Open Journal of Applied Sciences, 2012, 2, 78-85
doi:10.4236/ojapps.2012.22010 Published Online June 2012 (http://www.SciRP.org/journal/ojapps)
Electrochemical Degradation of Chlorsulfuron Herbicide
fr om Water Solution Using T i/IrO2-Pt Anode
Xu Guo1,2, Yingnan Yang1, Chuanping Feng2, Miao Li2, Rongzhi Chen1, Jinglu Li1, Zhenya Zhang1*
1Graduate School of Life and Environmental Science, University of Tsukuba, Tsukuba, Japan
2School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, China
Received March 27, 2012; revised April 26, 2012; accepted May 10, 2012
ABSTRACT
Chlorsulfuron (ChS) which is a nonbiodegradable herbicide was effectively removed using an electrochemical method
at the Ti/IrO2-Pt anode. The influences of current density, initial ChS concentration, initial solution pH and different
NaCl dosages on electrochemical degradation of ChS were investigated. HOCl formed during electrolysis and quickly
generated •OH radicals would likely play an important role in the electrochemical degradation of ChS with the presence
of NaCl. At current density of 20 mA·cm–2, ChS concentration decreased from 1 mg·L–1 to 0 mg·L–1 after 10 min elec-
trolysis with 0.2 g·L–1 NaCl dosage. It was found that the ChS removal rate increased with increasing current density
and the ChS degradation was similar at different initial pH values, which means that Ti/IrO2-Pt anode can be used in a
wide pH range. The electrochemical performance of Ti/IrO2-Pt anode for degradation of ChS will not decrease after
serviced for a long time. These results reveal that an electrochemical approach would be a novel treatment method for
effective and rapid degradation of ChS herbicide from aqueous solution.
Keywords: Electrochemical Degradation; Chlorsulfuron; Herbicide; Sodium Chloride
1. Introduction
Increased concerns about the herbicides in water have
arisen because of the danger they pose to aquatic life and
to any kind of life in contact with the polluted water.
These compounds are mostly recalcitrant (nonbiode-
gradable) and can persist for long periods of time [1].
Sulfonylurea herbicides were developed in the1970s, and
first commercialized for wheat and barley crops in1982.
Their broad spectrum of action with a low application
dose has led to a rapid acceptance of these compounds.
However, their high phytotoxicity and relatively high
solubility make them potential contaminants of ground-
waters [2,3]. Furthermore, sulfonylurea compounds which
are used as herbicides for agriculture undergo decompo-
sition into, among others, simpler sulfonamides. Sulfona-
mides are polar, amphoteric substances that are readily-
soluble in water. For this reason, they possess high mi-
grationability in the environment [4]. Chlorsulfuron (ChS)
whose chemical structure is shown in Figure 1, is a sys-
temic sulfonylurea herbicide for the selective pre- and
post-emergence control of broad-leaved and grass weeds
in cereal crops.
Technologies able to convert ChS to non-toxic com-
pounds are desirable, because contamination of ground-
water and drinking water could not be excluded. Urgent
needs exist also for detoxification procedures of herbi-
cide wastes [5]. Previous research showed that conven-
tional process cannot effectively decrease the sulfony-
lurea herbicides in the water, such as nature photolysis,
sorption and hydrolytic degradation [6-9]. Some re-
searchers focus on the photocatalytic degradation of
various pesticides herbicides especially the sulfonylurea
herbicides using the TiO2 photocatalyst [3-5,10-14]. It
has been proved that photocatalytic method is a good
method for removal persistent and nonbiodegradable
contaminants in the water. However, only photons with
energies greater than the band-gap energy (ΔE) can result
in the excitation of valence band (VB) electrons which
then promote the possible reactions with organic pollut-
ants [14], which means that it is difficult for efficient
degradation of the compounds under the visible light.
Moreover, the recombination of photo-generated electron
Figure 1. Structural formulae of Chlorsulfuro n (ChS).
*Corresponding author.

X. GUO ET AL. 79
and hole pairs is rapid without adding an oxidizing agent
such as oxygen, which will decrease the photocatalytic
reactivity. On the other hand, it is difficult for semicon-
ductor photocatalyst powder to disperse and be recycled
in aqueous solution, and the post-treatment recovery of
the photocatalysts can be costly [15,16].
Electrochemistry is a promising method for the water
and wastewater treatment and has received considerable
attention recently. Electrochemical method applied in
water treatment has been investigated by many research-
ers [17-23]. Toxic organics can be effectively oxidized
by the electrochemical method [1,18,21,24-29], demon-
strating that this approach may be feasible for sulfony-
lurea herbicides. Because of the simply in structure and
operation, it is possible that the electrochemical method
can be developed as a cost-effective technology for the
treatment of aromatic pollutants [24]. The efficiency and
selectivity of electrochemical oxidation of organic com-
pounds are mainly effected by the nature of the elec-
trodes that are used in the process [25,26]. Martínez et al.
[1] have demonstrated that the removal of chlorbromuron
urea herbicide achieved by the processes of electro-Fen-
ton with a stainless steel anode is regarded as high degree
of mineralization by the Fenton chemistry. However,
ferricirons are required to be in the solution for the elec-
tro-Fenton reaction, and it is too sensitive to pH. Dimen-
sionally stable anode (DSA), made by the deposition of a
thin layer of metal oxides on a base metal, usually tita-
nium, have been proved to be effective in organic degra-
dation [18,24-26,29]. Nowadays, IrO2-based type DSA
has been proved to maintain good catalytic activity and
dimensional stability for oxygen evolution reaction (OER)
[21,30-32], and has excellent performance for degrada-
tion of organic compounds [24,25]. Electrode of Ti
coated with IrO2 and doped with Pt (Ti/IrO2-Pt), as one
of the practical anodes, has been widely used as anode in
electrochemical treatment of contaminated water, which
has good performance for degradation of organic com-
pounds and long service life [24,25].
To our best knowledge, there is little information
about the electrochemical degradation of ChS herbicide
using Ti/IrO2-Pt anode in previous studies [1,3,5,12]. The
main aim of this study is to evaluate the electrochemical
degradation of ChS herbicide using Ti/IrO2-Pt anode. In
order to investigate the ChSdegradation effect and related
reaction mechanisms, current density, initial ChS con-
centration, initial pH value of the solution, NaCl dosage,
free radicals and oxidizing substance were measured, and
the role of hypochlorous acid formed during electrolysis
was also analyzed.
2. Materials and Methods
2.1. Materials
All chemicals were used as received without further pu-
rification. Chlorsulfuron (ChS) standard material (99.0%)
used in this study was purchased from WAKO Pure
Chemicals Ltd. Japan. 10 mg of ChS was dissolved in 10
mL of methanol (HPLC grade, WAKO Pure Chemicals
Ltd. Japan) to be the stock solution, and stored in the
dark at 4˚C prior to use. They were diluted with Milli-Q
water (resistivity 18.2 MΩ cm at 25˚C) prepared with a
water purification system (Purelite PRB-001A/002A) to
the desired concentration required for each experiment
and or analysis.
A simple cubic electrochemical cell was designed with
a working volume of 100 mL. A DC potentiostat (GW
INSTEK, GPS-183000) with a voltage range of 0 - 18 V
and a current range of 0 - 3 A was employed as power
supply. A Ti/IrO2-Pt electrode (TohoTech Company, Ja-
pan) of 51.6 cm2 (4.3 × 12 cm2) was used as the anode
and a Ti electrode with the same area was used as the
cathode, and a distance of 1 cm between the two elec-
trodes was set. The immersed areas of the anode and
cathode in the treated solution were the same at 25 cm2.
2.2. Methods
In the present study, all of the electrolysis experiments
were performed under galvanostatic control at different
current densities of 10, 20, 40 and 60 mA·cm–2, respec-
tively. ChS solution with different initial concentration of
0.5, 1.0, 2.0 and 5.0 mg·L–1 were prepared for electroly-
sis experiments. In all of the electrolysis processes, 1.5
g·L–1 Na2SO4 was added into the solution in order to en-
hance the conductivity of the solution. Different initial
pH (3, 7, 11) of ChS solution was also investigated.
Various concentration of sodium chloride (0.1, 0.2, 0.5
g·L–1) was added into the ChS solution to investigate the
degradation performance, respectively. A 100 mL of syn-
thetic ChS solution with different initial concentration
prepared with the stock solution and distilled water was
transferred into the electrochemical cell, and then the
electrolysis began with different current density. Samples
were taken from the electrochemical cell with different
interval (15, 30, 60, 90, 120 min) for analysis.
2.3. Detection of Free Radicals Species
To investigate the production of free radicals species and
oxidizing substance generated during the electrolysis,
0.005 mmol·L–1 sulforhodamine B (SRB) was used for
the electrolysis. Because the SRB rapidly reacts with the
hydroxyl radicals, and the changes in absorbance, ΔA,
corresponding to color intensity change of SRB can be
measured at λ 565 nm, so the amount of free radicals and
oxidizing substance produced can be determined indi-
rectly [33]. Samples were taken at intervals of 1, 2, 5 min
and absorbance of SRB was measured by UV-vis spec-
trophotometer (UV-1600, Shimadzu).

X. GUO ET AL.
80
To confirm the free radicals species generated during
the electrolysis, a photoluminescence (PL) technique was
applied. Terephthalic acid as a probe molecule easily
reacts with •OH to form highly fluorescent product, 2-
hydroxyterephthalicacid. This techniquehas been widely
used in radiation chemistry, biochemistry, andsonoche-
mistry for the detection of •OH generated in water [34].
The intensity of the PL peak of 2-hydroxyterephtalic acid
is inproportion to the amount of •OH radicals produced
in water. The optimal concentration of terephthalic acid
solution was about 5 × 10–4 mol·L–1 in a diluted NaOH
aqueous solution (2 × 10–3 mol·L–1) for the electrolysis.
PL spectra of the generated 2-hydroxyterephthalic acid
were measured on a fluorescence spectrophotometer (F-
4500, Hitachi) at 425 nm excited by 315 nm light of 2-
hydroxyterephthalic acid.
2.4. Analysis
The concentrations of ChS were determined by means of
HPLC (Jusco, Japan) with an auto sampler model. The
column was 5 C18-AR-II, 4.6 × 150 mm. The flow rate
was 1.0 mL·min–1 and the injection volume was 50.0 μL.
The mobile phase was the mixture of methanol and water
(1:1), whose pH was adjusted to 2.80 by using H3PO4.
The solution pH was measured by pH/iron meter (Met-
tler-Toledo AG 8603, Schwerzenbach, Switzerland). Sur-
face morphology of anode was characterized by scanning
electron microscope (SEM) (JSM-5600).
3. Results and Discussion
3.1. Effect of Current Density
At different current density of 10, 20, 40 and 60 mA·cm–2,
ChS concentration decreased from 1.00 mg·L–1 to 0.32,
0.19, 0.02 and 0.00 mg·L–1, respectively after 120 min
electrolysis (Figure 2(a)). The mechanism of ChS deg-
radation at different current densities was demonstrated
to be pseudo-first-order. The data showed that the rate of
degradation of ChS increased with the increasing of cur-
rent density. The rate constants are 0.0092 min–1 (R2 =
0.953) at 10 mA·cm–2, 0.0137 min–1 (R2 = 0.998) at 20
mA· c m–2, 0.0342 min–1 (R2 = 0.976) at 40 mA·cm–2 and
0.0424 min–1 (R2 = 0.950) at 60 mA·cm–2, respectively
(Figure 2(b)). High current density is benefit for the
electrochemical degradation of ChS, and complete ChS
removal was achieved after 90 min electrolysis at current
density of 60 mA·cm–2. As a higher current density en-
hances hydroxyl production, more ChS is likely to be
oxidized. However, increasing the current density is an
easy approach of improving the degradation reaction that
is usually accompanied by a decrease in both the current
efficiency and selectivity [35].
(a)
(b)
Figure 2. (a) Performance of ChS degradation with different
current densities; (b) Pseudo-first-oder kinetic plot using (a)
data.
3.2. Influences of Initial ChS Concentration
The expected concentration of ChS in drinking water was
less than 0.04 mg·L–1 [36]. However, the concentration of
ChS could be greater than 1.5 mg·L–1 for the short-term
or chronic exposure. In order to investigate the treatment
efficiency on different initial concentrations of ChS, the
electrochemical degradation of 0.50, 1.00, 2.00 and 5.00
mg· L –1 ChS solution were carried out at a current density
of 20 mA·cm–2. It is obvious from Figure 3(a) that at a
current density of 20 mA·cm–2 with 1.5 g·L–1 Na2SO4 as
supporting electrolyte, the ChS concentration decreased
from around 0.50, 1.00, 2.00 and 5.00 mg·L–1 to 0.06,
0.19, 0.31 and 1.01 mg·L–1 after 120 min electrolysis.
And with 1 kWh of the electricity power consumption,
about 73.3 mg, 135.0 mg, 281.7 mg, and 665.0 mg ChS
can be removed, respectively. The removal rate was rela-
tively high at high ChS concentration. Therefore, the Ti/
IrO2-Pt anode performed well for electrochemical de-
gradation of low and high concentration ChS solutions
with appropriate current density.
3.3. Effect of Initial pH
Three different initial pH values (3, 7 and 11) of ChS
solution were set to investigate the effect on ChS elec-
trochemical removal. As shown in Figure 3(b), the simi-
lar trend of the ChS degradation was observed at the

X. GUO ET AL. 81
current density of 20 mA·cm–2 with 1.5 g·L–1 Na2SO4 as
supporting electrolyte. ChS concentration decreased from
around 1.00 mg·L–1 to about 0.20 mg·L–1 after 120 min
electrolysis, which revealed almost the same degradation
efficiency. It means that the electrochemical degradation
of ChS could be used in a large range of pH, and pH is
not a limiting factor. As we know, some organic material
degradation methods are sensitive to pH in the solution.
Martínez et al. [1] used a stainless steel anode for re-
moval chlorbromuron urea herbicide by electro-Fenton
method. However, for the removal of the organic sub-
strate depends on the pH of the aqueous solution as the
pH influences the production of H2O2 and Fe2+, the pH of
the solution have to be lower than 5. Therefore, the elec-
trochemical degradation method at Ti/IrO2-Pt anode gives
us another approach for the degradation of ChS solution
with a wide pH range.
3.4. Effect of NaCl Dosages
The degradation efficiency of some organic materials
was significantly enhanced with the presence of NaCl in
some researchers [2,15,26]. In the present experiment,
three different NaCl dosages of 0.1, 0.2 and 0.5 g·L–1
were added into the ChS solution for ChS electrochemi-
cal degradation. Meanwhile, 1.5 g·L–1 Na2SO4 was used
as supporting electrolyte. As shown in the Figure 4(a),
(a)
(b)
Figure 3. (a) Effect of initial concentration on the degradation
efficiency; (b) Effect of initial pH on the removal of ChS.
(a)
(b)
Figure 4. (a) Performance of ChS degradation with different
NaCl dosages; (b) Pseudo-first-oder kinetic plot using data
from (a).
ChS concentration decreased sharply with the presence
of NaCl, from around 1 mg·L–1 to 0.01, 0.00, 0.00 mg·L–1
with the presence of NaCl dosages of 0.1, 0.2, 0.5 g·L–1,
respectively, at a current density of 20 mA·cm–2 at the
beginning 10 min electrolysis. However, the degradation
of ChS was much slower without NaCl addition. It was
suggested that NaCl, which could be oxidized to form a
strong oxidant of HOCl, could promote the degradation
of ChS. The possible process was listed below [2]:
1) Anode reaction:
2
2ClCl 2e


 (1)
2
HOOH H2e

C

(2)
2) Hydrolysis reaction:
22
ClHOHOClHe


 (3)
3) Degradation reaction:
HOCl RRO HCl

  (4)
2
OHRROH O  (5)
Furthermore, with the presence of NaCl, the ChS con-
centration decreased rapidly. After the beginning 10 min
electrolysis, ChS was almost completely removed, which
proved that the Equations (4), (5) were rapid. It was a
little different from study of Li et al. [25], who found that

X. GUO ET AL.
82
with the presence of 0.1 g·L–1 NaCl, at the initial 5 min,
the phenol concentration almost did not decrease. The
reason could be that in his study, the concentration of
treated materials was 8 mg·L–1, which was much higher
than the present experiment. And HOCl could not be
enough produced with lower NaCl at the beginning,
consequently, the phenol concentration did not decrease
obviously at the initial 5 min, and then was degraded
sharply. The electrochemical degradation of ChS at dif-
ferent NaCl dosages occurred via a pseudo-first-order
mechanism (Figure 4 (b)), with rate constants of 0.0137
min–1 (R2 = 0.999) without adding NaCl, 0.4742 min–1
(R2 = 0.975) at 0.1 g·L–1 NaCl, 0.5710 min–1 (R2 = 0.999)
at 0.2 g·L–1 NaCl, 0.5404 min–1 (R2 = 0.999) at 0.5 g·L–1
NaCl. It was revealed that NaCl existence is a signifi-
cant factor for efficient removal of ChS.
To investigate the generation of free radicals species
and oxidizing substance generated during the electrolysis,
0.005 mmol·L–1 sulforhodamine B (SRB) solution was
used for the electrolysis. It was clear from Figure 5 that
the absorbance of SRB solution sharply decreased in the
initial 10 min at 20 mA·cm–2 with 0.2 g·L–1 NaCl dosage,
and discoloration rate was up to 98.6%. However, no
obvious discoloration was observed without NaCl dosage,
indicating that formation of hypochlorous acid was an
important bleaching factor during the electrolysis. Com-
ninellis [6] and Xue [24] got the similar results using
RNO as the material. Comninellis [6] suggested that hy-
droxylradicals reacted selectively with RNO, but hy-
pochlorous acid played a very important role in the RNO
bleaching from the present study, which would enhance
the ChS degradation. To confirm that the NaCl dosage
promoted the formation of hydroxyl radical, the PL
emission spectra excited at 315 nm from terephthalic
acid solution were measured under the 0.2 g·L–1 NaCl
and no NaCl dosage at 20 mA·cm–2. Figure 6 shows the
PL spectra from 5 × 10–4 mol·L–1 terephthalic acid solu-
tion in 2 ×10–3 mol·L–1 NaOH after 1 min electrolysis
under the NaCl dosage and after 20 min electrolysis un-
der no NaCl addition. It can be seen that an obvious peak
was observed under the NaCl dosage only after 1 min
electrolysis, however, under no NaCl addition only an in-
conspicuous peak was observed after 20 min electrolysis
at about 425 nm. This suggests that the fluorescence is
caused by chemical reactions of terephthalic acid with
•OH formed during the electrolysis. Consequently, it can
be inferred that the hypochlorous acid which was gener-
ated in the solution can promote the formation of hy-
droxyl radicals, which was beneficial to degradation of
ChS. Therefore, NaCl existence is a significant factor for
efficient removal of ChS.
3.5. Electrode Surface
As shown in Figure 7, the surface of the Ti/IrO2-Pt an-
ode remains unchanged after more than 50 h electro-
chemical degradation of ChS. Furthermore, no formation
of polymeric film was observed, implying that the elec-
trochemical degradation efficiency of Ti/IrO2-Pt anode
did not decrease after repeated use under the same ex-
perimental condition (data not shown). Therefore, Ti/
IrO2-Pt anode has good performance for degradation of
ChS and long service life, which demonstrates that it was
suitable for ChS removal.
4. Conclusions
The electrochemical method is a novel approach for ef-
fective removal of ChS. In the present research, the ef-
fluence of current density, initial ChS concentration, ini-
tial solution pH and different NaCl dosage on the per-
formance of electrochemical degradation of ChS were
investigated using aTi/IrO2-Pt anode. The electrochemi-
cal method is a novel approach for effective removal of
ChS. In the present research, the effluence of current
density, initial ChS concentration, initial solution pH and
different NaCl dosage on the performance of electro-
chemical degradation of ChS were investigated using
aTi/IrO2-Pt anode.
Figure 5. Electrochemical bleaching of 0.005 mmol/L SRB
solution at 20 mA·cm–2.
Figure 6. Effect of NaCl dosages on PL spectral.

X. GUO ET AL. 83
(a)
(b)
Figure 7. SEM photograph of (a) unused (b) more than 50 h
used for electrolysis Ti/IrO2-Pt anod e.
It was found that the ChS removal rate increased with
increasing current density and the ChS degradation was
similar at different initial pH values, which means that
Ti/IrO2-Pt anode can be used with a wide pH range.
HOCl quickly formed during electrolysis would likely
play an important role in the electrochemical degradation
of ChS with the presence of NaCl. At 20 mA·cm–2 ChS
con- centration decreased from 1 mg/L to 0 mg·L–1 after
10 min electrolysis with 0.2 g·L–1 NaCl dosage. The
electrochemical performance of Ti/IrO2-Pt anode for
degradation of ChS will not decrease after serviced for
long time.
5. Acknowledgements
This work was supported in part by Grant-in-Aid for Re-
search Activity Start-up 22880007 and Scientific Re-
search (A) 22248075 from Japan Society for the Promo-
tion of Science (JSPS).
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