Journal of Hazardous Materials 171 (2009) 10811087

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Journal of Hazardous Materials

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Photocatalytic degradation of diuron in aqueous solution by platinized TiO2

Hideyuki Katsumata a, , Maki Sada a , Yusuke Nakaoka a , Satoshi Kaneco a , Tohru Suzuki b ,
Kiyohisa Ohta a
a
b

Department of Chemistry for Materials, Graduate School of Engineering, Mie University, Tsu, Mie 514-8507, Japan
Environmental Preservation Center, Mie University, Tsu, Mie 514-8507, Japan

a r t i c l e

i n f o

Article history:
Received 30 April 2009
Received in revised form 8 June 2009
Accepted 20 June 2009
Available online 27 June 2009
Keywords:
Diuron
Photocatalyst
Titanium dioxide
Platinum
Mineralization

a b s t r a c t
The photocatalytic degradation of diuron, which is one of phenylurea herbicides, was carried out in the
presence of platinized TiO2 photocatalyst. Platinization was found to increase the rate of diuron degradation. When 0.2 wt.% of platinum was deposited onto the surface of TiO2 , an initial diuron concentration
of 10 mg L1 was completely degraded after 20 min. Furthermore, the rst-order rate constant for diuron
degradation by PtTiO2 was ca. 4 times higher than P-25 TiO2 . In addition, the photocatalytic activity of
PtTiO2 was appeared under visible light. The decrease of TOC as a result of mineralization of diuron was
observed during the photocatalytic process. The degree of diuron mineralization was about 97% under
UV irradiation after 8 h. The formations of chloride, nitrate and ammonium ions as end-products were
observed during the photocatalytic system. The decomposition of diuron gave four kinds of intermediate products. The degradation mechanism of diuron was proposed on the base of the evidence of the
identied intermediates. Based on these results, the photocatalytic reaction by PtTiO2 could be useful
technology for the treatment of wastewater containing diuron.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Pollution of soils and aquatic systems by chemicals used
in agriculture is one of the main present environmental problems. Diuron (N -(3,4-dichlorophenyl)-N,N-dimethylurea), one of
the most commonly used herbicides, belongs to the family of
halogenophenylureas that represents an important class of contact
herbicides applied in pre- and post-emergence to control broadleaf
weeds in a wide variety of annual and perennial broadleaf and grass
weeds [1,2]. Diuron is considered as highly toxic and persistent
when applied in high dosages to the soil with a half-life of over 300
days [3]. As a result, it is often detected in groundwater and surface
water [4,5]. Recent studies indicated the role of urban and agricultural runoff in diuron transport to the environment. Revitt et al. [6]
detected concentrations of this compound as high as 238.4 mg L1
in urban runoff after a storm event. Determination of herbicides in
highway runoff showed diuron concentration up to 10.78 mg L1
[7,8].
Diuron has been listed as a priority substance in the Water
Framework Directive. Most commercial preparations containing
diuron are classied in the category of harmful chemicals, and they
are generally considered as dangerous for aquatic life and ora (for
instance, LC50 = 5.6 mg L1 in the case of trout) as well as for human

Corresponding author. Tel.: +81 59 231 9425; fax: +81 59 231 9425.
E-mail address: hidek@chem.mie-u.ac.jp (H. Katsumata).
0304-3894/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.06.110

being, for which the risk of provoking congenital malformations

has been reported [9]. In addition, diuron is suspected to be a carcinogenic and genotoxic compound [10]. Recent studies have also
shown that it is toxic to photosynthetic organisms at concentrations levels of a few mg L1 [11,12]. Therefore, the rapid and simple
wastewater treatment of diuron is now required urgently.
Indeed, several researchers have developed an intensive effort of
research on the chemical [13], physicochemical [14], photochemical [3,15], heterogeneous photocatalytic [3,1618], electrochemical
[19] and microbiological [20] degradation methods of diuron,
and the diuron transformation products. Especially, photocatalytic
method (TiO2 ) is highly promising because it can operate at ambient temperature and pressure with low energy photons, and does
not require expensive catalyst. However, its wide band-gap energy
(3.0 eV for rutile and 3.2 eV for anatase) means that only 5% of solar
spectrum can be used. Moreover, TiO2 presents a relatively high
electronhole recombination rate, which is detrimental to its photocatalytic activity. In order to solve these problems, one of the
approaches is that noble metals are doped onto TiO2 surface. Many
investigators have demonstrated that the photocatalytic activity
may be enhanced by impregnating the surface of titanium dioxide
with noble metals [2124].
In the present study, we have investigated the degradation
and mineralization of diuron in water using of platinized TiO2 .
Pt doping concentration affected on the photocatalytic degradation was evaluated. The progress of mineralization of diuron was
monitored by total organic carbon (TOC) content and ionic chro-

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H. Katsumata et al. / Journal of Hazardous Materials 171 (2009) 10811087

matography. Furthermore, the intermediate products of diuron

during this photocatalytic process have been identied by gas
chromatographymass spectrometry (GC/MS). The degradation
pathway was proposed on the basis of intermediates formed.
2. Experimental
2.1. Reagents
Diuron was supplied by Wako Pure Chemical Industries (Osaka,
Japan) and was used as received. TiO2 powder from Degussa (P-25)
was used throughout the experiments. Dihydrogen hexachloroplatinate hexahydrate (Wako Pure Chemical Industries, Osaka,
Japan) was used as the platinum precursor. All other chemicals
and solvents were of the purest grade commercially available and
were used without further purication. All aqueous solutions were
prepared with ultrapure water obtained from an ultrapure water
system (Advantec MFS Inc., Tokyo, Japan) resulting in a resistivity
of >18 M cm.
2.2. Preparation of PtTiO2
Platinized TiO2 catalysts were prepared by impregnation
method. The required amount of dihydrogen hexachloroplatinate
(VI) hexahydrate solution for doping was added to the calculated
amount of TiO2 (P-25) in such a way that they wet the catalyst completely. The slurry was stirred for 1 h at 90 C in the presence of
H2 PO3 and dried overnight in an air oven at 110 C. The dried powder was subjected to calcination in air atmosphere at 700 C for 5 h
and then cooled to room temperature.
2.3. Photocatalytic degradation procedure
Photocatalytic experiments were conducted in a 50 mL Pyrex
glass cell. 30 mL of diuron solution and 25 mg of platinized TiO2
catalysts were added into the reaction cell. The pH of the sample solution was adjusted with HCl and/or NaOH solution. The
initial concentration of diuron in all experiments was 10 mg L1
(4.3 105 mol L1 ). Reaction temperature was kept at 25 1 C
with a water bath. In all the studies, diuron solution containing the
appropriate quantity of the photocatalyst powder was magnetically
stirred before and during irradiation. Before irradiation, photocatalyst suspension containing diuron was allowed to equilibrate for
60 min in the dark. As a result, the adsorption of diuron onto PtTiO2
surface was negligible (<0.2% adsorption). The sample solution was
irradiated with a Xe lamp (990W, Ushio Electronics Co.). The beam
was parallel and the distance between lamp and the reactor wall
was 10 cm. The lamp was warmed up for 10 min to reach constant
output. In this case, the short UV radiation ( < 300 nm) was ltered
out by the vessel wall. The intensity of the light was measured by
a UV radiometer (UVR-400, Iuchi Co.) with a sensor of 320410 nm
wavelength. The radiometer was set up at the same position as the
reactor.
2.4. Analyses
After irradiation, PtTiO2 was separated through the 0.45-m
Advantec membrane lter. Diuron was not adsorbed onto the surface of the membrane lter. The progress in the degradation of
diuron was followed with a HPLC (GL Science Co., Tokyo, Japan)
equipped with a GL-7450 UV detector (GL Science Co.) and a Inertsil ODS-3 separation column (150 mm 4.6 mm i.d., GL Science Co.).
The elution was monitored at 250 nm. The mobile phase was a mixture of acetonitrile and water (50/50, v/v), and was pumped at a ow
rate of 1.0 mL min1 .

The progress of mineralization of diuron was monitored by measuring the TOC. TOC of the sample solution was measured with a
Shimadzu TOC analyzer (TOC-VE ) based on CO2 quantication by
non-dispersive infrared analysis after high-temperature catalytic
combustion. The formations of anions and cations were analyzed by
ionic chromatography using a Metrohm Compact IC 7611 equipped
with a Shodex anionic (IC SI-90 4E) and a Shodex cationic (IC YK421) columns, respectively.
The hydroxyl radical concentration was estimated using a
deoxyribose method [25]. Deoxyribose (5 mM) was reacted with
OH radicals generating by this photocatalytic system. Total reaction volume was 30 mL. The reaction was stopped by addition of
5 mL thiobarbituric acid (1% w/v in 50 mM NaOH) and 5 mL of
trichloroacetic acid (2.8% w/v). The mixture was heated at 80 C
for 30 min. The product of the reaction was quantied at 532 nm
using an UV-1650 double-beam spectrometer (Shimadzu Co., Kyoto,
Japan). The concentration of OH radicals was equated with thiobarbituric acid active substances using an extinction coefcient,
532 nm , of 153 mM1 cm1 .
XRD were collected using a RINT 2000/PC X-ray diffractometer
(Rigaku Co.), with a diffraction angle range 2 = 2080 using Cu K
radiation. The mass fraction of rutile (XR ) in the calcined samples
was calculated by Spurr formula (Eq. (1)) which is the relationship
between integrated intensities of anatase (1 0 1) and rutile (1 1 0)
peaks where IA and IR are the integrated peak intensities of anatase
and rutile peaks, respectively
XR =

1
1 + 0.8(IA /IR )

(1)

Particle size was determined by the Scherrer equation which calculates crystalline size using the expression (0.9/( cos )), where
 is the X-ray wavelength,  is the Bragg angle and is the line
broadening.
The intermediate products during photodegradation of diuron
were extracted by the solid phase extraction (C18 disk, 3M Empore).
Dichloromethane was used to elute the intermediate products. This
solution was concentrated under nitrogen ow for the analysis of
the by-products. A GC/MS (Shimadzu GCMS 5050A) was used for
separation and detection of the intermediate products. The GC was
equipped with a HP-5 capillary column (30 m 0.25 mm i.d.) in
helium carrier gas (1.5 mL min1 ) and with splitless injection system. The GC oven temperature was programmed to hold 50 C for
initial 3 min, to increase from 50 to 250 C at a rate of 5 C min1
and to hold at 250 C for 5 min. The injector and interface temperatures were kept at 250 and 280 C, respectively. Mass spectra were
obtained by the electron-impact (EI) mode at 70 eV using the full
scan mode.
3. Results and discussion
3.1. Effect of variables on the photocatalytic degradation of diuron
Effect of Pt doping concentration on the degradation of diuron
was examined in the range of 02.0 wt.%. The results are shown in
Fig. 1. The degradation percentage of diuron rapidly increased with
increasing Pt doping concentration up to 0.2 wt.%. Although TiO2
samples platinized over the range of 0.32.0 wt.% Pt enhanced the
photocatalytic activity for P-25 TiO2 , the degradation percentage
was lower than 0.2 wt.% Pt sample. It was therefore concluded that
the optimum platinum doping in this study for diuron degradation
was 0.2 wt.%.
The X-ray diffraction patterns of P-25 TiO2 and PtTiO2 are
shown in Fig. 2. The diffraction patterns of PtTiO2 samples almost
were in agreement with that of P-25 TiO2 showing no diffraction
peaks due to Pt suggesting that the Pt particles were well dispersed
on TiO2 surface. In addition, the crystal sizes of anatase and rutile

H. Katsumata et al. / Journal of Hazardous Materials 171 (2009) 10811087

1083

Table 1
Characteristics of TiO2 containing various platinum contents.
Platinum content (wt.%)

Anatase
Crystal size, D(101) (nm)

XA (%)

Crystal size, D(110) (nm)

XR (%)

[P-25]
0
0.2
0.3
2

22
24
23
22
21

84
83
83
83
83

34
34
32
34
32

16
17
17
17
17

Fig. 1. Effect of platinum doping concentration on the photocatalytic degradation of

diuron. (Catalyst dosage: 25 mg; pH: 6.5; light intensity: 2.0 mW cm2 ; irradiation
time: 5 min.)

phases calculated from the XRD patterns are presented in Table 1,

together with the mass fractions of anatase and rutile phases. As
can be seen from Fig. 2 and Table 1, there are no diffraction patterns
characteristics of the doped samples in the XRD patterns. Therefore,
these parameters of TiO2 were not changed by doping Pt.
On the other hand, the improved photocatalytic activity of TiO2
for the degradation of organic compounds in aqueous systems by
platinization has also been reported by other researchers [2631].
The observed increase in photocatalytic activity of TiO2 by platinization was attributed to the enhanced separation of electronhole

Fig. 2. XRD patterns of TiO2 containing various platinum contents. A: anatase; R:

rutile.

Rutile

pairs within TiO2 . When platinum species are deposited onto the
surface of TiO2 , a Schottky junction at the platinumTiO2 interface
is formed [32]. As a result, electrons are transferred from the conduction band of TiO2 to platinum and became trapped there. This
trapping mechanism slows down the recombination reaction of
electronhole pairs and allows a more efcient charge separation.
Consequently, the transfer of trapped electrons to dissolved oxygen
in the system become faster and more holes and hydroxyl radicals
are available for the oxidation of the target organic pollutants on the
catalyst surface as well as in the solution phase. Furthermore, the
presence of Ti3+ resulted from the deposited Pt on the TiO2 [33]. The
photodegradation of diuron might be enhanced with an increase of
Ti3+ vacancy sites on the TiO2 as a result of the deposition of Pt.
The presence of Ti3+ sites was reported to play an important role on
the photocatalysis with TiO2 [34,35]. The defect sites on the TiO2
surface are necessary for the photodegradation of pollutants. Sakthivel et al. [36] concluded that these defect sites were identied as
Ti3+ and were necessary for adsorption and photoactivation of oxygen. However, the lower photocatalytic activity for the degradation
was observed over the range of 0.32.0 wt.% Pt in this study. The Ti3+
vacancy sites of TiO2 would be covered because it is metalized by the
presence of excessive platinum. Similar results were also observed
by other researchers [33,35]. It has been evidenced that Ti3+ sites
covered with metal particles are detrimental to the degradation of
acid green 16 [36]. Sun et al. [37] have studied the degradation of
methylene blue with Au deposited TiO2 catalyst. Because excessive
Au dispersion on surface of TiO2 would be a recombination center,
the degradation of methylene blue has not any promotion.
Effect of irradiation time was investigated on the photocatalytic
degradation of diuron. The adsorption of diuron onto PtTiO2 was
negligible as described above. The results are shown in Fig. 3. The

Fig. 3. Effect of irradiation time on the photocatalytic degradation of diuron. Insert

gure: plot of Ln(C/C0 ) versus irradiation time. : PtTiO2 ; : TiO2 (P-25). (Catalyst
dosage: 25 mg; pH: 6.5; light intensity: 2.0 mW cm2 .)

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H. Katsumata et al. / Journal of Hazardous Materials 171 (2009) 10811087

Fig. 4. Concentration of OH radical during the photocatalytic processes. (Catalyst

dosage: 25 mg; [2-Deoxy-d-ribose]0 : 5 mM; light intensity: 2.0 mW cm2 .)

Fig. 5. Degradation of diuron by the photocatalysts under visible light irradiation.

(Catalyst dosage: 25 mg; [Diuron]0 : 5 mg L1 ; pH: 6.5.)

3.2. Mineralization
absence of diuron from the solution was reached within 20 min. The
primary degradation reaction is estimated to follow a pseudo rstorder kinetic law. In order to conrm the speculation, Ln(C/C0 )
was plotted as a function of irradiation time (the inset gure in
Fig. 3). Since the linear plots were observed in the insert gure as
expected, the kinetics of diuron in the PtTiO2 suspension solution
followed the rst-order degradation curve. When compared to the
photocatalytic activity of P-25 TiO2 , the pseudo rst-order rate constant in PtTiO2 photocatalytic process (0.426 min1 ) was about 4
times for P-25 (0.111 min1 , data not shown).
The photocatalytic system produced OH radical during the reaction. The radical is a strong oxidizing agent that reacts with diuron
and causes its degradation. In the case of P-25 TiO2 , the concentration of OH radical in the reaction mixture increased with increasing
up to 1 h, and then it reached a relatively stable value that lasted at
least 5 h (Fig. 4). On the other hand, the radical concentration produced by PtTiO2 increased with increasing reaction time. The OH
radical was thus produced during the whole reaction time (5 h),
which was conrmed by prolonged incubation with deoxyribose.
Accordingly, a continuous formation of OH radical is observed
allowing the complete mineralization of diuron.
The photocatalytic activity of diuron over both PtTiO2 and P25 TiO2 samples was evaluated under visible light irradiation. For
visible light irradiation, Xe lamp with a UV cut-off lter (<400 nm)
was used as a visible light source. Initial concentration of diuron was
5 mg L1 . These results are shown in Fig. 5. The photocatalytic activity of 0.2 wt.% PtTiO2 was higher than that of P-25 TiO2 both under
visible light and UV as can be seen in Figs. 3 and 5. The degradation
percentage of diuron by PtTiO2 was ca. 80% after 120 min, while
that was only ca. 20% in the case of P-25 TiO2 . These results indicate that PtTiO2 is potentially employable for photodegradation
processes under UV and visible light. It was reported that the optical absorption enhanced signicantly in the region of 360480 nm,
owing to the presence of Pt in comparison to pure TiO2 , that is,
Pt deposited on the surface of TiO2 can absorb visible light [35].
The enhancement of visible optical absorption was due to the presence of Pt, Pt(OH)2 and PtO2 [38]. This observation could be also
explained by two possible reasons: the presence of Ti3+ resulted
from the platinum deposited on the TiO2 surface, and the formation of Schottky barrier between platinum and TiO2 preventing the
recombination of electric holes and electrons [35].

When the total mineralization of diuron proceeds stoichiometrically using oxygen as oxidizing agent, the mineralization reaction
can be estimated as follows:
C9 H10 Cl2 N2 O + 13O2 2HCl + 2HNO3 + 9CO2 + 3H2 O

(2)

It should be remarked that nitrogen released has been measured

as a combination of ammonia and nitrate, but ammonia can be
oxidized to nitrate after long irradiation time [39,40].
The formation of chloride ion from diuron degradation was
investigated. The concentration of chloride ion quickly increased
with increasing the reaction time, suggesting a very fast degradation/dechlorination stage (Fig. 6a). The total amount of chloride
ion produced after 60 min of irradiation time was approximately
8.2 105 mol L1 (95% conversion of the diuron chloride content). Therefore, the quantity of chloride ion released from diuron
mineralization was lower than that expected from stoichiometry
indicating that chloride remained adsorbed onto the photocatalyst
surface [41].
The formations of ammonium and nitrate ions during the photocatalytic process as a function of reaction time are presented in
Fig. 6b. The nitrogen content of diuron was converted to ammonium
and nitrate ions during photocatalytic process, which has already
been described by other authors [42]. This information suggested
that this photocatalytic degradation of diuron would also yield
these ions as breakdown products. Both ammonium and nitrate
ions were detected in different relative concentrations. Only 60%
of the initial N was detected as ammonium and nitrate ions after
8 h of irradiation time. Therefore, a part of nitrogen atoms from
diuron could be mineralized by this photocatalytic system. This
incomplete nitrogen mass balance has frequently been observed
in similar process [3] and indicates that other nitrogen-containing
compounds must be present in the solution or evaporated during
the process. The possible existence of alkyl nitrogen, cianno derivatives [43], carbamic acids and amines could explain the residual TOC
as described later, but the analytical procedures applied to the samples have not been able to detect them. Other authors described N2
[44] and/or hydroxylamine [39] evolving from nitrogen-containing
compounds degraded by photocatalysis. N2 evolution constitutes
the ideal case for a decontamination reaction involving totally
innocuous nitrogen-containing nal product [45].

H. Katsumata et al. / Journal of Hazardous Materials 171 (2009) 10811087

1085

Fig. 6. Time courses of the mineralization during the photocatalytic degradation of diuron. (a) Chloride ion; (b) ammonium and nitrate ions; (c) TOC.

The progress of the mineralization of the diuron solution was

monitored by measuring the TOC. As shown in Fig. 6c, the complete
mineralization of diuron was not achieved after 20 min, although
diuron was not present in the solution after the irradiation time.
This difference indicates that intermediate products were produced
during the photocatalytic process. The generated photoproducts
are considered to be attacked in their turn by hydroxyl radicals,
which are formed in a continuous manner via a heterogeneous
photocatalytic process. TOC rapidly decreased with increasing the
reaction time up to 2 h, and then decreased gradually. TOC remained

about 0.14 mgC L1 (97% mineralization) after 8 h of irradiation

time. This result indicates the formation of persistent intermediate
compounds which are difcult to be degraded by this photocatalytic
system.

3.3. Identication of photoproducts and degradation mechanism

The intermediate products formed in this photocatalytic degradation of diuron in the aqueous solution after 5 min were

Fig. 7. Proposed degradation mechanism of diuron by the photocatalytic system. Numbers correspond to those in Table 2.

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H. Katsumata et al. / Journal of Hazardous Materials 171 (2009) 10811087

Table 2
Identied products by GC/MS in the photocatalytic degradation of diuron.
Product no.

Rt (min)

M.W.

Characteristic ions (m/z)

17.3

143

143, 71, 89

19.3

161

161, 90, 80

Diuron

33.6

232

232, 187, 72

35.0

248

248, 218, 71

40.3

218

218, 161, 71

investigated by GC/MS analysis. Four products were identied

by the molecular ion and mass fragment ions, and also through
comparison with NIST library data. The structures of the four photoproducts are represented in Table 2, together with the parent
compound. The similarities of these compounds to the NIST library
data were more than 85%. By mass spectrum conrmation and the
authentic standard comparison, diuron, the parent compound, was
found in the chromatogram. By interpreting the mass spectra, the
product no. 3 was found to be the products in which hydroxyl group
added to the benzene ring of diuron. The product nos. 1, 2 and 4
were identied as the compounds which were eliminated the alkyl
groups. In addition to these four compounds, other degradation
products still possibly would exist in the photocatalytic system but
were not detected because of their low concentration, extraction
efciency and limited sensitivity in GC/MS. Many researchers have
identied other degradation products during photocatalytic processes by HPLC, LC/MS and 1 H NMR, as well as these four products
[3,15,16].
Based on the intermediate products listed in Table 2, as well
as the literature data [3,16], the possible degradation pathway for
diuron is proposed in Fig. 7. The rst step was initiated by the attack
on the aromatic ring by OH radicals without dechlorination or alkyl
chains. The next step involved a series of oxidation processes that
eliminated alkyl groups and chlorine atoms. The last step involved
oxidative opening of the aromatic ring, leading to small organic
ions and inorganic species. This proposed degradation pathway was
consistent with previous work [15,46]. In any case, aniline, typical
degradation product which has been proposed as the main phenylurea chemical degradation intermediate [47,48] was not detected,
possibly because they were easily degraded by the OH radicals, as

Compound

demonstrated previously [49], and could not be found in a sufcient

concentration to be detected.
4. Conclusions
The photocatalytic degradation of diuron in aqueous solution
was investigated by platinized TiO2 catalyst. Platinization of TiO2
photocatalyst was found to increase the photocatalytic activity
for the degradation of diuron. The degradation rate was strongly
affected by Pt doping concentration. The optimum doping Pt
concentration found in this study was 0.2 wt.%. Under the optimum conditions, diuron could achieve complete degradation after
20 min. The rst-order rate constant for diuron degradation by
PtTiO2 was ca. 4 times higher than P-25 TiO2 . In addition, the photocatalytic activity of 0.2 wt.% PtTiO2 was higher than that of P-25
TiO2 both under visible light and UV irradiation.
The disappearance of TOC was observed during the photocatalytic process and the remaining TOC achieved 0.14 mgC L1 after
8 h (97% mineralization). The formations of chloride, ammonium
and nitrate ions were also observed. Therefore, we could reach the
complete mineralization of the starting compound. Furthermore,
we identied four kinds of intermediate products of diuron during
the photocatalytic process. The degradation pathway of diuron was
proposed based on the identied by-products under a given set of
reaction conditions.
The advantages of PtTiO2 photocatalytic process as an oxidative
treatment are rapid degradation and simple handling. Therefore,
this photocatalytic reaction would be applied to wastewater treatment works as a new developing methodology for reducing levels
of other pesticides and endocrine disrupting chemicals.

H. Katsumata et al. / Journal of Hazardous Materials 171 (2009) 10811087

Acknowledgements
The present research was partly supported by the Ministry of
Education, Culture, Sports, Science, and Technology of Japan.
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