Photocatalysed degradation of a herbicide derivative, bromacil,

in aqueous suspensions of titanium dioxide

H. K. Singh,a M. Muneer *a and D. Bahnemann b
a

Department of Chemistry, Aligarh Muslim University, Aligarh, 202002, India.

E-mail: cht12mm@amu.nic.in; Fax: 91-571-2702758; Tel: 91-571-2703515
b
Photocatalysis and Nanotechnology, Institut fuer Technische Chemie Universitat Hannover,
Callinstrasse-3 D-30167, Hannover, Germany. E-mail: bahnemann@iftc.uni-hannover.de;
Fax: 49-511-762-3004; Tel: 49-511-762-5560
Received 18th July 2002, Accepted 28th October 2002
First published as an Advance Article on the web 2nd December 2002

The photocatalysed degradation of a herbicide, 5-bromo-3-sec-butyl-6-methyl uracil (bromacil, 1) has been

investigated in aqueous suspensions of titanium dioxide under a variety of conditions. The degradation was
studied by monitoring the depletion in total organic carbon (TOC) content as a function of irradiation time.
The degradation kinetics of the model compound was studied under dierent conditions such as pH, catalyst
concentration, substrate concentration, dierent types of TiO2 and in the presence of electron acceptors such as
hydrogen peroxide (H2O2) and potassium bromate (KBrO3) besides molecular oxygen. The degradation rate was
found to be strongly inuenced by all the above factors. Higher degradation rate was observed with Degussa P25
as compared with other photocatalysts. The addition of bromate ion has been found to enhance the degradation
rate markedly. 5-Hydroxy-3-sec-butyl-6-methyl uracil (2) and diisopropyl urea (16) were identied as the
degradation products by GC-MS analysis and probable pathways for the formation of the products have been
proposed.

Introduction

A large number of herbicides are applied on agricultural

sites which due to their chemical stability, resistance to
biodegradation and with sucient water solubility penetrate
deep into the ground water.13 Their toxicity, stability to
natural decomposition and persistence in the environment has
been the cause of much concern by society and regulation
authorities around the world.4 Biodegradation, which is the
major mechanism in the wastewater treatment, is quite inecient at low levels of substrate concentration. Recent studies
have shown that a wide range of organic substances can be
photomineralized in the presence of semiconductor and
oxygen.515
An example of a pesticide in common use is a preemergent
herbicide bromacil. It is used as a selective herbicide to control
annual and perennial grasses, broad leaf weeds and woody
plants at non-crop land area.16 It is used at rates of 2 to 4 kg
ha1.17 It is a highly persistent herbicide with an average
half life of 56 months and in soil it may remain active for
about 7 months.18 It has been found in the groundwater of
Florida by Cohen et al.1 Earlier studies 19,20 have demonstrated rather poor biodegradability of bromacil. The photodegradation of water samples taken from a heavily polluted
well containing various types of herbicides have been reported
earlier by Muszkat et al.21 In a recent study a TiO2 photocatalytic degradation of bromacil in the presence of methylene
blue has also been reported.22 Torrents et al. reported earlier the
degradation of bromacil using chemical oxidation process such
as ozonolysis.23 No major eorts have been made to study the
details of the degradation kinetics, the knowledge of which is
essential for the proper design of the treatment plant. Therefore
we have undertaken a detailed kinetic study and analysis of the
intermediate product formed in the photocatalytic degradation
of bromacil (1) sensitized by titanium dioxide in aqueous
suspensions.
DOI: 10.1039/b206918k

2
2.1

Experimental methods
Reagents

Analytical grade bromacil was obtained from Riedel-de Hen

and used as such without any further purication. Double
distilled water was employed in this study to make stock solution for irradiation experiments. The photocatalyst, titanium
dioxide Degussa P25 was used in most of the experiments,
other catalyst powders, namely, Hombikat UV100 (Sachtleben
Chemie GmbH), PC500 (Millennium Inorganics) and TiO2
obtained from Travancore Titanium Products (TTP), India,
were used for comparative studies. P25 contains 75% anatase
and 25% rutile with a specic BET surface area of 50 m2 g1
and a primary particle size of 20 nm.24 Hombikat UV100 consists of 100% pure anatase with a specic BET surface area of
250 m2 g1and a primary particle size of 5 nm.25 The photocatalyst PC500 has a BET-surface area of 287 m2 g1 with 100%
anatase and primary particle size of 510 nm 26 and TiO2
obtained from Travancore Titanium Products (TTP) India, has
a surface area of 9.82 m2 g1. Hydrogen peroxide, potassium
bromate, NaOH and HNO3 used in the study were obtained
from Merck Darmstadt.
2.2

Procedure

Stock solutions of bromacil with desired concentrations were

prepared in double distilled water. An immersion well
Photochem. Photobiol. Sci., 2003, 2, 151156

This journal is The Royal Society of Chemistry and Owner Societies 2003

151

photochemical reactor made of Pyrex glass was used in this

study. For irradiation experiments 200 mL of the desired solution was put into the reactor and the required amount of photocatalyst was added and the solution was stirred for at least 30
min in the dark to allow equilibration of the system so that the
loss of compound due to adsorption could be taken into
account. The pH of the reaction mixture was adjusted by adding dilute aqueous solutions of NaOH or HNO3. The zero time
reading was obtained from a blank solution kept in the dark but
otherwise treated similarly to the irradiated solution. The suspensions were continuously purged with molecular oxygen
throughout each experiment. Irradiations were carried out using
a 125 W medium pressure mercury lamp (Philips). Samples
(10 mL) were collected before and at regular intervals during
the irradiation. They were centrifuged and analyzed by measuring the total organic carbon (TOC) content with a Shimadzu
TOC 5000A Analyzer by directly injecting the aqueous solution. The degradation rates were calculated in units of M min1.
2.3

Characterization of intermediate photoproducts

For characterization of the intermediate products, aqueous

solutions (250 mL) of the compound containing TiO2 (P25, 1 g
L1) were put in a photochemical reactor made of Duran glass
with a plain quartz window (through which a parallel light
beam enters) equipped with a magnetic stirring bar, a water
circulating jacket and an opening for gas supplies. Irradiations
were carried out using a high-pressure mercury lamp (Osram
HBO 500 W). A 320 nm cut-o lter was used to avoid any
direct excitation of the compound under investigation. Samples
(20 mL) were collected at dierent time intervals during the
irradiation, centrifuged and extracted with methylene chloride,
which was subsequently dried over anhydrous sodium sulfate
and analyzed by GC-MS. For GC-MS analysis a Shimadzu gas
chromatograph and mass spectrometer (GCMS-QP 5050)
equipped with a 25 m CP SIL 19 CB (d = 0.25 mm) capillary
column, operating temperature programmed (220 C for 40 min
at the rate of 10 C min1) in split mode injection volume
(1.0 L) with helium as a carrier gas was used.

3
3.1

The rate constant was calculated in two ways: (i) from the
initial slope obtained by the linear regression from a plot of the
natural logarithm of the TOC content of the model compound
as a function of irradiation time i.e. rst order degradation
kinetics, and (ii) from the initial slope obtained by linear regression of the TOC content vs. time prole i.e. zeroth order degradation kinetics, as shown in Fig. 2. It has been found that rst

Results
Photolysis of TiO2 suspensions containing bromacil

Fig. 1 shows the depletion in TOC vs. time on irradiation of an

aqueous solution of bromacil (0.48 mM) in the presence and
absence of Degussa P25 (1 g L1) photocatalyst by the Pyrex
ltered output of a 125 W medium pressure mercury lamp. It
has been observed that 38.86% mineralization of bromacil
takes place after 240 min of irradiation in the presence of TiO2
photocatalyst whereas no observable loss of the compound
takes place when irradiations were carried out in the absence of
TiO2.

Fig. 2 Comparision of curve t data for the zero order and rst order
degradation kinetics of bromacil. Experimental conditions: 0.48 mM
bromacil, V = 200 mL, photocatalyst (Degussa P25 1 g L1), immersion
well photoreactor, 125 W Hg lamp, continuous O2 purging and stirring,
irradiation time = 240 min.

order kinetics ts reasonably well and hence the resulting rst

order rate constant was used in all subsequent plots to calculate
the degradation rate using the formula given below,
d [TOC]/dt = kC n
k = apparent rst order rate constant, C = initial concentration
of the model compound, n = order of the reaction, here the
order of the reaction was taken as 1
Control experiments were carried out in all cases, employing
unirradiated blank solutions. There was no observable loss of
the compound due to adsorption on the TiO2 in unirradiated
blank solutions. The zero irradiation time readings were
obtained from blank solutions kept in the dark, but otherwise
treated similarly to the irradiated solutions.
3.2

The degradation of bromacil was tested with four dierent

photocatalyst, namely, Degussa P25, Hombikat UV100, PC500
and TTP. Table 1 shows the degradation rate for the mineralization of bromacil in the presence of dierent photocatalysts. It
was observed that bromacil degradation proceeds much more
rapidly in the presence of Degussa P25, as compared with
other employed photocatalysts and the order of eciency was
found to be P25 > UV100 > PC500 > TTP. In all following
experiments, Degussa P25 was used as the photocatalyst
since this material exhibited the highest overall activity for the
degradation of the model compound under investigation.
3.3

Fig. 1 Inuence of photocatalyst on the degradation of bromacil.

Experimental conditions: 0.48 mM bromacil, V = 200 mL, photocatalyst (Degussa P25 1 g L1), immersion well photoreactor, 125 W Hg
lamp, continuous O2 purging and stirring, irradiation time = 240 min.

152

Photochem. Photobiol. Sci., 2003, 2, 151156

Comparison of dierent photocatalysts

pH Eect

Employing dierent types of TiO2 namely Degussa P25,

Hombikat UV100 and PC500 as photocatalysts the mineralization of bromacil in aqueous suspensions was studied at pH 3,
5, 7 and 9. The pH of the reaction mixture was adjusted
by adding dilute aqueous solutions of NaOH or HNO3. The
degradation rate for TOC depletion of bromacil as a function
of reaction pH is shown in Table 1. The eciency for the
degradation of the pollutant was found to increase with the
increasing pH for all the employed photocatalysts. For all
investigated pH values the degradation of the model compound
followed rst-order kinetics. These results indicate that the
model compound can be photocatalytically mineralized
considerably faster at higher pH values.

Table 1 Photocatalytic degradation of bromacil in aqueous suspensions under dierent parameters

Rate/106 M min1

Parameter
Catalyst/1 g L1

pH

Initial substrate concentration/mM

Catalyst concentration/g L1

Additive

3.4

Eect of substrate concentration

It is important both from mechanistic and from application

points of view to study the dependence of photocatalytic reaction rate on the initial substrate concentration. Hence the
eect of initial substrate concentration on the degradation of
bromacil was studied at four dierent initial substrate concentrations: 0.12, 0.24, 0.48 and 0.96 mM. Table 1 shows the degradation rate for the TOC depletion of bromacil as a function
of initial substrate concentration employing Degussa P25 as
photocatalyst. The studies were carried out at pH 5 (the original pH of the solution after adding the catalyst). As expected,
the eciency for the degradation of the model compound
increases with the increase in the initial substrate concentration.
3.5

Eect of catalyst concentration

The inuence of the photcatalyst concentration on the degradation kinetics of bromacil was investigated employing dierent
concentrations of Degussa P25 varying from 0.5 to 5 g L1. The
degradation rate for the mineralization of bromacil as a function of catalyst concentration at pH 5 is shown in Table 1. As
expected the degradation rate for the mineralization of the
model compound was found to increase with the increase in the
catalyst loading. At all TiO2 concentrations, the TOC depletion
of bromacil obeyed rst order kinetics; the rate constants along
with correlation factors for 0.5, 1, 2, 5 g L1 were 0.001974
(r = 0.9906), 0.002425 (r = 0.9899), 0.002518 (r = 0.9794),
0.003124 (r = 0.9807) respectively.
3.6

Eect of electron acceptors

The eect of electron acceptors such as hydrogen peroxide and

potassium bromate on the photcatalytic degradation of
bromacil in addition to the molecular oxygen was investigated.
Table 1 shows the degradation rate for the TOC depletion of
bromacil in the presence of two dierent electron acceptors.
It was observed that bromate ions markedly enhanced the
degradation rate of bromacil, while in the presence of
hydrogen peroxide a slight increase in the degradation rate was
observed.
3.7

Intermediate product

The GC-MS analysis of an irradiated mixture of bromacil

showed several peaks of which two products, 5-hydroxy-3-secbutyl-6-methyl uracil (2) and diisopropyl urea (16) appearing at
retention times (tR) 9.48 and 15.293 min respectively were

P25
UV100
PC500
TTP

3.0
5.0
7.0
9.0
0.12
0.24
0.48
0.96
0.5
1.0
2.0
5.0
KBrO3
H2O2
None

1.116
1.094
0.755
0.334
P25

UV100

PC500

0.8830
1.1165
1.2288
2.7648
0.887
0.948
1.116
1.440
0.948
1.116
1.209
1.499
3.324
1.645
1.116

0.8057
0.9754
1.2398
1.4961

0.6207
0.9327
1.1424
1.1900

identied. The photoproduct (2) was identied based on the

molecular ion and mass spectrometric fragmentation peaks,
whereas the product (16) was identied by comparing the
molecular ion and mass fragmentation peaks with those
reported in the GC-MS library, which are indicated here: compound 2: m/z, 198 (M), 141, 113, 99, 71 and 57; compound 16:
m/z, 144 (M), 129, 84, 70, 58, 44 and 41.

Discussion

It is proposed that titanium dioxide mediated photocatalysed

degradation involves the generation of electron-hole (eh)
pairs, which migrates to the photocatalyst surface forming the
surface bound hydroxyl and superoxide radicals according to
eqn. (1)(3),
TiO2 h
O2 ecb
H2O hvb

ecb hvb

(1)

O2

(2)

OH H

(3)

It is commonly accepted that the hydroxyl radical and superoxide radical anions are the primary oxidizing species in the
photocatalytic oxidation process.2730 These oxidative reactions
would result in the degradation of the organic pollutants and
the eciency of the degradation will depend upon the oxygen
concentration, which determines the eciency with which the
conduction band electrons are scavenged and the (eh) pair
recombination is prevented.
The results obtained for the photodegradation of the model
compounds using dierent kinds of TiO2 photocatalysts exhibiting dierent bulk and surface properties, i.e., BET-surface
area, impurities, lattice mismatches, or density of hydroxyl
groups on the catalysts surface, are apparently responsible for
the photocatalytic activity, since they will aect the adsorption
behaviour of a pollutant or intermediate molecule and the
lifetime and recombination rate of electronhole pairs. Previously,31 it has been shown that Degussa P25 owes its high
photoreactivity to a slow recombination of electrons and holes
whereas Sachtleben Hombikat UV 100 has a high photoreactivity due to fast interfacial electron-transfer rate. Since the
photocatalyst Degussa P25 was found to be a more active
photocatalyst, it is obvious that the rate limiting step cannot be
the amount of interfacial electron-transfer rate, but rather the
lifetime of electronhole pairs. Assuming that the adsorption/
desorption of substrate and reaction intermediates is relatively
Photochem. Photobiol. Sci., 2003, 2, 151156

153

slow in comparison to the recombination rate of electron

hole pairs, one should expect higher degradation rates when a
photocatalyst such as Degussa P25 is used which guarantees
longer lifetime of the electronhole pairs. Thus, higher concentrations of electrons and holes are available for suitable
reactants to initiate the photocatalytic reaction.
An important parameter in the heterogeneous photocatalysis
is the reaction pH, since it determines the surface charge
properties of the photocatalyst and therefore the adsorption
behavior of the pollutant and also the size of aggregates it
forms. The zero point of charge (pHzpc) of dierent photocatalysts such as P25, UV100 and PC500 has been reported as
6.25, 5.78 and 6.05 respectively. Hence at more acidic pH
values, the particle surface is positively charged, while at pH
values above pHzpc, it is negatively charged. In this study it has
been shown that the degradation rate for the model compound
under investigation is strongly inuenced by the reaction pH as
shown in Table 1.
The model compound contains NH protons and hence it
can be protonated and deprotonated under acidic and basic
conditions respectively, depending upon its pKa value. At the
same time the lone pair of electrons present at the nitrogen
atom is highly delocalized across carboncarbon double bonds
and carbonyl groups. Due to the high pKa value (9.3) of
bromacil 32 the molecule will be present in its protonated form
below pH 9. At pH 9, where the molecule will be in equilibrium
between its protonated and deprotonated form, the eciency of
mineralization has been found to be maximum. Apparently the
photocatalytic oxidation of bromacil seems to be favored in this
structural orientation of the molecule.
Whether in static, slurry, or dynamic ow reactors, the initial
reaction rates were found to be directly proportional to catalyst
concentration, indicating a heterogeneous regime. However, it
was observed that above a certain concentration, the reaction
rate even decreases and becomes independent of the catalyst
concentration. This limit depends on the geometry and working conditions of the photoreactor and for a denite amount
of TiO2 in which all the particles, i.e., the entire exposed
surface, are totally illuminated. When the catalyst concentration is very high, after traveling a certain distance on an
optical path, turbidity impedes further penetration of light in
the reactor. In any given application, this optimum catalyst
concentration [(TiO2)OPT] has to be found, in order to avoid
excess catalyst and ensure total absorption of ecient photons.
Our results on the eect of catalyst concentration on the
degradation rate for the mineralization of bromacil, shown in
Table 1, are in agreement with numerous studies reported in the
literature.
One practical problem in using (TiO2) as a photcatalyst is the
undesired electronhole recombination, which, in the absence
of proper electron acceptor or donor, is extremely ecient and
thus represents the major energy wasting step thus limiting the
achievable quantum yield. One strategy to inhibit electronhole
pair recombination is to add other (irreversible) electron
acceptors to the reaction. In highly toxic wastewater where the
degradation of organic pollutants is the major concern, the
addition of additives to enhance the organic degradation rate
may often be justied. In this connection, we have studied the
eect of electron acceptors such as hydrogen peroxide and
bromate ions on the photocatalytic degradation of the model
compound under investigation. These acceptors are known to
generate reactive radicals according to the following equations
[eqn. (4)(6)]
H2O2 eCB

OH OH

BrO3 2H eCB
BrO3 6H 6 eCB
[BrO2, HOBr]
154

BrO2 H2O
Br 3H2O

Photochem. Photobiol. Sci., 2003, 2, 151156

(4)
(5)

(6)

Scheme 1

As expected both the additives showed benecial eects on

the photocatalytic degradation of bromacil as shown in the
Table 1. However the addition of bromate ions markedly
enhances the degradation of bromacil, indicating that this
compound is the most eective electron acceptor as compared
with other oxidants employed in this study. The respective one
electron reduction potentials (measured against NHE) of different species are E(O2/O2) = 155 mV, E(H2O2/OH) = 800
mV) and E(BrO3/BrO2) = 1150 mV.33 From the thermodynamic point of view both the additives should therefore be
more ecient electron acceptors than molecular oxygen. Since
the addition of bromate ions markedly enhances the degradation of bromacil, the enhancement can be attributed to the
increased number of electron involved, as shown in eqn. (6).
Another possible explanation might be a change in the reaction
mechanism of the photocatalytic degradation, since the reduction of bromate ions by electrons does not lead directly to the
formation of hydroxyl radicals, but rather to the formation of
other reactive radicals or oxidizing reagents, e.g. BrO2 and
HOBr. Furthermore, bromate ions by themselves can act as
oxidizing agents. Lindner has recently proposed a mechanism
for the photocatalytic degradation of 4-chlorophenol in the
presence of bromate ions considering direct oxidation of
the substrate by bromate ions.34 A similar mechanism may be
operative in the case of the model compound studied in this
work.

oxygen. The observations of these investigations clearly demonstrate the importance of choosing the optimum degradation
parameters to obtain a high degradation rate, which is essential
for any practical application of photocatalytic oxidation processes. The best degradation conditions depend strongly on the
specic kind of pollutant to be attacked. In particular, the
pH inuences markedly the overall eciency of the process.
Degussa P25 was found to be a more active catalyst as compared with other commercially available TiO2 powders. In addition, potassium bromate was a more ecient electron acceptor
as compared with hydrogen peroxide. The analysis of the
intermediate products formed during the photodegradation
process is a useful source of information for the degradation
pathways.

Acknowledgements
Financial support by the Department of Science and Technology (DST) Government Of India, New Delhi and Volkswagen
Foundation Hannover, Germany (Contract No.: 1/76085)
is gratefully acknowledged. The total organic carbon (TOC)
analyzer used in this study was a gift from the Alexander von
Humboldt Foundation, Bonn Germany.

References

Scheme 2

The photocatalysed degradation of bromacil has been found

to yield 5-hydroxy-3-sec-butyl-6-methyl uracil (2) and diisopropyl urea (16) as the intermediate products. The formation
of 2 and 16 involving electron transfer reactions and reaction
with hydroxyl radicals formed in the photocatalytic system
could be understood in terms of the pathways shown in
Schemes 1 and 2 respectively. The model compound 1 upon the
addition of a hydroxyl radical followed by loss of bromine
radical can lead to the formation of the observed product 2.
The compound 2, upon the transfer of an electron, can form
the radical cation 4, which may undergo loss of a hydrogen
atom followed by methyl cation forming 5. This compound on
further transfer of an electron followed by loss of an isopropyl
cation may subsequently lead to the formation of 9. Further
transfer of an electron from irradiated TiO2 to the species 6
may lead to the formation of radical anion species 10, which
may undergo addition of a hydroxyl radical followed by ring
cleavage to give 11 (Scheme 2). This compound on subsequent
transfer of an electron may undergo addition of an hydroxyl
radical, ring cleavage and abstraction of an isopropyl cation
ultimately leading to the formation of the observed diisopropyl
urea (16).

Conclusion

TiO2 can eciently catalyse the photomineralisation of the

pesticide derivative bromacil in the presence of light and

1 Z. Z. Cohen, C. Eiden and M. N. Lober, in Evalution of Pesticide in

Ground Water, ed. W. Y. Gerner, ACS Symp. Ser. 315, American
Chemical Society, Washington, DC, 1986, pp. 170196.
2 L. Muszkat, D. Raucher, M. Mogaritz and D. Ronen, in
Groundwater Contamination and Control, ed. U. Zoller, Marcel
Dekker, 1994, pp. 257271.
3 M. Rosner, I. T. Yasur, A. Hadas, D. Russo and B. Yaron, Leaching
of Tebuthylazine and Bromacil through Field Soils, Water Air Soil
Pollut., 1999, 113, 319335.
4 R. M. Dowd, M. P. Anderson and M. L. Johnson, Proceedings of the
Second National Outdoor Action Conference on Aquifer Restoration,
Groundwater Monitoring Geophysical Methods, National Water Well
Association, Dublin, OH, 1998, pp. 13651379.
5 D. M. Blake, Bibliography of Work on the Photocatalytic Removal
of Hazardous Compounds from Water and Air, National Renewal
Energy Laboratory, Cole Boulevard Golden, CO, USA, 1999.
6 J. M. Herrmann, Heterogeneous photocatalysis fundamentals and
applications to the removal of various types of aqueous pollutants,
Catal. Today, 1999, 53, 115129.
7 M. I. Litter, Heterogeneous photocatalysis transition metal ions in
photocatalytic system, Appl. Catal. B: Environ., 1999, 23, 89114.
8 A. Vidal, Z. Dinya, F. Mogyorodi, Jr. and F. Mogyorodi,
Photocatalytic degradation of thiocarbamate herbicide active
ingredients in water, Appl. Catal. B: Environ., 1999, 21, 259267.
9 A. Assabane, Y. A. Ichou, H. Tahiri, C. Guillard and J. M.
Herrmann, Photocatalytic degradation of polycarboxylic benzoic
acids in UV-irradiated aqueous suspensions of titania: Identication of intermediates and reaction pathway of photomineralization of trimellitic acid, Appl. Catal. B: Environ., 2000, 24,
7187.
10 O. M. Alfano, D. Bahnemann, A. E. Cassano, R. Dillert and
R. Goslich, Photocatalysis in water environments using articial
and solar light, Catal. Today, 2000, 58, 199230.
11 A. Fujishima, T. N. Rao and D. A. Tryk, Titanium dioxide
photocatalysis, J. Photochem. Photobiol. C: Photochem. Rev., 2000,
1, 121.
12 K. Macounova, J. Urban, H. Krysova, J. Krysa, J. Jirkovsky and
J. Ludvik, Photodegradation of metamitron on TiO2, J. Photochem.
Photobiol. A: Chem., 2001, 140, 9398.
13 A. Topalov, B. Abramovie, D. M. Gabor, J. Csanadi and O. Arcson,
Photocatalytic oxidation of the herbicide (4-chloro-2-methyl
phenoxy acetic acid MCPA) over TiO2, J. Photochem. Photobiol. A:
Chem., 2001, 140, 249253.
14 X. Li, J. W. Cubbage and W. S. Jenks, Variation in the chemistry of
the TiO2-mediated degradation of hydroxyl and methoxy benzenes:
electron transfer and OH initiated chemistry, J. Photochem.
Photobiol. A: Chem., 2001, 143, 6985.
15 D. Q. Hung, J. Wohlers and W. Thiemann, The mineralization of
methamidophos using an ionised air water treatment pilot system
and ultraviolet irradiation, Water Res., 2002, 36, 29592966.

Photochem. Photobiol. Sci., 2003, 2, 151156

155

16 R. Meister, Farm Chemicals Handbook, Meister Publishing

Company, Willoughby, OH, 1998, p. 101116.
17 K. A. Hassall, The Biochemistry and Uses of Pesticides, Macmillan
Press, Basingstoke, Hampshire, 1990, pp. 455456.
18 D. C. Wolf and J. P. Martin, Microbial degradation of bromacil2-14C & terbacil-2-14C, Soil Sci. Soc. Am. Proc., 1974, 38, 921
925.
19 D. C. Wolf, Degradation of bromacil, terbacil 2,4-D and atrazine
in soil and pure culture and their eect on microbial activity, Diss.
Abstr. Int., B, 1974, 34, 47834784.
20 A. J. Acher, C. J. Hapeman, D. R. Shelton, M. T. Muldoon,
W. R. Lusby, A. Avni and R. Water, Comparison of formation &
biodegradation of bromacil oxidation products in aqueous
solutions, J. Agric. Food Chem., 1994, 421, 20402047.
21 L. Muszkat, M. Halmann, D. Raucher and L. Bir, Solar
photodegradation of xenobiotic contaminants in polluted well
water, J. Photochem. Photobiol. A: Chem., 1992, 65, 409417.
22 L. Feigelson, L. Muszkat, L. Bir and K. A. Muszkat, Dye
photoenhancement of TiO2 photocatalyzed degradation of organic
pollutants: the organobromine herbicide bromacil, Water Sci.
Technol., 2000, 42, 275279.
23 A. Torrents, B. G. Anderson and C. J. Hapeman, Kinetics of
bromacil ozonolysis, J. Agric. Food Chem., 1998, 45, 16301636.
24 R. I. Bickley, T. G. Carreno, J. S. Lees, L. Palmisano and R. J. D.
Tilley, A spectral investigation of titanium dioxide photocatalyst,
J. Solid State Chem., 1992, 92, 178190.
25 M. Lindner, D. W. Bahnemann, B. Hirthe and W. D. Griebler, Solar
water detoxication: Novel TiO2 powders as highly active
photocatalysts, J. Solar Energy Eng., 1997, 119, 120125.

156

Photochem. Photobiol. Sci., 2003, 2, 151156

26 S. Rauer, Untersunchung von kommerziell erhaltlichen Titandioxiden

hinsichtlich
ihrer
photokatalytischen
Aktivtat,
Diplomarbeit,
fachhochschule
Hannover,
Fachbereich
Maschinenbau
Vertiefung
Umwelt-und
Verfahrenstechnil,
Hannover, Germany, 1998.
27 H. Gerischer, Solar photocatalysis with semiconductor electrodes,
Top. Appl. Phys., 1979, 31, 115172.
28 C. Kormann, D. W. Bahnemann and M. R. Homan, Preparation
and characterization of quantum size titanium dioxide, J. Phys.
Chem., 1988, 92, 51965201.
29 M. R. Homan, S. T. Martin, W. Y. Choi and D. W. Bahnemann,
Environmental application of semiconductor photocatalysis, Chem.
Rev., 1995, 95, 6996.
30 D. W. Bahnemann, J. Cunningham, M. A. Fox, E. Pelizzetti,
P. Pichat, N. Serpone, in Aquatic and Surface Photochemistry,
ed. D. Crosby, G. Helz and R. Zepp, Lewis Publishers, Boca Raton,
E L, 1994, pp. 261316.
31 S. T. Martin, H. Hermann, W. Choi and M. R. Homann, Time
resolved microwave conductivity. Part I- TiO2 photoreactivity and
size quantization, J. Chem. Soc., Faraday Trans., 1994, 90, 3315
3322.
32 J. B. Weber and T. J. Monaco, Review of the chemical and physical
properties of substituted herbicides, Proc. South Weed Sci. Soc.,
1972, 25, 3137.
33 P. Wardman, J. Phys. Chem. Ref. Data, 1989, 18, 16571755.
34 M. Lindner, Optimierung der Photokatalytischen Wasserreinigung
mit Titandioxid : Festkoerper und Oberaechenstruktur des
Photokatalysators, PhD Thesis, Department of Chemistry,
University of Hannover, Hannover, Germany, 1997.