Radiation Physics and Chemistry 65 (2002) 549–558

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 effluent has not been achieved by ordinary processes. Ionizing
radiation has been considered a promising process for the treatment of textile dye waste effluents.
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
0.1–15 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 76–80% 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 effluent 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 effluent 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 effluents, because
the effect of radiation can be intensified 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 0.1–15 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.
PII: S 0 9 6 9 - 8 0 6 X ( 0 2 ) 0 0 3 6 6 - 3

2. 3. Experimental 2. The pH of the solutions was measured by a JENWAY 3010 model pH meter before and after irradiation.1. 150 mg/l of the two reactive dyes. In the present work. Results and discussion 3. COD was determined by using chromic acid method (Shevchuck et al. The degree of decoloration was estimated from the reduction in optical density. O. 7 (curve 6).87 kGy/h.1. 2. 1 (curve 2). at the wavelength of maximum absorbance. dose rate. 15 (curve 6). . 2 (curve 3). Dyes: (a) (Reactive Blue 15) (Chrozol turquose blue G) RB15. 75. For this particular study. Synergetic effects resulting from additives such as oxygen and hydrogen peroxide on the degradation process were investigated. 100. 2 (curve 2). dye concentration. [H2O2]=1.550 D. The UV absorbance. Changes of absorption spectra The absorption spectra of the unirradiated and irradiated aqueous RB15 solutions at 50 ppm concen- Fig. 4 (curve 3).olpan. Irradiation was done at doses of 0.2.. 10 (curve 5).87 and 0. 5(curve 5). Absorption spectra of unirradiated and irradiated RB15 aqueous solutions. 9 (curve 7). Materials Commercial textile dyes manufactured in Germany were obtained from three major textile industries in Turkey. Dye concentration: 50 mg/l.87 kGy/h. 1. S / Radiation Physics and Chemistry 65 (2002) 549–558 . Methods Deionized water was used to prepare four concentrations 50. Absorption spectra of unirradiated and irradiated RB15 aqueous solutions. 6 (curve 4). was measured by a Philips PU 8715 model UV-vis spectrophotometer. 1993).1–15 kGy at 2.2 mM. (b) (Reactive black 5) (Chrozol black 5) RB5. dose rate: 2.14 kGy/h dose rates. oxidizing and decolorizing agent was used to minimize the consumption of gamma irradiation doses. Fig. 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. dose rate: 2. 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. dose (kGy): 0 (curve 1). 2. dose (kGy): 0 (curve 1). Dye concentration: 50 mg/l. Guven degree of decoloration (percent reduction in optical density) were examined as a function of irradiation dose. . 3 (curve 4). for the irradiation and unirradiated solutions.

640. 15 (curve 6). Absorption spectra of unirradiated and irradiated RB15 aqueous solutions. The absorption band at 340 nm decreased less rapidly with increasing dose than those at 664 and 640 nm. Dye concentration: 50 mg/l. The unirradiated aqueous RB15 solution has four strong absorption bands at 664. 2. 640. curve 6). 1 (curve 2). The absorption bands at 664. 3. Fig. There is no absorption band at 260 nm in the presence of 1. 340 nm decreased with the increasing irradiation dose but required an irradiation dose of 9. Dye concentration: 50 mg/l. dose rate: 0. These absorption bands disappeared almost completely at 10 kGy irradiation dose in the absence of H2O2 (Fig. 640. curve 7) to achieve the same results as above. S / Radiation Physics and Chemistry 65 (2002) 549–558 .2 mM H2O2 concentration (Fig. 340 and 260 nm decreased with increasing irradiation dose and disappeared almost completely at 15 kGy (Fig.olpan. 1 and 2.87 kGy/h dose rate are shown in Figs. Guven tration in the absence and presence of 1. curve 6). O. 4 (curve 3). 1. 2 (curve 2). dose rate: 0. 7 (curve 5). [H2O2]=1. dose (kGy): 0 (curve 1). 340. 3 (curve 4). 260 nm. In the Fig.14 kGy/h dose rate are shown in Figs. These absorption spectra were similar to those for aqueous RB15 solution at 50 ppm concentration in 1. The absorption spectra. Absorption spectra of unirradiated and irradiated RB15 aqueous solutions. dose (kGy): 0 (curve 1).2 mM 551 H2O2 concentration and the absorption bands at 664.2 mM H2O2 at 0.0 kGy (Fig.D. 340. measured for unirradiated and irradiated 50ppm RB15 solutions without H2O2 and containing 1.2 mM H2O2 concentration at 2.2 mM. 10 (curve 5). 3. 3 and 4.14 kGy/h. . curve 1). 260 nm (Figs. . 6 (curve 4). RB15 showed strong absorption at 664. 9 (curve 6). 4. 640. 2).14 kGy/h. 3 and 4. 2 (curve 3).

2 (curve 3).0 kGy in the absence of H2O2. 312 nm decreased more rapidly with increasing dose than those of RB15 solutions.87 kGy/h.4 (curve 5). S / Radiation Physics and Chemistry 65 (2002) 549–558 . 3 (curve 4). 0. While the absorption bands at 596.14 kGy/h dose rate are given in Figs.2 mM.2 (curve 3). .2 mM H2O2 concentration at 0. 0. 0. 0. .552 D. presence of 1. 7 and 8. 1(curve 2). Dye concentration: 50 mg/l. dose (kGy): 0 (curve 1). 312 nm decreased with increasing dose and disappeared completely at 3.2 mM H2O2 at 2. dose rate: 2.1 (curve 2).0 kGy in 1. 6. 0. 0. 3. The absorption spectra of the unirradiated and irradiated 50 ppm RB5 solutions in the absence and presence of 1. O. The absorption band at 260 nm was attributed to azo groups and its auxochromic substituents.2.6 (curve 6).6 (curve 7). Guven Fig.4 (curve 5). Dye concentration: 50 mg/l. The differences spectra between unirradiated and irradiated dye solutions are given in Figs. 392. Absorption spectra of unirradiated and irradiated RB5 aqueous solutions. dose (kGy): 0 (curve 1).14 kGy/h.3 (curve 4). 0. Dye concentration: 50 mg/l. 392.2 (curve 3).5 (curve 6).olpan.1 (curve 2). The absorption bands at 596. 1993). dose rate: 0. 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. When the absorption spectra of unirradiated and irradiated 50 ppm RB5 solutions in the absence and presence of 1. 0.87 kGy/h. 0. [H2O2]= 1. 0.87 kGy/h dose rate are shown in Figs. 4 (curve 5). 0.87 kGy/h dose rate. 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.2 mM H2O2 was required. 5 (curve 6). 7. Absorption spectra of unirradiated and irradiated RB5 aqueous solutions. Absorption spectra of unirradiated and irradiated RB5 aqueous solutions. dose rate: 2. 4)..3 (curve 4). while the required dose of 1. 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. dose (kGy): 0 (curve 1). 5 and 6. 9 and 10. 5.2 mM H2O2 concentration and at lower dose rate a higher degree of decoloration (%) was achieved (Fig. Fig.

Dye concentration: 50 mg/l. studied. 0. 75.6). 9. 0. where the absorbance was strongest. (4) (0.14 kGy/h dose rates and the results are shown in Figs. the results are given in Tables 1 and 2.14 kGy/h. The results show that the decoloration of RB5 by irradiation was much more than those of RB15 at all of the dye concentrations. the increase in the degree of decoloration (%) was more rapidly for the lowest concentration (50 ppm) dye solutions than for the higher concentrations. The (NQN–) groups are very sensitive to radiation and the ruptured immediately when exposed to low doses of gamma irradiation (Suzuki et al. O.1). RB15 solutions at 50. dose (kGy): 0 (curve 1). 1975). Absorption spectra of unirradiated and irradiated RB5 aqueous solutions.4).2). [H2O2]=1. . 100.0–0. For RB5 solutions. 8. dose rate: 0.4 (curve 3).0–0. 11 and 12. Differences spectra of absorption between unirratiated and irradiated aqueous solutions.6 (curve 4). The results (Figs. [DAbsDIrradiation doses (kGy)]: (1) (0. The required irradiation dose to decoloration of RB5 is lower than those of RB15.87 and 0. When the maximum absorbance or the degree of decoloration (%) of two reactive dye solutions which have different concentrations compared with eachother.3). Dye concentration: 50 ppm.olpan. 150 ppm concentrations were subjected to different irradiation doses at 2.1 (curve 2).. (3) (0.0–0.2 mM. 9–14 and Tables 1 and 2) suggest that the degree .14 kGy/h.0–0. This may be attributed to the difference in the structure of both dyes. dose rate: 0.0–0.D. S / Radiation Physics and Chemistry 65 (2002) 549–558 . (5) (0. Fig. 0. (2) (0. The degree of decoloration of two reactive dye solutions with irradiation dose was estimated as the reduction in optical density at corresponding wavelength. Guven 553 Fig.

4. dye concentration: 50. O.. S / Radiation Physics and Chemistry 65 (2002) 549–558 .14 kGy/h. 11. The pH of the solution was lower at the low dye concentrations than the higher dye concentrations. (Solid symbols are used for RB15 concentrations containing H2O2.554 D. Degree of decoloration as a function of irradiation dose (kGy) at various concentrations of RB15 in the absence and presence of 1.0–0. 3. 75. 150 mg/l. Guven Fig. dose rate: 0.1). [DAbsIrradiation doses (kGy)]: (1) (0. 100.4). (3) (0.) of decoloration (%) is the highest at the lowest dose rate (0. 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. [H2O2]=1.0–0.87 kGy/h.6).2 mM H2O2.olpan. Tables 3 and 4 show that pH of the solutions decreased sharply with the irradia- tion dose. (2) (0. Differences spectra of absorption between unirratiated and irradiated aqueous solutions. Fig. Dose rate: 2. 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 .3. 3. .14 kGy/h dose rate. 1996). pH values of the unirradiated and irradiated dye solutions were measured. Dye concentration: 50 mg/l.2 mM.14 kGy/h).0–0. 10. The change in pH depended on the structure of dye molecule (Pikaev et al.

4 0.2 mM H2O2. 12. 150 mg/l. 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) 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 1.3 0. respectively.3 0. 75.D.2 mM H2O2.0 3.0 1. 100.87 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.0 4.0 and 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. dye concentration: 50.. Dose rate: 2.2 0.0 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.olpan.5 0.1 0.4 0. S / Radiation Physics and Chemistry 65 (2002) 549–558 . Dose rate: 0.2 mM H2O2.2 0.0 kGy irradiation dose for RB15 and RB5.) 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 1.1 0.0 Concentration (mg/l) (in the presence of 1. in Figs.0 2. 1975).0 5.6 1. O. The degree of decoloration for both solutions increased with hydrogen Concentration (mg/l) 50 75 100 150 0.0 0. .0 0. Guven 555 Fig.6 1. .14 kGy/h.2 0.4 0.6 1.3 0. Dose rate: 0. This suggests that the decoloration reaction is promoted by addition of hydrogen peroxide (Suzuki et al. (Solid symbols are used for RB15 concentrations containing H2O2.0 Concentration (mg/l) (in the presence of 1.0 0.0 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 0.5 0. 13 and 14.1 0.14 kGy/h Dose (kGy) Dose (kGy) Concentration (mg/l) 50 75 100 150 0.5 0.

Irradiation dose: 1. dose rate: 0. This finding suggested that the OH radical destroyed the dye chromophore more efficiently than the hydrated electron Fig. 2. Irradiation dose: 10. dose rate: 0. RB5 concentration: 50 mg/l. . . RB15 concentration: 50 mg/l. Effect of hydrogen peroxide on the degree of decoloration.87 kGy/h. S / Radiation Physics and Chemistry 65 (2002) 549–558 .14. O.556 D. 13.0 kGy. Fig.14.0 kGy. leading to the formation of OH radical  H2 O2 þ e aq -OH þ OH : Therefore. Guven Hydrogen peroxide reacts rapidly with hydrated electron formed in the radiolysis of water. 2. the increase in the degree of decoloration by the addition of hydrogen peroxide would be mainly attributable to an increase in the OH radical. Effect of hydrogen peroxide on the degree of decoloration.olpan.87 kGy/h. 14.

As the hydrogen peroxide concentration Getoff.80 3.85 4. .90 3.0 0.20 3.0 2.20 4.88 3.5 0.0 and 1.90 4.25 3.2 mM H2O2.90 4. O.90 3.96 3.15 6. 21–26.20 0. 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. S / Radiation Physics and Chemistry 65 (2002) 549–558 .86 3. 1985.00 3.80 3.00 3.2 mM resulted in a decrease in the degree of degradation.10 3.0 46 48 62 62 70 59 65 78 80 82 Reactive Black 5 0.00 4.46 4.0 10. 4.4 0. Chem.5 0.98 4.70 3.98 4.10 4.0 1.0 2..84 3. W.20 3.90 4.40 4. COD corresponds to the amount of oxygen required to oxidize the organic fraction of a sample.2 0.3 0.98 4.10 4.80 5.98 4. Phys.70 6. Radiation induced decomposition of hydrocarbons in water resources.70 6. promising for the treatment of textile dye wastewater.25 3.00 4.14 kGy/h solution Dose (kGy) Concentration (mg/l) 50 75 100 150 0.88 6.0 10.0 0.40 4.0 6.80 3.80 3.2 mM 6. therefore.40 4.0 15.68 3.38 3.20 4.86 0. References does. The dye solutions are easily decolored by gamma irradiation.0 6.10 3.0 4.88 3.0 2.14 kGy/h solution Dose (kGy) Concentration (mg/l) 50 75 100 150 0.15 4.0 15.40 4.6 1.D.0 0.5 1.10 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 1.85 4.40 4.6 1.70 4. Lutz. .0 15.90 3.90 4.68 3. a part of the OH radicals are scavenged by the excess hydrogen peroxide.0 6.80 3.1 0.90 4.86 3.2 mM 5.0 4.90 3.40 4.2 0.95 3. N.80 6.20 4.0 Concentration (mg/l) ( in the presence H2O2) 6.98 3.90 3.40 4.40 4.40 3.2 mM H2O2.90 4.60 4. increases.20 3.70 3.40 3.60 4.05 4.96 4.30 4.98 6. Guven 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 1.45 4.0 7.20 4.38 3.00 3.3 0.2 0.0 1.0 46 48 50 58 66 52 54 60 64 68 a Commercial reactive dyes.86 557 Table 5 Changes of COD by irradiation Reactive dyesa Dose (kGy) [H2O2]=0 mM COD reduction (%) [H2O2]=1. respectively. The COD reduction of the 50 mg/l reactive dye solutions are summarized in Table 5.80 3.00 4.70 3.98 4.40 4.40 4.60 3.88 of 1.25 4.84 3.40 3.98 4. The destruction of the skeleton of the dye molecule.4 0.05 4.90 3. Dose rate: 0.20 4. initial dye concentration: 50 mg/l. which is susceptible to permanganate or dichromate oxidation in an acid solution.0 5.0 6.80 3.86 of 1.90 4.40 4.0 kGy irradiation dose for RB15 and RB5.80 3.90 3.05 4.46 4. Conclusions The decoloration and degradation of reactive dyes in aqueous solutions by gamma irradiation has been demonstrated.86 4.70 6. 25 (1–3).90 4.20 4.05 6.0 3.olpan.90 3.10 4.20 3.90 3. Dose rate: 0.1 0.0 Concentration (mg/l) ( in the presence H2O2) 6.50 3.98 4.90 4.2 mM Reactive Blue 15 0.1 0.3 0.0 9.20 3. The COD reduction for two reactive dye solutions were approximately 80% and 68% at 10.10 3.20 3. Increasing the hydrogen peroxide concentration above 1.40 4. Radiat. Decoloration and degradation of textile wastewater can be carried out but necessary dose varies with the types of the waste. which may be.10 6..

.. Isot. 1975. Hosono. A. H. Shimizu. Miyata.. 726–730.olpan. Suzuki. M. Radiat. Pikaev. K. N. Int. A. I. J. 1993. Arai..N. Hotta. Radiat. T. K. S / Radiation Physics and Chemistry 65 (2002) 549–558 . Int.V. Decoloration and degradation of azo dye in aqueous solution supersaturated with oxygen by irradiation of high energy electron beam. Suzuki. A. Yamamoto.E. Suzuki. Appl. Nagai. N.. Chem. Kawahara.. J... 44. Vody 15 (4). Hashimato.. Kawakami. 1978. Isot. Isot. 75–80. The degradation of an azo dye in aqueous solution by high intensity electron beam irradiation. Khim. 27. I. T. O.. A. Int. Aizawa. Washino. Guven Higashi. 1996.V.I. Phys.. 103–108. Shevchuck. 1978.. Nagai. Ponomarev. 29. T. Sakumato. Appl. Minin.A.A.. Appl. 48 (1). S. 1993. Appl. Int. V.V. O. The radiation-induced degradation of antroquinone dyes in aqueous solutions... W. . M. A. L. 199–204. Ditrikh.. Bludenko.. S. H.. Electron-beam treatment of highly-coloured river water.558 D. Rapid determination of chemical oxygen demand in glucose water solutions. Maharov... N. Mizushorigijutsu 37.K. Yamane. 187–200. Tekhnol.. Radiat. A. 26... Research survey on prevention of pollution by wastewaters.. Makhno.. Radiat. Radiat. V... M. 699–705. M. J. Ponomarev. I.. 262–263.Ya.. The radiation-induced degradation of azo dyes in aqueous solutions. . J. Linnik.. 1996. Isot. S.. Wakida. Takeda.