Degradation of wine industry wastewaters by photocatalytic

Water Science and Technology Vol 51 No 1 pp 113–120 ª IWA Publishing 2005

advanced oxidation
P. Navarro1, J. Sarasa2, D. Sierra, S. Esteban and J.L. Ovelleiro
Department of Chemical Engineering and Environmental Technology, University of Zaragoza, C/Pedro
Cerbuna, 12, 50009 Zaragoza, Spain (E-mail: 434530@unizar.es1; jsarasa@unizar.es2)

Abstract Wine industry wastewaters contain a high concentration of organic biodegradable compounds
as well as a great amount of suspended solids. These waters are difficult to treat by conventional
biological processes because they are seasonal and a great flow variation exists. Photocatalytic advanced
oxidation is a promising technology for waters containing high amounts of organic matter. In this study we
firstly investigated the application of H2O2 as oxidant combined with light (artificial or natural) in order to
reduce the organic matter in samples from wine industry effluents. Secondly, we studied its combination
with heterogeneous catalysts: titanium dioxide and clays containing iron minerals. The addition of
photocatalysts to the system reduces the required H2O2 concentration. Although the H2O2/TiO2 system
produces higher efficiencies, the H2O2/clays system requires a H2O2 dosage between three and six
times lower.
Keywords Advanced oxidation; clays; hydrogen peroxide; photocatalysis; titanium dioxide; winery
wastewaters

Introduction
Wine industry produces wastewaters which are characterized by their high content of organic
biodegradable compounds and suspended solids. Although these effluents are not considered
to have high toxicity, they are seasonal and a great flow variation is observed during wine
production (Martı́n Espada, 2001). Consequently, these waters are difficult to treat by
conventional biological processes and it is necessary to find new ways to achieve organic
matter removal. Advanced oxidation processes are promising technologies for waters
containing high amounts of organic matter since they provide hydroxyl radicals (OH• ),
which are extremely powerful and non-selective oxidants, and they are capable of oxidizing
the majority of organic compounds very quickly (Bauer et al., 1999).
The hydroxyl radicals can be generated by many different sources (O3, H2O2, UV
light . . .), but one of the most emerging systems includes the use of catalysts for carrying out
the necessary reactions. The photocatalytic oxidation can be considered a very attractive
technology, in particular due to the increasing development of water purification processes
using solar energy as the source of radiation. The selection of the adequate catalyst must
consider the following properties: chemical activity, stability, availability and handiness,
cost and lack of toxicity (Cassano and Alfano, 2000).
In this study different photocatalytic systems using hydrogen peroxide were investigated
in order to reduce the organic matter in samples proceeding from wine industry effluents.
The combination of hydrogen peroxide with light (from artificial or natural source) was
firstly investigated, and secondly, its combination with heterogeneous catalysts was studied.
Two catalysts were selected: titanium dioxide (TiO2), one of the most efficient photoactive
catalysts (Fernández-Ibañez et al., 1999; Doong et al., 2000); and clays containing iron
minerals, due to their low cost and high availability. 113
 Hydrogen peroxide can behave as a direct oxidant for organic compounds, with a standard
redox potential equal to 1.78 V. The oxidant power can be increased by application of
radiation to the system, since the H2O2 produces hydroxyl radicals, whose redox potential is
2.80 V (Domènech et al., 2001). During the process carried out with H2O2 and UV radiation
the following reactions occur (Andreozzi et al., 1999):
H2 O2 +hnp2OH
P. Navarro et al.

H2 O2 +OHpH2 O+HO2
2HO2 pH2 O2 +O2

Titanium dioxide is one of the most used photocatalyst, due to its cheapness, stability,
lack of toxicity, activity and availability. It only requires 1 W/m2 of light and it can be
activated by sunlight (Ray, 1998). The photocatalysis with titanium dioxide can be explained
by the following simplified reaction (Kiwi et al., 1993):
TiO2 (OH )+H2 O2 +hnpTiO2 (OH)adsorbed +OH +OH

Iron minerals have been investigated by many authors as catalysts of hydrogen peroxide
systems applied to toxic organic compounds removal (Kong et al., 1998; Teel et al., 2001).
When hydrogen peroxide is combined with clays and light, the iron minerals which are
present in the catalyst are responsible of the OH• generation, according to the following
reactions (Fallman et al., 1999):
Fe2+ +H2 O2 pFe3+ +OH +OH
Fe3+ +H2 O+hnpFe2+ +H+ +OH

There are also other metals present in the clays (Al, Ti) that can increase the oxidant radicals
generation.

Methods
Samples
The different oxidation systems were previously investigated with synthetic samples, which
were representative of real winery wastewaters. Similar properties were achieved by diluting
commercial red wine with ultra-pure water, obtaining approximately the same amount of
organic matter as real wastewaters. Real samples proceeded from a wine industry located in
Cariñena (Zaragoza, Spain).

Materials
The hydrogen peroxide was 30% (w/w, Carlo Erba). The titanium dioxide was pure anatase
(PRS-Codex, Panreac), which has been demonstrated as the most efficient TiO2 allotropic
form (Arslan et al., 2001). The selected clays (P.C., Euroarce) contained high amounts of
different minerals: Fe2O3 (1.96%), Al2O3 (30.22%) and TiO2 (0.66%).

Analytical methods
The amount of organic matter was quantified by means of two different parameters:
Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC). The COD was
measured by Open Reflux Method (Method 5220 B of Standard Methods). Before the COD
analysis, the samples were conditioned removing the H2O2 excess by addition of NaOH.
TOC measurement was carried out via a TOC-V Shimadzu analyser, with a non-dispersive
infrared detector (NDIR). It was necessary to filter the samples before the analysis (Millipore
114 0.45 mm HA filters).
 Hydrogen peroxide concentration was controlled during and after the treatments using
Merck PeroxidTest (O22x) (0 to 25 mg H2O2/L and 0 to 100 mg H2O2/L). When necessary,
iron concentration was measured by flame atomic absorption, with a VARIAN SpectraA-10
Plus spectrometer. pH and conductivity evolution was determined by means of a pH-meter
(CRISON 507) and a conductimeter (CRISON Basic 30), respectively.

P. Navarro et al.
Experimental methods
Both synthetic and real samples were filtrated before carrying out the oxidation experiments
(Whatman 0.45 mm filters). The sample and the corresponding reactives were added in
transparent 100 mL glass vials, which were provided with continuous stirring and radiation.
For treatments with artificial radiation source, the vials were introduced in a solar
chamber (Atlas Suntest CPS+), that supplies radiation mainly in the visible spectrum. The
samples were irradiated with 500W/m2 for 80 minutes. For carrying out the experiments with
solar radiation, the vials were situated facing the natural light for 24 hours. According to the
calculated estimations, the solar radiation dosage applied was just slightly lower than the
artificial radiation dosage.
The efficiency of the different experiments was determined by means of the percentage of
removal of COD, which initially was 4000 mg O2/L.

Results and discussion

Preliminary studies: experiments with synthetic samples
Preliminary investigations with synthetic samples were performed using H2O2 alone,
H2O2/TiO2 and H2O2/clays systems, in order to study the influence of reactive dosages under
radiation. It was observed that the photocatalytic treatments were more efficient than H2O2
alone, since they provided similar COD removal with lower H2O2 concentration. When clays
are used as catalyst, the required H2O2 dosage is lower than in the H2O2/TiO2 system,
although the maximum COD removal is lower too. Too high catalyst dosages (3.0 g/L)
decreased the efficiency of the treatment, probably due to the suspended solids in the water
preventing the sample irradiation.
Optimum dosages and their corresponding efficiency for synthetic samples are shown in
Table 1, for both artificial and natural radiation experiments.

Experiments with real samples

The best conditions found with synthetic samples for each catalytic oxidation system were
applied to real samples. The selected dosages were newly optimised, obtaining the condi-
tions and the photocatalytic treatment that provided the highest COD removal.

Table 1 Optimum dosages of hydrogen peroxide, catalyst and efficiency for synthetic samples

Synthetic samples

Treatment Radiation H2O2 (mL/L) Catalyst (g/L) Efficiencya

H2O2 Artificial 10.0 0.0 67.5%

Natural 10.0 0.0 45.6%
H2O2 and titanium dioxide Artificial 2.5 1.0 71.9%
Natural 2.5 1.0 48.0%
H2O2 and Fe-clays Artificial 0.4 0.5 59.8%
Natural 0.4 0.5 32.9%
a
Measured as COD removal 115
 70
60

COD removal (%)

50 H2O2 = 0 mL/L
TiO2 =1.0 g/L
40
H2O2 = 2.5 mL/L
30 TiO2 = 0 g/L
20 H2O2 =2.5 mL/L
TiO2 =1.0 g/L
10
P. Navarro et al.

0
0 20 40 60 80
Time (minutes)

Figure 1 H2O2/TiO2 and artificial radiation system with real samples

H2O2/TiO2 and artificial radiation system

The TiO2 was shown to be efficient as a catalyst without H2O2 addition, although
it provided the lowest efficiency (Figure 1). The highest efficiency after 80 minutes
(58% of COD removal) is reached by combining H2O2 and TiO2. However, when no
catalyst is added, the system achieves a good COD removal too (51.8%) and the
organic matter degradation seems to be slightly faster than that occurring when both
H2O2 and TiO2 are added. The best efficiency was achieved with 2.5 mL/L H2O2 and
1.0 g/L TiO2.
Other parameters as pH, conductivity and TOC were measured during the optimum
treatment with artificial radiation in order to study the behaviour of the real samples
under the selected conditions. The initial pH remains constant at pH=4, and the
conductivity increases slightly during the treatment (Figure 2a). After 80 minutes
of treatment under artificial radiation, we observed a TOC removal of 30% (TOC initially
was 1,723 mg C/L) and a COD removal of 58% (Figure 2b). This fact indicates that the
mineralization of organic matter during the treatment is not complete after the oxidation
treatment.

H2O2/clays and artificial radiation system

Results for H2O2/clays system (Figure 3) show that the presence of both reactives is needed
in order to achieve an efficient treatment, since low H2O2 dosages alone or clays alone do not
provide a high COD removal. The best efficiency was achieved with 0.8 mL/L of H2O2 and
0.5 g/L of clays. As was observed with synthetic samples, reactives dosages for the H2O2/
clays treatment are considerably lower than the dosages needed when TiO2 is used as
catalyst, whereas the COD removal is almost 50%.
During the H2O2/clays treatment with the selected dosages, pH, conductivity and TOC
were also measured. As well as with the H2O2/TiO2 system, the pH remains practically
constant and the conductivity increases, probably due to the clays are partially dissolved in
the winery samples (Figure 4a). The TOC removal (20% after 80 minutes) is lower than the
COD removal (45% at the same time, Figure 4b).
In this system, the iron concentration in the wine industry samples, as well as before and
after the optimum treatment (t=0 minutes and t=80 minutes) were also measured. Results
are shown in Table 2.
A low concentration of iron was observed in the real sample. Before the treatment, but
116 after adding the reactives to the sample, an increase in iron concentration is observed due to
 (a) (Real Samples: H2O2 =2.5 mL/L, TiO2 =1 g/L)
14 1500
pH
12

Conductivity (µS/cm)
Conductivity 1480
10
1460
8

P. Navarro et al.
pH 6 1440
4
1420
2

0 1400
0 20 40 60 80
Time (minutes)

(b) (Real Samples: H2O2 =2.5 mL/L, TiO2 =1 g/L)

70 TOC removal (%)

TOC and COD removal (%)

60 COD removal (%)

50

40
30
20

10
0
0 20 40 60 80
Time (minutes)

Figure 2 H2O2/TiO2 and artificial radiation system with real samples. (a), pH and conductivity evolution;
(b), TOC and COD evolution

50
COD removal (%)

40
H2O2 =0 mL/L
30 clays=0.5 g/L
H2O2 =0.8 mL/L
20 clays=0 g/L
H2O2 =0.8 mL/L
10 clays=0.5 g/L

0
0 20 40 60 80
Time (minutes)

Figure 3 H2O2/clays and artificial radiation system with real samples

the iron contained in the clays being partially dissolved, helped by stirring and low pH.
During the treatment, dissolved iron in the sample is increased, which contribute to enhance
the efficiency of the photo-Fenton treatment. After 80 minutes of treatment, a remaining
concentration of 0.395 mg Fe/L is detected. 117
 (a) (Real Samples: H2O2 =0.8 mL/L, clays =0.5 g/L)

14 1800
pH
12

Conductivity (µS/cm)
Conductivity
1700
10
8

pH
1600
P. Navarro et al.

6
4 1500
2

0 1400
0 20 40 60 80
Time (minutes)

(b) (Real Samples: H2O2 =0.8 mL/L, clays =0.5 g/L)

70
TOC and COD removal (%)

TOC removal (%)

60 COD removal (%)
50
40

30

20
10

0
0 20 40 60 80
Time (minutes)

Figure 4 H2O2/clays and artificial radiation system with real samples: (a) pH and conductivity evolution;
(b) TOC and COD evolution

Table 2 Iron concentration in winery samples, before and after the H2O2/clays treatment

Iron concentration – wine industry samples

Samples H2O2 (mL/L) Clays (g/L) Fe (mg/L)

Winery sample 0 0 0.081

Winery sample with optimum dosages before treatment (t=0) 0.80 0.5 0.113
Winery sample after treatment (t=80 min) 0.09 0.5 0.395

Comparison between both photocatalytic systems

Once the best conditions for both systems were selected, they were applied under solar
radiation for 24 hours. In the same way that the experiments carried out with synthetic
samples (Table 1), natural radiation provided lower COD removal with real samples from the
wine industry. In this case, the TiO2 was demonstrated to be the best catalyst for organic
matter removal (Figure 5).
The optimum dosages for both TiO2 and clays systems, and their corresponding
118 efficiency in terms of COD removal, are summarized in Table 3.
 60
50

COD removal (%)

40
H2O2 =2.5 mL/L
30 TiO2 =1.0 g/L
H2O2 =0.8 mL/L
20
clays=0.5 g/L
10

P. Navarro et al.
0
0 5 10 15 20 25
Time (hours)

Figure 5 H2O2/TiO2 and H2O2/clays under natural radiation system with real samples

Table 3 Optimum dosages of hydrogen peroxide, catalyst and efficiency for real samples

Wine industry samples

Treatment Radiation H2O2 (mL/L) Catalyst (g/L) Efficiencya

H2O2 and titanium dioxide Artificial 2.5 1.0 58.0%

Natural 2.5 1.0 52.1%
H2O2 and Fe-clays Artificial 0.8 0.5 45.2%
Natural 0.8 0.5 34.2%
a
Measured as COD removal

Conclusions
In this study it has been found that the photocatalytic advanced oxidation based on H2O2 is an
appropriate purification treatment for winery wastewaters. The results lead to the following
conclusions: first, the H2O2/TiO2 treatment produces the highest efficiency, reaching to
52–58% of COD removal in real samples. The optimum dosage is: 2.5 mL/L H2O2 and
1.0 g/L TiO2 for both synthetic and real samples.
Secondly, although the H2O2/clays system produces lower COD removal (34–45% in real
samples), it requires a H2O2 dosage between three and six times lower than the H2O2/TiO2
treatment.
Thirdly, the degradation of organic matter is not efficient when no H2O2 is added to the
photocatalytic systems. However, direct titanium dioxide photo-activation acts as an
oxidation system, since the addition of TiO2 alone (1.0 g/L) produces a COD removal of
26% in winery samples.
Fourthly, artificial radiation provided better results than natural light for all the cases.
Fifthly, the TOC removal achieved in both systems after 80 minutes of treatment is lower
than the COD removal, which indicates that the mineralization of organic matter is not
complete.
And, finally, the iron that the clays contain is partially dissolved in the samples, which can
contribute to enhancing the photo-Fenton reaction. The iron can operate as a homogeneous
catalyst as well as a heterogeneous one.

Acknowledgements
The authors wish to thank Ministerio de Ciencia y Tecnologı́a (Proyecto REN2000-1410-
TECNO) and Gobierno de Aragón (Proyecto P042-2000) for their financial support. 119
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