Chemosphere 40 (2000) 369±373

Degradation and toxicity reduction of textile e‚uent by

combined photocatalytic and ozonation processes
Sandra Gomes de Moraes*, Renato Sanches Freire, Nelson Dur
an
Biological Chemistry Laboratory, Instituto de Quõmica, Universidade Estadual de Campinas, C.P. 6154, CEP 13083-970, Campinas-SP,
Brazil
Received 10 May 1999; accepted 8 June 1999

Abstract

To minimize the environmental impact of textile e‚uents, mainly related to their high coloration and the presence of
toxic or carcinogenic reactive dyes, the eciency of photochemical and ozonation processes, applied in the form of
isolated and combined procedures, were evaluated. The investigation was focused on the reduction of total organic
carbon content (TOC), color and acute toxicity (monitoring by inhibition of Escherichia coli respiration). For a reaction
time of 60 min, the anatase TiO2 -assisted photocatalytic process produces color and TOC reduction of about 90% and
50%, respectively. Meanwhile, the ozonation process gives a decolorization of about 60% but negligible TOC reduction.
When the processes were applied in a simultaneous form, the decolorization was almost complete and the TOC re-
duction was higher than 60%. The three treatments studied yield an acute toxicity reduction of around 50%. Ó 1999
Elsevier Science Ltd. All rights reserved.

Keywords: Photocatalysis; Ozonation; Textile e‚uent; Remediation

1. Introduction development of alternative treatment methods will be-

At the present time, textile activities are in constant
expansion showing a high pollutant potential. A medi-
um sized textile mill shows a polluting potential of 7000
persons (in relation to hydraulic charge), or 20,000
persons (in relation to organic charge). In Brazil, the
textile industry utilizes 20 ton/yr of dyes (Peralta-
Zamora et al., 1999) with about 10% of them lost in the
e‚uents. In the absence of any speci®c government
regulations on the eventual disposal of these dyes, the
problem remains as the main environmental problem
related to textile activities. Since some regulations have
been introduced to control the disposal of dyestu€s,
mainly because of their high polluting potential, the
*
Corresponding author.
E-mail address: sgomes@iqm.unicamp.br (S.G. de Moraes).
come important (Nasr et al., 1997).
Besides the substituent groups that allow dye ®xation
onto the ®bers, the dye molecule contains an aromatic
structure that absorbs visible light (chromogen group).
There are about 12 classes of chromogenic groups, the
most common being the azo type which makes up to 60±
70% of all textile dyestu€s produced, followed by the
anthraquinone type (Vandevivere et al., 1998). The ease
of manufacture, and the enormous variety of such dyes,
ranging from the insoluble disperse class to simple an-
ionic monoazo dyes, have made azo dyes ubiquitous
chemicals which are used in a variety of colorant ap-
plications ranging from synthetic to natural ones (Nasr
et al., 1997).
The more complex environmental problems associ-
ated with the e‚uents are due to extensive use of car-
cinogenic or mutagenic azo dyes which are resistant to
microbial degradation. Some azo dyes are either toxic or

0045-6535/00/$ - see front matter Ó 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 2 3 9 - 8
370 S. Gomes de Moraes et al. / Chemosphere 40 (2000) 369±373
can be modi®ed biologically to produce toxic or car-
cinogenic compounds. The nonbiodegradability of tex-
tile wastewater is due to their high content of dyestu€s,
surfactants and additives. There is no universally useful
method available for treatment of dye wastes, probably
because of the complex and very varied chemical struc-
tures of these compounds (Peralta-Zamora et al., 1998).
The eciency of advanced oxidation processes for
degradation of recalcitrant compounds has been exten-
sively documented. Photochemical processes are used to
degrade toxic organic compounds to CO2 and H2 O
without the use of additional chemical oxidants, because
the degradation is assisted by high concentrations of
hydroxyl radicals generated in the process. In this case,
the photoexcitation of TiO2 particles promotes an elec-
tron from the valence band to the conduction band,
generating an electron/hole pair. Both reductive and
oxidative processes can occur at or near the surface of
the photoexcited TiO2 particle. In general, oxygen is
used to scavenge the conduction band electron, pro-
ducing a superoxide anion radical, e€ectively preventing
electron/hole recombination, and prolonging the lifetime
of the hole. The photogenerated hole has the potential to
oxidize several substrates by electron transfer. In aque-
ous solutions, oxidation of water to hydroxyl radical by
the photogenerated hole appears to be the predominant
pathway. Hydroxyl radicals and, to a lesser extent, su-
peroxide anion can act as oxidants, ultimately leading to
the mineralization of organic compounds (Nasr et al.,
1997; O'Shea et al., 1997). In aerated aqueous suspen-
sions, the photogenerated electrons promote the reduc-
tion of dissolved oxygen:
O2 ‡ eÿ ! Oáÿ …I†
2
whereas the photogenerated holes oxidize adsorbed
water molecules to give hydroxyl radicals:
H2 O ‡ h‡ ! OHá ‡ H‡ …II†
The Oáÿ2 formed from reaction (I) can lead, after several
steps, to the generation of H2 O2 (Brillas et al., 1998):
Oáÿ ‡ ÿ á
2 ‡ H 2e ! HO2 …III†
HOá2 ‡ eÿ ! HOÿ
2 …IV†
HOÿ ‡ A volume of 200 ml of e‚uent (pH 11) and 200 mg of
2 ‡ H ! H2 O 2 …V†
The application of photocatalytic procedures for reme-
diation of textile e‚uents has been less explored, but
papers on environmental photochemistry with isolated
dyes have been published recently (Vinodgopal and
Wynkoop, 1996).
The use of ozone in textile e‚uent treatment appears
as a very attractive alternative with considerable appli-
cation potential. Ozone is a powerful oxidizing agent
(E0 ˆ 2:08 V), when compared to other well known
oxidizing agents, such as H2 O2 (E0 ˆ 1:78 V), and can
react with several classes of compounds through direct
or indirect reactions (mainly, OH). Electrophilic attack
by ozone molecules may occur at atoms with a negative
charge density (e.g.: N, P, O or nucleophilic carbons) or
to double/triple bonds like carbon±carbon, carbon±ni-
trogen and nitrogen±nitrogen. In alcohols, ethers, alde-
hydes and carboxylic acids, the reaction occurs at the
oxygen, forming peroxides (Masten and Davies, 1994).
Indirectly, ozone can react by the free radical (á OH) that
is generated by ozone decomposition (Hoigne and Ba-
der, 1976; Stockinger et al., 1995). The hydroxyl radical
is a powerful and non selective oxidant that can react
through three possible mechanisms: (i) hydrogen ab-
straction, (ii) electron transfer or (iii) radical addition.
The secondary radicals formed during this reaction can
react with ozone or other compounds.
The chromophor groups generally are organic com-
pounds with conjugated double bonds that can be bro-
ken by ozone (directly or indirectly) forming smaller
molecules, which decreases the e‚uent color (Masten
and Davis, 1994; Liakou et al., 1997).
The aim of the present work is the degradation of
textile e‚uent by using isolated and combined photo-
catalytic and ozonation processes.
2. Materials and methods
2.1. Reagents
Titanium dioxide (Degusa P-25, 80% anatase 20%
rutile, average particle size of 30 nm and BET surface of
50 ‹ 15 m2 gÿ1 ) was used without any pre-treatment.
Aqueous suspensions of 0.1 g lÿ1 TiO2 were used in all
experiments.
The textile e‚uent was obtained from a textile in-
dustry in the Campinas region (Sao Paulo, Brazil). The
e‚uent was stored at 0°C in glass ¯asks and used
without previous ®ltration.
2.2. Photocatalysis treatment
the TiO2 were placed in a 250-ml cylindrical photore-
actor. The illumination was provided by a high-pressure
mercury lamp (Philips HPL-N, 125 W, ¯uency rate 31.1
J m2 sÿ1 ), with the glass bulb removed, which was ®xed
in the center of the reactor and cooled by a water jacket.
The suspension was bubbled with oxygen (through a
sintered glass placed in the bottom of the reactor) at
¯ows of about 6 ( ‹ 0.2) l hÿ1 . The treatment time was 60
min. For analytical control, samples were taken at
convenient times and centrifuged at 3500 rpm.
 S. Gomes de Moraes et al. / Chemosphere 40 (2000) 369±373
2.3. Treatment by ozonation
Ozone was generated from pure oxygen using a
OZOCAV ZT-2 (Inter Ozone Ingeneria Ecologica,
Santiago-Chile) equipment. This apparatus has a ca-
pacity of ozone generation in a range between 0.20 and
0.70 g hÿ1 . The produced ozone was determined spec-
trophotometrically at 258 nm by passing the gas phase,
that contains the mixture of oxygen and ozone, through
a ¯ow cell (Kunz et al., 1998).
Samples of textile e‚uent were submitted to the
ozonation at pH 11 and room temperature, using a tu-
bular reactor of 500 ml with sintered glass disperse that
releases the gas from the bottom to the top of the re-
actor. The ozonized sample volumes were 400 ml, the
oxygen ¯ow rate was adjusted to 15 ( ‹ 1) l hÿ1 , ob-
taining an ozone production of 14 mg lÿ1 . The treatment
time was 60 min.
2.4. Simultaneous photocatalytic-ozonation treatment
A volume of 200 ml of e‚uent (pH 11) and 200 mg of
the TiO2 were placed in a 250-ml cylindrical photore-
actor. The illumination was provided by a high-pressure
mercury lamp (Philips HPL-N, 125 W, ¯uency rate 31.1
J m2 sÿ1 ), with the glass bulb removed, which was ®xed
in the center of the reactor and cooled by a water jacket.
The suspension was bubbled with a mixture of oxygen
and ozone at ¯ow rates of about 15 ( ‹ 1) l hÿ1 , that
corresponds to an ozone production of 14 mg lÿ1 . The
treatment time was 60 min. For analytical control,
samples were taken at convenient times and centrifuged
at 3500 rpm.
2.5. Analytical methodology
The eciency of these processes was evaluated by
monitoring e‚uent decolorization, measuring absor-
bance at 515 nm, using a Hitachi U-2000 spectropho-
tometer. The total organic carbon (TOC) reduction, was
measured with a Shimadzu TOC-5000 Total Organic
Analyzer, according to ISO (ISo, 1987).
2.6. Acute toxicity tests
The toxicity of the e‚uent was evaluated in com-
parison to the toxicity of irradiated/ozonized solutions
by measuring the inhibition of the respiration of Esc-
herichia coli cultures. The toxicity test is described in
detail elsewhere (Jardim et al., 1990). Basically, the assay
comprises of the incubation of E. coli cultures at 37°C
with known amounts of the stressing agent. When the
CO2 concentration produced by microbial respiration
reached 0.5 mmol lÿ1 , or approximately 9 ´ 108 cells
mlÿ1 , 45 ml of the E. coli culture was transferred into
several ¯asks and each one received 5 ml of one sample
371
withdrawn at a selected irradiation/ozonation time. As a
control, 5 ml of distilled water was introduced in one of
the ¯asks and the CO2 production monitored every 20
min using Flow Injection Analysis (FIA). The toxicity
test was followed for a maximum period of 120 min. For
incubation periods of more than 120 min, there is loss of
CO2 to the atmosphere due to CO2 over-saturation ( > 5
mmol lÿ1 ) in the aqueous culture medium. The bacteria
(ATCC 25922) used in the respirometric acute toxicity
test was provided by the microbiological laboratory of
the UNICAMP Hospital.
3. Results and discussions
The absorption spectrum of the textile e‚uent is
shown in Fig. 1. This e‚uent absorbs strongly in the
visible region, and a wavelength of 515 nm was selected
to be used in our study. The absorption at this wave-
length serves as a characteristic feature to monitor the
disappearance of the e‚uent during the isolated and
combinated degradation processes.
One of the main characteristics of the ozonation
process is the signi®cant decrease of the pH (more than
5 units), due to formation of organic and inorganic acids
in the ozone reaction with nucleophilic centers (Ku-
czkowski, 1992). In view of a little or no modi®cation
observed in the pro®le of the spectra with a modi®cation
of the pH, the decolorization monitoring was carried out
at a bu€ered pH of 7.6.
By monitoring the decolorization at 550 nm (Fig. 2),
it was possible to observe that the ozonation process
allowed a color removal of about 60%. As usually the
color of reactive dyes can be quickly removed by ozone,
we presume that the low eciency observed with e‚uent
decolorization is related to the high concentration of
starch. Probably, the direct reaction of ozone with
starch produced species with a high capacity to scavenge
Fig. 1. Absorption spectra of textile e‚uent at pH of 7.6.
372 S. Gomes de Moraes et al. / Chemosphere 40 (2000) 369±373
Fig. 2. Color reduction by the processes studied. Treatment
time: 60 min.
the hydroxyl radical (e.g. formiate and polyhydroxyl
derivatives), preventing the indirect degrading mecha-
nism of ozone (Laat et al., 1995).
The photochemical process shows the usual high
decolorization eciency (around 90%), while the com-
bined photochemical-ozonation process allowed an al-
most total decolorization (higher than 95%).
As the decolorization study can be correlated only
with the modi®cation of the chromogen group, and not
with the real mineralization of the substrate, determi-
nation of the total organic carbon content is absolutely
essential. The results (Fig. 3) indicated negligible TOC
reduction by application of the ozonation process alone.
By using the UV/TiO2 system and applying a standard
heterogeneous photocatalytical procedure, an important
degree of e‚uent degradation was observed after a short
treatment time. When the photochemical treatment was
extended up to 60 min, a total organic carbon degra-
dation of about 50% was observed. The best degradation
ratios were observed for the simultaneous combined
photocatalytic-ozonation process, allowing a higher
mineralization degree of about 60%.
Fig. 3. Total organic carbon reduction by the processes stud-
ied. Treatment time: 60 min.
Fig. 4. Acute toxicity reduction by the di€erent processes using
E. coli cultures. Treatment time: 60 min.
Frequently, the products obtained by application of
an ozonation and a photocatalytical processes show
higher toxicity than the precursor compounds (Jardim
et al., 1997). As the total organic carbon content was not
completely removed, the remediation capacity of the
processes was ®nally evaluated by determining the acute
toxicity. The results (Fig. 4) were expressed as microbial
respiration (CO2 ) of samples collected after treatments
of 60 minutes, using a non-stressed sample (culture
medium only) as a control. In these conditions, the
combined treatment shows a higher toxicity reduction,
reaching a maximum of about 50%.
4. Conclusion
Three process were studied for degradation of a
textile e‚uent. Each process shows speci®c merits. The
ozonation process was the less ecient, since this pro-
cess promotes only partial decolorization of the e‚uent
and the results of TOC determinations indicate but a
small modi®cation of the substrate, and not a real de-
gradation or mineralization. However, some decrease of
toxicity was observed.
The photocatalytic process promotes a rapid dec-
olorization and an e€ective TOC reduction. However,
the best results were found for the simultaneous com-
bined process, which allowed total decolorization and
also the highest TOC reduction.
The low capacity of the UV radiation to penetrate in
a media that contains a ®ne suspension of photocatalyst
is one of the more important limitations of the photo-
chemical procedure. For this reason the viability of a
large-scale photochemical process is still an open ques-
tion. However, due to its high degradation capacity, for
relatively low reaction times, the use of photochemical
processes as a post-treatment or as a combined proce-
dure remains as an interesting alternative, mainly for
application to very recalcitrant compounds.
 S. Gomes de Moraes et al. / Chemosphere 40 (2000) 369±373
Acknowledgements
Support from FAPESP and PRONEX-FINEP ac-
knowledged
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