Ultrasonics Sonochemistry 10 (2003) 235240

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Degradation and toxicity reduction of textile dyestu by ultrasound

G. Tezcanli-Guyer, N.H. Ince

Institute of Environmental Sciences, Bo

gazici University, 80815 Bebek-Istanbul, Turkey
Received 7 October 2002; accepted 6 February 2003

Abstract
Degradability of four textile dyes was investigated in deionized water solutions during 520 kHz ultrasonic irradiation. It was
found that for all dyes, the rate of color decay was rst order in the visible absorption of the dye, and related to the type of
functional groups that characterized the chromophore in the dye molecules. The destruction of aromatic/olenic carbons in azo dyes
was slower than that of colorto be attributed to the priority of hydroxyl radical attack on the N@N bonds, and to the formation
of numerous oxidation intermediates of organic character during the course of dye degradation. Toxicity analysis of the dye solutions prior to sonolysis revealed that reactive dyes were non-toxic, but basic ones were toxic at the test concentrations
employed in the study. Signicant degrees of toxicity reduction were accomplished along with color and aromatic carbon degradation.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Toxicity; Microtox; Azo; Oxazine; Ultrasonic cavitation; UV254

1. Introduction
Euents of textile dyeing processes are intensely
colored and contaminated with high concentrations of
chemical oxygen demand, suspended and dissolved salts
and traces of recalcitrant material [1,2]. If improperly
processed, these euents not only deteriorate the aesthetics of receiving waters and may hinder the penetration of oxygen, but also pose signicant threat to life
forms upon hydrolysis of some dyes in the wastewater to
form toxic products [3]. The reason for the presence of
dye residuals in wasted euents is that some dyes have
poor exhaustion capacities such that an important
fraction of them is ultimately discharged with spent
dyebaths.
Among such poorly exhausting dyes, those with azo
bonds have the largest consumption in textile dyeing
processes owing to their brilliant shades. Hence, much
research has been conducted on methods of azo dye
destruction, many of them being centered on advanced
oxidation processes (AOP). Treatability of azo dye so*

Corresponding author. Tel.: +90-212-3581540; fax: +90-2122575033.

E-mail address: ince@boun.edu.tr (N.H. Ince).

lutions by AOP, which generate hydroxyl radicals ( OH)

via a variety of common methods, has been widely reported in the literature [46]. A less common way of
onsite  OH generation is ultrasonic irradiation of the
liquid. By such, the dissolved vapors and gases in the
liquid are entrapped by cavitation bubbles, which release very high temperatures during their adiabatic collapse [7,8]. In sonolysis of water containing hydrophilic
compounds such as textile dyes, hydroxyl radicals are
generated only by water fragmentation in the collapsing
bubbles, and oxidative dye destruction is possible if the
radicals are eectively ejected into the solution bulk. The
eciency of  OH diusion into the aqueous phase is
related to system parameters such as frequency, reactor
geometry, presence of cavitation nuclei, and the ambient
conditions [9,10]. The mechanism and kinetics of ultrasonic azo dye degradation has been recently investigated
in pure dye solutions using simple compounds such as
azo benzene and methyl orange [11,12].
The purpose of this study was to investigate the effectiveness of 520 kHz ultrasonic pressure waves on the
destruction of textile dyestu in aqueous solutions. The
method involved exposure of three azo and one oxazine
dye of various strengths to ultrasound for 4 h, during
which euent samples were analyzed for color,

1350-4177/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S1350-4177(03)00089-0

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G. Tezcanli-Guyer, N.H. Ince / Ultrasonics Sonochemistry 10 (2003) 235240

aromatic/olenic content and Microtox toxicity. Test

solutions were made in mass concentrations (rather than
molar) to be consistent with actual dyeing recipes made
of xed mass concentrations of dyes and dyebath auxiliaries, dictated by the desired shade depth and not the
structure of the dye [13]. The test concentrations were
selected by referring to typical dye concentrations found
in dyeing mill euents, and operation parameters were
set in accordance with the maximum rate of color removal obtained during 1 h sonolysis of a model dye at
various ultrasonic power and dye concentrations.

2. Materials and methods

Two reactive and two basic dyes were used as
probe chemicals throughout the study. Color index (CI)
codes, molecular properties, maximum visible absorption bands, characteristic chromophore, manufacturing
source and the purity of commercially available products are presented in Table 1. No information was

provided by the companies about the impurities except

for the common knowledge that basic dyes contained
heavy metals such as zinc and chromium [14]. All of
Microtox reagents and supplies were obtained from
Azur Environment, UK.
2.1. Setup
The experimental set-up schematized in a previous
study [15] was made of a 1.2 l glass reactor surrounded
by a water cooling jacket to keep the contents at constant temperature (20
0.5 C); a plate type piezoelectric transducer (A 22.05 cm2 ) emitting ultrasonic
waves at 520 kHz, and a generator operating at 100 W
to convert electrical power input to mechanical energy
(Undatim Ultrasonics, Belgium).
2.2. Preparation of the test solutions
Stock dye solutions were prepared by dissolving 5 g
of each dye in 1 l of boiling deionized water in accordance

Table 1
Physicochemical and commercial properties of the test dyes
Chemical structure C.I./symbol

Vis-ABS/type functional Gr

MW (g mol1 )

Source/purity

544 nm disazo 2x(AN@NA)

1791

BASF 75%

596 nm disazo 2x(AN@NA)

991.8

DYESTAR-HOECHST 8085%

464 nm disazo 2x(AN@NA)

461.4

Aldrich 40%

654 nm oxazine

359.9

Aldrich 50%

G. Tezcanli-Guyer, N.H. Ince / Ultrasonics Sonochemistry 10 (2003) 235240

with dyeing recipes provided by a textile dyehouse for

5% shade depth [13]. Test solutions were made by diluting the stocks to typical euent dye concentrations
(2060 mg l1 ) using deionized water followed by 1 h
aeration. The pH of all test solutions was adjusted to a
range of 5.56.5 prior to sonication.
It is well known that reactive dyes used for shading
cellulosed bers have poor exhaustion capacities, while
the majority of basic dyes used in shading of synthetic
bers are xed quite well on the fabric [14]. Despite this
fact, we selected to investigate the degradability of basic
dyes as well, because even at very low concentrations
most of them are toxic in the aquatic environment,
owing to traces of heavy metals in the dye matrix [14].
2.3. Analytical
2.3.1. Spectrophotometry
The optical absorption spectra (200800 nm) of the
test solutions during sonication were recorded by a
Unicam, Hekios Alpha/Beta double beam spectrophotometer through a 1 cm optical path length.
2.3.2. Toxicity
Toxicity of the dye solutions was determined using a
Microtox Model 500 Analyzer, which utilizes freezedried luminescent bacteria (V. sheri) as test organisms.
The test system is based on the principle that bacterial
luminescence is tied directly to cell respiration, so that
any inhibition of cellular activity (due to toxicity) results
in a reduction in the degree of luminescence. The
Microtox analyzer is made of an array of sample wells
for holding dilutions of bacterial suspensions, and a
photometer to measure the light output of V. sheri at 0,
5 and 15 min after contact with the toxicant. Light
readings are compared to those of control bacteria
(healthy) to determine the inhibition of light emission,
and to estimate the EC50 of the sample. (EC50 is dened
as the eective concentration of the toxicantexpressed
as percentage relative to the original sample strength
that causes a 50% reduction in the light output of the
test organisms during the designated time interval.)
Sample preparation, osmotic adjustment and serial dilution procedures were carried out by reference to the
Basic Protocol of the Microtox assay [16].
2.4. Experimental
2.4.1. Selection of system parameters
The power density in solution was measured calorimetrically at various liquid volumes and power outputs
in accordance with the procedure described in the literature [17]. The working dye concentration was selected
on the basis of color degradation rates estimated for
various initial concentrations of CI Reactive Black5
under 1 h sonication of the solutions at the optimum
power density calorimetrically determined.

237

2.4.2. Determination of dye degradability

Three hundred milliliter of pre-aerated dye solutions
of 20 mg l1 (working dye concentration) were irradiated at 0.126 W ml1 (optimum power density) for 4 h to
monitor absorption abatements at the visible and UV254
bands. The degradability of the dyes was also assessed
by monitoring the toxicity of the reactor euents at
various intervals during sonication. Argon was bubbled
into the reactor at a ow rate of 3 ml min1 to promote
cavity formation and to overcome degassing.
2.4.3. Toxicity measurements
The toxicity of all dye solutions was determined prior
to sonication, and those that were found toxic were
monitored throughout the contact time to follow the
trends for detoxication. Color correction was found
necessary in those samples collected during the rst
30 min of irradiation, and was performed in accordance
with the procedure described in the Basic Protocol for
colored samples [16]. (The referred protocol is aimed to
overcome the potential hindrance of bacterial luminescence by the visible absorption of the dye solution.)

3. Results and discussion

3.1. Selection of system parameters
The degradation of color was found to follow pseudo-rst order kinetics with respect to the absorption
maximum of the dye in the visible band as:
dA
kA
1
dt
where A is the maximum absorbance of the solution in
the visible band at time t and k is the pseudo-rst order
absorbance decay coecient (min1 ). It was found that
the rate of color decay was accelerated by increases in
the electrical power output of the generator within
1040 W, but decelerated as the power was further increased. Variations in the estimated values of k at 10, 20,
40, 60, 80 and 100 W applications of electrical power to
300 ml dye solutions is presented in Fig. 1(a), where
maximum degradation of color was shown to occur at a
power output of 40 W, at which the power dissipated
into the solution was 0.126 W ml1 (see Fig. 1(b)).
The working dye concentration was selected by
monitoring the rate of color decay in 20, 30 and
40 mg l1 of RBk-5 during 1 h sonication at 0.126
W ml1 . Comparison of color degradation rate proles
in three concentrations of RBk5 and estimated rate coecients are presented in Fig. 2. The rate coecient was
found to be only slightly sensitive to the mass concentration of the dye, being a maximum at 20 mg l1 , which
was therefore selected as the working initial dye concentration.

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G. Tezcanli-Guyer, N.H. Ince / Ultrasonics Sonochemistry 10 (2003) 235240

Table 2
Fractions of color and organic carbon removal during 2 and 4 h of
sonolysis, and estimated coecients of color decay

12
10

Dye

8
-1

0.14

Wml

-3

-1

k x10 (min )

14

4
0

0.08

(b)

10

20

30

40

(a)

50

10

60

40

70
P(W)

RR141
RBk5
BBr4
BBl3

70

80

100

90 100

power(W)

Fig. 1. (a) Proles of color decay in 30 mg/l RBk5 at various power

outputs and (b) calorimetric measurements of power density. Volume
of solution in both cases was 300 ml.

1.4
k=-0.014
k=-0.012
k=-0.011

1.2

A 596

20 mg l-1
30 mg l-1
40 mg l-1

0.8
0.6
0.4
0.2
0

10

20

30

40

50

60

time (min)
Fig. 2. Selection of the working dye concentration based on color
decay rates. The solid lines represent the t of Eq. (1) to each data set
with regression coecients P0.98.

3.2. Dye degradation by color and organic carbon

The degradation of all dyes during the reaction period was assessed by absorption abatements at two
bands: the visible, which is responsible for the chromophoric components and the UV-254, which represents
the absorption of aromatic and/or olenic carbons in the
dye. The rate of absorption decay at 254 nm did not
follow a common kinetic pattern as it did in the visible
band as a consequence of aromatic intermediate formation by oxidative degradation of the dyes. Moreover,
it was found that complete decolorization was achieved
in all dye solutions within 150 min, while 4 h of sonication was required for appreciable degrees of aromatic/
olenic carbon destruction. Comparative fractions of
color and organic component decay in 2 and 4 h of
sonication respectively are listed in Table 2.
Note that the degree of UV-254 destruction in the
rst three azo dyes is signicantly lower than that of
color, signifying the priority of OH attack on N@N
bonds and the increased mass of aromatic intermediates
upon oxidation, which likely absorb UV light at 254 nm.
The fact that the basic dye BBl3 bleached much faster

A254
k  103
(min1 )

Reduction in
4h

82.9%
81.1%
86.3%
99.8%

14.8
13.9
15.6
53.7

11.2%
18.8%
49.0%
92.7%

0.11

0.05

Avisible
Reduction in 2 h

than the others and the abatement in its UV-254 band

was close to that in the visible band may be attributed to
its non-azo character, the oxazine chromophore and/or
its lower molecular mass.
The eect of sonolysis on the absorption of the dyes
in 200800 nm band is presented in Fig. 3. Note that the
two reactive dyes had absorption peaks at 310 nm in
addition to their absorption in the visible band, and
both of them faded with increased contact. On the other
hand, the spectra of the basic dyes were dierent; while
BBl3 had a peak at 253 nm, which also faded with time,
BBr4 had no distinct peaks in the same region. Note also
that despite the slight pH reduction (57%) observed in
all test solutions during the rst 15 min of contact (indicating the formation of organic acids), no shift in the
absorption peaks occurred during the same period.
3.3. Dye degradation by toxicity
Five and fteen minute toxicity of the dye solutions
prior to sonolysis showed that RR141 and RBk5 were
non-toxic at 20 and 30 mg l1 , while BBl3 and BBr4
were toxic at both concentrations. Hence, toxicity was
monitored only in the latter two dyes during 240 min of
sonolysis. Estimated values of EC50 were converted to a
relative index TI as:
%EC50 t 0
2
TI
%EC50 t t
where TI is the relative toxicity index, and EC50 is the
5 min Microtox toxicity of the sample.
Comparable proles of color, organic component and
toxicity decay in the two originally toxic dyes are presented in Fig. 4. It was found that despite the slower rate
of color and organic carbon degradation in BBr4 than
that in BBl3, the reduction in the toxicity of the former
was faster, with complete detoxication before color
decay was completed. This implies that toxicity causing
components in BBr4 were primarily due to the chromophoric characteristics of the dye, which may have
been further enhanced by the addition of some impurities in the commercial product. Since some of these
impurities are made of heavy metals, it is likely that
changes in the valence state of the metals upon their
potential combination with organic sites resulted in
detoxication of the euents. The observed rise in

G. Tezcanli-Guyer, N.H. Ince / Ultrasonics Sonochemistry 10 (2003) 235240

239

RBk5

RR141

1.5

0 min

0.8
1

0.5

120 min

Absorbance

Absorbance

0 min

0.6
0.4

120 min

0.2
0
200

400
600
Wavelength (nm)

0
200

800

0.6

120 min

400
600
Wavelength (nm)

800

Absorbance

Absorbance

0.4

0 min

0
200

800

BBr4

BBl3
3
2

400
600
Wavelength (nm)

0 min

0.2
120 min
0
200

400
600
Wavelength (nm)

800

Fig. 3. Spectral changes in 20 mg l1 of the test dyes during 1 h exposure to ultrasonic irradiation.

Fig. 4. Relative proles of color, organic carbon and toxicity degradation in 20 mg l1 of CI Basic Blue3 and CI Basic Brown4 during 4 h exposure to
ultrasound.

toxicity after 120 min of irradiation may be attributed to

the production of some toxic intermediates at this stage
and the accumulation of hydrogen peroxide upon enhanced sonication. The slower detoxication of BBI3
implies that toxicity was not only due to color, but to
other features of the dye as well. Note also that no rises
in toxicity was recorded once total detoxiation was
accomplished at 150 min of sonication.

4. Conclusions
Textile dyehouse euents are of signicant environmental concern, due to the presence of dye residuals in

wasted dyebaths. The study presented herein signies

features of dye degradability by ultrasonically generated
hydroxyl radicals. It was shown that the degradation of
azo and oxazine dyes is initiated by color decay followed
by the destruction of organic and/or aromatic carbons in
the molecule. The rate of color degradation was rst
order in the visible absorption of the dyes and slower in
azo dyes than that in oxazine-origin dye structures. The
degradation of aromatic/olenic contents in azo dyes
proceeded at a slower rate than that of color, as a
consequence of increased mass of organic intermediates,
which absorb at the UV-254 band. It was also shown
that if the parent dye were toxic, the degradation
products were less so, and total toxicity removal was

240

G. Tezcanli-Guyer, N.H. Ince / Ultrasonics Sonochemistry 10 (2003) 235240

accomplished within shorter contact than necessary for

total dye degradation.
Acknowledgements
The study was funded by a collaborate grant of the
State Planning Organization of Turkey (through DPT 98
K120900), Bogazici University Research Fund (through)
and EUREKA (throughE!2051 Textefuse). The authors also thank Norwest Laboratories of Canada for
the courtesy of donating the Microtox System.
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