Chemosphere 48 (2002) 393–399

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Photodegradation of an azo dye of the textile industry 
pez Cisneros a, Abel Gutarra Espinoza b, Marta I. Litter
Rosario Lo

c,*

a

c

Escuela Profesional de Quımica, Laboratorio de Pelıculas Delgadas, Facultad de Ciencias,
Universidad Nacional de Ingenierıa, Av. Tupac Amaru 280, 31-139 Lima, Peru
b
Escuela Profesional de Ingenierıa Fısica, Laboratorio de Pelıculas Delgadas, Facultad de Ciencias,
Universidad Nacional de Ingenierıa, Av. Tupac Amaru 280, 31-139 Lima, Peru
Unidad de Actividad Quımica, Centro At
omico Constituyentes, Comisi
on Nacional de Energıa At
omica,
Av. Gral. Paz 1499, 1650 San Martın, Prov. de Buenos Aires, Argentina
Received 3 September 2001; received in revised form 1 March 2002; accepted 1 March 2002

Abstract
An advanced oxidation treatment, UV/H2 O2 , was applied to an azo dye, Hispamin Black CA, widely used in the
Peruvian textile industry. Rates of color removal and degradation of the dye have been evaluated. A strongly absorbing
solution was completely decolorized after 35 min of treatment, and after 60 min an 82% reduction of the total organic
carbon (TOC) was obtained. It has been found that the degradation rate increased until an optimum value, beyond
which the reagent exerted an inhibitory effect. The degradation rate was also function of pH. Ó 2002 Elsevier Science
Ltd. All rights reserved.
Keywords: AOTs; UV/hydrogen peroxide; Decolorization

1. Introduction
High levels of environmental contamination are
produced in dyeing processes of textile plants, due to
the high toxicity of the chemical components of the
wastewaters. The most detrimental aspects for the discharge of textile wastewaters are the strong color, high
and unstable pH, high chemical oxygen demand (COD),
and the presence of suspended solids, considerable
amounts of heavy metals (e.g. Cr, Ni or Cu), chlorinated organic compounds and surfactants (Bircher
et al., 1997; Ince et al., 1997). In addition, azo dyes and
their derived products, commonly used in this industry
and in others, are known to present serious carcinogenic effects.

*

Corresponding author. Tel.: +54-11-6772-7016; fax: +5411-6772-7121/7886.
E-mail address: litter@cnea.gov.ar (M.I. Litter).

Textile industry in Per
u involves large production
volumes for internal consumption and for export. Despite some retraction in 1998 and 1999, the economical
level of the manufacture registered a remarkable enhancement in last years. Therefore, efforts to reduce
costs by control of different stages of the processes were
attempted. In this sense, reuse of dyeing waters appears
to be a very convenient target to minimize volumes of
water. For this, decolorization of the effluent is essential
(Vel
asquez, 1998).
Because the chemical structures of dyes are rather
complicated, biological treatments are not efficient for
their degradation. Hence, the use of conventional oxidants has been for years the standard chemical method
for the treatment of dye wastewaters. However, these
procedures are not always feasible owing to thermodynamic and kinetic limitations of the common reagents to
attack refractory compounds. To remedy this situation,
advanced oxidation processes or techniques (AOPs,
AOTs, Glaze, 1987; Glaze et al., 1987; Huang et al., 1993;
Legrini et al., 1993; Bolton and Cater, 1994), which

0045-6535/02/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 1 1 7 - 0

In the UV region. provided with a quartz jacket and immersed into the solution. The initial aim of this work was the bleaching of a model sample of a textile wastewater by the UV/H2 O2 technology. Chun and Yizhong. E0 ¼ 2:8 V vs. 2 are depicted the UV–Vis spectra of the dye in water at three different pH values: 2. was used as irradiation source. Actinometry was performed using potassium ferrioxalate (Hatchard and Parker. Particularly. Photoreactor and irradiation experiments The photoreactor was an 1. the presence of H2 O2 was checked by a qualitative test with ammonium metavanadate (Oliveira et al.A. A 125 W-medium pressure Hg lamp (General Electric). 1. Magnetic stirring in the reservoir as well as in the photoreactor assured the good mixing of the solution.5 and 11. converting the original species to products of lower toxicity. Hydrogen peroxide (Merck. MW ¼ 1083. reaching color levels proper for reuse in dyeing or rinsing processes. The measured photon flux was 2.. total mineralization requires large light power and oxidant dose. The structure of the dye. Analytical methods Absorbances in the UV and visible range were measured with a Hewlett–Packard HP-8453 diode array spectrophotometer. 2. 7.52-l min1 rate. with the addition of a prefixed amount of H2 O2 . In Fig. Periodically. the feasibility of the technique for the complete degradation of the pollutant. Structure of Hispamin Black CA. 2001). Samples were periodically withdrawn from the reservoir. 30% w/w) was used. This setup allowed having permanently 1. Fung et al. 1998). 1999. preventing thereby the formation of intermediates more harmful than the initial compound.3. and changes in absorbance and TOC were measured. . 1997).5 l of solution in the photoreactor. partial oxidation is preferred as treatment.394 R. Experimental 3.. is shown in Fig. Rott and Minke. and can be attributed to the n ! p transition of non-bonding nitrogen electrons to the antibonding p group orbital of the double-bond system (Calvert and Pitts. 1996. A direct method for HO generation is hydrogen peroxide photocleavage by means of short UV radiation.. Additionally.2. the solution was filtered to remove any solid impurity. characteristic of Fig. All other reagents were reagent grade and used without further purification. treatability tests must be done to evaluate the best technique for a particular case and to decide the convenience either of a prolonged single treatment or a combined one (Calgon. Sometimes. a direct azo dye commercially called Hispamin Black CA. color index Direct Black 22) was provided by Textil Consorcio Industrial La Parcela S. The solution was continuously recycled from an 1. The UV/H2 O2 process has the potential ability to oxidize most of the organic contaminants to carbon dioxide and water. At the two first pH values.5-l glass cylindrical cell. 2. and no depletion of the reagent was found in any case. 1997. Lopez Cisneros et al. After dissolving the corresponding amount of dye in water. pH was adjusted with HCl or NaOH diluted solutions. which was kept at 25 °C. Irradiation experiments were performed using a 40mg l1 aqueous solution of the dye. In those cases. 1. was tested. Stock et al. EPA.5. 2000). normal hydrogen electrode). 1999. which are the most used textile colorants (Ince et al. there is a second group of bands. UV–Vis spectra of the solution before and after filtration were identical. Consequently.0-l reservoir with a peristaltic pump at a 0. the spectra are rather similar. (Lima-Per u) as a technical product. / Chemosphere 48 (2002) 393–399 generate powerful hydroxyl radicals (HO . 2. Two inlets in the reservoir allowed control of pH and temperature. with an increasing absorbance towards lower wavelengths. higher biodegradability or aptitude to be eliminated by a more economical treatment (Bircher et al. 1999. 1967).. Results and discussion 2. Materials and methods Hispamin Black CA (C44 H32 N13 Na3 O11 S3 . implying high costs in comparison with conventional treatments such as air stripping or activated carbon adsorption. TOC changes were followed with a TOC-5000A Shimadzu equipment.1.2 mEinstein min1 . have been proposed for color removal and degradation of dyes. these techniques have been found suitable for azo-type dyes.. The peak with a maximum at 471 nm accounts for the violet color of the solutions. 1956).

. Theoretically. with a hydrogen peroxide to dye molar ratio close to 451:1 (considering dye is totally pure). One experiment in identical conditions but in the absence of H2 O2 was carried out to compare the results due to direct UV photolysis.e. a non-selective and powerful oxidant. the absorption at 471 nm is still important. 2.. whose absorbance at 471 nm was close to 1. occurring through several stages with the formation of different intermediates. 1993. probably conjugate base species. The point of inflexion might indicate depletion of H2 O2 . Fig. R1 –N@N–R2 þ HO ! degradation products ð2Þ This is a simplified scheme. / Chemosphere 48 (2002) 393–399 395 Fig. competitive reactions take place..e. 1997): hm HO–OH ! 2HO ð/ ¼ 0:98Þ ð1Þ where / is the quantum yield of the homolytic H2 O2 photodissociation. the chemical bond of azo compounds can be directly photolyzed by UV irradiation.5). At the end. i. Under short UV light. the spectrum changes. Lopez Cisneros et al. 3 are shown the spectra obtained at different times.. exhibiting a red shift of the maximum to 582 nm. UV–Vis spectra of Hispamin Black CA (40 mg l1 in water) at three different pH values. the fastest degradation occurred with 565. However. 4 shows the variation of the peak at 471 nm with time expressed as normalized absorbance. Without H2 O2 . From these data..002 min1 . and it will be not analyzed here.8 mg l1 (16. A=A0 . aromatic rings. i.6 mM) H2 O2 . The decolorization of the dye was studied starting with a 40 mg l1 aqueous dye solution at natural pH (7. producing HO . the rate determined from the plot was 0. In Fig. which indicates the predominance of other forms of the dye. 1994. 1997). followed by a slower variation. but this is a slow process that can be substantially improved in the presence of H2 O2 (Ince et al. being A0 the absorbance at the initial time. hydrogen peroxide is rapidly dissociated. an initial rate value R0 ¼ 0:050 min1 was calculated from the slope of the linear part. At pH 11. more than one order of magnitude lower than in the presence of the oxidant. indicating that at this H2 O2 concentration the total transparency (A < 0:01) of the solution was obtained after approximately 35 min. producing an . From the various concentrations. the products can be mineralized: HO þ products ! CO2 þ H2 O þ other inorganic products ð3Þ In excess of peroxide and with high HO concentrations. the decay was very small and linear. which decomposes the dye very quickly (Legrini et al. Bircher et al. Preliminary experiments were performed irradiating the system in the presence of different amounts of H2 O2 . Bolton and Cater.R. The plot indicates a high decolorization rate in the first 20 min. Control experiments in the dark at the same H2 O2 concentration yielded a negligible degradation of the dye. in the range 500–700 mg l1 . formation of compounds resistant to the oxidative processes or presence of intermediate products competing for the produced HO radicals.

8 mg l1 H2 O2 . 4. / Chemosphere 48 (2002) 393–399 Fig. g ¼ 25. k ¼ 45. e ¼ 15. d ¼ 10. 1957): HO2 þ H2 O2 ! HO þ H2 O þ O2 ð5Þ 2HO2 ! H2 O2 þ O2 ð6Þ HO þ H2 O2 ! HO2 þ H2 O HO2 þ HO ! H2 O þ O2 ð7Þ ð4Þ . c ¼ 5. Fig.8 mg l1 H2 O2 . (a) In the presence of 565. Conditions as in Fig. n ¼ 60 min. inhibitory effect for the degradation. l ¼ 50. a ¼ 0. For illumination conditions see text. j ¼ 40. i ¼ 35. h ¼ 30. Variation of the spectral absorbance with time of a 40 mg l1 Hispamin Black CA aqueous solution at pH 7. Lopez Cisneros et al.5 during irradiation under UV light in the presence of 565. (b) without H2 O2 . b ¼ 2.396 R. 3. HO radicals are prone to recombination or to react according to the following scheme (Baxendale and Wilson. Variation of the normalized absorption at 471 nm with irradiation time. m ¼ 55. f ¼ 20. 3.

The enhanced rate at neutral and alkaline pH could be explained by the increase of the concentration of the conjugate anion of hydrogen peroxide as pH increases: þ H2 O2 ! HO 2 þH pKa ¼ 11:6 ð8Þ This species has a higher cross-section (240 M1 cm1 ) at 254 nm than H2 O2 (18. which favors the absorption of light by the reactive and increases the HO production (Legrini et al. Nevertheless. 5. and then decreased rather sharply.R. all curves presented a similar shape. Beltr an et al. 7). 3. Therefore. with a rather linear behavior up to approximately 15–20 min. the degree of mineralization of the dye. but the reaction is slower at the most acidic pH. with the expected consequences for the quality . to avoid an excess of reagent that can retard the degradation. using 565. 4. quantified by TOC evaluation (Fig. the bleaching of the solution occurred approximately in 35 min. Using the optimum H2 O2 concentration. 565. but a high concentration is detrimental. As already said. Reactions (4) and (7) are HO consuming. Further experiments have been performed in the presence of different hydrogen peroxide concentrations and the profiles of normalized absorbances at 471 nm with time at all the used hydrogen peroxide concentrations were plotted (not shown). presenting also a different kinetic profile.8 mg l1 H2 O2 at pH 7. Initial rates. these results suggest that degradation compounds. Although the relative concentration of protolytic species in equilibrium is not the same at the three pH values.. Lopez Cisneros et al. an important step for the optimization of the method is the determination of the adequate amount of H2 O2 . still a relative comparison can be made taking into account the normalized absorbances at 471 nm. 5 point out the negative effect of a defect or an excess of H2 O2 on the reaction rate. A different reactivity of the dye at acid pH cannot be either discarded.8 mg l1 . 5.5. the results were compared with those at pH 7. the differences are not remarkable. The concentration of the reagent must be enough for the formation of a considerable amount of HO radicals. still remain in solution. probably low molecular weight aldehydes and organic acids. the effect of pH on the rate of bleaching was assessed.5 (Fig. only 18% of nondegraded organic carbon remained. However. 1993. 1996). was only 52% in the same period of time. / Chemosphere 48 (2002) 393–399 397 Fig. and then with a drastic change in slope. As in the case of Fig. indicating that no very resistant compounds are formed during the reaction. As it can be seen.5 and 11 and irradiation experiments were performed following the evolution of the absorbance with time. Variation of the initial rate of degradation of the dye with the H2 O2 concentration.. To achieve the quasi-total mineralization. after 60 min of irradiation. The solution of the dye was adjusted to pH 2. 6). increased with H2 O2 concentration up to the maximum. a rather linear TOC decrease is observed. calculated from the slopes of the linear part of these profiles. Conditions as in Fig. Although the experimental points present a relatively large dispersion.6 M1 cm1 ). These compounds can be even more toxic than the original dye molecule. decreasing the probability of oxidation of the substrate. as shown in Fig. The results of Fig. a longer irradiation time was necessary.

Lopez Cisneros et al. In our case. . Fig. Conclusions In this work we have demonstrated not only the effective and rapid decolorizing power of the UV/H2 O2 procedure when applied to a colored solution of Hispamin Black CA. Conditions of Fig. collected from an industrial plant and filtered. 4. a more prolonged irradiation is needed to achieve the total mineralization and avoid toxicity problems. Therefore.398 R.5-l volume of a strongly colored solution of absorbance close to 1 could be totally decolorized in 35 min and almost totally decomposed in 60 min under the present illumination conditions. 3. 7. 6. Effect of the initial pH on the photochemical decolorization. Other conditions as in Fig. monitored at 471 nm. / Chemosphere 48 (2002) 393–399 Fig. an 1. 3. It is worthwhile to point out that a real sample. of the water. but also the ability of the oxidant to almost completely mineralize the samples in a very reasonable period of time. Variation of TOC during the irradiation.

1997. Photochemical processes for water treatment. Stefan. Hatchard.. Photolysis of hydrogen peroxide at high light intensities.. a case study. Cater.. 671–698. Drinkingwater treatment with ozone. J.. C. Boca Raton.. EPA/625/R-98/004.V.G. New York. Chem. Aquatic and Surface Photochemistry. Huang. Ch.R.C.. Lewis. 1987. Environ. Kamat.. Eng. Soc. W. M. Treatability study of organic and colour removal in desizing/ dyeing wastewater by UV/us system combined with hydrogen peroxide..R. Crosby.. J. Mundo Textil (Lima. for financing this research.R. J.H. 40 (1). 34. (Lima-Per u) for proposing this study and providing relevant information. 1747–1750. 344–356. The AOT Handbook. Nogueira. In: Helz. Yizhong.L..A. Rott.. 29–36.J. Ovejero. J. 1993..L. C. Bolton. p. 1956. II. Water Sci..L. Vinodgopal. UV/H2 O2 degradation and toxicity reduction of textile azo dyes: Remazol Black-B. References Baxendale. To Compa~ nıa Textil Consorcio Industrial La Parcela S. 2 (3).N. Beltr an. Per u) 49. Eng. (London) A 235. etc.R. Faraday Soc. J.J. Sci... 188–190. Chapin. 53.. Quımica Nova 24. Water Sci.. respectively.. Tsui. 1996.F.G. G.. 2001. 137–144. Glaze. defining previously the degree of destruction and mineralization desirable for the next application of the wastewater. Oxidation of polynuclear aromatic hydrocarbons in water. the technique seems to be applicable to any industrial wastewater containing azo dyes. Stock. 224–230. Advanced chemical oxidation: its present role and potential future in hazardous waste treatment.W.H.. Simms. a ‘‘Scientific Iberoamerican Cooperation Action’’ (CYTED VIII-G) for partial financing their stays in Argentina and Per u. Parker.5. and M.A. 1994. Potassium ferrioxalate as a standard chemical actinometer. Technol. 1999. Waste Manage. N...L. N. J. Rev. P. J. A. Velasquez. P. Technol.. Jardim. The selection of the method will be dictated by the compromise between the economy and the required final quality of the water.. 93. Environ.M. Adv. Rohwedder.S. 1997.M. Ozone Sci. 153–160. 1967. J.I. Peller. 452.P. . 1996.. Lima. Adv. J. C. 467–490. M.R.. as a certain amount of TOC still remained in solution. Chemosphere 39 (12). thank the CYTED Program. O. Q..). Sistema de Injecß~ao em Fluxo Espectrofotometrico para Monitorar Per oxido de Hidrog^enio em Processo de Fotodegradacß~ao por Reacß~ao Foto-Fenton. P. / Chemosphere 48 (2002) 393–399 has an absorbance around 0. pp. Glaze. Minke. Legrini.A. Kang.. D. 21 (3).. Overview of wastewater treatment and recycling in the textile processing industry. The chemistry of water treatment processes involving ozone. EEUU. Technol. Comparison of the oxidative technique here presented with other AOTs such as TiO2 photocatalysis or photoFenton are underway. 1957. Technol. D. 435–441. Poon. Fung. Trans. Oxid.. Res. G. R. the diameter and shape of the reactor.N.C. Combination of UV oxidation with other treatment technologies for remediation of contaminated water. Rivas. 1999. 335–352. Sci. the use of reflecting walls to increase UV radiation inside the photoreactor. Ind. R. Chem. In: Photochemistry. Huang. A new sensitive chemical actinometer. R.I. Dussert.. J. Aguas residuales en la industria textil. K. Per u.G. Tang. W.. Chun.F. 2 (3). W. Dong. 883–890.M. Lopez Cisneros et al.C. Technol. 2107–2115. The optimum molar ratio of hydrogen peroxide to dye for the process was determined.. Roy. Pitts Jr.. These results can be taken as a starting step to establish the economical feasibility of the method. Decolorization and biodegradability of photocatalytic treated azo dyes and wool textile wastewater. (Eds. FL. 3.W. G. is a member from CONICET (Argentina). W. Ince. 361–377. Oliveira. 1993. U.. H. 1999..P.H.. C. W.. Oxid. 40 (1).. Acknowledgements To Facultad de Ciencias. J. US/EPA Handbook of Advanced Photochemical Oxidation Processes. Universidad de Ingenierıa.H. M.G. 1998.. Calvert. Oliveros.. Proc... Z. Braun. Bircher. indicating a high potentiality of the AOT here proposed. J. Technol. Ontario. Homogeneous photodegradation of pollutants in contaminated water: an introduction. S. R. 13. 2000. E. 35. 442–448.H. Combinative sonolysis and photocatalysis for textile dye degradation.. K.R.I.. Work performed as part of Comisi on Nacional de Energıa At omica CNEA-CAC-UAQ project #95-Q-03-05. S.A.. B. hydrogen peroxide and UV radiation. John Wiley & Sons. Lem. 1987. K. F. 1998. Zepp. However.. UV radi- 399 ation combined with hydrogen peroxide. Bolton. Although the decolorization rate will depend on the particular type of the dye. Gomes Neto. The process can be optimized by the modification of parameters such as the recycling flux. Calgon Carbon Oxidation Technologies. 9.. toxicity tests should be made at the end of the process to carefully determine the presence of species even more noxious than the original dye and to evaluate the requirement of a more powerful degradation technique.. Wilson. 518–536.