Chemosphere 46 (2002) 905912

www.elsevier.com/locate/chemosphere

Degradation of azo dye Procion Red MX-5B by

photocatalytic oxidation
C.M. So a, M.Y. Cheng a, J.C. Yu b, P.K. Wong

a,*

a
b

Department of Biology, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong

Received 15 November 2000; received in revised form 11 June 2001; accepted 11 June 2001

Abstract
The photocatalytic oxidation (PCO) of a monoazo dye Procion Red MX-5B under various physico-chemical conditions was investigated. Degradation of the dye by PCO was enhanced by augmentation in UV intensity, titanium
dioxide and hydrogen peroxide concentrations but was inhibited by increase in initial dye concentration. The PCO
process was aected by pH in a peculiar way. In the presence of 100 mg/l of TiO2 and the absence of H2 O2 , the highest
reaction rate was observed when the initial pH was 10. With 500 mg/l of TiO2 and 10 mM of H2 O2 , the reaction was the
fastest at initial pH of 35. The optimal conditions for the degradation of the dye, at an UV intensity of 17 mW=cm2 ,
were determined to be: TiO2 concentration, 500 mg/l; initial H2 O2 concentration, 10 mM; initial pH, 5.0. Monitoring of
TOC loss showed that the dye was mineralized by 90% within 80 min under these conditions. Nevertheless, the persistence of a low level of TOC indicated that mineralization was not complete and dead-end product(s) which was
(were) resistant to PCO might have accumulated. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: PCO; Mineralization; Titanium dioxide; UV

1. Introduction
Dye-laden wastewaters discharged by dyeing and
textile industries pollute natural waters and lower their
value in use. Azo dyes, which contain one or more azo
bonds (AN@NA), are among the most widely used
synthetic dyes and usually become major pollutants in
these wastewaters. It has been documented that some
azo dyes are toxic (Meyer, 1981) and even mutagenic
(Chung et al., 1981) to living organisms in aquatic environments. In addition, the stability of their molecular
structures renders them resistant to biological and even
chemical degradation (Dai et al., 1995, 1996a,b). Due to

Corresponding author. Tel.: +852-2609-6383; fax: +8522603-5767.

E-mail address: pkwong@cuhk.edu.hk (P.K. Wong).

their toxicity and recalcitrance, these dyes can be hazardous to the environment though present at low concentrations.
Recently, numerous studies on the application of
photocatalytic oxidation (PCO) for the removal of azo
dyes (Hustert and Zepp, 1992; Davis et al., 1994; Goncalves et al., 1999; Hu and Wang, 1999; Tanaka et al.,
2000) and other organic pollutants (Mills et al., 1993;
Herrmann, 1999) in aqueous solutions have been reported. The process commonly involves irradiation by
UV k < 400 nm in the presence of a semiconductor
catalyst like titanium dioxide (TiO2 ). Upon absorption
of light energy equal to or larger than the band gap
energy, a valence band electron of the semiconductor
can be excited to the conduction band (e
CB ), leaving a
positive hole in the valence band h

VB

TiO2 hv ! e
CB hVB

0045-6535/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 1 ) 0 0 1 5 3 - 9

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C.M. So et al. / Chemosphere 46 (2002) 905912

The positive hole is a strong oxidant which can either

oxidize a compound directly, or react with electron donors like water or hydroxide ions to form hydroxyl
radical  OH, which is also a potent oxidizer:


h
VB H2 O ! OH H



hVB OH ! OH

2
3

On the other hand, it is important for the excited electron in the conduction band to be scavenged by an external agent to prevent its recombination with the
positive hole. One ecient electron acceptor is molecular
oxygen O2 , which forms a superoxide anion radical
after capturing the electron

Fig. 1. The chemical structure of Procion Red MX-5B.

2. Materials and methods

2.1. Chemical reagents


e
CB O2 ! O2

In addition, such a PCO process can be accelerated by

hydrogen peroxide H2 O2 as demonstrated in some
studies (Malato et al., 1998; Poulios and Aetopoulou,
1999; Poulios and Tsachpinis, 1999). During the reaction, H2 O2 can produce  OH by reacting with O
2 or by
direct photolysis:


H2 O 2 O 
2 ! OH OH O2

H2 O2 hv ! 2 OH

5
6

Besides, it can act as a conduction-band electron acceptor like O2 and form  OH subsequently


H2 O2 e
CB ! OH OH

Such a UV-TiO2 -based PCO system exhibits some attractive characteristics. First, TiO2 is environmentally
acceptable by being fairly inert biologically and chemically. Second, both TiO2 and H2 O2 are inexpensive and
TiO2 is reusable. Third, degradation of major classes of
organic pollutants can be achieved at ambient conditions. PCO also appears to be a better treatment method
for azo dye-containing wastes than conventional biological processes. While these compound are highly recalcitrant to biodegradation (Dai et al., 1995), they can
be destroyed by PCO within hours (Mills et al., 1993).
Furthermore, during the anaerobic digestion stage of the
conventional sewage treatment process, azo dyes can be
readily transformed to aromatic amines which are usually more toxic than the parental dyes (Tan et al., 1999).
PCO, on the contrary, can oxidize these dyes to CO2 and
mineral ions (Tan et al., 1999).
In the present study, we investigated the PCO of a
common monoazo dye Procion Red MX-5B. The dye is
highly water-soluble and can be used for dyeing cellulose, nylon, silk and wool. The eects of various physico-chemical conditions on the degradation of the dye by
PCO were studied and mineralization of the dye was
monitored.

The monoazo dye Procion Red MX-5B, also called

Reactive Red 2 (C.I. number 18200), was manufactured
by Imperial Chemicals Industries (ICI). It has an elemental composition of C19 H10 Cl2 N6 Na2 O7 S2 and its
chemical structure is shown in Fig. 1 (Society of Dyers
and Colorists, 1995). The dye was from the Biology
Department, The Chinese University of Hong Kong and
used as received without further purication. TiO2 was
obtained from the Degussa Company (P 25; Frankfurt,
Germany). H2 O2 (35% w/v) was from Riedel-de Haen
(Seelze, Germany). All experiments were conducted in
deionized water (<5 lS=cm.
2.2. Construction of the photoreactor
All photocatalytic experiments were carried out in a
reactor depicted in Fig. 2. A glass column of 430 mm
height, 25 mm external diameter, and with a wall 1.5 mm
thick was used as a container for the dye solution. The
top of the glass column was open to the atmosphere.
Neither forced aeration nor stirring of the dye solution
was conducted in all experiments. The glass column was
surrounded by eight UV lights with a maximum emis-

Fig. 2. Top view of the photoreactor. It was constituted of a

glass column surrounded by eight UV lights and enclosed in a
stainless steel shield.

C.M. So et al. / Chemosphere 46 (2002) 905912

907

sion at 365 nm (Vilber-Lourmat, Model T-15L/8D).

Each has a power consumption rate of 15 W and an
average UV output intensity of 2:13 mW=cm2 (ranging
from 2.06 to 2:21 mW=cm2 ) at 365 nm as determined at
the center of the photoreactor. The total UV intensity
was controlled by turning on dierent number of UV
lights and the maximum intensity was 17 mW=cm2 (with
all eight UV lights on). The UV lights and the glass
column were enclosed in a stainless steel shield with an
open top where an electrical fan was mounted to vent
the heat inside the reactor.

length of 538 nm after adjusting the pH of the sample to

10. UV intensity (at 365 nm) of each light was determined by a digital radiometer (model UVX, UVP).
Total organic carbon (TOC) was analyzed by a Shimadzu TOC analyzer (model 5000A). All TOC data
reported had been subtracted for background concentration of TOC. Sulfate ions were analyzed by a Dionex
ion chromatograph (model LC20) equipped with an
anion-exchange column (IonPac AS-4A-SC) and a
conductivity detector.

2.3. Characterization of the photocatalytic oxidation

reaction

3. Results and discussion

Experiments for characterization and optimization of

the PCO process were generally conducted with a 150ml, 40-mg/l dye solution under the following conditions:
TiO2 , 100 mg/l; UV intensity, 4:26 mW=cm2 ; initial
temperature, 23C (room temperature); initial pH, 4.5
5.0 (the natural pH of the reaction solution). A suspension of TiO2 and the dye was rst mixed well and
equilibrated in the dark for at least 10 min. The suspension was then irradiated by UV and 1-ml samples
were collected at specic time intervals to monitor the
change in dye concentration. Sampled suspensions were
centrifuged at 13,000 rpm for 15 min in eppendorf tubes
to remove the TiO2 powder. The supernatants were
analyzed for dye concentration by spectrophotometry.
To study the eects of the dierent physico-chemical
parameters, only the one of interest was varied while the
others were maintained at levels as described earlier. The
initial pH was varied from 2 to 10 by the addition of
HCl or NaOH.

Since the PCO reaction with Procion Red MX-5B,

like other azo dyes (Hustert and Zepp, 1992; Davis et al.,
1994) and other organic compounds (Mills et al., 1993),
apparently followed rst-order kinetics with the pseudorst-order rate constant k 0 . For the calculation of k 0 in
this study, absorbance value at 538 nm of the reaction
solution measured by spectrophotometry (see Section
2.5) was used in place of dye concentration as the two
bear a linear relationship as determined previously. The
ks thus calculated were used as the basis for comparison
of reaction rates under dierent conditions.
3.1. Eect of initial dye concentration
The eect of initial dye concentrations ranging from
5 to 40 mg/l on decolorization of Procion Red MX-5B
by PCO was investigated. As depicted in Fig. 3, a decrease in the rate constant was observed upon the increase of initial dye concentration. Similar observations

2.4. Mineralization of the dye

Mineralization of Procion Red MX-5B by PCO was
studied with a 40-mg/l dye solution under optimal conditions that resulted in maximum decolorization rates.
These conditions were (at a UV intensity of 17 mW=cm2
and a temperature of 23C): TiO2 , 500 mg/l; H2 O2 , 10
mM; initial pH, 5.0. Degradation and mineralization
was monitored by determining sulfate ion and total organic carbon (TOC) concentrations in the reaction solution. For monitoring of sulfate ion concentration,
samples of 1.3 ml were collected and centrifuged (13,000
rpm; 15 min) to remove the TiO2 particles before analysis. For TOC determination, 5-ml aliquots were collected and ltered 0:2 lm pore size) before analysis.
2.5. Chemical analysis
Decolorization of Procion Red MX-5B was monitored by measuring absorbance with a Milton Roy
Spectronic 3000 Array spectrophotometer at a wave-

Fig. 3. Eect of initial dye concentration on the pseudo-rstorder rate constant for the photocatalytic oxidation of Procion
Red MX-5B. Results are means of duplicates and error bars
represent 1 S.D. (Experimental conditions: TiO2 , 100 mg/l;
initial pH, 4.55.0; UV intensity, 4:26 mW=cm2 ; temperature,
23C.)

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C.M. So et al. / Chemosphere 46 (2002) 905912

have also been reported for the PCO of other dyes and
organic compounds (Davis et al., 1994; Lea and Adesina, 1998; Poulios and Aetopoulou, 1999). One possible
cause for such results is the UV-screening eect of the
dye itself. At a high dye concentration, a signicant
amount of UV may be absorbed by the dye molecules
rather than the TiO2 particles and thus reduces the efciency of the catalytic reaction (Mills et al., 1993).
Another possible cause is the interference from intermediates formed upon PCO of the parental dye.
These intermediates may include aromatics, aldehydes,
ketones and organic acids as shown by previous studies
with various aromatic compounds (Serpone et al., 1993;
dHennezel et al., 1998; Tanaka et al., 2000). They may
compete with the dye molecules for the limited adsorption and catalytic sites on the TiO2 particles (Ollis et al.,
1989) and thus inhibit decolorization. Such a suppression would be even more pronounced in the presence of
an elevated level of degradation intermediates formed
upon an increased initial dye concentration. Although
we have not yet identied the intermediates formed
during the PCO of Procion Red MX-5B, their occurrence was clearly indicated by the presence of about 8%
of organic carbon (TOC) remaining when more than
90% of the dye was decolorized.

(Mills et al., 1993; Lea and Adesina, 1998). Such an

eect was expected as UV intensity determines the
amount of photon absorbed by the catalyst. In addition,
previous studies also show that the relationship between
reaction rate and UV intensity starts to change from
rst-order (rate / UV intensity) to half-order [rate /
(UV intensity)1=2 ] when UV intensity is increased beyond
a certain value (approximately 25 mW=cm2 ) (Herrmann, 1999). It appears that the UV intensities tested in
our study lie within the linear range where utilization of
the light energy is the most ecient.
3.3. Eect of catalyst loading

The eect of UV intensity on the decolorization of

Procion Red MX-5B is shown in Fig. 4. The pseudorst-order rate constant steadily increased with UV intensity and showed a largely linear relationship. The
result is consistent with previous studies which generally
observed an increase in PCO rate with UV intensity

The eect of TiO2 loading on decolorization rate is

presented in Fig. 5. In the absence of the catalyst, no
decolorization was observed. Decolorization started
when 100 mg/l of TiO2 was added and the rate increased
sharply with catalyst loading up to 500 mg/l. However,
only a slight enhancement was observed when TiO2
concentration further increased to 2000 mg/l. Similar
observations were also reported in other studies on dyes
and various organics (Davis et al., 1994; Lea and Adesina, 1998; Goncalves et al., 1999).
At the concentration range from 100 to 500 mg/l, the
observed enhancement in decolorization is probably due
to an increased number of available adsorption and
catalytic sites on TiO2 . A further increase in catalyst
loading, however, may cause light scattering and
screening eect and thus reducing the specic activity of
the catalyst (Lea and Adesina, 1998). In addition, agglomeration and sedimentation of the TiO2 particles
were observed in our study when 2000 mg/l of TiO2 was
added to the dye solution. In such a condition, part of

Fig. 4. Eect of UV intensity on the pseudo-rst-order rate

constant for the photocatalytic oxidation of Procion Red MX5B. Results are means of duplicates and error bars represent 1
S.D. (Experimental conditions: dye, 40 mg/l; TiO2 , 100 mg/l;
initial pH, 5.0; temperature, 23C.)

Fig. 5. Eect of titanium dioxide concentration on the pseudorst-order rate constant for the photocatalytic oxidation of
Procion Red MX-5B. Results are means of duplicates and error
bars represent 1 S.D. (Experimental conditions: dye, 40 mg/l;
initial pH, 5.0; UV intensity, 4:26 mW=cm2 , temperature,
23C.)

3.2. Eect of UV intensity

C.M. So et al. / Chemosphere 46 (2002) 905912

the catalyst surface probably became unavailable for

photon absorption and dye adsorption, thus bringing
little stimulation to the catalytic reaction.
3.4. Eect of hydrogen peroxide

909

H2 O2 level gets too high. Furthermore, H2 O2 can be

adsorbed onto TiO2 particles to modify their surfaces
and subsequently decrease its catalytic activity (Malato
et al., 1998).
3.5. Eect of pH

Decolorization of Procion Red MX-5B was markedly

enhanced by the addition of H2 O2 . As seen in Fig. 6, the
pseudo-rst-order rate constant increased by about 10fold when H2 O2 concentration changed from 0 to 10
mM. Little enhancement, however, was observed when
the concentration further increased to 20 and 40 mM. A
concentration of 10 mM appears to be optimal. Similar
observations were also reported in previous studies
where an increase in H2 O2 level enhanced PCO rate up
to an optimal point beyond which inhibition occurred
(Malato et al., 1998; Poulios and Aetopoulou, 1999).
As described in Section 1, H2 O2 serves two roles in
PCO to cause an enhancement eect. It can both act as a
source of  OH (Eqs. (5) and (6)) and as a conductionband electron acceptor (Eq. (7)) to prevent electronhole
recombination. However, when present at high concentration, H2 O2 can also become a scavenger of valenceband holes (Eq. (8)) and  OH (Eqs. (9) and (10)) (Legrini
et al., 1993; Malato et al., 1998):


As both h
VB and OH are strong oxidants for organic
compounds, the PCO reaction will be inhibited when

Fig. 7 shows the eect of pH on the decolorization of

Procion Red MX-5B in the presence of 100 mg/l of TiO2
and the absence of hydrogen peroxide. Decolorization
was the fastest at pH 10 and the pseudo-rst-rate constant gradually decreased with the lowering of pH.
Similar results were also reported by Hustert and Zepp
(1992) and Tang and An (1995) for acidic azo dyes
bearing sulfonate groups, whose degradation was the
fastest at more alkaline pHs. However, dierent optimal
pHs (67) have also been observed for the PCO of other
sulfonated azo dyes (Tang et al., 1997; Poulios and
Aetopoulou, 1999).
Previous studies indicate that pH may aect PCO in a
number of ways. First, the charge of the dye molecules
with ionizable functional groups and the surface of the
TiO2 catalyst are both pH dependent. pH changes can
thus inuence the adsorption of dye molecules onto the
catalyst surfaces, an important step for PCO to take
place (Fox and Dulay, 1993). Second, as indicated in
Equation 3,  OH can be formed by the reaction between
hydroxide ion and positive hole. An alkaline condition
would thus favor  OH formation and enhance degradation. Third, the TiO2 particles tend to agglomerate
under acidic condition and the surface area available for
dye adsorption and photon absorption would be reduced (Fox and Dulay, 1993).

Fig. 6. Eect of hydrogen peroxide concentration on the

pseudo-rst-order rate constant for the photocatalytic oxidation of Procion Red MX-5B. Results are means of duplicates
and error bars represent 1 S.D. (Experimental conditions:
dye, 40 mg/l; TiO2 , 100 mg/l; initial pH, 5.0; UV intensity,
4:26 mW=cm2 , temperature, 23C.)

Fig. 7. Eect of initial pH on the pseudo-rst-order rate constant for the photocatalytic oxidation of Procion Red MX-5B.
Results are means of duplicates and error bars represent 1
S.D. (Experimental conditions: dye, 40 mg/l; TiO2 , 100 mg/l;
UV intensity, 4:26 mW=cm2 , temperature, 23C; no H2 O2 .)

H2 O2 2h
VB ! O2 2H

H2 O2  OH ! H2 O HO2
HO2  OH ! H2 O O2

8
9
10

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C.M. So et al. / Chemosphere 46 (2002) 905912

Fig. 8. Eect of initial pH on the pseudo-rst-order rate constant for the photocatalytic oxidation of Procion Red MX-5B
at elevated TiO2 and H2 O2 concentrations. Results are means of
duplicates and error bars represent 1 S.D. (Experimental
conditions: dye, 40 mg/l; TiO2 , 500 mg/l; H2 O2 , 10 mM; UV
intensity, 4:26 mW=cm2 ; temperature, 23C.)

In this study, a high pH would have hindered the

adsorption of Procion Red MX-5B onto the TiO2 surfaces as both would be predominantly negatively
charged. However, pH 10 was found to be the optimal
point under the given experimental conditions (TiO2 ,
100 mg/l; no H2 O2 ). This may indicate that the dye is
highly susceptible to be attacked by  OH despite a weak
adsorption of the dye onto the catalyst. On the other

hand, at pH 24, agglomeration of TiO2 particles was

indeed observed in our study. This might have reduced
the availability of catalyst surface for dye adsorption
and photon absorption, thus lowering the PCO rate at
acidic pH.
We also investigated the eect of pH in the presence
of 500 mg/l of TiO2 and 10 mM of H2 O2 , the two conditions which were shown to bring the greatest enhancement to decolorization. The results, however, were
very dierent from those obtained with 100 mg/l of TiO2
and no H2 O2 . As seen in Fig. 8, the highest decolorization rate was observed at pH 35 and the pseudorst-order rate constant decreased with pH. At this
point, we cannot explain why only the signicant interaction between pH and concentration of TiO2 or H2 O2
in the PCO degradation of the dye; and how the elevated
TiO2 and H2 O2 concentrations would have such a different impact on the optimal pH of the PCO reaction. A
more thorough study will be undertaken to seek an explanation for such observations.
3.6. Mineralization of Procion red MX-5B under optimal
conditions
Based on the results obtained in the characterization
experiments, the optimal conditions for the PCO of
Procion Red MX-5B, at a UV intensity of 17 mW=cm2
and a temperature of 23C, were found to be: TiO2
concentration, 500 mg/l; H2 O2 concentration, 10 mM;
pH, 5.0. Degradation and mineralization of Procion Red
MX-5B by PCO under such conditions was studied by

Fig. 9. Decolorization, total organic carbon loss and sulfate ion formation during the photocatalytic oxidation of Procion Red MX-5B
under optimal conditions. Results are means of duplicates and error bars represent 1 S.D. (Experimental conditions: dye, 40 mg/l;
TiO2 , 500 mg/l; H2 O2 , 10 mM; initial pH, 5.0; UV intensity, 17 mW=cm2 ; temperature, 23C.)

C.M. So et al. / Chemosphere 46 (2002) 905912

monitoring TOC loss and sulfate ion formation in the

dye solution.
Fig. 9 shows the changes of dye, TOC and sulfate ion
concentrations in the reaction solution during the PCO
process. As indicated by the absorbance at 538 nm, the
parental dye was decolorized by >90% within the rst 10
min. TOC in the solution, however, remained almost
unchanged within the same period of time, indicating the
formation of organic intermediates derived from the
dye. The TOC level then declined with time but almost
remained at a constant level (about 1.2 mg/l) up to 120
min of irradiation. In a later experiment with a 200-mg/l
dye solution, the persistence of a higher level of residual
TOC (c.a. 4 mg/l) was also observed after 7 h of irradiation (data not shown). Release of sulfate ions upon
dye degradation was a little slower than decolorization
but was much faster than TOC loss.
These results indicate that the fast decolorized dye
was followed by much slower mineralization of intermediates formed subsequently. Furthermore, most of
the total sulfate ions released were observed within the
rst 20 min, indicating that the removal of sulfonate
groups is an early step in the degradation process. On
the other hand, the persistence of a low but constant
level of TOC in solution suggests the accumulation of
dead-end product(s) which is(are) resistant to degradation by the PCO reaction. Similar results have also been
reported for other azo dyes constituted of triazine derivatives (Hu and Wang, 1999; Wang, 2000). In addition, previous works show that TiO2 -mediated PCO of
some triazine-derived compounds can be very slow (with
half-life in hours) and cyanuric acid (2,4,6-trihydroxy1,3,5-triazine) is usually found as a dead-end product
due to its high resistance to degradation by the PCO
process (Minero et al., 1997). Thus, the residual TOC
observed in our study may be attributed to some triazine-related compound(s) like cyanuric acid. Despite its
resistance to PCO, cyanuric acid has a relatively low
toxicity and is biodegradable (Minero et al., 1997).
Therefore, it should be readily removed by biological
treatment systems and is unlikely to pose a problem to
the environment.

4. Conclusions
We characterized the PCO of a monoazo dye Procion
Red MX-5B. Optimal physico-chemical conditions for
the degradation a 40-mg/l dye solution, at 17 mW=cm2
of UV irradiation and room temperature (23C), were
determined to be: TiO2 concentration, 500 mg/l; initial
H2 O2 concentration, 10 mM; initial pH, 5.0. Under
these conditions, the dye can be decolorized in 20 min
and mineralized by 90% in 80 min. The short reaction
times (20 min and 80 min for decolorization and min-

911

eralization, respectively) indicate that PCO can be used

as a simple, ecient and economic treatment of wastewater containing azo dye. Mineralization, however, was
not complete. Dead-end product(s), probably triazine
derivative(s), may have accumulated probably due to
resistance to degradation by the TiO2 -mediated PCO
reaction. Further study under these optimized conditions to decolorize/degrade azo dyes with mono-, di-, triand tetra-azo bonds by PCO will determine the relations
between the structure and PCO degradation. In addition, using other azo dyes with structure similar to
Procion Red MX-5B may provide further information
to identify intermediate products of PCO degradation of
azo dyes.

Acknowledgements
The study was supported by a research grant of Research Grant Council, Hong Kong SAR Government to
P.K. Wong. C.M. So was partially supported by a Postdoctoral Fellowship of the Research Committee, The
Chinese University of Hong Kong.

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