Chemosphere 48 (2002) 393399

www.elsevier.com/locate/chemosphere

Photodegradation of an azo dye of the textile industry

pez Cisneros a, Abel Gutarra Espinoza b, Marta I. Litter
Rosario Lo

c,*

Escuela Profesional de Qu
mica, Laboratorio de Pel
culas Delgadas, Facultad de Ciencias,

Universidad Nacional de Ingenier
a, Av. Tupac Amaru 280, 31-139 Lima, Peru
b
Escuela Profesional de Ingenier
a F
sica, Laboratorio de Pel
culas Delgadas, Facultad de Ciencias,
Universidad Nacional de Ingenier
a, Av. Tupac Amaru 280, 31-139 Lima, Peru
Unidad de Actividad Qu
mica, Centro At

omico Constituyentes, Comisi

on Nacional de Energ
a At

omica,
Av. Gral. Paz 1499, 1650 San Mart
n, 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 eect. The degradation rate was also function of pH. 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 eects.

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, eorts to reduce
costs by control of dierent 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 euent is essential
(Vel

asquez, 1998).
Because the chemical structures of dyes are rather
complicated, biological treatments are not ecient 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 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

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R. L
opez Cisneros et al. / Chemosphere 48 (2002) 393399

generate powerful hydroxyl radicals (HO , E0 2:8 V

vs. normal hydrogen electrode), have been proposed for
color removal and degradation of dyes. Particularly,
these techniques have been found suitable for azo-type
dyes, which are the most used textile colorants (Ince
et al., 1997; Chun and Yizhong, 1999; Fung et al., 1999;
Rott and Minke, 1999; Stock et al., 2000).
A direct method for HO generation is hydrogen
peroxide photocleavage by means of short UV radiation.
The UV/H2 O2 process has the potential ability to oxidize
most of the organic contaminants to carbon dioxide and
water. Sometimes, total mineralization requires large
light power and oxidant dose, implying high costs in
comparison with conventional treatments such as air
stripping or activated carbon adsorption. In those cases,
partial oxidation is preferred as treatment, converting
the original species to products of lower toxicity, higher
biodegradability or aptitude to be eliminated by a more
economical treatment (Bircher et al., 1997). Consequently, 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, 1996; EPA, 1998).
The initial aim of this work was the bleaching of a
model sample of a textile wastewater by the UV/H2 O2
technology, reaching color levels proper for reuse in
dyeing or rinsing processes. Additionally, the feasibility
of the technique for the complete degradation of the
pollutant, preventing thereby the formation of intermediates more harmful than the initial compound, was
tested.

2.2. Photoreactor and irradiation experiments

The photoreactor was an 1.5-l glass cylindrical cell.
The solution was continuously recycled from an 1.0-l
reservoir with a peristaltic pump at a 0.52-l min1 rate.
This setup allowed having permanently 1.5 l of solution
in the photoreactor. A 125 W-medium pressure Hg lamp
(General Electric), provided with a quartz jacket and
immersed into the solution, was used as irradiation
source. Two inlets in the reservoir allowed control of pH
and temperature, which was kept at 25 C. Magnetic
stirring in the reservoir as well as in the photoreactor
assured the good mixing of the solution.
Irradiation experiments were performed using a 40mg l1 aqueous solution of the dye, with the addition of
a prexed amount of H2 O2 . Samples were periodically
withdrawn from the reservoir, and changes in absorbance and TOC were measured. Periodically, the presence of H2 O2 was checked by a qualitative test with
ammonium metavanadate (Oliveira et al., 2001), and no
depletion of the reagent was found in any case.

2.3. Analytical methods

Absorbances in the UV and visible range were measured with a HewlettPackard HP-8453 diode array
spectrophotometer. Actinometry was performed using
potassium ferrioxalate (Hatchard and Parker, 1956).
The measured photon ux was 2.2 mEinstein min1 .
TOC changes were followed with a TOC-5000A Shimadzu equipment.

2. Experimental
3. Results and discussion
2.1. Materials and methods
Hispamin Black CA (C44 H32 N13 Na3 O11 S3 , MW
1083, color index Direct Black 22) was provided by
Textil Consorcio Industrial La Parcela S.A. (Lima-Per

u)
as a technical product. After dissolving the corresponding amount of dye in water, the solution was ltered to remove any solid impurity. UVVis spectra of
the solution before and after ltration were identical.
Hydrogen peroxide (Merck, 30% w/w) was used. All
other reagents were reagent grade and used without
further purication. pH was adjusted with HCl or
NaOH diluted solutions.

The structure of the dye, a direct azo dye commercially called Hispamin Black CA, is shown in Fig. 1.
In Fig. 2 are depicted the UVVis spectra of the dye
in water at three dierent pH values: 2.5, 7.5 and 11. At
the two rst pH values, the spectra are rather similar.
The peak with a maximum at 471 nm accounts for the
violet color of the solutions, 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, 1967). In the UV region, there
is a second group of bands, with an increasing absorbance towards lower wavelengths, characteristic of

Fig. 1. Structure of Hispamin Black CA.

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opez Cisneros et al. / Chemosphere 48 (2002) 393399

395

Fig. 2. UVVis spectra of Hispamin Black CA (40 mg l1 in water) at three dierent pH values.

aromatic rings. At pH 11, the spectrum changes, exhibiting a red shift of the maximum to 582 nm, which
indicates the predominance of other forms of the dye,
probably conjugate base species. However, the absorption at 471 nm is still important.
The decolorization of the dye was studied starting
with a 40 mg l1 aqueous dye solution at natural pH
(7.5), whose absorbance at 471 nm was close to 1. Preliminary experiments were performed irradiating the
system in the presence of dierent amounts of H2 O2 , in
the range 500700 mg l1 . From the various concentrations, the fastest degradation occurred with 565.8 mg l1
(16.6 mM) H2 O2 , i.e., with a hydrogen peroxide to dye
molar ratio close to 451:1 (considering dye is totally
pure). Control experiments in the dark at the same H2 O2
concentration yielded a negligible degradation of the
dye. In Fig. 3 are shown the spectra obtained at dierent
times, indicating that at this H2 O2 concentration the
total transparency (A < 0:01) of the solution was obtained after approximately 35 min.
Fig. 4 shows the variation of the peak at 471 nm with
time expressed as normalized absorbance, A=A0 , being
A0 the absorbance at the initial time. The plot indicates
a high decolorization rate in the rst 20 min, followed
by a slower variation. The point of inexion might
indicate depletion of H2 O2 , formation of compounds
resistant to the oxidative processes or presence of intermediate products competing for the produced HO
radicals. From these data, an initial rate value R0
0:050 min1 was calculated from the slope of the linear
part. One experiment in identical conditions but in
the absence of H2 O2 was carried out to compare the

results due to direct UV photolysis. Without H2 O2 , the

decay was very small and linear; the rate determined
from the plot was 0.002 min1 , i.e., more than one
order of magnitude lower than in the presence of the
oxidant.
Theoretically, the chemical bond of azo compounds
can be directly photolyzed by UV irradiation, but this is
a slow process that can be substantially improved in the
presence of H2 O2 (Ince et al., 1997). Under short UV
light, hydrogen peroxide is rapidly dissociated, producing HO , a non-selective and powerful oxidant, which
decomposes the dye very quickly (Legrini et al., 1993;
Bolton and Cater, 1994; Bircher et al., 1997):
hm

HOOH ! 2HO

/ 0:98

where / is the quantum yield of the homolytic H2 O2

photodissociation,
R1 N@NR2 HO ! degradation products

This is a simplied scheme, occurring through several

stages with the formation of dierent intermediates, and
it will be not analyzed here. At the end, the products can
be mineralized:
HO products !
CO2 H2 O other inorganic products

In excess of peroxide and with high HO concentrations, competitive reactions take place, producing an

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R. L
opez Cisneros et al. / Chemosphere 48 (2002) 393399

Fig. 3. Variation of the spectral absorbance with time of a 40 mg l1 Hispamin Black CA aqueous solution at pH 7.5 during irradiation
under UV light in the presence of 565.8 mg l1 H2 O2 . a 0, b 2, c 5, d 10, e 15, f 20, g 25, h 30, i 35, j 40, k 45,
l 50, m 55, n 60 min. For illumination conditions see text.

Fig. 4. Variation of the normalized absorption at 471 nm with irradiation time. Conditions as in Fig. 3. (a) In the presence of 565.8
mg l1 H2 O2 ; (b) without H2 O2 .

inhibitory eect for the degradation. HO radicals are

prone to recombination or to react according to the
following scheme (Baxendale and Wilson, 1957):

HO2 H2 O2 ! HO H2 O O2

2HO2 ! H2 O2 O2

HO H2 O2 ! HO2 H2 O

HO2 HO ! H2 O O2

R. L
opez Cisneros et al. / Chemosphere 48 (2002) 393399

397

Fig. 5. Variation of the initial rate of degradation of the dye with the H2 O2 concentration. Conditions as in Fig. 3.

Reactions (4) and (7) are HO consuming, decreasing

the probability of oxidation of the substrate. Therefore,
an important step for the optimization of the method is
the determination of the adequate amount of H2 O2 , to
avoid an excess of reagent that can retard the degradation. Further experiments have been performed in the
presence of dierent hydrogen peroxide concentrations
and the proles of normalized absorbances at 471 nm
with time at all the used hydrogen peroxide concentrations were plotted (not shown). As in the case of Fig. 4,
all curves presented a similar shape, with a rather linear
behavior up to approximately 1520 min, and then with
a drastic change in slope. Initial rates, calculated from
the slopes of the linear part of these proles, increased
with H2 O2 concentration up to the maximum, 565.8
mg l1 , and then decreased rather sharply, as shown in
Fig. 5.
The results of Fig. 5 point out the negative eect of a
defect or an excess of H2 O2 on the reaction rate. The
concentration of the reagent must be enough for the
formation of a considerable amount of HO radicals, but
a high concentration is detrimental.
Using the optimum H2 O2 concentration, the eect of
pH on the rate of bleaching was assessed. The solution
of the dye was adjusted to pH 2.5 and 11 and irradiation
experiments were performed following the evolution of
the absorbance with time; the results were compared
with those at pH 7.5 (Fig. 6). Although the relative
concentration of protolytic species in equilibrium is not
the same at the three pH values, still a relative comparison can be made taking into account the normalized
absorbances at 471 nm. As it can be seen, the dierences

are not remarkable, but the reaction is slower at the

most acidic pH, presenting also a dierent kinetic prole.
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:

H2 O2 ! HO
2 H

pKa 11:6

This species has a higher cross-section (240 M1 cm1 ) at

254 nm than H2 O2 (18.6 M1 cm1 ), which favors the
absorption of light by the reactive and increases the HO
production (Legrini et al., 1993; Beltr

an et al., 1996). A
dierent reactivity of the dye at acid pH cannot be either
discarded.
As already said, using 565.8 mg l1 H2 O2 at pH 7.5,
the bleaching of the solution occurred approximately
in 35 min. Nevertheless, the degree of mineralization
of the dye, quantied by TOC evaluation (Fig. 7), was
only 52% in the same period of time. To achieve the
quasi-total mineralization, a longer irradiation time was
necessary; after 60 min of irradiation, only 18% of nondegraded organic carbon remained. Although the experimental points present a relatively large dispersion, a
rather linear TOC decrease is observed, indicating that
no very resistant compounds are formed during the reaction. However, these results suggest that degradation
compounds, probably low molecular weight aldehydes
and organic acids, still remain in solution. These compounds can be even more toxic than the original dye
molecule, with the expected consequences for the quality

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R. L
opez Cisneros et al. / Chemosphere 48 (2002) 393399

Fig. 6. Eect of the initial pH on the photochemical decolorization, monitored at 471 nm. Other conditions as in Fig. 3.

Fig. 7. Variation of TOC during the irradiation. Conditions of Fig. 3.

of the water. Therefore, a more prolonged irradiation is

needed to achieve the total mineralization and avoid
toxicity problems.

4. 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, but also the ability of the oxidant to
almost completely mineralize the samples in a very
reasonable period of time. In our case, an 1.5-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. It is worthwhile to point out that a real
sample, collected from an industrial plant and ltered,

R. L
opez Cisneros et al. / Chemosphere 48 (2002) 393399

has an absorbance around 0.5, indicating a high potentiality of the AOT here proposed. The optimum
molar ratio of hydrogen peroxide to dye for the process
was determined. However, as a certain amount of TOC
still remained in solution, 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.
Although the decolorization rate will depend on the
particular type of the dye, the technique seems to be
applicable to any industrial wastewater containing azo
dyes. The process can be optimized by the modication
of parameters such as the recycling ux, the diameter
and shape of the reactor, the use of reecting walls to
increase UV radiation inside the photoreactor, etc.
These results can be taken as a starting step to establish
the economical feasibility of the method, dening previously the degree of destruction and mineralization
desirable for the next application of the wastewater.
Comparison of the oxidative technique here presented
with other AOTs such as TiO2 photocatalysis or photoFenton are underway. The selection of the method will
be dictated by the compromise between the economy
and the required nal quality of the water.

Acknowledgements
To Facultad de Ciencias, Universidad de Ingenier
a,
Lima, Per

u, for nancing this research. Work performed
as part of Comisi

on Nacional de Energ
a At

omica
CNEA-CAC-UAQ project #95-Q-03-05. To Compa~
n
a
Textil Consorcio Industrial La Parcela S.A. (Lima-Per

u)
for proposing this study and providing relevant information. R.L.C. and M.I.L. thank the CYTED Program,
a Scientic Iberoamerican Cooperation Action (CYTED VIII-G) for partial nancing their stays in Argentina and Per

u, respectively. M.I.L. is a member from
CONICET (Argentina).

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