Chemosphere 66 (2007) 17821788

www.elsevier.com/locate/chemosphere

Technical Note

Mechanism of decolorization and degradation of CI Direct Red 23

by ozonation combined with sonolysis
Shuang Song *, Haiping Ying, Zhiqiao He, Jianmeng Chen
College of Biological and Environmental Engineering, Zhejiang University of Technology,
Hangzhou 310032, Peoples Republic of China

Received 15 December 2005; received in revised form 28 July 2006; accepted 30 July 2006
Available online 14 September 2006

Abstract

The decolorization and degradation of CI Direct Red 23, which is suspected to be carcinogenic, were investigated using ozonation
combined with sonolysis. The results showed that the combination of ozonation and sonolysis was a highly eective way to remove color
from waste water. The operational parameters, namely concentration of the dye, pH, ozone dose and ultrasonic density, were investi-
gated during the process. The decolorization of the dye followed pseudo-rst-order kinetics. Increasing the initial concentration of Direct
Red 23 led to a decreasing rate constant. The optimum pH for the reaction was 8.0, and both lower and higher pH decreased the removal
rate. The eect of the ozone dose on the dye decolorization was much greater than that of the sonolysis density. Intermediates such as
naphthalene-2-sulfonic acid, 1-naphthol, urea and acetamide were detected by gas chromatography coupled with mass spectrometry in
the absence of pH buer, while nitrate and sulfate ions and formic, acetic and oxalic acids were detected by ion chromatography. A ten-
tative degradation pathway was proposed without any further quantitative analyses. During the degradation, all nitrogen atoms and
phenyl groups of Direct Red 23 were degraded into urea, nitrate ion, nitrogen and formic, acetic and oxalic acids, etc.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Ozonation; Sonolysis; Azo dye; Degradation pathway; Pseudo-rst-order kinetics

1. Introduction
There are many dierent classes of dyes, such as azo,
anthraquinone, metal complex, azo metal complex and
phythalocynanine, reecting the chromophoric structure
of their constituent molecules. Of these dyestus, the azo
dyes are the most frequently used. They contain one or
more azo groups (N@N) bound to an aromatic group.
As they have been designed to resist chemical and photo-
chemical degradation, conventional chemical and biologi-
cal methods are not ecient means of degrading azo
dyes. On the other hand, anaerobic reductions often gener-
ate aryl amines, which are generally more toxic than the
parent compounds (Acuner and Dilek, 2004). It is known
*
Corresponding author. Tel.: +86 571 88320726; fax: +86 571
88320276.
E-mail address: ss@zjut.edu.cn (S. Song).
that soluble azo dyes, when incorporated into the body,
are split into the corresponding aromatic amines by the
liver enzymes and intestinal microora, which can cause
cancer in humans (Weisburger, 2002; Bhaskar et al.,
2003; Golka et al., 2004). Therefore, it is necessary to nd
an eective method to remove colored dyes from euents.
Ozone is a powerful oxidizing agent that can degrade a
wide variety of dyes in aqueous solution by destroying most
of the double bonds, such as C@C, C@N, and N@N
(Gogate and Pandit, 2004a; Martins et al., 2006). Ozone
can react with aqueous compounds either by direct O3
attack or indirect attack via hydroxyl radical (OH) chains
resulting from the decomposition of O3, depending on the
operational pH (Chen et al., 2002; Zhao et al., 2004). How-
ever, there are limitations to the use of O3, such as the inten-
sity of energy required to generate ozone, its pH sensitivity
and its selectivity for organic substrates. The ozonation
process requires further research and development.

0045-6535/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2006.07.090
 S. Song et al. / Chemosphere 66 (2007) 17821788
The joint application of ultrasound (US) and other oxi-
dation techniques has yielded some interesting investiga-
tions that can improve degradation rates (Narechoux
et al., 2000; Ince and Tezcanl, 2001; Gogate and Pandit,
2004b). In US/O3, the mass transfer and decomposition
processes of O3 can be enhanced by US to improve the pro-
duction of free radicals (e.g., OH) to achieve better degra-
dation eects (Hart and Henglein, 1986; Weavers and
Homann, 1998; Destaillats et al., 2000). This is a new area
of investigation, and studies are still being conducted on a
laboratory scale.
The role of ozonation with US and the related oxidation
process in treating several organic dyes has been examined
by dierent authors (Alaton et al., 2002; Neamtu et al.,
2004; Tezcanli-Guyer and Ince, 2004; Martins et al.,
2006). However, most of these studies paid little attention
to the pathway of degradation.
CI Direct Red 23 (4BS) was selected for study because it
is not quickly biodegraded and is widely used in the textile
industries. He et al. (2004) studied the degradation of
50 mg l1 4BS solution in a 100 ml reactor with dierent
microorganisms and treatment processes. It was reported
that 4BS was completely eliminated in at least 6 h by mea-
suring the optical density at 500 nm using a spectropho-
tometer. When the concentration of 4BS was increased, a
longer reaction time was required. Zhu et al. (2000) used
photocatalytic technology during 4BS degradation but
did not investigate the degradation pathway.
The objectives of this study were to investigate the opti-
mum conditions for degradation of the azo dye 4BS and
the degradation mechanism itself when combining ozona-
tion and sonolysis.
2. Experimental
2.1. Reagents
4BS (MW = 813.73 g mol1) was obtained from Zhe-
jiang Runtu Co., Ltd., in over 99% purity and used without
further purication. The solubility of 4BS in water is
30 g l1 at 80 C.
2.2. Apparatus
The experimental apparatus employed in this work is
shown in Fig. 1. The cylindrical pyrex glass reactor (diameter
100 mm, height 150 mm) was coupled with an ultrasonic
processor (YIY-UL04-B, Shanghai Yiyuan Ultrasonic
Equipment Co., Ltd.), an O3 supply system (CHYF-3 A,
rated ow 50 mg min1, Hangzhou Rongxin Electronic
Equipment Co., Ltd.) generated onsite by electricity using
dry pure oxygen and an exhaust treatment system. The ultra-
sonic processor (400 W output, variable power control) was
equipped with a 20 kHz converter (diameter 106 mm, height
225 mm) and a pure titanium probe (tip diameter 16 mm,
height 164 mm), the processing capability of which was
1001000 ml. The glass reactor was sealed by a polyethylene
1783
7
3
off gas
2 4
1
oxygen 5 6 8
Fig. 1. Schematic of the experimental set-up. (1) Ozone generator; (2)
rotameter; (3) three-way valve; (4) to input ozone gas detection; (5)
thermostatic bath; (6) reactor; (7) ultrasonic generator; (8) absorption
bottle.
cap during operation. The probe was partially immersed in
the liquid and xed at the center of the polyethylene cap.
The oxygen ow rate to the generator was monitored with
a rotameter incorporated into the ozone generator. In this
experiment, the ozone concentrations in the feed were kept
at 0.63.2 g h1. Surplus ozone was passed into gas absorp-
tion bottles containing 2% KI solution. The experiments
were carried out in a thermostated bath.
Aqueous solutions (500 ml) containing 4BS at dierent
concentrations were used. 4BS was degraded with the
desired O3 dose and/or US density. All experiments were
carried out at 25 0.5 C. Samples withdrawn by a glass
syringe at various reaction times were passed through a
0.45 lm membrane lter and analyzed for solutes.
2.3. Analytical methods
The determination of 4BS in aqueous solution was car-
ried out on a UV-9200 ultravioletvisible spectrophotome-
ter (Beijing Rayleigh Analytical Instrument Corp, Beijing,
China) equipped with a photoelectric detector at the maxi-
mum absorption wavelength of 500 nm.
Aromatic intermediates were detected by gas chroma-
tography coupled with mass spectrometry (GC/MS) (GC,
Varian cp3800 system; MS, Varian Saturn 2000 mass spec-
trometer). The GC was equipped with a WCOT fused silica
series column (30 m 0.25 mm) and 0.25 lm lm thick-
nesses and interfaced directly to the MS. The GC column
was operated for 2 min at a temperature of 80 C, which
was then increased to 250 C at the rate of 15 C min1.
The other experimental conditions were EI impact ioniza-
tion 70 eV, helium as carrier gas, injection temperature
280 C, and source temperature 80 C.
Carboxylic acids and nitrate and sulfate ions were deter-
mined by an ion chromatograph (792Basic IC, Metrohm,
Switzerland) with a separating column (Metrosep A Supp
5250, 250 mm 4.0 mm), electrical conductivity detector
using NaHCO3 (1.0 mM)/Na2CO3 (3.2 mM)/methanol
(3%) eluent and a total ow rate of 0.6 ml min1. The sam-
ples (20 ll) were injected manually through an injection
port.
1784 S. Song et al. / Chemosphere 66 (2007) 17821788
The pH values were measured via a pHs-25 (Rex Ana-
lytical Instrument Co. Ltd., Shanghai, China). The US
power dissipated into the reactor was adjusted and esti-
mated by calorimetry in order to ensure comparative US
conditions (Kimura et al., 1996). The ozone concentration
was determined by an iodometric method (IOA, 1987).
2.4. Procedures
Phosphate buers were prepared previously in deionized
water by the reaction of calculated amounts of sodium
hydroxide solution and phosphoric acid solution to yield
an ionic strength of 0.0667 M. A 500 mg l1 stock dye solu-
tion, which was used in a test scheme and stored at 4 C, was
prepared by dissolving 500 mg of 4BS in 1000 ml of phos-
phate buer. Dye solutions of various strengths were made
from the stock by proper dilutions with phosphate buers.
In order to avoid interference from other substances and
to identify accurately the intermediates of the 4BS reaction
sequence and the pH changes during the US/O3 process,
500 mg of 4BS were dissolved in 1000 ml of deionized
water, which was classied as a non-buered dye solu-
tion. Samples of 10 ml were removed from the reactor at
30 and 80 min for the GC/MS analysis.
3. Results and discussion
3.1. Eect of initial dye concentration
The dye had a maximum absorption at 500 nm in aque-
ous solution in the UVvis spectrum. During the decolor-
ization studies, the change in peak absorption of the dye
solution was monitored. The 4BS decolorization kinetics
obtained during US/O3 tted a rst-order curve as illus-
trated in Fig. 2. Fig. 2a shows the decolorization of 4BS
at dierent initial concentrations at pH 8.0 with a US den-
sity of 176 W l1 and an ozone dose of 3.2 g h1.
Pseudo-rst-order rate constants at various initial con-
centrations of 4BS are given in Table 1. It is noticeable that
the rate constants decreased with increasing initial concen-
tration of 4BS. The rate constants for the degradation of
4BS are 3.7 and 0.9 min1 at the initial concentrations of
100 and 500 mg l1, respectively. As the other operations
were not changed, the numbers of cavities and OH radicals
generated in solution approached a steady state. Addition-
ally, competition between the dye metabolites and the sub-
strate for OH became intense owing to the non-selective
properties of OH. Considering the above factors, the
removal rate of the apparent color could be decreased by
increasing the initial concentration of 4BS. Thus, reaction
mixtures containing more dilute initial solutions could be
expected to exhibit faster rates of decolorization.
3.2. Eect of pH
The pH of the solution is an important factor in deter-
mining the rate constant. The impact of pH (in the range
4.012.0) on the color decay of a 100 mg l1 solution of
4BS with a US density of 176 W l1 and an ozone dose
of 3.2 g h1 was studied by comparing the absorbance
decay rates. The results are shown in Fig. 2b and Table
1, where rate coecients and regression statistics are pre-
sented. During the reaction, the pH of these solutions
changed by less than 0.2. As can been seen, the decay rate
coecient at pH = 8.0 (rate constant was 3.7 min1) was
much larger than the others. The rate constants obtained
at pH values of 4.0, 6.0, 10.0 and 12.0 were 2.2, 3.1, 2.7
and 2.4 min1, respectively. This is due to competition
between several reactions. The various phosphate species
will react with the OH at dierent rates depending upon
the particular species present. The reaction of OH with
the various phosphate species would be expected to be
slowest in the pH range of 2.84.5 (Jiang et al., 2002). In
addition, the reaction of OH with the dye might be easier
under alkaline than under acidic conditions. As a result,
the optimal operational pH was 8.0 during these experi-
ments.
3.3. Eect of ozone dose and US density
Dierent doses of ozone were injected into the dye solu-
tions during sonolysis (176 W l1) and the results are shown
in Fig. 2c and Table 1. After 1 min of reaction, the 4BS
removal observed was 64%, 78%, 89% and 98% with O3
doses of 0.6, 1.8, 2.7 and 3.2 g h1, respectively. The
pseudo-rst-order rate constant increased from 1.0 min1
with an O3 dose of 0.6 g h1 to 3.7 min1 with an O3 dose
of 3.2 g h1. This indicated that the dye degradation
depended upon the dissolution of ozone, which determines
the amount of OH generation and aects the transfer of
ozone into the reaction solution. It also indicates that the
reaction is mass transfer limited. An increase in O3 dose
could improve the mass transfer of O3 and cause an
increased O3 concentration in the liquid phase and a higher
rate constant (Sevimli and Sarikaya, 2002). However, when
the O3 dose and ozonation time were increased, the O3 uti-
lization ratio decreased. Therefore, it was not necessary to
try to increase the concentration of O3 to saturation level.
In order to understand the eect of US density on the
degradation rate, the reaction was conducted using
an ultrasonic horn (20 kHz) with dierent power settings
at pH 8.0 with a 4BS concentration of 100 mg l1 and an
ozone dose of 3.2 g h1. The results are presented in
Fig. 2d and Table 1. When the US density ranged from
88 to 352 W l1, approximately 98% of the 4BS was re-
moved after 1 min of US/O3treatment. Rate constants of
3.6, 3.7, 3.7 and 3.8 min1 were obtained at US densities
of 88, 176, 264 and 352 W l1, respectively. In other words,
with an increase in US density, the change in the coecient
of decay was negligible. According to Neppolian et al.
(2002), there are at least three factors aecting the charac-
teristics of US: power density, frequency and amplitude of
the system. The ultrasonicator used in this experiment was
kept at a constant frequency (20 kHz). A greater US
 S. Song et al. / Chemosphere 66 (2007) 17821788 1785

1.0 1.0
-1
100 mg l pH = 4.0
0.8 200 mg l
-1 0.8 pH = 6.0
-1 pH = 8.0
300 mg l
-1 pH = 10.0
0.6 400 mg l 0.6
-1
pH = 12.0
A/A0

A/A0
500 mg l
0.4 0.4

0.2 0.2

0.0 0.0
0 2 4 6 8 0 1 2 3 4
Time (min) Time (min)

c 1.0
d 1.0
-1 -1
C(O3) = 0.6 g h P(US) = 88 W l
0.8 C(O3) = 1.8 g h
-1 0.8 P(US) = 176 W l
-1

-1 -1
C(O3) = 2.7 g h P(US) = 264 W l
-1 -1
0.6 C(O3) = 3.2 g h 0.6 P(US) = 352 W l
A/A0

A/A0
0.4 0.4

0.2 0.2

0.0 0.0
0 1 2 3 4 5 6 7 8 0.0 0.5 1.0 1.5 2.0 2.5
Time (min) Time (min)

Fig. 2. Eect of process variables on decolorization of dye: (a) eect of initial concentrations of dye: pH = 8.0; O3 dose = 3.2 g h1; US
density = 176 W l1, (b) eect of pHs: initial dye concentration = 100 mg l1; O3 dose = 3.2 g h1; US density = 176 W l1, (c) eect of O3 dose: initial
dye concentration = 100 mg l1; pH = 8.0; US density = 176 W l1, (d) eect of US density: initial dye concentration = 100 mg l1; pH = 8.0; O3
dose = 3.2 g h1.

Table 1 and acoustic screen; the degassing rates of O3 gas will

Pseudo-rst-order rate coecients of various operation parameters during become higher, resulting in lower concentrations of O3 or
degradation
radicals. Thereby, with an increasing US density, the incre-
Operation parameters Pseudo-rst-order ment of decolorization rate would be attenuated.
(k) (min1)
Initial pH Ozone US Fig. 3 shows the decolorization of the dye solution
concentration dose density (100 mg l1) at pH 8.0 using US, O3 and US/O3, respec-
(C0) (mg l1) (g h1) (W l1)
tively. US and O3 alone are less eective than the combina-
100 8.0 3.2 176 3.7
200 8.0 3.2 176 2.2
300 8.0 3.2 176 1.7
400 8.0 3.2 176 1.1 1.0
500 8.0 3.2 176 0.9
100 4.0 3.2 176 2.2 0.9
100 6.0 3.2 176 3.1 0.8
100 10.0 3.2 176 2.7
100 12.0 3.2 176 2.4 0.7 US
100 8.0 0.6 176 1.0 O3
0.6
100 8.0 1.8 176 1.5 US + O3
100 8.0 2.7 176 2.4 0.5
A/A0

100 8.0 3.2 88 3.6

0.4
100 8.0 3.2 264 3.7
100 8.0 3.2 352 3.8 0.3

0.2

density means greater energy supplied so as to cause cavi- 0.1

tation bubbles at a higher temperature. Hence, the degra- 0.0
dation rate of 4BS should increase with power density. 0 1 2 3 4 5 6 7 8
However, when the US density increases, the dissipated Time (min)
energy will increase. Meanwhile, the cavitation bubbles will Fig. 3. Comparison of US, O3 and US/O3 for color decay: initial dye
grow very large in the negative phase of the sound wave, concentration = 100 mg l1; pH = 8.0; O3 dose = 3.2 g h1; US density =
resulting in insucient collapse of the cavitation bubbles 176 W l1.
1786 S. Song et al. / Chemosphere 66 (2007) 17821788
tion of US and O3. During US only treatment, the investi-
gated azo dyes were found to be fairly stable, with only 4%
of 4BS removed from solution in 8 min. Ozonation alone
can remove 16% and 97% of the dye in 1 and 8 min, respec-
tively. In the combined method, approximately 98% of 4BS
has been removed from solution in 1 min. Tezcanli-Guyer
and Ince (2004) also reported that the degradation rate
using O3, as well as US/O3, was much greater than that
using US alone during RB5 degradation. Both sonolysis
and ozonation are known to produce OH radicals in aque-
ous solution, which may attack the 4BS molecule, thus
beginning the degradation. The poor eect of US alone
on the degradation may be attributed to the fact that US
treatment usually demands a long contact time (Ince and
Tezcanl, 2001; Martins et al., 2006). In the combined
method, the US waves can improve the degradation e-
ciency by enhancing the eciency of O3 dissolution and
the yield of free radicals via the mechanical action of US.
On the other hand, aeration of O3 might increase the turbu-
lence of the aqueous solution, which would increase the
migration of some related substances from the collapsing
cavities into the bulk of the solution.
3.4. Degradation mechanism
In this part of the study, samples were taken from the
reactor periodically to analyze pH and nitrate and sulfate
ion concentrations. During the reaction, the pH changed
from 5.7 to 2.9. Organic intermediates generated during
the degradation of the oxidative dye detected by GC/MS
or IC are shown in Table 2. The reason that quantitative
analyses of these species was not done is because the reac-
Table 2
Intermediates identied by GC/MS and IC
Symbol Compounds Structural formula
NaO 3 S
D1 Naphthalene-2-sulfonic acid
O
D2 Urea
H2N
D3 1-Naphthol
OH
O
D4 Acetamide H2 N
CH 3
D5 Acetic acid CH3COOH
D6 Oxalic acid HOOCCOOH
D7 Formic acid HCOOH
tion system was very complex and a certain amount of
inorganic salts, such as Na2SO4, produced during the reac-
tion in water would aect the quantitative analysis of
organic moieties (Ohsawa et al., 2004).
The synergistic eect of combining ozonation with ultra-
sonic irradiation is observed only when free radical attack
is the controlling mechanism (Gogate and Pandit, 2004b).
Among the radicals, OH is an important one and has the
highest oxidation potential of 2.8 V (Muthukumar and Sel-
vakumar, 2004). Hence, based on our results and assuming
that OH radicals are the major reactive species, a substitu-
tion reaction mechanism was established for this system. A
tentative pathway for the degradation of 4BS during US/
O3 was postulated and is presented in Fig. 4.
The partial charge shows that the OH adds to the N(8),
C(14), C(22), C(27), and C(37) positions to form the state
S2. With the help of a hydrogen radical, N(8)C(9),
C(14)N(19), N(21)C(22), C(27)N(32), and C(37)
N(40) are potentially cleaved to form S3, D1, D2, D3, and
D4. Owing to the non-selective nature of radical reactions,
it is possible for the reaction of R1 to yield D3 and for the
reaction of R3 to form D1.
For compound S3, azobenzol can be hydrolyzed in
aqueous solution to yield phenylium which is further oxi-
dized by OH to form hydroquinone and benzo-1,4-qui-
none. Then, the benzene ring is cleaved to form but-2-
enedioic acid and nally to form carboxylic acids such as
acetic acid and formic acid.
Under the inuence of the OH and aqueous solution,
state D1 is then transformed into compound S5. The ben-
zene ring in 2-hydroxynaphthoquinone is then cleaved to
form state S11 by further oxidation.
Analytical methods Samples time (min)
GC/MS IC 30 80
p p
p p p
NH2
p p
p p
p p
p p
p p
 S. Song et al. / Chemosphere 66 (2007) 17821788 1787

O
NaO 3 S 11 13 23 25 SO 3 Na
4 5 10 12 14 NH 20 NH 22 24 26 O
19 21 35 36
3 6 N N 9 17 15 31 29 27
7 8 18 16 30 28 N N 34 37 NH 41 CH 3
2 1 32 33 40
39 38 42
OH OH
a (S1)

O H H O
O SO 3 Na
NaO 3 S
NH NH H O H
O
N N O
N N NH CH 3
O OH OH
(S2)
H
R1 R2 R3 R4

NaO 3 S 2 O 1 O
N N O 1

C H2 N C CH 3
(S3) 3 H2 N NH2
(D1) (D2) (D3) (D4 )
a OH
a
a a

C OH OH
HO
CH3COOH, HCOOH, NO3-
(S4) (D5) (D7)
, SO4- b
a
(S5)
OH OH (S6)
a CO2
HO OH
a
(S7) O
a O
HO

O O (S9)
a a O
(S10) (S8) O
O
a
O a) hydroxyl radical
COOH b) hydroxyl radical or ozone
(S11) O c) hydroxyl radical and water
d) hydroxyl radical and hydrogen radical
COOH
(S12) c S: tentative states
b D: intermediates that determined by
COOH IC or GC/MS
CH3COOH, HOOCCOOH, CO2, etc a/b
(D5) (D6) COOH , CO2, etc
(S12)

Fig. 4. The probable degradation pathway of 4BS: initial dye concentration = 500 mg l1; initial pH = 5.7; O3 dose = 3.2 g h1; US density = 176 W l1.

As the hydroxyl group of state D3 is an active group, site Fig. 4 shows that overall the degradation processes are
1 is active. State D3 is then transformed into compound S6, attributed to hydroxyl radical reactions. With the help of
which can be further oxidized into state S9 by OH. As combined US/O3, OH radicals can be easily produced
above, the benzene ring in naphthoquinone can be cleaved (Shu and Chang, 2005).
to form state S11.
The benzene ring in 2-benzofuran-1,3-dione can be 4. Conclusions
cleaved by the cooperation of OH and water. Then the
compound S11 breaks down into the compounds but-2- The results obtained in this study show that ozonation
enedioic acid, acetic acid, carbon dioxide, etc. combined with sonolysis is an eective technology for the
The CN and CC bonds in acetamide can be cleaved by treatment of 4BS solutions.

OH. The state D4 is transformed into acetic acid, formic In brief, it was found that the rate of color decay
acid and nitrate owing to the non-selectivity of OH. For- followed pseudo-rst-order kinetics with respect to the
mic acid can be transformed into carbon dioxide by further UVvis absorption of the test dye during reaction. The
oxidation. decay kinetics mainly depended upon the initial dye
1788 S. Song et al. / Chemosphere 66 (2007) 17821788
concentration, pH and O3 dose present in the aqueous
solution. Ozone alone was more eective than ultrasound
alone for color removal. The combination of US and O3
could enhance the mass transfer of ozone and the oxidative
species. From the experimental data obtained it was obvi-
ous that the impact of a change in US density was negligi-
ble, while increasing the dose of O3 considerably increased
the rate of reaction.
The major organic intermediates were detected by GC/
MS, and nitrate and sulfate ions and formic, acetic and
oxalic acids were detected by IC. A possible degradation
pathway involving a OH reaction mechanism was pro-
posed without further quantitative analyses. During the
tentative degradation, all of the intermediates derived from
the experiments except urea could be decomposed and oxi-
dized into formic, acetic or oxalic acids.
Acknowledgements
The authors are grateful for the nancial support pro-
vided by the Science and Technology Project of Zhejiang
Province, Peoples Republic of China (No. 021103548).
References
Acuner, E., Dilek, F.B., 2004. Treatment of tectilon yellow 2 G by
Chlorella vulgaris. Process Biochem. 39, 623631.
Alaton, I.A., Balcioglu, I.A., Bahnemann, D.W., 2002. Advanced oxida-
tion of a reactive dyebath euent: comparison of O3, H2O2/UV-C and
TiO2/UV-A processes. Water Res. 36, 11431154.
Bhaskar, M., Gnanamani, A., Ganeshjeevan, R.J., Chandrasekar, R.,
Sadulla, S., Radhakrishnan, G., 2003. Analyses of carcinogenic
aromatic amines released from harmful azo colorants by Streptomyces
SP. SS07. J. Chromatogr. A. 1018, 117123.
Chen, Y.H., Chang, C.Y., Huang, S.F., Chiu, C.Y., Ji, D., Shang, N.C.,
Yu, Y.H., Chiang, P.C., Ku, Y., Chen, J.N., 2002. Decomposition of
2-naphthalenesulfonate in aqueous solution by ozonation with UV
radiation. Water Res. 36, 41444154.
Destaillats, H., Colussi, A.J., Joseph, J.M., Homann, M.R., 2000.
Synergistic eects of sonolysis combined with ozonolysis for the
oxidation of azobenzene and methyl orange. J. Phys. Chem. 104, 8930
8935.
Gogate, P.R., Pandit, A.B., 2004a. A review of imperative technologies for
wastewater treatment I: oxidation technologies at ambient conditions.
Adv. Environ. Res. 8, 501551.
Gogate, P.R., Pandit, A.B., 2004b. A review of imperative technologies for
wastewater treatment II: hybrid methods. Adv. Environ. Res. 8, 553
597.
Golka, K., Kopps, S., Myslak, Z.W., 2004. Carcinogenicity of azo
colorants: inuence of solubility and bioavailability. Toxicol. Lett. 151,
203210.
Hart, E.J., Henglein, A., 1986. Sonolysis of O3 in aqueous solution. J.
Phys. Chem. 90, 30613062.
He, F., Hu, W., Li, Y., 2004. Biodegradation mechanisms and kinetics
of azo dye 4BS by microbial consortium. Chemosphere 57, 293
301.
Ince, N.H., Tezcanl, G., 2001. Reactive dyestu degradation by combined
sonolysis and ozonation. Dyes Pigments 49, 145153.
IOA Standardisation Committee-Europe, 001/87-F, 1987. Iodometric
Method for the Determination of Ozone in a Process Gas, Brussels.
Jiang, Y., Petrier, C., Waite, T.D., 2002. Eect of pH on the ultrasonic
degradation of ionic aromatic compounds in aqueous solution.
Ultrason. Sonochem. 9, 163168.
Kimura, T., Sakamoto, T., Leveque, J., Sohmiya, H., Fujita, M., Ikeda,
S., Ando, T., 1996. Standardization of ultrasonic power for sono-
chemical reaction. Ultrason. Sonochem. 3, S157S161.
Martins, A.O., Canalli, V.M., Azevedo, C.M.N., Pires, M., 2006.
Degradation of pararosaniline (CI Basic Red 9 monohydrochloride)
dye by ozonation and sonolysis. Dyes Pigments 68, 227234.
Muthukumar, M., Selvakumar, N., 2004. Studies on the eect of inorganic
salts on decolouration of acid dye euents by ozonation. Dyes
Pigments 62, 221228.
Narechoux, E., Chanoux, S., Petrier, C., Suptil, J., 2000. Sonochemical
and photochemical oxidation of organic matter. Ultrason. Sonochem.
7, 255259.
Neamtu, M., Yediler, A., Siminiceanu, I., Macoveanu, M., Kettrup, A.,
2004. Decolorization of disperse red 354 azo dye in water by
several oxidation processesa comparative study. Dyes Pigments 60,
6168.
Neppolian, B., Jung, H., Choi, H., Lee, J.H., Kang, J.W., 2002. Sonolytic
degradation of methyl tert-butyl ether: the role of coupled Fenton
process and persulphate ion. Water Res. 32, 46994708.
Ohsawa, I., Kanamori-Kataoka, M., Tsuge, K., Seto, Y., 2004. Determi-
nation of thiodiglycol, a mustard gas hydrolysis product by gas
chromatographymass spectrometry after tert-butyldimethylsilylation.
J. Chromatogr. A 1061, 235241.
Sevimli, M.F., Sarikaya, H.Z., 2002. Ozone treatment of textile euents
and dyes: eect of applied ozone dose, pH and dye concentration. J.
Chem. Technol. Biotechnol. 77, 842850.
Shu, H.Y., Chang, M.C., 2005. Decolorization eects of six azo dyes by
O3, UV/O3 and UV/H2O2 processes. Dyes Pigments 65, 2531.
Tezcanli-Guyer, G., Ince, N.H., 2004. Individual and combined eects of
ultrasound, ozone and UV irradiation: a case study with textile dyes.
Ultrasonics 42, 603609.
Weavers, L.K., Homann, M.R., 1998. Sonolytic decomposition of ozone
in aqueous solution: mass transfer eects. Environ. Sci. Technol. 32,
39413947.
Weisburger, J.H., 2002. Comments on the history and importance of
aromatic and heterocyclic amines in public health. Mutat. Res-Fund.
Mol. M. 506-507, 920.
Zhao, W., Shi, H., Wang, D., 2004. Ozonation of Cationic Red X-GRL in
aqueous solution: degradation and mechanism. Chemosphere 57,
11891199.
Zhu, C., Wang, L., Kong, L., Yang, X., Wang, L., Zheng, S., Chen, F.,
Zhi, F., Zong, H., 2000. Photocatalytic degradation of AZO dyes
by supported TiO2 + UV in aqueous solution. Chemosphere 41, 303
309.