a) (b)
10 10
8 8

TOC (mg L-1)

TOC (mg L-1)
6 6
4 4
2 2
0 0
0 100 200 300 400 0 100 200 300 400
Time (min) Time (min)

12 12
(c) (d)
10 10

8 8

TOC (mg L-1)

TOC (mg L-1)

6 6

4 4

2 2

0 0
0 100 200 300 400 500 0 100 200 300 400
Time (min) Time (min)

Fig. 5. Mineralization 2,4,5-T solution with: (a): EF-Pt, (b): EF-BDD, (c): AO-Pt, (d): AO-BDD as a function of current intensity. I ¼ (A):100 mA, (): 200 mA, (:): 300 mA, (C):
500 mA, (): 1000 mA.

3.2. Identification of aromatic and aliphatic intermediates

It is important to identify by-products formed during electrol- Table 3

Identification of aromatic intermediate compounds formed during the treatment of
ysis to understand the oxidative/mineralization mechanism of the
by EF process of 2,4,5-T by GCeMS analysis.
target pollutant with hydroxyl radicals. The aromatic intermediates
were identified by HPLC or GCeMS analyses while identification of Intermediate Molecular structure Molecular Retention
compounds weight (m/z) time (min)
aliphatic intermediates was carried out by ion-exclusion HPLC. The
formation and evolution of chloride ion released during minerali-
zation was followed using ion chromatography.
2,4,5-trichlorophenol 197.99 20.29

3.2.1. Identification of aromatic intermediates

In this part, a high concentration (0.5 mM) of catalyst and a low
current (50 mA) were used in order to promote the accumulation of 2,5-dichloro-1,
178.01 19.84
4-benzenediol
intermediate products. The chemical structures of five identified
intermediate products are shown in Table 3. The first intermediate,
2,4,5-trichlorophenol is a result of breaking phenoxy group (CeO
4,5-dichloro-1,
bond). Other intermediates are formed by dechlorination following 2-benzenediol
178.01 19.84
of ipso attack of
OH on chloro positions. These results are in
agreement with those of other researchers who studied degrada-
tion of this herbicide [11,14].

1,2,4-trichloro-
3.2.2. Formation and evolution of carboxylic acids 211.5 21.71
5-methoxybenzene
The subsequent oxidation of aromatic molecules by the hy-
droxyl radicals and their oxidation to quinone form lead to the
opening of the aromatic ring. Therefore, saturated and unsaturated
C1eC6 molecules carrying carboxyl functional groups, aldehyde,
ketone or alcohol are obtained. The aldehyde functional groups are
2,5-dichloro-
oxidized to alcohols which in turn converted to carboxylic acids. 192.02 21.30
4-methoxyphenol
Fig. 6 shows the formation and concentration-time profiles of
different short-chain acids during mineralization of 2,4,5-T. Malic,
glyoxylic, glycolic and oxalic acids are formed at the beginning of

Please cite this article in press as: Zazou H, et al., Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric
optimization and mineralization pathway, Sustainable Environment Research (2016), http://dx.doi.org/10.1016/j.serj.2016.11.008
 H. Zazou et al. / Sustainable Environment Research xxx (2016) 1e9 7

0.12 (a) 0.12 (b)

Concentration (mM)

Concentration (mM)
0.08 0.08

0.04 0.04

0 0
0 120 240 360 480 0 120 240 360 480
Time (min) Time (min)

Fig. 6. Evolution of the carboxylic acid concentrations during electrolysis of 2,4,5-T acid (C0 ¼ 0.1 mM) by electro-Fenton process at 300 mA with (a): Pt, (b): BDD anodes. (:):
oxalic, (◊): Glyoxylic, (D): glycolic and (C): malic acids. [Fe2þ] ¼ 0.1 mM, [Na2SO4] ¼ 50 mM.

electrolysis. They reach their maximum accumulation at
20e90 min and then undertake oxidation to smaller carboxylic acid
molecules or mineralization to CO2. Despite the high oxidizing
power of
OH, oxalic acid is present in the solution at low con-
centration at the end of treatment (360 min) even with BDD anode.
This behavior can be partially ascribed to the formation of the
Fe(III)-oxalate which is hardly mineralized by BDD(
OH). This
behavior is in agreement with previous reports [45,46].
3.2.3. Mineralization pathway of 2,4,5-T by hydroxyl radicals
Based on identification of aromatic intermediates, short-chain
carboxylic acids, Cle ion as well as TOC removal data, we propose
a plausible mineralization pathway (Fig. 7) for oxidation of 2,4,5-T
by
OH/M(
OH) produced during EF process. Mineralization pro-
cess begins by oxidation of the side chain conducting to the for-
mation of 1,2,4-trichloro-5 metoxybenzene (decarboxylation) or to
the 2,4,5-trichloropenolo (mineralization of the side-chain). These

Fig. 7. Proposed mineralization pathway of 2,4,5-T by hydroxyl radicals during EF process.

Please cite this article in press as: Zazou H, et al., Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric
optimization and mineralization pathway, Sustainable Environment Research (2016), http://dx.doi.org/10.1016/j.serj.2016.11.008
8 H. Zazou et al. / Sustainable Environment Research xxx (2016) 1e9

formed primary intermediates are further oxidized to poly-
hydroxylated intermediates that are not stables and undertake
oxidative ring opening reaction to form carboxylic acids. Mineral-
ization of these later to CO2 and water constitutes the last step of
the process.
3.2.4. Identification and evolution of chloride ion
2.4.5-T molecule has three chlorine atoms; therefore, the release
of Cl ion to the solution is expected during the mineralization
experiments. The evolution of this ion was followed during treat-
ment by ion chromatography and shown in Fig. 8. The release of
chloride ions is fast with both anodes. Dechlorination of the aro-
matics occurs before the ring opening reactions [47,48] as high-
lighted in Table 3. The concentration of chloride reaches almost to
the stoichiometric value (z99%) at about 60 min and then remains
almost constant. In contrast, the accumulation and evolution
behavior of chloride ion is quite different with BDD anode since its
concentration decreases beyond 30 min, due to its oxidation to
chlorine that then hydrolyses to HOCl, a moderately strong oxidant.
3.2.5. Toxicity assessment of 2,4,5-T solution during EF treatment
An aqueous solution of 2,4,5-T is treated by EF at 300 mA current
and pH 3 in 0.05 M Na2SO4 solution including 0.1 mM Fe2þ as
0.35
0.3
0.25
[Cl-] (mM)
catalyst. The evolution of the acute toxicity, determined by Micro-
tox® method from the inhibition of luminescence of V. fischeri
bacteria, after 5 min exposition, is shown in Fig. 9. The inhibition of
the luminescence is more than 96%, showing the high acute toxicity
of 2,4,5-T to the bacteria V. fischeri. The toxicity decreases during
treatment with Pt and BDD anodes, then begins to increase
(especially for EF-Pt cell) between 5 and 60 min on Pt anode indi-
cating the formation of toxic intermediates. Beyond 60 min, the
inhibition ratio continuously decreases to 3.6% for BDD anode and
17% for Pt anode, after 360 min of treatment. These results highlight
the higher mineralization power of BDD compared to Pt anode on
the one hand and the ability of the EF process to remove toxicity
due to the presence of persistent/toxic pollutants, on the other
hand. Similar results have been published for other organic pol-
lutants [24,34,49].
4. Conclusions
The following conclusions can be withdrawn from the present
study:
- EF process was shown to be more efficient than AO process in
the degradation of the herbicide 2,4,5-T and mineralization of its
aqueous solution.
- The absolute rate constant of oxidation of 2,4,5-T by hydroxyl
radicals was determined as (3.7 ± 0.2)  109 M1 s1 by using
competition kinetics method.
- EF process with BDD anode exhibited higher performance than
Pt anode.

- Almost complete mineralization (>96%) of 0.1 mM 2,4,5-T so-

0.2 lution was achieved using EF-BDD cell;
- EF process was shown with both BDD and Pt anodes to remove
0.15 completely the acute toxicity of the herbicide 2,4,5-T.

0.1
Acknowledgement
0.05
This work was done in the framework of the Moroccan-French
0 integrated action program VOLUBILIS (PHC No. MA/11/250) and
0 60 120 180 240 300 under the MESRSFC/SCAC program. The authors are grateful for
their financial support.
Time (min)
Fig. 8. Formation and evolution of Cl ions during electrolysis of 2,4,5-T (C0 ¼ 0.1 mM) References
at 300 mA with EF-Pt (A) and EF-BDD (:). [Fe2þ] ¼ 0.1 mM, [Na2SO4] ¼ 50 mM.
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