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Radiation Physics and Chemistry 65 (2002) 549558

Decoloration and degradation of some textile dyes by gamma


irradiation
Dilek S- olpan*, Olgun Guven
.
Department of Chemistry, Hacettepe University, 06532 Beytepe, Ankara, Turkey

Abstract
The textile industry has long been one of the largest water users and polluters. Wastewater released by textile
industries contains toxic refractory dye stuff at high concentration. Most of the dyes in the textile industry are nondegradable, therefore, effective treatment of dye waste efuent has not been achieved by ordinary processes. Ionizing
radiation has been considered a promising process for the treatment of textile dye waste efuents.
In this study, the possibility of using gamma rays to degrade or decolorize reactive dyes in water was investigated.
Two different reactive dyes (Reactive Blue 15 and Reactive Black 5) in aqueous solutions were irradiated at doses of
0.115 kGy, at 2.87 and 0.14 kGy/h dose rates. The change of absorption spectra, pH, chemical oxygen demand (COD),
and the degree of decoloration (percent reduction in optical density) were examined in the presence of air and H2O2.
The absorption bands at 664, 640, 340, 260 nm and 596, 392, 312 nm for RB15 and RB5 decreased rapidly with
increasing irradiation dose. The degree of decoloration of each dye solution with irradiation dose appeared to be 100
percent for the lower concentration (50 ppm) dye solutions. The complete decoloration was observed after 1 and 15 kGy
doses for RB5 and RB15, respectively. pH of RB5 and RB15 solutions was decreased from 6.15 and 6.98 to 3.40 and
3.68 with the irradiation dose. The COD reduction for all the dye solutions was approximately 7680% at 1 and 15 kGy
for RB5 and RB15. The COD reduction and the change of pH for all the dye solutions were examined similar to each
other.
r 2002 Published by Elsevier Science Ltd.

1. Introduction
Turkey is one of the exporters of textiles so that the
waste coming from textile industries has a major impact
on the environment. Wastewater released by those
industries contains toxic refractory dyestuff at high
concentration. Disposal of efuent from textile industries has become a serious environmental concern in
many countries. Most of the dyes used in the textile
industry are non-biodegradable, therefore, effective
treatment of dye waste efuent has not been achieved
by ordinary processes (Suzuki et al., 1978; Nagai and
Suzuki, 1978; Suzuki et al., 1975; Higashi et al., 1996).
Earlier studies have shown that most colored materials
undergo bleaching or color changes when exposed to
*Corresponding author. Tel.: +90-312-2992163; fax: +90312-2992163.
E-mail address: solpan@eti.cc.hun.edu.tr (D. S- olpan).

ionizing radiation. Ionizing radiation may be promising


for the treatment of textile dye waste efuents, because
the effect of radiation can be intensied in aqueous
solution in which the dye molecules are degraded
effectively by the primary products formed from the
radiolysis of water (Getoff and Lutz, 1985).
The irradiation dose necessary for complete decomposition of a dye depends principally on its molecular
structure and reactivity towards the primary water
radiolysis products, the presence of oxygen or oxidizing
agents, temperature and pH and concentration of the
solution.
The aim of this study was to study the possibility of
using gamma rays to degrade or decolorize reactive dyes
in the presence and absence of H2O2 in water. Two
different reactive dyes in aqueous solutions were
irradiated with doses of 0.115 kGy at 2.87 and
0.14 kGy/h dose rates. The change of absorption
spectra, pH, chemical oxygen demand (COD), the

0969-806X/02/$ - see front matter r 2002 Published by Elsevier Science Ltd.


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D. S
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- olpan, O. Guven

degree of decoloration (percent reduction in optical


density) were examined as a function of irradiation dose,
dose rate, dye concentration. Synergetic effects resulting
from additives such as oxygen and hydrogen peroxide
on the degradation process were investigated.

2. Experimental
2.1. Materials
Commercial textile dyes manufactured in Germany
were obtained from three major textile industries in
Turkey. For this particular study, two reactive dyes:
(Chrozol turquose Blue G) (Reactive Blue 15) RB15 and
(Chrozol Black 5) (Reactive Black 5) RB5 were used
without any further treatment. Deionized distilled water
was used in the preparation of dye solutions without any
contaminants.
Dyes:
(a) (Reactive Blue 15) (Chrozol turquose blue G)
RB15,

(b) (Reactive black 5) (Chrozol black 5) RB5.

was measured by a Philips PU 8715 model UV-vis


spectrophotometer, for the irradiation and unirradiated
solutions. Irradiation was done at doses of 0.115 kGy
at 2.87 and 0.14 kGy/h dose rates. In the present work,
oxidizing and decolorizing agent was used to minimize
the consumption of gamma irradiation doses. Hydrogen
peroxide as an oxidizing agent coupled with gamma
irradiation were added to the dye solutions to study the
synergistic effect on the degradation of the two reactive
dyes. COD was determined by using chromic acid
method (Shevchuck et al., 1993). The degree of
decoloration was estimated from the reduction in optical
density.

3. Results and discussion


3.1. Changes of absorption spectra
The absorption spectra of the unirradiated and
irradiated aqueous RB15 solutions at 50 ppm concen-

Fig. 1. Absorption spectra of unirradiated and irradiated RB15


aqueous solutions. Dye concentration: 50 mg/l, dose rate:
2.87 kGy/h, dose (kGy): 0 (curve 1), 2 (curve 2), 4 (curve 3), 6
(curve 4), 10 (curve 5), 15 (curve 6).

2.2. Methods
Deionized water was used to prepare four concentrations 50, 75, 100, 150 mg/l of the two reactive dyes. The
pH of the solutions was measured by a JENWAY 3010
model pH meter before and after irradiation. The UV
absorbance, at the wavelength of maximum absorbance,

Fig. 2. Absorption spectra of unirradiated and irradiated RB15


aqueous
solutions.
Dye
concentration:
50 mg/l,
[H2O2]=1.2 mM, dose rate: 2.87 kGy/h, dose (kGy): 0 (curve
1), 1 (curve 2), 2 (curve 3), 3 (curve 4), 5(curve 5), 7 (curve 6), 9
(curve 7).

D. S
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tration in the absence and presence of 1.2 mM H2O2


concentration at 2.87 kGy/h dose rate are shown in
Figs. 1 and 2. RB15 showed strong absorption at 664,
640, 340, 260 nm. The absorption bands at 664, 640, 340
and 260 nm decreased with increasing irradiation dose
and disappeared almost completely at 15 kGy (Fig. 1,
curve 6). The absorption band at 340 nm decreased less
rapidly with increasing dose than those at 664 and
640 nm. These absorption spectra were similar to those
for aqueous RB15 solution at 50 ppm concentration in
1.2 mM H2O2 concentration (Fig. 2). There is no
absorption band at 260 nm in the presence of 1.2 mM

551

H2O2 concentration and the absorption bands at 664,


640, 340 nm decreased with the increasing irradiation
dose but required an irradiation dose of 9.0 kGy (Fig. 2,
curve 7) to achieve the same results as above.
The absorption spectra, measured for unirradiated
and irradiated 50ppm RB15 solutions without H2O2 and
containing 1.2 mM H2O2 at 0.14 kGy/h dose rate are
shown in Figs. 3 and 4. The unirradiated aqueous RB15
solution has four strong absorption bands at 664, 640,
340, 260 nm (Figs. 3 and 4, curve 1). These absorption
bands disappeared almost completely at 10 kGy irradiation dose in the absence of H2O2 (Fig. 3, curve 6). In the

Fig. 3. Absorption spectra of unirradiated and irradiated RB15 aqueous solutions. Dye concentration: 50 mg/l, dose rate: 0.14 kGy/h,
dose (kGy): 0 (curve 1), 2 (curve 2), 4 (curve 3), 6 (curve 4), 10 (curve 5), 15 (curve 6).

Fig. 4. Absorption spectra of unirradiated and irradiated RB15 aqueous solutions. Dye concentration: 50 mg/l, [H2O2]=1.2 mM, dose
rate: 0.14 kGy/h, dose (kGy): 0 (curve 1), 1 (curve 2), 2 (curve 3), 3 (curve 4), 7 (curve 5), 9 (curve 6).

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Fig. 5. Absorption spectra of unirradiated and irradiated RB5


aqueous solutions. Dye concentration: 50 mg/l, dose rate:
2.87 kGy/h, dose (kGy): 0 (curve 1), 1(curve 2), 2 (curve 3), 3
(curve 4), 4 (curve 5), 5 (curve 6).

Fig. 6. Absorption spectra of unirradiated and irradiated


RB5 aqueous solutions. Dye concentration: 50 mg/l, [H2O2]=
1.2 mM, dose rate: 2.87 kGy/h, dose (kGy): 0 (curve 1), 0.1
(curve 2), 0.2 (curve 3), 0.3 (curve 4), 0.4 (curve 5), 0.5 (curve 6),
0.6 (curve 7).

presence of 1.2 mM H2O2 concentration and at lower


dose rate a higher degree of decoloration (%) was
achieved (Fig. 4). The absorption band at 260 nm was
attributed to azo groups and its auxochromic substituents. The changes observed in the absorption spectra
with irradiation dose would suggest destruction of only
the chromophoric groups with little or no effect on the
substituted aromatic rings in the dye molecules (Hosono
et al., 1993).
The absorption spectra of the unirradiated and
irradiated 50 ppm RB5 solutions in the absence and
presence of 1.2 mM H2O2 at 2.87 kGy/h dose rate are
shown in Figs. 5 and 6. While the absorption bands at
596, 392, 312 nm decreased with increasing dose and
disappeared completely at 3.0 kGy in the absence of
H2O2, while the required dose of 1.0 kGy in 1.2 mM
H2O2 was required. When the absorption spectra of
unirradiated and irradiated 50 ppm RB5 solutions in the
absence and presence of 1.2 mM H2O2 concentration at
0.14 kGy/h dose rate are given in Figs. 7 and 8. The
absorption spectra were very similar to each other but
the degree of decoloration (%) for RB5 solutions was
higher than those for RB5 solutions at 2.87 kGy/h dose
rate. The absorption bands at 596, 392, 312 nm
decreased more rapidly with increasing dose than those
of RB15 solutions. The differences spectra between
unirradiated and irradiated dye solutions are given in
Figs. 9 and 10.
3.2. Effect of irradiation dose and dose rate on
decoloration and degradation
The effect of irradiation dose in kGy and dose rate in
kGy/h on the different reactive dye concentrations was

Fig. 7. Absorption spectra of unirradiated and irradiated RB5 aqueous solutions. Dye concentration: 50 mg/l, dose rate: 0.14 kGy/h,
dose (kGy): 0 (curve 1), 0.1 (curve 2), 0.2 (curve 3), 0.3 (curve 4), 0.4 (curve 5), 0.6 (curve 6).

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Fig. 8. Absorption spectra of unirradiated and irradiated RB5 aqueous solutions. Dye concentration: 50 mg/l, [H2O2]=1.2 mM, dose
rate: 0.14 kGy/h, dose (kGy): 0 (curve 1), 0.1 (curve 2), 0.4 (curve 3), 0.6 (curve 4).

Fig. 9. Differences spectra of absorption between unirratiated and irradiated aqueous solutions. Dye concentration: 50 ppm, dose rate:
0.14 kGy/h, [DAbsDIrradiation doses (kGy)]: (1) (0.00.6), (2) (0.00.4), (3) (0.00.3), (4) (0.00.2), (5) (0.00.1).

studied. RB15 solutions at 50, 75, 100, 150 ppm


concentrations were subjected to different irradiation
doses at 2.87 and 0.14 kGy/h dose rates and the results
are shown in Figs. 11 and 12. For RB5 solutions, the
results are given in Tables 1 and 2. The results show that
the decoloration of RB5 by irradiation was much more
than those of RB15 at all of the dye concentrations.
When the maximum absorbance or the degree of
decoloration (%) of two reactive dye solutions which
have different concentrations compared with eachother,
the increase in the degree of decoloration (%) was more
rapidly for the lowest concentration (50 ppm) dye

solutions than for the higher concentrations. The


required irradiation dose to decoloration of RB5 is
lower than those of RB15. This may be attributed to the
difference in the structure of both dyes. The (NQN)
groups are very sensitive to radiation and the ruptured
immediately when exposed to low doses of gamma
irradiation (Suzuki et al., 1975).
The degree of decoloration of two reactive dye
solutions with irradiation dose was estimated as the
reduction in optical density at corresponding wavelength, where the absorbance was strongest. The results
(Figs. 914 and Tables 1 and 2) suggest that the degree

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Fig. 10. Differences spectra of absorption between unirratiated and irradiated aqueous solutions. Dye concentration: 50 mg/l,
[H2O2]=1.2 mM, dose rate: 0.14 kGy/h, [DAbsIrradiation doses (kGy)]: (1) (0.00.6), (2) (0.00.4), (3) (0.00.1).

Fig. 11. Degree of decoloration as a function of irradiation dose (kGy) at various concentrations of RB15 in the absence and presence
of 1.2 mM H2O2. Dose rate: 2.87 kGy/h, dye concentration: 50, 75, 100, 150 mg/l. (Solid symbols are used for RB15 concentrations
containing H2O2.)

of decoloration (%) is the highest at the lowest dose rate


(0.14 kGy/h).
3.3. Effect of pH on decoloration and degradation
To investigate the effect of irradiation dose on the pH
of the 50 ppm RB15 and RB5 solutions at 0.14 kGy/h
dose rate, pH values of the unirradiated and irradiated
dye solutions were measured. Tables 3 and 4 show that
pH of the solutions decreased sharply with the irradia-

tion dose. The pH of the solution was lower at the low


dye concentrations than the higher dye concentrations.
The change in pH depended on the structure of dye
molecule (Pikaev et al., 1996).
3.4. Effect of hydrogen peroxide on decoloration and
degradation
The degree of decoloration for 50 ppm RB15 and
50 ppm RB5 solutions containing hydrogen peroxide is

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555

Fig. 12. Degree of decoloration as a function of irradiation dose (kGy) at various concentrations of RB15 in the absence and presence
of 1.2 mM H2O2. Dose rate: 0.14 kGy/h, dye concentration: 50, 75, 100, 150 mg/l. (Solid symbols are used for RB15 concentrations
containing H2O2.)

Table 1
Degree of decoloration as a function of irradiation dose (kGy)
at various concentrations of Reactive Black 5 (RB5) in the
absence and presence of 1.2 mM H2O2. Dose rate: 2.87 kGy/h

Table 2
Degree of decoloration as a function of irradiation dose (kGy)
at various concentrations of Reactive Black 5 (RB5) in the
absence and presence of 1.2 mM H2O2. Dose rate: 0.14 kGy/h

Dose
(kGy)

Dose
(kGy)

Concentration (mg/l)
50

75

100

150

0.0
1.0
2.0
3.0
4.0
5.0

0
80
94
96
96
96

0
74
80
85
85
88

0
60
65
68
70
70

0
52
56
60
60
62

0.0
0.1
0.2
0.3
0.4
0.5
0.6
1.0

Concentration (mg/l) (in the presence of 1.2 mM


H2O2)
0
0
0
0
33
30
25
20
42
35
25
20
54
46
30
25
58
48
38
28
68
50
40
30
80
60
52
50
90
78
70
60

shown as a function of hydrogen peroxide concentration


at 10.0 and 1.0 kGy irradiation dose for RB15 and RB5,
respectively, in Figs. 13 and 14. The degree of decoloration for both solutions increased with hydrogen

Concentration (mg/l)
50

75

100

150

0.0
0.1
0.2
0.3
0.4
0.5
0.6
1.0

0
54
64
72
86
90
93
93

0
50
54
62
76
80
85
88

0
46
50
57
67
70
80
85

0
38
46
50
57
60
76
80

0.0
0.1
0.2
0.3
0.4
0.5
0.6
1.0

Concentration (mg/l) (in the presence of 1.2 mM


H2O2)
0
0
0
0
60
55
50
44
67
57
52
46
76
68
60
54
90
82
74
64
98
94
86
76
98
92
86
76
98
94
86
80

peroxide concentration up to about 1.2 mM. This


suggests that the decoloration reaction is promoted by
addition of hydrogen peroxide (Suzuki et al., 1975).

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Hydrogen peroxide reacts rapidly with hydrated electron


formed in the radiolysis of water, leading to the
formation of OH radical

H2 O2 e
aq -OH OH :

Therefore, the increase in the degree of decoloration by


the addition of hydrogen peroxide would be mainly
attributable to an increase in the OH radical. This
nding suggested that the OH radical destroyed the dye
chromophore more efciently than the hydrated electron

Fig. 13. Effect of hydrogen peroxide on the degree of decoloration. Irradiation dose: 10.0 kGy, RB15 concentration: 50 mg/l, dose rate:
0.14, 2.87 kGy/h.

Fig. 14. Effect of hydrogen peroxide on the degree of decoloration. Irradiation dose: 1.0 kGy, RB5 concentration: 50 mg/l, dose rate:
0.14, 2.87 kGy/h.

D. S
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Table 3
Change of pH as a function of irradiation dose (kGy) at various
concentrations of Reactive Blue 15 (RB15) in the absence and
presence of 1.2 mM H2O2. Dose rate: 0.14 kGy/h solution
Dose
(kGy)

Concentration (mg/l)
50

75

100

150

0.0
1.0
2.0
4.0
6.0
10.0
15.0

6.70
4.25
3.80
3.70
3.70
3.88
3.88

6.96
4.20
4.00
3.98
3.60
4.10
4.10

6.98
4.90
4.46
4.60
4.38
3.90
3.98

6.98
4.90
4.90
4.45
4.40
4.40
4.20

0.0
1.0
2.0
3.0
5.0
7.0
9.0
15.0

Concentration (mg/l) ( in the presence


H2O2)
6.70
6.70
6.98
4.00
4.20
4.90
4.10
3.98
4.00
4.10
3.98
4.00
4.20
3.60
3.96
3.86
4.10
4.10
3.68
3.90
3.88
3.68
3.90
3.88

of 1.2 mM
6.98
4.90
4.46
4.40
4.38
3.98
4.10
4.10

Table 4
Change of pH as a function of irradiation dose (kGy) at various
concentrations of Reactive Black 5 (RB5) in the absence and
presence of 1.2 mM H2O2. Dose rate: 0.14 kGy/h solution
Dose
(kGy)

Concentration (mg/l)
50

75

100

150

0.0
0.1
0.2
0.3
0.4
0.5
0.6
1.0

6.15
4.20
4.20
4.00
3.84
3.80
3.80
3.70

6.05
4.40
4.20
4.20
3.90
3.90
3.80
3.80

6.05
4.40
4.40
4.40
4.20
3.95
3.86
3.80

5.85
4.90
4.40
4.40
4.30
4.25
3.90
3.86

0.0
0.1
0.2
0.3
0.4
0.5
0.6
1.0

Concentration (mg/l) ( in the presence


H2O2)
6.15
6.05
6.05
4.25
4.40
4.40
3.90
4.20
4.20
3.90
3.90
4.20
3.80
3.90
4.00
3.40
3.80
3.84
3.40
3.80
3.86
3.50
3.70
3.86

of 1.2 mM
5.85
4.40
4.40
4.20
3.80
3.90
3.90
3.86

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Table 5
Changes of COD by irradiation
Reactive dyesa

Dose (kGy)
[H2O2]=0 mM

COD reduction (%)


[H2O2]=1.2 mM

Reactive Blue 15
0.0
2.0
4.0
6.0
10.0
15.0

46
48
62
62
70

59
65
78
80
82

Reactive Black 5
0.0
0.1
0.2
0.3
0.5
1.0

46
48
50
58
66

52
54
60
64
68

Commercial reactive dyes, initial dye concentration: 50 mg/l.

increases, a part of the OH radicals are scavenged by the


excess hydrogen peroxide.
COD corresponds to the amount of oxygen required
to oxidize the organic fraction of a sample, which is
susceptible to permanganate or dichromate oxidation in
an acid solution. The COD reduction of the 50 mg/l
reactive dye solutions are summarized in Table 5. The
COD reduction for two reactive dye solutions were
approximately 80% and 68% at 10.0 and 1.0 kGy
irradiation dose for RB15 and RB5, respectively.

4. Conclusions
The decoloration and degradation of reactive dyes in
aqueous solutions by gamma irradiation has been
demonstrated. The dye solutions are easily decolored
by gamma irradiation, which may be, therefore,
promising for the treatment of textile dye wastewater.
Decoloration and degradation of textile wastewater can
be carried out but necessary dose varies with the types of
the waste. The destruction of the skeleton of the dye
molecule, or decoloration and degradation of the
reactive dyes in aqueous solutions can be achieved by
gamma irradiation alone or by gamma irradiation of
aqueous dye solutions that contain H2O2 at lower dose
rate.

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