PHD Mpgslucas

APPLICATION OF ADVANCED OXIDATION PROCESSES TO WASTEWATER TREATMENT
MARCO LUCAS
APPLICATION OF ADVANCED OXIDATION PROCESSES

TO WASTEWATER TREATMENT
Dissertation presented for the

Doctor of Philosophy degree in Chemistry at the
University of Trs-os-Montes and Alto Douro by
MARCO PAULO GOMES DE SOUSA LUCAS
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quarta-feira, 14 de Outubro de 2009 12:00:34
APPLICATION OF ADVANCED OXIDATION PROCESSES TO

WASTEWATER TREATMENT
Dissertation presented for the

Doctor of Philosophy degree in Chemistry at the
University of Trs-os-Montes and Alto Douro by
MARCO PAULO GOMES DE SOUSA LUCAS
Supervisor: Prof. Dr. Jos Alcides Silvestre Peres
CQVR - Chemistry Centre of Vila Real

Chemistry Department
School of Life Sciences and Environment
University of Trs-os-Montes and Alto Douro
October 2009
Acknowledgements
ACKNOWLEDGEMENTS
I will try to express my gratitude to people who made this thesis possible and
enriched my life.
I am profoundly grateful to my research Supervisor, Prof. Jos Alcides Silvestre
Peres for his proficient guidance, for interesting scientific discussions we had, for the
preparation of scientific papers, support and encouraging attitude during the course of this
research work. From deep inside, thank you Professor Peres for your unconditional and
invaluable support and your always opportune and heartfelt help and friendship.
I want to thank to the Chemistry Department Directors Prof. Lus Carvalho and
Prof. Vernica Bermudez and also to the CQVR Director Prof. Pedro Tavares for their
great facilities.
My acknowledgment also to Prof. Albino Dias, Dra. Carla Amaral, Prof. Ana
Sampaio, Prof. Rui Bezerra and Prof. Antnio Pirra (University of Trs-os-Montes and
Alto Douro - UTAD) for their technical guidance and support during the work developed.
I want to thank to the technicians of the UTAD laboratories were I have worked:
Mrs. Irene Fraga, Mrs. Augusta Fraga, Mr. Lus Fernando and Mr. Carlos Matos for their
friendship and valuable help.
During my Ph.D. work I performed laboratory work at the Plataforma Solar de
Almera (PSA), Spain, under the supervision of Dr. Manuel Ignacio Maldonado and Dr.
Sixto Malato to whom I am very grateful for receiving me in their laboratories, for the
interesting scientific discussions and technical guidance during my stay and for the
preparation of scientific papers. I also would like to offer my sincere thanks and my special
recognition to all friends that I have made along my stay in Almera. They are: Elena
Guillen, Nikolaus Klamerth, Carla Sirtori, Theodora Velegraki, Ana Zapata, Elli, Agustin,
Rosa Mosteo and Gemma Raluy. Also a special thanks to Vitor Vilar for his friendship and
help during our stay in Almera and for the delicious Paella and also for the not so
delicious but necessary pasta with tuna!!!
In my stay in the United Kingdom, at the University of Nottingham, Department of
Chemical and Environmental Engineering, I was supervised by Prof. Gianluca Li Puma to
who I am very grateful for receiving me, for the scientific discussions and for the
preparation of scientific papers. I also would like to offer my thanks and my recognition to
Acknowledgements
all friends that I made in Nottingham: Yan, Steve Bouzalakos, Marco Kostadinov, Aimaro,
Ana Luisa, Bin Gao, Mark, Richelieu Barranco, Maria Mediero and special thanks to
Silvana Arajo who hosted me at her home in Nottingham.
I would like to thank to all the members of the Jury for accepting being examiners
of this work.
I want to thank to my family, first of all to my wife Carmen. I am immensely
grateful to who has always supported me and has believed in me. Her love, patience, help,
and understanding during the past few years have been determinant for the good
development of my work and for everything we have shared, my deepest gratitude.
Although my son has not born yet, I would like to thank to Dinis for giving quiet nights to
his mommy and to me until now!
To my parents Antnio Lucas and Ceclia Gomes, and my brother Nuno, who have
supported me and have been willing to make considerable sacrifices for giving to me all
the possible advantages in my life. I thank them for their affection and love.
To my parents-in-law Jos Carneiro and Amlia Carneiro for there availability and
support along this period. Also to my brothers-in-law Jos Lus and Goretti for their
friendship and especially to my nephews Carolina and Francisco who are a source of
happiness and peace each time that I am with them.
My thanks to Joo Azevedo and his wife Isabel Guedes for their notable friendship
and valuable help whenever needed.
Also thanks to my special Confratis friends for their invaluable and resistant
friendship: Telmo, Francisco, Fernando and Pica which make our encounters an
opportunity to share the joys and blues of life as well as transforming our dinners in very
interesting, remarkable occasions and a place to recharge the batteries. Thanks to all of
them for the opportunities in celebrating life.
Finally, I would like to thank the financial support of Fundao para a Cincia e a
Tecnologia (FCT) and guas de Trs-os-Montes e Alto Douro (with special emphasis
to Dr. Alexandre Chaves) for the grant SFRH/BDE/15576/2005, for making this thesis
possible through the financing of my scholarship.
My deepest gratitude to them all!
Preface
PREFACE
This Ph.D. thesis structure results from different papers published and/or submitted
for publication in international journals, during the work carried out mainly at CQVR
(Centro de Qumica de Vila Real) in the Chemistry Department, School of Life Sciences
and Environment, University of Trs-os-Montes and Alto Douro (UTAD), throughout the
period between May 2006 and September 2009.
The main goal of this dissertation was trying to understand the application of
several Advanced Oxidation Processes (AOPs) and determine the main operational factors
that control the decomposition of the organic content present in textile and winery
wastewaters. These types of wastewaters were selected as the study target objects for two
main reasons: first, because they are an important environmental problem in the North of
Portugal. The textile industry biggest factories can be found spreading throughout Porto
and Braga districts, especially in the Ave hydrographic basin. Second, since we would like
work with a synthetic wastewater (textile effluents) and a wastewater generated by an
agricultural process characterised by the presence of natural organic matter (winery
effluents). Therefore, in the experiments where there were simulated textile wastewater
was used a model compound, a synthetic azo dye named Reactive Black 5 (RB5). Winery
wastewater experiments were performed with authentic effluent provided by some local
cellars and at other times by the dilution of wine and grape juice.
To achieve this knowledge can be a remarkable contribution in increasing the
efficiency of AOPs treatment processes when applied to textile and winery wastewaters, as
well as to acquire a more detailed understanding of the main advantages and drawbacks of
each technology.
The dissertation is organized in 9 chapters. Chapter 1 considers a general
introduction and review of the state-of-the-art focused in the textile and winery
wastewaters, and also in the treatment technologies that will be tested in this thesis advanced oxidation processes (Fentons reagent, photo-Fenton, photo-ferrioxalate,
heterogeneous photocatalysis (TiO2), ozone, ozone/UV and ozone/UV/H2O2) to the above
mentioned wastewaters.
In chapter 2 starts the study related to textile wastewaters. It is shown the treatment
of a model textile compound, the azo dye Reactive Black 5, with Fenton/UV-C and
Preface
ferrioxalate/H2O2/solar light processes. Here the main objective was analysing the
feasibility of decolourization and mineralization of RB5 by the cited AOPs. The influences
of different operational parameters (source and intensity of light, pH, hydrogen peroxide,
ferrous iron and RB5 concentration) and the reaction kinetics of each process is also
studied. An important issue to take into account within this study is to evaluate the
treatment capacity of the ferrioxalate/H2O2/solar light process once the utilization of solar
light as a UV source clearly reduces the environmental and economical impact of the
treatment process.
The combination of an AOP with an aerobic biological process is studied in
chapter 3. In this study the Fentons reagent capacity to treat high concentrated RB5
solutions by itself is first tested and then selected the optimal ferrous iron and hydrogen
peroxide dosages. Afterwards the treatment capacity of the Candida oleophila yeast with
the same RB5 concentrations studied in the Fentons reagent experiments is evaluated.
Finally, the experimental work regarding the textile wastewater is concluded through the
combination of Fentons reagent and Candida oleophila. As additional information it is
important highlight that the application of the Candida oleophila yeast to wastewaters with
high phenolic content is protected by a Portuguese national patent (Lucas M.S., Peres J.A.,
Amaral C., Sampaio A., Dias A.A. Processo biolgico aerbio de tratamento de efluentes
agro-industriais com elevado teor em compostos aromticos baseado na aplicao de
microrganismos da espcie Candida oleophila. Portuguese Patent n 103 738 assigned at
13th August 2009.
In chapter 4, starts the application of advanced oxidation processes to the treatment
of winery wastewaters. In this chapter the performance of several AOPs is evaluated,
specifically the Fentons reagent, ferrioxalate and heterogeneous photocatalysis (TiO2)
processes combined with different UV radiation sources, in the degradation of one of the
most representative phenolic compounds present in the winery wastewaters: the gallic acid.
From this AOPs screening we tried to select the optimal process to further application to
winery wastewaters. A toxicological assessment will be carried out with the marine
bacteria Vibrio fischeri to evaluate the influence of each AOP studied in the gallic acid
detoxification.
Chapter 5 presents the work done during a research stay performed in the
Plataforma Solar de Almera (Spain) during the Ph.D. scholarship. Despite in chapter 4 the
AOP selected as best treatment option was photo-Fenton with the UV TNN 15/32 lamp, an
Preface
attempt was made to test the application of the photo-Fenton process but using solar light
as UV radiation source in a Compound Parabolic Collector (CPC) pilot-solar plant to
winery wastewaters treatment. This study was done trying to meet the optimal conditions
in the use of solar light in the wastewater treatment once it is applied in a CPC reactor.
This work makes possible to evaluate the performance of solar photochemical AOPs, such
as heterogeneous photocatalysis (with TiO2, TiO2/H2O2 and TiO2/S2O82-) and
homogeneous photocatalysis like photo-Fenton.
Chapters 6 and 7 are addressed to the use of ozone and ozone-related processes to
the treatment of winery wastewaters. This work was carried during a research stay at the
Department of Chemical and Environmental Engineering, University of Nottingham,
United Kingdom. In chapter 6 the kinetics of ozonation of winery wastewater is studied in
detail in a pilot-scale, semi-batch bubble column reactor. The performance of both
processes was compared, as well as the effect of the most relevant operating conditions.
The study investigates the relationship between pH, ORP, COD, UV absorbance (254 nm),
total polyphenol content and ozone consumption as a function of time and the prevalent
kinetic conditions (fast, intermediate and slow kinetic regime) for the reaction of ozone
with the dissolved organic species. Furthermore, a kinetic ozonation model is presented
and used to estimate the kinetic coefficients of the ozonation of winery wastewater under
the prevailing experimental conditions. In chapter 7 the effectiveness of different ozonebased AOP (O3, O3/UV and O3/UV/H2O2) on the treatment of winery wastewater, in a
pilot-plant scale reactor is researched. The effect of initial pH, organic load of winery
wastewater and hydrogen peroxide concentration is investigated in the same pilot scale
reactor.
Chapter 8 presents a combined treatment: long term aerated storage and Fentons
reagent, to winery wastewaters. The main goal is to evaluate the capacity of treating
winery wastewater in a long term biologic aerated storage, with different aeration schemes,
combined with Fentons reagent. This chemical oxidation process, that uses low-priced
reactants, was used as a secondary chemical treatment step for the oxidation of the
recalcitrant organic compounds or metabolites that could not be oxidized biologically.
Finally, in chapter 9, the main conclusions are summarized and future research
developments are proposed.
CONTENTS
Abstract
xv
Resumo
xix
Nomenclature
xxiii
Figure Caption
xxvii
Table Captions
xxxv
1. INTRODUCTION
1.1. The water resource
1.2. Textile industry
1.2.1. Dyes
1.2.2. Dyes and the environment
1.2.3. Textile wastewater treatment processes
1.3. Winery wastewater
10
1.3.1. Production process and sources of wastes
11
1.3.2. Winery wastewater treatment processes
14
1.4. Advanced oxidation processes
17
1.4.1. Fentons reagent
19
1.4.2. Photo-Fenton system
20
1.4.3. Photo-ferrioxalate
22
1.4.4. Heterogeneous photocatalysis
23
1.4.5. Ozonation
25
1.4.6. Ozone/UV
27
1.4.7. Ozone/UV/H2O2
28
REFERENCES
29
ix
2. DEGRADATION OF REACTIVE BLACK 5 BY FENTON/UV-C AND

FERRIOXALATE/H2O2/SOLAR LIGHT PROCESSES
ABSTRACT
39
2.1. Introduction
40
2.2. Experimental
42
2.2.1.
Material
42
2.2.2.
Photoreactor
42
2.2.3.
Analysis
43
2.3. Results and Discussion
44
2.3.1. Photochemical decolorization of Reactive Black 5
44
2.3.2. Kinetic analysis of ferrioxalate processes
47
2.3.3. Effect of pH
48
2.3.4. Effect of H2O2 dosage
49
2.3.5. Effect of iron dosage
51
2.3.6. Effect of dye concentration
53
2.3.7. Effect of solar light intensity
55
2.3.8. Mineralization study
55
2.4. Conclusions
REFERENCES
3. DEGRADATION OF A TEXTILE REACTIVE AZO DYE BY A COMBINED

CHEMICAL-BIOLOGICAL PROCESS: FENTONS REAGENT-YEAST
57
57
61
ABSTRACT
61
3.1. Introduction
62
3.2. Experimental
63
3.2.1.
39
Reagents and microbiological media
63
3.2.2. Fentons reagent experiments
64
3.2.3. Yeast (Candida oleophila) experiments
64
65
3.2.4. Other analytical procedures

3.3. Results and discussion
65
3.3.1. Reactive Black 5 decolorization with Fentons reagent
65
3.3.2. Reactive Black 5 decolorization with Candida oleophila
66
3.3.3. Kinetic analysis
67
3.3.4. Fentons reagent process
67
3.3.5. Candida oleophila process
68
3.3.6. Optimization of Reactive Black 5 decolorization by Fentons reagent
69
3.3.7. Combining Fentons

decolorization
reagent
and
Candida
oleophila
on
RB5
70
3.4. Conclusions
72
REFERENCES
72
4. GALLIC ACID PHOTOCHEMICAL OXIDATION AS A MODEL COMPOUND OF WINERY

WASTEWATER
75
ABSTRACT
75
4.1. Introduction
78
4.2. Materials and methods
78
4.2.1. Chemicals
78
4.2.2. Experiments and analysis
78
4.2.3. TiO2 characterization
80
4.3. Results and discussion
80
4.3.1. Gallic acid photoxidation
80
4.3.2. Influence of H2O2 on gallic acid photoxidation
82
4.3.3. Influence of Fentons processes on gallic acid photoxidation
85
4.3.4. Influence of TiO2 on gallic acid photoxidation
87
4.3.5. Toxicity assessment
89
4.4. Conclusions
91
REFERENCES
91
xi
5. SOLAR PHOTOCHEMICAL TREATMENT OF WINERY WASTEWATER IN A CPC

95
REACTOR
ABSTRACT
95
5.1. Introduction
96
5.2. Material and methods
97
5.2.1. Winery wastewater
97
5.2.2. Chemicals
98
5.2.3. Analytical determinations
98
5.2.4. Toxicity measurements
99
5.2.5. Experimental set-up
99
5.3. Results and Discussions
101
5.3.1. Degradation of winery wastewaters by TiO2
101
5.3.2. Degradation of winery wastewaters by TiO2/H2O2 and TiO2/S2O82-
102
5.3.3. Degradation of winery wastewaters by photo-Fenton oxidation
103
5.3.3.1.
Influence of ferrous iron concentration
104
5.3.3.2.
Influence of the winery wastewater composition
106
5.3.3.3.
Influence of the ethanol presence in winery wastewaters
107
5.3.3.4.
COD, total polyphenols and toxicity evolution in photo-Fenton
process
108
5.4. Conclusions
REFERENCES
110
110
6. OZONATION KINETICS OF WINERY WASTEWATER IN A PILOT-SCALE BUBBLE

COLUMN REACTOR
xii
115
ABSTRACT
115
6.1. Introduction
116
117
117
6.2.2. Ozonation
118
6.2.3. Analytical methods
119
6.2.4. Ozone consumption
119
6.2.5. Stoichiometric ratio
120
120
6.3.1. Ozonation kinetics of winery wastewater
120
125
6.3.3. Ozonation kinetics model
128
6.3.4. Estimation of reaction rate coefficient and kinetic regimes
131
6.4. Conclusions
135
REFERENCES
136
7. APPLICATION OF O3/UV AND O3/UV/H2O2 PROCESSES TO WINERY WASTEWATER

141
IN A PILOT BUBBLE COLUMN REACTOR
ABSTRACT
141
7.1. Introduction
142
143
143
7.2.2. Ozonation
144
7.2.3. Analytical methods
146
146
7.3.1. AOP comparison
146
7.3.2. Ozone/UV
149
7.3.3. Ozone/UV/H2O2
150
152
7.3.5. Reaction kinetics
153
7.3.6. Effect of initial hydrogen peroxide concentration and organic load
154
7.3.7. Operating costs
156
7.4. Conclusions
158
REFERENCES
158
xiii
8. WINERY WASTEWATER TREATMENT BY A COMBINED PROCESS: LONG TERM

AERATED STORAGE AND FENTONS REAGENT
ABSTRACT
161
8.1. Introduction
162
163
163
8.2.2. Chemicals
163
8.2.3. Analytical determinations
164
8.2.4. Aerobic biodegradation
164
8.2.5. Oxidation by Fentons reagent
165
8.3. Results and discussions

8.3.1. Aerobic biodegradation
165
165
8.3.1.1.
Lab scale
165
8.3.1.2.
Pilot scale
168
8.3.2. Oxidation by Fentons reagent

8.4. Conclusions
REFERENCES
9. CONCLUSIONS AND SUGGESTIONS OF FUTURE WORK
171
172
173
175
9.1 Conclusions
175
9.2 Suggestions of future work
179
PUBLICATIONS RELATED WITH THIS WORK
xiv
161
183
Abstract
ABSTRACT
This research contributes to the study and development of advanced oxidation

technologies applied to two different problematic wastewaters: textile and winery
wastewaters. In this dissertation the factors that influence the oxidation of the model
compound of textile wastewaters, the azo dye Reactive Black 5 (RB5), and of the winery
wastewaters were investigated.
The first part of the thesis experimental work is dedicated to the decolorization of
RB5 solutions. The RB5 dye was selected as model molecule to represent the concerned
dye group because is widely used in the textile and paper industries, hardly biodegradable
and inexpensive. Firstly, an experimental comparison among two photoxidation systems,
Fenton/UV-C and ferrioxalate/H2O2/solar light, was performed. The variables considered
were pH, H2O2 dosage, iron dosage, RB5 concentration and source of light. The
experiments indicate that RB5 can be effectively decolorized using Fenton/UV-C and
ferrioxalate/H2O2/solar light processes with a small difference between the two processes,
98.1 and 93.2%, respectively, after 30 minutes. Although the lesser difference in dye
decolorization, significant increment in TOC removal was found with Fenton/UV-C
process (46.4% TOC removal) relative to ferrioxalate/H2O2/solar light process (29.6%
TOC removal). This fact reveals that UV-C low pressure mercury lamp although with its
small effect on dye decolorization is particularly important in dye mineralization, when
compared to solar light.
Further, it was tested the decolorization of aqueous azo dye RB5 solution
combining an Advanced Oxidation Process (Fentons reagent) followed by an aerobic
biological process (mediated by the yeast Candida oleophila). Fentons process alone, as
well as aerobic treatment by Candida oleophila alone, exhibited the capacity to
significantly decolorize azo dye solutions up to 200 mg/L, within about 1 and 24 hours
respectively. By contrast, neither Fentons reagent nor Candida oleophila sole treatments
showed acceptable decolorizing abilities for higher initial dye concentrations (300 and 500
mg/L). But the combination between the two processes, with Fentons reagent process as
primary treatment, at 1.0x10-3 mol/L H2O2 and 1.0x10-4 mol/L Fe2+, and growing yeast
cells as a secondary treatment, achieves a color removal of about 91% for an initial RB5
concentration of 500 mg/L.
xv
Abstract
In a second stage, is presented the experimental work done with winery

wastewaters. This study starts with the evaluation of the capacity of different Advanced
Oxidation Processes (AOP) combined with several radiation sources to degrade the
phenolic compound Gallic Acid (GA), the most representative phenolic compound present
in the winery wastewaters. From the experiments conducted it was possible to suggest that
the AOP, Fe2+ + H2O2 + UV TNN 15/32 (photo-Fenton process), was the most efficient
process thereby achieving the GA degradation value of 95.6% in 7.5 minutes and resulting
in a total elimination of toxicity.
Afterwards, the degradation of simulated winery wastewater was studied in a pilotscale Compound Parabolic Collector (CPC) solar reactor. Total organic carbon (TOC)
reduction with heterogeneous photocatalysis (TiO2) and homogeneous photocatalysis with
photo-Fenton is observed. Heterogeneous photocatalysis with TiO2, TiO2/H2O2 and
TiO2/S2O82- is revealed to be inefficient in removing TOC, achieving TOC degradation of
10%, 11% and 25%, respectively, at best. However, photo-Fenton experiments achieved
46% TOC degradation in simulated wastewater prepared with diluted wine (WV) and 93%
in wastewater prepared with diluted grape juice (WG), and if ethanol is previously
eliminated from mixed wine and grape juice wastewater (WW) by air stripping, it removes
96% of TOC.
Ozonation of organic substances present in winery wastewater was studied in a
pilot-scale bubble column reactor. A steady reduction of chemical oxygen demand (COD)
was observed under the action of ozone at the natural pH of the wastewater (pH 4). At
alkaline and neutral pH the degradation rate was accelerated by the formation of radical
species from the decomposition of ozone. The monitoring of pH, redox potential (ORP),
UV absorbance (254 nm), polyphenols content and ozone consumption was correlated with
the oxidation of the organic species in the water. The ozonation of winery wastewater in
the bubble column was analysed in terms of a mole balance coupled with ozonation
kinetics modeled by the two-film theory of mass transfer and chemical reaction. It was
determined that the ozonation reaction can develop both in and across different kinetic
regimes: fast, moderate and slow, depending on the experimental conditions.
Besides ozonation also the effectiveness of different ozone-based advanced
oxidation processes (O3, O3/UV and O3/UV/H2O2) on the treatment of winery wastewater
was investigated in the same pilot-scale bubble column reactor. In all the experiments the
disappearance of the winery wastewater organic load was described by pseudo-first order
xvi
Abstract
apparent reaction kinetics. The faster rate constant (6.5 x 10-3 min-1), at the natural pH of
the wastewater, was observed with the O3/UV/H2O2 process under optimised oxidant dose
(COD/H2O2 = 2). An economical analysis on the operating costs of the AOPs processes
investigated revealed the O3/UV/H2O2 to be the most economical process (1.31 Euro m-3g-1
of TOC mineralised under optimised conditions) to treat the winery wastewater.
Finally, the degradation of the organic pollutants present in winery wastewater was
carried out by the combination of two successive steps: a long term aerated storage
bioreactor followed by a chemical oxidation process using Fentons reagent. The long term
hydraulic retention time, 11 weeks, contributed remarkably to the reduction of COD (about
90%) and the combination with the Fentons reagent led to a high overall COD reduction
that reached 99.5% when the mass ratio (R=H2O2/COD) used was equal to 2.5,
maintaining constant the molar ratio H2O2/Fe2+=15.
xvii
Resumo
RESUMO
A presente tese de doutoramento pretende contribuir para o estudo e o

desenvolvimento de tecnologias de oxidao avanada aplicadas a dois tipos de guas
residuais: efluentes txteis e efluentes vincolas.
O objectivo principal deste trabalho foi o de compreender a aplicao de vrios
Processos de Oxidao Avanada (POA) e determinar os principais factores operacionais
que condicionam a degradao de certos tipos de compostos e a decomposio da matria
orgnica presente em guas residuais txteis e em efluentes vincolas. Estes tipos de guas
residuais foram seleccionados como alvo de estudo por duas ordens de razes. Em
primeiro lugar, porque constituem problemas ambientais relevantes na regio Norte de
Portugal. De facto, encontra-se um grande nmero de indstrias txteis dispersas pelos
distritos do Porto e Braga, especialmente na bacia hidrogrfica do Ave, enquanto a
produo de vinho assume uma particular importncia na Regio Demarcada do Douro.
Em segundo lugar, porque se pretendiam estudar efluentes contendo compostos de origem
sinttica (designadamente os corantes txteis) e, em contraponto, estudar guas residuais
geradas por processos agrcolas caracterizadas pela presena preponderante de matria
orgnica de origem natural, seleccionando-se, neste caso, os efluentes vincolas.
Estruturalmente, a primeira parte do trabalho dedicada ao estudo da descolorao
de solues do corante sinttico Reactive Black 5 (RB5). O corante RB5 foi seleccionado
como composto modelo para representar os corantes txteis uma vez que apresenta uma
difcil biodegradabilidade e muito utilizado na indstria txtil. Inicialmente fez-se a
comparao experimental entre dois sistemas de foto-oxidao, Fenton/UV-C e
ferrioxalato/H2O2/radiao solar. As variveis consideradas foram: pH, concentrao de
H2O2, concentrao de io ferroso, concentrao de RB5 e fonte de radiao. Os ensaios
indicam que as solues de RB5 podem ser efectivamente descoloradas usando
Fenton/UV-C e ferrioxalato/H2O2/radiao solar com uma pequena diferena entre os dois
processos, 98,1 e 93,2%, respectivamente, aps um perodo de 30 minutos. Apesar da
escassa diferena de descolorao verificada entre os dois POA, ntido um incremento
significativo na remoo de carbono orgnico total (COT) com o processo Fenton/UV-C
(46,4% de remoo de COT) comparativamente com o processo ferrioxalato/H2O2/luz
solar (29,6% de remoo de COT). Este facto revela que a fonte de radiao utilizada,
xix
Resumo
lmpada de mercrio de baixa presso (UV-C), particularmente importante na

mineralizao do corante RB5 quando comparada com a luz solar.
Foi depois testada a descolorao da soluo aquosa de RB5 com o reagente de
Fenton (H2O2/Fe2+) combinado com um processo biolgico aerbio (desenvolvido pela
levedura Candida oleophila). O processo Fenton e o tratamento aerbio pela Candida
oleophila mostraram, individualmente, uma capacidade significativa para descolorar
solues de RB5 com concentraes at 200 mg/L, no perodo de 1 e 24 horas,
respectivamente. Por outro lado, nem o reagente de Fenton nem a levedura Candida
oleophila apresentaram de per si uma capacidade aprecivel para descolorar solues com
concentraes elevadas de corante (300 e 500 mg/L). No entanto, a combinao dos dois
processos anteriores: reagente de Fenton, como tratamento primrio, utilizando as
concentraes de 1,0x10-3 mol L-1 de H2O2 e 1,0x10-4 mol L-1 de Fe2+, com a levedura
Candida oleophila, como tratamento secundrio, permitiram alcanar uma remoo de cor
de aproximadamente 91% para uma concentrao inicial de RB5 de 500 mg L-1.
Numa segunda fase, apresentado o trabalho experimental realizado com efluentes
vincolas. Este estudo teve incio com a avaliao da capacidade de diferentes POA,
quando combinados com vrias fontes de radiao, em degradarem o cido glico: o cido
fenlico presente em maior quantidade nos efluentes vincolas e considerado como
composto modelo neste estudo. Atravs dos ensaios realizados foi possvel verificar que o
processo foto-Fenton (Fe2+ + H2O2 + UV TNN 15/32), foi o que apresentou maior
eficincia na degradao do referido cido, 95,6% em 7,5 minutos.
Posteriormente, foi estudada a degradao de um efluente vincola simulado, numa
escala piloto, usando um reactor solar do tipo Compound Parabolic Collector (CPC). Foi
avaliada a reduo do teor em carbono orgnico total (COT) por fotocatlise heterognea
(TiO2) e por fotocatlise homognea (foto-Fenton). Os ensaios de fotocatlise heterognea
com TiO2, TiO2/H2O2 e TiO2/S2O82- revelaram-se ineficientes na remoo de COT
atingindo, na melhor das situaes, degradaes de 10%, 11% e 25%, respectivamente.
Nas experincias realizadas com o processo foto-Fenton foi possvel atingir 46% de
degradao de COT no efluente simulado preparado com vinho diludo e 93% no efluente
simulado preparado com sumo de uva. Se o etanol presente no efluente simulado for
previamente eliminado por air stripping possvel atingir uma remoo de 96% do
carbono orgnico total.
xx
Resumo
A ozonizao de compostos orgnicos presentes no efluente vincola foi estudada

em escala piloto recorrendo a um reactor bubble column. A reduo progressiva da
carncia qumica de oxignio (CQO) foi observada atravs da aco do ozono sobre as
guas residuais a pH natural (pH 4). A pH alcalino e neutro a taxa de degradao foi
acelerada pela formao de espcies radicais geradas a partir da decomposio do ozono. A
monitorizao do pH, do potencial de oxidao-reduo (ORP), da aromaticidade
(absorvncia a 254 nm), dos polifenis totais e do consumo de ozono foram
correlacionados com a oxidao das espcies orgnicas na gua residual. Estudou-se a
ozonizao de efluentes vincolas no reactor bubble column em funo do equilbrio
molar em conjunto com a cintica de ozonizao modelada pela teoria dos dois filmes de
transferncia de massa e de reaco qumica. Deduziu-se que a reaco de ozonizao pode
desenvolver-se em regimes cinticos diferentes: rpido, moderado e lento, dependendo das
condies experimentais.
Avaliou-se ainda a eficincia de diferentes POA baseados em ozono (O3, O3/UV e
O3/UV/H2O2) no tratamento dos efluentes vincolas no reactor bubble column escala
piloto. A reduo da carga orgnica dos efluentes vincolas foi descrita como uma reaco
de pseudo-1 ordem em todos os ensaios. A constante de velocidade de degradao mais
rpida (6,5x10-3 min-1), a pH natural, foi obtida para o processo O3/UV/H2O2 em condies
optimizadas (COD/H2O2 = 2). Uma anlise econmica sobre os custos de operao dos
POA investigados revelou que o processo mais competitivo para tratar os efluentes
vincolas
processo
O3/UV/H2O2
(com
custos
de
1,31
Euro
m-3 g-1 de COT mineralizado sob condies optimizadas).

Finalmente, estudou-se a degradao da carga orgnica presente em efluentes
vincolas atravs da combinao de duas etapas sucessivas: uma primeira, envolvendo o
tratamento biolgico aerbio com um longo tempo de residncia, seguido por um processo
de oxidao qumica utilizando o reagente de Fenton. O tempo prolongado de reteno
hidrulica no biorreactor, 11 semanas, contribuiu notavelmente para a reduo de CQO
(cerca de 90%). A combinao posterior com o reagente de Fenton conduziu a uma
reduo global de CQO de 99,5% quando a razo mssica aplicada (R = H2O2/COD) foi
igual a 2,5, mantendo-se constante a razo molar H2O2/Fe2+ = 15.
xxi
Nomenclature
NOMENCLATURE
Latin characters
Absorbance
Interfacial area, m2 m-3
AOP
Advanced oxidation process
ASBR
Anaerobic sequencing batch reactor
BC
Before Christ
BOD5
Biological oxygen demand, g L-1
COD
Chemical oxygen demand, g L-1
COD0
Initial chemical oxygen demand
CODf
Final chemical oxygen demand
CO3
Ozone concentration in gas phase, g L-1
CO* 3
Fictional concentration of ozone in the liquid film in equilibrium with the

bulk gas, g L-1
CPC
Compound Parabolic Collector
d bs
Sauter bubble diameter, m
DO3
Ozone diffusivity in liquid phase, m2 s-1
DOM
Diffusivity of organic species dissolved in water, m2 s-1
DCP
2,4 dichlorophenol
Enhancement factor (reaction factor), dimensionless
Ei
Instantaneous enhancement factor (reaction factor), dimensionless
FBBR
Fixed bed bio-reactor
FeOx
Ferrioxalate
GA
Gallic acid
Henrys law constant, k Pa L mol-1
Ha
Hatta number, dimensionless
Ha
Dimensionless coefficient defined by Eq. 6.10
xxiii
Nomenclature
Hg
Gas-hold up, %
HRT
Hydraulic retention time
kL
Individual volumetric mass transfer coefficient, m s-1
kLa
Volumetric mass transfer coefficient, s-1
k O3
Reaction rate coefficient with respect to ozone consumption, L g-1 s-1
mO3
Ozone mass flow rate, g s-1
MO3
Molecular weight of O3, g moL-1
MBR
Membrane bioreactor
MBBR
Moving bed bioreactor
NB
Nitrobenzene
NOM
Natural organic matter
Nt
Total Nitrogen
[O*3 ]
Ozone interfacial concentration, g L-1
PO3
Ozone partial pressure in gas phase, kPa
PSA
Plataforma Solar de Almera
Qg
Volumetric flow rate of gas phase, L s-1
rO3
Rate of ozone consumption, g L-1 s-1
Gas constant, kPa L mol-1 k-1
RB5
Reactive Black 5
SBR
Sequencing batch reactor
SBBR
Sequencing biofilm batch reactor
Temperature, K
Time, s
TN
Total nitrogen
TOC
Total organic carbon, g L-1
TS
Total solids
TSS
Total suspended solids, g L-1
t1/2
Half-life time
t30W
Normalised illumination time, min
xxiv
Nomenclature
Ug
Superficial gas velocity, m s-1
UASB
Upflow anaerobic sludge blanket
UASF
Upflow anaerobic sludge filter
UV
Ultraviolet radiation
Reactor volume, L
VSS
Volatile suspended solids, g L-1
VT
Total volume
WG
Winery wastewater performed with grape juice
WHO
World health organization
WV
Winery wastewater performed with wine
WW
Winery wastewater
XCOD
COD conversion, %
Stoichiometric ratio, dimensionless
Greek symbols
Molar extinction coefficient
Wavelength
Space time, s
Frequency
xxv
Figure Captions
FIGURE CAPTIONS
Fig. 1.1
Water in the third world.
Fig. 1.2
Dyed textile cloth.
Fig. 1.3
Molecular structure of some textile azo dyes.
Fig. 1.4
Vineyard.
11
Fig. 1.5
Grape crushing.
11
Fig. 1.6
Fermentation vats.
11
Fig. 1.7
Maturation.
12
Fig. 1.8
Bottling.
12
Fig. 1.9
Wine-making flow diagram as well as the produced wastewater (Vlyssides et

al., 2005; Pirra, 2005; Brito et al., 2007)
13
Fig. 1.10 Mass balance applied to a Portuguese winery in the year of 2004 (Brito et al.,
2007).
Fig. 1.11 WW treatment plant
14
14
Fig. 1.12 Efficiency comparison of different biological treatments applied to winery

wastewaters (Andreotolla, 2009).
Fig. 1.13 Sequence of reactions occurring in the photo-Fenton system.
16
21
Fig. 1.14 TiO2-semiconductor photocatalysis process. Representative scheme of some

photochemical and photophysical events that might take place in an irradiated
semiconductor particle.
24
Fig. 1.15 Scheme of reactions of ozone added to an aqueous solution (Hoign and
Bader, 1983a).
27
Fig. 1.16 Scheme of the degradation mechanism by means of the O3/UV process
(Peyton and Glaze, 1988).
28
Fig. 2.1
UV-Visible absorption spectra and chemical structure of Reactive Black 5.
42
Fig. 2.2
Reactive Black 5 decolorization evolution during Fenton/UV-C and

ferrioxalate/H2O2/solar light processes. Experimental conditions: [RB5] = 44
xxvii
Figure Captions
1.0x10-4 mol/L; Iron concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x103
mol/L; [H2O2] = 1.5x10-3 mol/L; pH = 5; Solar light intensity average = 530
Wm-2; UV Lamp = TNN 15/32 Heraeus and reaction time = 60 min.

Fig. 2.3
Effect of pH on the decolorization of RB5 by Fenton/UV-C and

ferrioxalate/H2O2/solar light processes. Experimental conditions: [RB5] =
1.0x10-4 mol/L; Iron concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x103
mol/L; [H2O2] = 1.5x10-3 mol/L; UV Lamp = TNN 15/32 Heraeus; Reaction
time = 30 min; Solar light intensity average = 530 Wm-2.
49
Fig. 2.4a Effect of the peroxide dosage on the decolorization of RB5 by Fenton/UV-C
and ferrioxalate/H2O2/solar light processes. Experimental conditions: [RB5]
= 1.0x10-4 mol/L; Iron concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x103
mol/L; pH = 5; UV Lamp = TNN 15/32 Heraeus; Reaction time = 20 min;
Solar light intensity average = 530 Wm-2.
50
Fig. 2.4b Effect of the peroxide dosage on the decolorization of RB5 by Fenton/UV-C
and ferrioxalate/H2O2/solar light processes. Experimental conditions: [RB5]
= 1.0x10-4 mol/L; Iron concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x103
mol/L; pH = 5; UV Lamp = TNN 15/32 Heraeus; Reaction time = 60 min;
Solar light intensity average = 530 Wm-2.
50
Fig. 2.5a Effect of the iron dosage on the decolorization of RB5 by Fenton/UV-C and
1.0x10-4 mol/L; [H2O2] = 1.5x10-3 mol/L; Oxalic acid = 9.0x10-3mol/L; pH =
5; UV Lamp = TNN 15/32 Heraeus; Reaction time = 20 min; Solar light
intensity average = 530 Wm-2.
52
Fig. 2.5b Effect of the iron dosage on the decolorization of RB5 by Fenton/UV-C and
1.0x10-4 mol/L; [H2O2] = 1.5x10-3 mol/L; Oxalic acid = 9.0x10-3mol/L; pH =
5; UV Lamp = TNN 15/32 Heraeus; Reaction time = 60 min; Solar light
intensity average = 530 Wm-2.
52
Fig. 2.6a Effect of dye initial concentration on the decolorization of RB5 by

Fenton/UV-C and ferrioxalate/H2O2/solar light processes. Experimental
conditions: Iron concentration = 1.5x10-4 mol/L; [H2O2] = 1.5x10-3 mol/L;
Oxalic acid = 9.0x10-3mol/L; pH = 5; UV Lamp = TNN 15/32 Heraeus;
Reaction time = 20 min; Solar light intensity average = 530 Wm-2.
xxviii
54
Figure Captions
Fig. 2.6b Effect of dye initial concentration on the decolorization of RB5 by

conditions: Iron concentration = 1.5x10-4 mol/L; [H2O2] = 1.5x10-3 mol/L;
Oxalic acid = 9.0x10-3mol/L; pH = 5; UV Lamp = TNN 15/32 Heraeus;
Reaction time = 60 min; Solar light intensity average = 530 Wm-2.
Fig. 2.7
54
Effect of solar light intensity on the decolorization of RB5 by

ferrioxalate/H2O2/solar light processes. Experimental conditions: Iron
concentration = 1.5x10-4 mol/L; [H2O2] = 1.5x10-3 mol/L; Oxalic acid =
9.0x10-3 mol/L; pH = 5; Solar light intensity average: sunny day = 530 Wm-2;
cloudy day = 230 Wm-2.
Fig. 2.8
55
Comparison between decolorization and TOC removal of RB5 after

conditions: [RB5] = 1.0x10-4 mol/L; [H2O2] = 1.5x10-3 mol/L; Oxalic acid =
9.0x10-3 mol/L; Iron concentration = 1.5x10-4 mol/L; UV Lamp = TNN 15/32
Heraeus; Solar light intensity average = 530 Wm-2; Reaction time = 1 hour;
pH = 5.
Fig. 3.1
56
Effect of RB5 concentration on decolorization by Fentons reagent process.

Experimental conditions: [Fe2+] = 1.5x10-4 mol/L; [H2O2] = 1.5x103 mol/L;
Temperature = 20C; pH = 5.0.
Fig. 3.2
66
Time course decolorization of RB5 at 100 mg/L (), 200 mg/L (c), 300
mg/L () and 500 mg/L () initial concentrations in batch cultures of
Candida oleophila.
Fig. 3.3
67
RB5 decolorization by Fentons reagent oxidation at different H2O2

concentrations. Experimental conditions: [RB5] = 500 mg/L; Temperature =
20C; pH = 5.0.
Fig. 3.4
70
Decolorization of a RB5 solution at 500 mg/L with a combined process a)

Fentons reagent (1 hour shaded portion of the graph); b) Candida oleophila
(7 days). Experimental conditions in Fentons reagent: (A) = 5.0x10-3 mol/L
H2O2; (B) = 2.0x10-3 mol/L H2O2; (C) = 1.0x10-3 mol/L H2O2. In all
experiments molar ratio H2O2:Fe2+ = 10:1.
Fig. 4.1
71
Gallic acid degradation in aqueous solution by different sources of radiation:

solar and ultraviolet radiation (Heraeus lamps TNN 15/32 and TQ 150).
Experimental conditions: [GA]0 = 5.3x10-4 mol/L; Solar intensity (sunny day) 81
xxix
Figure Captions
= 545 Wm-2; Initial pH 4.0.

Fig. 4.2
Gallic acid degradation in aqueous solution by different sources of radiation:

solar and ultraviolet radiation (Heraeus lamps TNN 15/32 and TQ 150)
combined with hydrogen peroxide. Experimental conditions: [GA]0 = 5.3x104
mol/L; [H2O2] = 2.7x10-3 mol/L; Solar intensity (sunny day) = 545 Wm-2;
Initial pH 4.0.
Fig. 4.3
83
Comparison of the gallic acid degradation with Fentons reagent after 7.5 min
of reaction using different radiation sources. [GA]0 = 5.3x10-4 mol/L; [Fe2+] =
5.3x10-5 mol/L; [H2O2] = 2.7x10-3 mol/L; Solar intensity (sunny day) =
545 Wm-2; Initial pH 4.0.
Fig. 4.4
86
Comparison of the gallic acid degradation with ferrioxalate after 7.5 min of
reaction using different radiation sources. [GA]0 = 5.3x10-4 mol/L; [H2O2] =
2.7x10-3 mol/L; [Fe3+] = 5.3x10-5 mol/L; [Oxalic Acid.] = 1.7x10-4 mol/L;
Solar intensity (sunny day) = 545 Wm-2; Initial pH 4.0.
Fig. 4.5
87
Gallic acid degradation in aqueous solution by heterogeneous photocatalysis

using different radiation sources: solar and ultraviolet radiation (lamps
Heraeus TNN 15/32 and Heraeus TQ 150). Experimental conditions: [GA]0 =
5.3x10-4 mol/L; [TiO2] = 0.5 g/L; Solar intensity (sunny day) = 545 Wm-2;
Initial pH 4.0.
Fig. 4.6
88
Gallic acid degradation by heterogeneous photocatalysis using different

radiation sources: solar and ultraviolet radiation (lamps Heraeus TNN 15/32
and Heraeus TQ 150) combined with hydrogen peroxide. Experimental
conditions: [GA]0 = 5.3x10-4 mol/L; [TiO2] = 0.5 g/L; [H2O2] = 2.7x10-3
mol/L; Solar intensity (sunny day) = 545 Wm-2; Initial pH 4.0.
Fig. 4.7
89
Toxicity development assessment from gallic acid in aqueous solution

through the oxidation reaction during the different AOP processes. Values
obtained by luminescence of the bacteria Vibrio fischeri after 15 min of
incubation, achieved with BiotoxTM. Experimental conditions: [GA]0 =
5.3x10-4 mol/L; [H2O2] = 2.7x10-3 mol/L; [TiO2] = 0.5 g/L.
Fig. 5.1
Photo and schematic drawing of the CPC reactor used in the photochemical
experiments.
Fig. 5.2
100
Total organic carbon in winery wastewater (WV and WG) during solar
photolysis and heterogeneous photocatalysis (TiO2) in a CPC reactor.
xxx
90
101
Figure Captions
Experimental conditions: [TiO2]0 = 200 mg/L and 500 mg/L; initial pH = 3.8.
Fig. 5.3
Influence of hydrogen peroxide (H2O2) and sodium persulfate (Na2S2O8) in

heterogeneous photocatalysis (TiO2) treatment of a winery wastewater (WV
or WG) in a CPC reactor. Experimental conditions: [TiO2]0 = 200 mg/L;
initial pH = 3.8.
Fig. 5.4
102
Winery wastewater (WV) treatment by solar photo-Fenton using a CPC

reactor. Evolutions of TOC (), hydrogen peroxide (y) and iron (c)
concentrations during reaction. Experimental conditions: [Fe2+]0 = 55 mg/L;
[H2O2]0 = 12 mM; initial pH = 3.0.
Fig. 5.5
103
Winery wastewater (WV) treatment by solar photo-Fenton in a CPC reactor.

TOC (), hydrogen peroxide (y) and iron (c) concentrations during
reaction. Experimental conditions: [Fe2+]0 = 110 mg/L; [H2O2]0 = 12 mM;
initial pH = 3.0.
Fig. 5.6
104
Effect of several additions of iron on TOC removal and accumulated iron

concentration during photo-Fenton experiment. Experimental conditions:
winery wastewater (WV); [Fe2+]const. = 110 mg/L (y) and [Fe2+]const. = 55
mg/L (); [H2O2] = 12 mM; original pH = 3.0.
Fig. 5.7
105
Influence of winery wastewater composition on TOC removal during photoFenton oxidation. Experimental conditions: [H2O2]0 = 12 mM; original pH =
3.0. () WV with [Fe2+]0 = 55 mg/L; () WG with [Fe2+]0 = 55 mg/L; (c)
WW with [Fe2+]0 = 55 mg/L; (y) WW with [Fe2+]0 = 20 mg/L; (*) WW
without ethanol with [Fe2+]0 = 20 mg/L.
Fig. 5.8
106
Total polyphenols, COD and toxicity during photo-Fenton oxidation of

winery wastewater. Experimental conditions: [Fe2+]0 = 20 mg/L; [H2O2]0 =
12 mM; initial pH = 3.0.
Fig. 6.1
109
Evolution of pH during the ozonation experiments. Experimental conditions:

liquid volume 9 L; Qg = 5.4 L min-1; ozone partial pressure 1.31 kPa; initial
COD 4650 mg L-1; initial pH 4 (c), 7 (y) and 10 ().
Fig. 6.2
120
COD (a) and total aromatic content (A) (b) evolution during the ozonation
carried out at initial pH of 4, 7 and 10. Experimental conditions: liquid
volume 9 L; Qg = 5.4 L min-1; ozone partial pressure 1.31 kPa; initial COD
4650 mg L-1; initial pH 4 (), 7 (y) and 10 (c).
Fig. 6.3
121
UV/Vis spectra evolution of the winery wastewater during the ozonation 122
xxxi
Figure Captions
process starting at pH 10, from 0 min to 180 min. Experimental conditions:

liquid volume 9 L; Qg = 5.4 L min-1; ozone partial pressure 1.31 kPa; initial
COD 4650 mg L-1.
Fig. 6.4
Total polyphenol content evolution during ozonation expressed as equivalent

gallic acid concentration. Reaction conditions: liquid volume 9 L; Qg = 5.4 L
min-1; ozone partial pressure 1.31 kPa; initial COD 4650 mg L-1; initial pH 4
(c), 7 (y) and 10 ().
Fig. 6.5
123
Hydrogen peroxide generated during the treatment of winery wastewater with

ozone. Experimental conditions: initial pH 4; ozone partial pressure 1.31 kPa;
liquid volume 9 L; Qg = 5.4 L min-1 (for COD0 equal to 4650 mg L-1 and 230
mg L-1); Qg = 3.6 L min-1 (for COD0 equal to 460 mg L-1 and 230 mg L-1).
Fig. 6.6
124
Evolution of the ozone mass flow rate (a) and ORP (b) during winery
wastewater ozonation of winery wastewater at different initial pH. The ozone
mass rate at the reactor inlet is constant and equal to 124.7 mg O3 min-1 (o).
Experimental conditions: liquid volume 9 L; Qg = 5.4 L min-1; ozone partial
pressure 1.31 kPa; initial COD 4650 mg L-1; initial pH 4 (), 7 (y) and 10
(c).
Fig. 6.7
127
The dynamic change of the global ozonation reaction rate coefficient (a) and
of the Hatta number (b) as a function of time for experiment at different
initial pH and COD concentrations. Experimental conditions: liquid volume 9
L; ozone partial pressure 1.31 kPa. Exp 1, Exp 3 and Exp 4: Qg = 5.4 L min1
Fig. 7.1
; initial COD 4650 mg L-1. Exp 2: Qg = 3.6 L min-1; initial COD 487 mg L-1. 133
Schematic representation of the pilot plant used in this study. The plant
consists in: [1]. Oxygen Cylinder; [2]. Silica Filter; [3]. Ozone Generator;
[4]. Flowmeter; [5]. Dreschel Bottle (In); [6]. Ozonation Reactor; [7]. UVC
Lamp; [8]. Variable Power Transformer; [9]. Recirculation Pump; [10].
Ozone Monitor; [11]. Dreschel Bottle (Out); [12]. Ozone Destructor; [13]
Extractor; [14] Ozone Detector.
Fig. 7.2
144
COD evolution during the UV, O3, O3/UV and O3/UV/H2O2 treatment of
winery wastewater. Experimental conditions from Tables 7.1 and 7.2. Liquid
volume 9 L; COD/H2O2 (w/w) = 4, initial pH 4.
Fig. 7.3
147
(a) COD evolution during the O3/UV treatment of winery wastewater. (b)
Evolution of pH. Experimental conditions from Tables 7.1 and 7.2. Liquid
volume 9 L; Initial pH 4 (), 7 (y) and 10 (c).
xxxii
150
Figure Captions
Fig. 7.4
(a) COD evolution during the O3/UV/H2O2 treatment of winery wastewater.

b) Evolution of pH. Experimental conditions from Tables 7.1 and 7.2. Liquid
volume 9 L; COD/H2O2 (w/w) = 4; initial pH 4 (), 7 (y) and 10 (c).
Fig. 7.5
151
Evolution of the ozone mass flow rate at different initial pH for the treatment
of winery wastewater with O3/UV (open symbols) and O3/UV/H2O2 (filled
symbols). The ozone mass rate at the reactor inlet is constant and equal to
100.1 mg O3 min-1 (o) in all cases. Experimental conditions from Tables 7.1
and 7.2. Liquid volume 9 L; COD/H2O2 (w/w) = 4.
Fig. 7.6
152
Influence of initial hydrogen peroxide dosage in the mineralization of winery

wastewater with the O3/UV/H2O2 process. Inset shows the apparent firstorder rate constant of TOC removal. Experimental conditions from Tables
7.1 and 7.2. Liquid volume 9 L; initial pH 4, COD/H2O2 (w/w) = 1, 1.3, 2 and
4.
Fig. 7.7
155
Effect of initial TOC on the treatment of winery wastewater by the

O3/UV/H2O2 process. Experimental conditions from Table 7.2. Liquid
volume 9 L; COD/H2O2 (w/w) = 2; initial pH = 4.
Fig. 8.1
155
COD removal a) evolution along time and b) final degradation rate achieved
in laboratory scale experiments with biological treatment of a winery
wastewater supplied with different aeration periods.
Fig. 8.2
VSS evolution in laboratory scale experiments during biologic treatment of a

winery wastewater supplied with different aeration periods.
Fig. 8.3
167
pH evolution in laboratory scale experiments during biologic treatment of a

Fig. 8.4
166
168
COD removal a) evolution along time and b) final degradation rate achieved
in pilot scale experiments with biologic treatment of a winery wastewater
supplied with different aeration periods.
Fig. 8.5
VSS evolution in pilot scale experiments during biologic treatment of a

Fig. 8.6
169
170
pH evolution in pilot scale experiments during biologic treatment of a winery

170
xxxiii
Table Captions
TABLE CAPTIONS
Table 1.1 Dyes target fibres, degree of fixation and percentage of dye lost to the effluent
7
(ONeill, 2002).
Table 1.2 Characterization of winery wastewater from four different wineries (adapted
from Brito et al., 2007).
15
Table 1.3 Oxidation potential against Standard Hydrogen Electrode of some relevant
oxidants (Legrini et al., 1993; Domnech et al., 2001).
18
Table 2.1 Reactive Black 5 decolorization efficiencies with different processes.
46
Table 2.2 First order rate kinetics (k) and half-life (t1/2) of dye decolorization.
47
Table 3.1 First-order rate constant (k), R2 values and half-life (t1/2) of RB5 decolorization
by Fentons reagent.
68
Table 3.2 First-order rate constant (k), R2 values and half-life (t1/2) of RB5 decolorization
by C. oleophila.
69
Table 4.1 Molecular formula, molecular structure and molar weight of gallic acid.
78
Table 4.2 Gallic acid photoxidation: conversions at 15 and 60 minutes and pseudo-first
order rate constant (kP) using different sources of radiation.
82
Table 4.3 Gallic acid oxidation through the combination of different sources of radiation
and hydrogen peroxide: conversions at 15 and 60 minutes and pseudo-first order
rate constants (kT and kR).
84
Table 5.1 Winery wastewater characterization.
98
118
Table 6.2 Hydrodynamic and operational conditions of the ozonation reactor.
118
144
Table 7.2 Hydrodynamic and operational conditions of the ozonation reactor
145
xxxv
Table Captions
Table 7.3 Initial pseudo-first order rate constants (k') obtained from COD removal, R2 and
TOC values after a reaction time of 300 minutes with ozone and ozone related
AOPs at different initial pH.
154
Table 7.4 Operating costs for the 9 L pilot scale bubble column reactor operated for 5 hours
under the hydrodynamic conditions in Table 7.2.
156
Table 7.5 Operating costs (Euro m-3 g-1 of TOC mineralised) for each experiment.
157
Table 8.1 Winery wastewater characteristics.
163
Table 8.2 Characterization of the winery wastewater after biologic pre-treatment.
171
Table 8.3 COD conversion (%) obtained for different R=H2O2/COD values, after chemical
oxidation of winery wastewater with Fenton reagent. Operational conditions:
initial T = 30C, initial pH = 3.5, molar ratio H2O2/Fe2+=15.
xxxvi
172
Chapter 1. Introduction
CHAPTER 1. INTRODUCTION
1.1. The water resource
Water is an essential compound for all forms of life on Earth and its quality is
crucial for the future of Humanity. Many sources have been exhausted and other sources
are likely to be polluted due to the industrial activity, with special impact among the
developed or developing countries. According to the United Nations World Health
Organization (WHO), lack of adequate sanitary facilities and poor hygienic practices are
common throughout the developing countries, due to political, economical and climatic
reasons (WHO, 2005) (Figure 1.1).
Due to the high population density (Earth
WHO, 2009
population almost doubled in the last 30 years) and

to the increasing level of industrialization, the
hydrosphere became much more polluted with
organic and inorganic compounds. The hydrosphere
covers about 73% of land area. The entire water is
distributed for the oceans, biosphere, continents and
Figure 1.1 Water in the third world.
in the different layers of the atmosphere. In the

oceans the mass of water is estimated around 1.37 x1021 kg (van Loon and Duffy, 2000).
This value corresponds to 97% of water on Earth. In turn, the mass of freshwater
represents only 3% of total resources of water and are mainly in the polar caps (79%).
From the total volume of freshwater approximately 20% corresponds to groundwater
remaining. Therefore, only about 1% is available at the Earths surface distributed by the
biomass, rivers, lakes, soil and in the form of vapour in atmosphere.
The distribution of freshwater throughout the world makes its quality highly
variable in terms of chemical, physical and microbiological composition. In addition to
natural phenomena, this variability in water quality is also due to the influence of
anthropogenic processes. The use of water by man, from agriculture to the several
industrial activities, with the inherent increase of chemicals dissolved in it, promotes the
reduction of water quality with consequent production of liquid wastewaters deprived of
treatment. Around 1.2 billion people in the world have no access to safe drinking water
(Inglezakis and Poulopoulos, 2006).
1
More than eight million compounds are chemically characterized, of these,

approximately 60 000 are traded in Europe. However, only a part is evaluated in terms of
toxic and other unknown effects on public health. Most pollutants resulting from oil
refining, chemical and textile industry, use of oil for transport and heating, use of
pesticides, fertilizers and detergents. Furthermore, it is also necessary quantify the
domestic effluent, the uncontrolled release of hazardous wastes and accidental spills (Ollis
et al., 1989). The effluents generated by these and other anthropogenic activities cause a
serious imbalance in the environment since they are released into the atmosphere (such as
particulate matter or gases), soil (such as fertilizers and pesticides) or means receptors
(such as industrial effluent or wastewater).
In Europe, environmental and consequently water-related policies are promoted by
the European Parliament. The European Union has established a Community framework
for water protection and management. The framework Directive provides, among other
things, the identification of European waters and their characteristics, based on individual
river basin districts, and the adoption of management plans and programmes of measures
appropriate for each body of water. The most recent update is the European Water
Framework Directive 2000/60/EC of the European Parliament and of the Council of 23th
October 2000, establishing a framework for community action in the field of water policy
(EU, 2000). This directive replaces, harmonises and further develops the community
controls under Council Directive 76/464/EEC. The framework directive identifies different
specific uses of water, such as drinking water, bathing water, water suitable for fishbreeding, shellfish water quality and urban wastewater treatment.
The need to restore water for new uses makes purification of wastewater practically
essential to achieve a desired degree of quality. To this end, other suitable wastewater
treatment technologies have to be studied. Recently, an important class of technologies
named Advanced Oxidation Processes (AOPs) has emerged as suitable for accelerating the
oxidation and destruction of a wide range of organic contaminants in polluted water (Glaze
et al., 1987).
1.2. Textile industry

The textile industry consumes large quantities of water and chemicals, from
polymers to inorganic salts and organic compounds, producing large volumes of effluent
2
(Paar et al., 2001). This industry plays an important part in the economy of several
countries in the world. China is the largest exporter of textile products around the world,
and the European Union (mainly Italy, Germany, France and United Kingdom), USA,
Japan, Pakistan, Turkey, Taiwan and Korea are the top ten of world exporters (Rocha et al.,
2006).
Portuguese textiles and clothes (Figure 1.2) have permitted to Portugal to hold a
relevant position in the ranking of exporters from the European Union. Since 2000,
Portugal has been ranked in the first ten highest exporters of textiles in the European
Union, corresponding to 4.3% of the total exportations and 18.5% of national exportations
(Figueiredo, 2002). In Portugal the textile industry is concentrated in three regions: North,
Centre and Lisbon. It is however evident a slight increase of this industry in the North and
even Centre of the country when compared with the Lisbon zone (Vasconcelos, 2006). The
biggest factories of the most important industries within the textile sector can be found
spreading throughout Porto and Braga districts, especially in the Ave hydrographic basin.
The wastewater resulting from textile dyeing industry
processes
are
dangerous
source
of
environmental
contamination (Solozhenko et al., 1995), since they produce

about 100 litres per kilogram of dyed tissue (Abdullah et al.,
2000). This shows high values of Chemical Oxygen Demand
(COD), Total Solids (TS), high pH, temperature fluctuating
according to the industrial process involved, high amounts of
surfactants and intense colour. These may also present high
Figure 1.2 Dyed textile cloth.
concentrations of heavy metals such as chromium, copper and

mercury used sometimes in dyes formulation (Grau, 1991). Thus, given the high pollution
load, the discharge of textile effluents into the surrounding water bodies is a serious
problem, not only from an aesthetic point of view but also due to its toxicity to aquatic life
(Chung and Stevens, 1993). Similarly these represent a potential mutagenic character to
humans (Chung et al., 1992).
The textile activity is regulated by the Portaria Sectorial n 423/97 of June 25th and
by Annex XVIII of Decree Law no 236/98 of August 1st, with the objective to compel for
an efficient treatment of textile effluents (Figueiredo, 2002).
1.2.1 Dyes
Dyes are chemical compounds characterised by absorbing in the visible region of
the electromagnetic spectrum (400 to 700 nm). This is the reason why they are coloured.
Their application over the different affined substrates (textile materials, leather, paper, hair,
etc.) is performed from a liquid in which they are completely or partially soluble
(Zollinger, 1991).
The use of dyes is made by Man since the beginning of Humanity since the
painting and staining their clothes, their skin and the spaces occupied, such as rocks and
caves. The wide availability of inorganic pigments of natural origin, such as manganese
oxides, hematite and ochre, facilitated the use of colours by the first humans in many
different functions. It was detected the presence of dye in samples of tissue in the Egyptian
tombs and ancient hieroglyphics dating from 2500 BC. The natural organic dyes,
originating mainly from plants, insects, snails, fungi and lichens, were always used as
preferred colours of fabrics.
Dyes are classified based on two criteria (both used by the Colour Index (Colour
Index International, 2002), which lists all dyes and pigments commercially used for large
scale colouration purposes): according to their chemical structure or according to their
method of application over the substrate. The Colour Index is published since 1924 (and
revised every three months) by the Society of Dyers and Colourists and the American
Association of Textile Chemists and Colorists.
In particular, the chemical structure classification divides them into azo dyes,
triarylmethanes, diphenyl-methanes, anthraquinones, stilbenes, methines, polymethines,
xanthenes, phthalocyanines, sulfurs and so on. Usually the setting of the dye to the fibre is
made through chemical reactions or by adsorption of the dye or derivatives generated by
chemical reactions during the process of dyeing (van der Zee, 2002). Figure 1.1 sets out
some textile dyes belonging to different classes and different modes of application.
(B)
(A)
NH2 O
HO3S
NaO3S
N
H
NH
H
N
SO3Na
HO3SOCH2CH2O2S
Acid Blue 74 (C.I. 73015)
Reactive Blue 19 (C.I. 61200)
(C)
(D)
NH2
NaO3SOCH2CH2O2S
SO3Na
HO
Cl
H2N
H2N
NH2
NaO3SOCH2CH2O2S
Basic Red 9 (C.I. 42500)
SO3Na
Reactive Black 5 (C.I. 20505)
(E)
NaO3S
N
NaO3S
N
Cu
N
N
NaO3S
SO2NH
NH
N
N
N
N
SO3Na
Cl
N
N
NH2
Reactive Blue 15 (C.I. 74459)
Figure 1.3 Molecular structure of some textile azo dyes.
Azo dyes can be divided into monoazo, diazo and triazo classes, according to the
presence of one or more azo bonds (N=N). Nevertheless, according to the classifications
above mentioned, they are found in various other categories, i.e. acid, basic, direct,
disperse, reactive, azoic and pigments (Rafols and Barcelo, 1997; Vandevivere et al.,
1998).
Some azo dyes and their dye precursors have been shown to be or are suspected to
be human carcinogens as they form toxic aromatic amines (Brown and DeVito, 1993;
Stylidi et al., 2003; Silva and Faria, 2003). Actually, azo dyes make up 60-70% of all
textile dyestuffs and are not removed from wastewaters via conventional biological
treatments (Carliell et al., 1995).
Within the azo dyes, the most used are the reactive dyes. These dyes have been
identified as the most problematic compounds in textile dye effluents (Carliell et al., 1994,
Carliell et al., 1996). They are characterised by their readily water solubility as well as
their high stability and persistence, essentially due to their complex structure and synthetic
origin. Since they are intentionally designed to resist degradation, they consequently offer
a large resistance against chemical and photolytic degradation. Moreover, as many of
textile dyes, reactive dyes are usually non biodegradable under typical aerobic conditions
found in conventional biological treatment systems (Brown and Hamburger, 1987). They
are usually of non toxic nature, they may generate, under anaerobic conditions (e.g., in
anaerobic sediments and in intestinal environments), breakdown products as aromatic
amines considered to be potentially carcinogenic, mutagenic and toxic (Pinheiro et al.,
2004; van der Zee and Villaverde, 2005).
1.2.2. Dyes and the environment
The industry has generated over the past decades, millions of tons of synthetic dyes.
Over 700 tons of about 10 000 different dyes and pigments are used annually worldwide.
The main route by which the dyes affect the environment is through effluents from textile
industries. The pollution of water bodies with these compounds results, in addition to the
visual impact, in changes of flora and fauna biological cycles of the ecosystem receiver. To
assess the degree of impact, each class of dye must be taken into account, in addition to the
amount of colour produced, the degree of attachment to the fibres and the consequent loss
to the wastewater. Table 1.1 presents for each class of dye, the rate of attachment to the
fibres and the percentage of dye lost to the effluent.
Table 1.1 Dyes target fibres, degree of fixation and percentage of dye lost to the effluent (ONeill, 2002).
Dye class
Fibre
Degree of fixation (%)
Loss to effluent (%)
Acid
Polyamide
80-95
5-20
Basic
Acrylic
95-100
0-5
Direct
Cellulose
70-95
5-30
Disperse
Polyester
90-100
0-10
Metal-complex
Wool
90-98
2-10
Reactive
Cellulose
50-90
10-50
Sulfur
Cellulose
60-90
10-40
Vat
Cellulose
80-95
5-20
Due to the high molar extinction coefficient, the colours are visible in water even at
concentrations as low as 1 mg/L. So, to get an idea of the seriousness of the problem it is
important to stress that the textile industry generates wastewater with concentrations of
dyes that can vary between 5 and 1500 mg/L (Pierce, 1994). By decreasing the
transparency of the water and prevent the penetration of solar radiation, these compounds
decrease the coloured photosynthetic activity and cause disturbances in the solubility of
gases, causing damage to the gills of aquatic organisms and disrupt their places of refuge
and spawning. These compounds can remain for decades in aquatic environments
endangering the stability and lives of these ecosystems.
The degradation products of the dyes in these environments and in Humans may be
more harmful than the dyes themselves. This is due to breaking of azo connections that
could origin aromatic amines potentially carcinogenic and/or mutagenic (Brown and
Devito, 1997; Cisneros et al., 2002; El-Dein et al., 2003; Meri et al., 2004; Pinheiro et al.,
2004). Another serious problem of textile dyes is their high chemical stability, enabling
them to remain unchanged for long periods of time. This favours bioaccumulation
phenomena and toxicity to the flora and fauna present in natural ecosystems.
1.2.3. Textile wastewater treatment processes
The removal of dyes from wastewater in the textile industry is one of the major
environmental problems faced by the textile sector (Correia et al., 1994). In general, the
current practice in textile mills is to discharge the wastewater directly into the local
environment or into the municipal sewer system. In any case, to accomplish with current
local legislations (which are becoming more stringent), textile mills are sometimes forced
to have their own treatment plant prior discharge. A varied range of methods have been
developed for textile wastewater treatment at laboratory, pilot or full scale.
The technologies most widely used are membrane filtration (inverse osmosis,
microfiltration, nanofiltration and ultrafiltration), adsorption (activated carbon, inorganic
adsorbents,
ion
exchange
resins
and
natural
and
synthetic
biosorbents),
coagulation/flocculation, biological treatments (mainly conventional aerobic activated

sludge treatments) and chemical oxidation (e.g., electrochemical methods) (Reife and
Freeman, 1996; Vandevivere et al., 1998; Robison et al., 2001; Forgacs et al., 2004; Rai et
al., 2005). However, its efficiency is sometimes limited by several factors. Coagulationflocculation, adsorption, foam flotation and membrane filtration are common practices, but
result in a phase transfer of pollutants, leading to another form of waste, such as spent
carbon or sludge, that would require additional treatment or disposal (e.g., incineration). In
view of that, destructive methods such as chemical or biological processes are desirable.
Biological processes are a good choice for wastewater treatment. The aerobic
biological treatment of textile effluents most commonly used is the activated sludges. They
are relatively inexpensive, the running costs are low and the end products of complete
degradation are not toxic (Forgacs et al., 2004). However, due to the refractory nature of
some constituents of the effluents, the biological treatment by activated sludge is
sometimes quite difficult. The refractory character displayed by these effluents should be
on the physical and chemical stability of textile dyes and their low content of
biodegradable organic matter creates a high resistance to their degradation by
microorganisms. In particular, reactive dyes, acid and direct are hardly biodegradable
passing, in most cases, unchanged by the traditional methods of treatment because of their
high solubility and low molecular weight (Reife and Freeman, 1996). The anaerobic
biological treatment has shown good results in the removal of colour from textile effluents.
However, these processes have the potential disadvantage of converting dyes into more
toxic products than the original dyes. This increase in toxicity is due to the breaking of the
links with the consequent rise of carcinogenic aromatic amines formation (Brown and
Devito, 1997; McMullan et al., 2001).
Membrane filtration can be applied mainly to the separation of salts and large
molecules such as dyes. These technologies are very attractive because they allow the
reuse of water in industry. Its major limitations are the high cost and potential clogging of
the membranes. This last limitation involves the frequent cleaning and replacement of
filtration membranes with consequent increased costs.
The adsorption technologies are limited to the amount of flow produced since high
flow rates for these techniques are not feasible due to rapid saturation of the adsorbents,
leading to its regeneration. This limitation plus the fact that both adsorption process and
membrane filtration are not destructive. This technology is essentially limited to the
contaminants phase transfer and does not allow the definitive elimination of the dyes.
The use of coagulation/flocculation processes for decolourisation of high flow rates
of textile effluents is very expensive, mainly due to large quantities of reagents required
(e.g. lime, aluminium sulphate, chloride, iron) for an effective treatment. Moreover, the
high production of sludge is also a factor to take into account given the economic
evaluation of this technology as the treatment/disposal of sludge produced is significantly
expensive. Thus, considering the obvious difficulty of treatment of effluents from textile
industry, in particular the removal of colour, there should be the study of one or more
alternative treatment processes that allow total removal of the colour of the final effluent,
preferably without the generation of sludge, with obvious economical, aesthetic and
environmental advantages.
Therefore, chemical processes are destructive alternatives when biological
treatments are not capable to reduce both colour and COD from textile wastewater. Among
them, Advanced Oxidation Processes (AOPs) have been proposed in the last years as
powerful advanced technologies for the treatment of biorecalcitrant organic compounds
(Legrini et al., 1993). With their incorporation, the complete decontamination of textile
wastewaters becomes realistic.
1.3 Winery wastewater

Wastewaters from the wine-producing, named as winery wastewaters (WW), are
mainly originated from various washing operations during the crushing and pressing of
grapes, as well as rinsing of fermentation tanks, barrels, bottles and other equipments or
surfaces (Arnaiz et al., 2007). Volumes and pollution loads significantly change over the
year, in relation to the working period (vintage, racking, bottling) and to the winemaking
technologies used (e.g. in the production of red, white and special wines (Rochard, 1995)).
The wineries have seasonal activity. Therefore, the wastewater production occurs
mainly during harvesting and at the time of wine making. The wastewaters can be treated
as they are produced, or they can be stored (generally after good sieving) and treated
within several months. The objectives of wastewater management are to be protective of
the receiving environment and enhance water reuse opportunities. Reduction of organic
strength, measured as biochemical oxygen demand (BOD5) or chemical oxygen demand
(COD), is the single most important wastewater treatment parameter necessary monitorizes
to reach a supported vineyard. The organic content of winery wastewater consists of highly
soluble sugars, alcohols, acids and recalcitrant high-molecular-weight compounds (e.g.,
polyphenols, tannins and lignins) not easily removable by physical or chemical means
alone.
There are several types of treatment systems for the management of winery
wastewaters. However, due to rapidly increasing global demand on manufacturing
processes and to the fact that final product exert minimal or no environmental footprints
(Wackernagel et al., 1996), the wine industry has begun to experience legislative pressure
to become more efficient and environmentally friendly (Katsiri et al., 1994; Mller et al.,
1999). Thus, the increasing demand for greening of industrial production processes and
products, both from customers and legislative authorities, coupled with rising operational
and waste treatment costs in the wine industry has started to move towards the adoption of
integrated waste preventive approaches, as opposed to the traditional reparatory
environmental engineering practices (Lorenzen et al., 2000).
10
1.3.1 Production process and sources of wastewaters

Winemaking, or vinification, is the production of wine, starting with selection of
the grapes and ending with bottling of wine. Although most wine is made from grapes, it
may also be made from other fruit or non-toxic plant material. Mead is a wine that is made
with honey being the primary ingredient after water. The main stages of the production
process of a winery are as follows (Vlyssides et al., 2005; Pirra, 2005):
1. Grape reception: Grapes are usually
harvested from the vineyard (Figure 1.4) in the
autumn (fall), in the northern hemisphere from early
September until the beginning of November. The
produced wastewater from this stage comes from the
washing of the mechanical machinery and that of the
Figure 1.4 Vineyard.
floors.
2. Crushing: Crushing is the process of squeeze the berries and break the skins to
start to liberate its content (Figure 1.5). The grapes come through a pneumatic press and
produce the must and the solid residues. The produced amount of must is about 80 L/100
kg of grapes. The wastewater generated from this stage comes
from the washing of the machinery, the washing of the
production room, the loss of must due to its transfer to the
fermentation vessels as well as the pre-washing of the
fermentation vessels. The amount of water that is used for the
cleaning of the fermentation vessels and the wine storage
Figure 1.5 Grape crushing.
tanks depends on the size of the tanks.
3. Fermentation: This takes place in the fermentation

vats (Figure 1.6) and lasts about 15 days for each tank from the
day they are filled with 80% must. During the fermentation, the
yeast cells feed on the sugars in the must and multiply,
producing carbon dioxide gas and alcohol. From this stage, no
wastewater is produced.
Figure 1.6 Fermentation vats.
11
4. Decanting: During the decanting, the supernatant wine is separated from the
produced wine lees and is fed by pumps to empty tanks that are filled 100% for further
stabilization. The produced wastewater from this stage comes from the washing of the
tanks, from the pre-washing of the stabilization tanks, from the cleaning of the decanting
pump, from the washing of the production room as well as from losses during wine
decanting.
5. Maturation and stabilization: Stabilization is
a process used in winemaking to reduce tartrate crystals
(generally potassium bitartrate) in wine. It takes place in
the tanks (Figure 1.7) and lasts about 15 days for each
tank from the day it is filled 100% with decanted wine.
From this stage, there is no wastewater produced.
Figure 1.7 Maturation.
6. Filtration: The produced wine is filtered in order to improve its quality and is
used to accomplish two objectives, clarification and microbial stabilization. In
clarification, large particles that affect the visual appearance of the wine are removed. In
microbial stabilization, organisms that affect the stability of the wine are removed
therefore reducing the likelihood of re-fermentation or spoilage. The produced wastewater
of this stage comes from the washing of the tanks, from the pre-washing of the storage
tanks, from the cleaning of filters, from the transportation pump, from the washing of the
production room as well as the possible wine losses during its transfer.
7. Bottling and packaging: The produced wine is sold
either in bulk or as bottled (Figure 1.8) which is transferred
from tanks to transportation trucks or in the packaging unit.
The produced wastewater comes from the washing of tanks, the
washing of the transportation pump and the washing of
Figure 1.8 Bottling.
12
packaging room.
The stages of production process as well as the produced by-products and

wastewater are presented in the following diagram (Figure 1.9).
Fresh Grapes
Reception
Wastewater
Crushing
Wastewater
Fermentation
Decanting
Wastewater
Maturation and Stabilization
Filtration
Wastewater
Bottling and packaging
Wastewater
Bottled wine
Figure 1.9 Wine-making flow diagram as well as the produced wastewater (Vlyssides et al., 2005; Pirra,
2005; Brito et al., 2007).
13
In order to present a global perception of the total inputs/outputs of a wine unit production,
a mass balance is presented in Figure 1.10, showing water and energy inputs, and the
outputs of residues, sub-products, liquid effluents and air emissions.
Water
9.25 m3/m3
Wine
production
Electric energy
3
159.6 kWh/m
Wastewater
9.25 m3/m3
Solid wastes: 27.4 kg/m3

Valorization ndex = 43%
Sub-products: 406.3 kg/m3
Valorization ndex: 100%
Figure 1.10 - Mass balance applied to a Portuguese winery in the year of 2004 (Brito et al., 2007).
1.3.2 Winery wastewater treatment processes

Musts and wines constituents are present in winery wastewaters (Figure 1.11), in
variable proportions: sugars, ethanol, esters, glycerol, organic acids (e.g. citric, tartaric,
malic, lactic, acetic) phenolic compounds and a numerous
population of bacteria and yeasts. Effluents have a daily
great variability, in both quantity and quality, making
evaluation of daily pollution complex. Rejected volumes per
volume of produced wine vary from one wine to another,
with extreme values comprised between 0.1 m3/m3 and
3
2.4m /m . Table 1.2 presents some characteristics of winery

wastewaters from different wineries.
14
Figure 1.11 WW treatment plant.
Table 1.2 Characterization of winery wastewater from four different wineries (adapted from Brito et al.,
2007).
Wine cellara
Aa
Bb
Cc
Dd
5.7
4.9
4.7
4.0-4.3
COD (mg/L)
1200-10 266
5200
14 150
9240-17 900
BOD5 (mg/L)
130-5320
2500
8100
5540-11 340
TSS (mg/L)
385-5200
522
1060
1960-5800
TVS (mg/L)
---
---
742
81-86% of the TSS
12-93
61
48.2
74-260
23
25
5.5
16-68
pH
Total Nkjedahl (mg/L)

Total P (mg/L)
a
Brito et al., (2007). bTorrijos and Moletta (1998). cVintage period, mean value after 24 h. dExtreme values.
Among the several biological and chemical processes applied to winery

wastewaters it is possible highlight the following: anaerobic digestion, aerated lagoons,
activated-sludge units, adsorption on activated carbon and coagulation/flocculation.
Anaerobic digestion is particularly suitable for winery wastewater due to the high
organic content of these wastewaters and widely accepted as a first treatment step. The
high organic content allied to the COD/N/P ratio is inappropriate for direct aerobic
treatment - which needs phosphorus and nitrogen addition. The COD/N/P ratio for
anaerobic treatment may be in the order of 800/5/1 (Moletta, 2005).
Aerobic systems, such as aerated lagoons or activated-sludge units, are hence
frequently used to remove the pollution generated by wastewaters from agro-industrial
plants (Brenes et al., 2000). The activated-sludge process was developed in England in
1914 by Ardern & Lockett (1914) and was so-called because it involved the production of
an activated mass of microrganisms capable of stabilising a waste aerobically. Several
versions of the original process are still in use nowadays, but fundamentally they are all
similar.
In Figure 1.12 it is show the efficiency comparison of different biological
treatments applied to winery wastewaters, presenting COD removals among 65 and 98%
(Andreotolla, 2009). Although this significant organic matter degradation, the aerobic
processes have high-operating costs and generate large quantities of waste sludge which
15
must be further disposed (Benitez et al., 1999). Winery wastewater production occurs
mainly during harvesting and at the wine making period. This seasonal activity of the
wineries becomes the biological wastewater treatment process selection (aerobic or
anaerobic) very important. The main question is if the wastewaters will be treated when
they are being produced or stored and treated within several months. If it is possible to
create a storage tank, both processes can be applied. But if it is not possible to construct a
tank to the wastewaters storage, for example, due to the smallest available area, the aerobic
treatment may not be viable because this process needs a permanently feed of wastewater
during all the year and the seasonal activity of this industry does not allow that supply.
Fluidised bed reactors

Hybrid USBF
Anaerobic filters
UASB (two reactors at 4-10C)
UASB
ASBR
An. digestion (susp. biomass)
SBBR
MBBR
FBBR
SBR
MBR
Jet-loop activated sludge
Activated sludge
Activ.sludge (co-treatment)
Constructed wetlands
50
55
60
65
70
75
80
85
90
95
100
COD removal efficiency (%)
Figure 1.12 Efficiency comparison of different biological treatments applied to winery wastewaters
(Andreotolla, 2009).
Adsorption on activated carbon (AC) is widely employed for colour removal and
specific organic pollutants due to its extended surface area, microporus structure, high
adsorption capacity and high degree of surface reactivity. Studies on decolourization of
distillery spentwash include adsorption on commercial as well as indigenously prepared
activated carbons (Bernardo et al., 1997; Chandra and Pandey, 2000; Mane et al., 2006).
Coagulation and flocculation with alum and iron salts was not effective for colour
removal in fermentation industry effluents, due to the nature of colour causing compounds
which are almost totally dissolved and resistant to biodegradation (Inanc et al., 1999).
However, it was explored lime treatment with anaerobically digested effluent. The
16
optimum dosage of lime was found to be 10.0 g/L resulting in 82.5% COD removal and
67.6% reduction in colour in a 30 min period.
Biological oxidation is the process of wastewater treatment plants where most of
the organic content is removed. Several pollutants can be fully biodegraded by the
microorganisms in such processes, whereas many physical and chemical processes just
concentrate the pollutants or transfer them from one medium to another. Unfortunately, not
all compounds are biodegradable. Wastewater submitted to biological oxidation should be
free of substances resistant to biodegradation or toxic to the bioculture. A possible way to
overcome these problems could be the introduction of treatment schemes combining
chemical and biological processes: a chemical treatment would typically be a pre-treatment
of non-biodegradable or toxic wastewater (once many oxidation products of biorefractory
pollutants are easily biodegradable) or a chemical process applied as polishing step after
biological treatment.
1.4 Advanced Oxidation Processes
A wide range of sewage treatment technologies are available on the market.
However, considering that the effluents to be treated are often composed by substances
with high toxicity, to destroy the pollutants is more effective than simply transfer them
from stage. Therefore in recent years new processes have been studied and developed
seeking the total oxidation of contaminants or their conversion into less toxic compounds.
These processes are known as Advanced Oxidation Processes (AOPs).
Advanced Oxidation Processes were defined by Glaze et al., (1987) as the near
ambient temperature and pressure water treatment processes which involve the generation
of highly reactive radicals (especially hydroxyl radicals (HO)) in sufficient quantity to
influence water purification. HO radicals are extraordinarily reactive species that attack
most of the organic molecules. The kinetics of reaction is generally first order with respect
to the concentration of hydroxyl radicals and to the concentration of the species to be
oxidized.
The AOPs are used to destroy the complex refractory organic constituents even
after treatment with conventional methods. These processes have shown great potential in
the treatment of pollutants, either in high or in low concentrations. The ultimate goal of the
oxidation process is to mineralize the organic contaminants present in water in carbon
17
dioxide, water and inorganic ions through degradation reactions involving species strongly
oxidizing. Rate constants are usually in the range of 1081011 M-1s-1, whereas the
concentration of hydroxyl radicals lays between 10-10 and 10-12 M, thus a pseudo-first order
constant between 1 and 10-4 s-1 is obtained (Glaze and Kang, 1989). As it can be observed
from Table 1.3, hydroxyl radicals are more powerful oxidants than the chemical agents
used in traditional chemical processes.
The mechanism of reaction usually involves the abstraction of a hydrogen atom or
the addition to unsaturated carbon-carbon links, starting a sequence of oxidative reactions
that can lead to complete mineralization of organic contaminant (Oliveros et al., 1997).
Table 1.3 Oxidation potential against Standard Hydrogen Electrode of some relevant oxidants (Legrini et
al., 1993; Domnech et al., 2001).
Oxidant
E (V)
Fluorine
3.03
Hydroxyl radical
2.80
Singlet oxygen
2.42
Ozone
2.07
Hydrogen peroxide
1.78
Perhydroxyl radical
1.70
Permanganate
1.68
Hypobromous acid
1.59
Chlordioxide
1.57
Hypochlorous acid
1.49
Hypochloric acid
1.45
Chlorine
1.36
Bromine
1.09
Iodine
0.54
The hydroxyl radicals can be generated by different oxidation processes, such as

ozone (O3), ultraviolet (UV) (Mansilla et al., 1997), hydrogen peroxide combined with
ultraviolet radiation (H2O2/UV), Fenton reagent (Fe2+/H2O2) (Walling, 1974), photoFenton process (Pignatello, 1992), O3/UV (Baxendale and Wilson, 1957), O3/H2O2 and
heterogeneous photocatalysis using semiconductors such as zinc oxide (ZnO) but mainly
titanium dioxide (TiO2) - TiO2/UV process (Ollis and Al-Ekabi, 1993).
18
1.4.1 Fentons reagent

The Fenton reagent is a homogeneous catalytic oxidation process which is the
combination of an oxidizing agent (hydrogen peroxide) and a catalyst (an oxide or metal
salt, usually iron) to produce hydroxyl radicals. The Fenton reaction was discovered by H.
J. Fenton in 1894 (Fenton, 1894), when intended to oxidize polycarboxylic acids (malic
acid and tartaric acid) with H2O2 and noted that there was a strong promotion in the
presence of ferrous ions (Fe2+). Forty years later the Haber-Weiss (1934) mechanism was
postulated, revealing that the effective oxidative agent in the Fenton reaction was the
hydroxyl radical (HO). The hydroxyl radicals are generally referred to as the primary
oxidizing chemical species generated in accordance with the fundamental equation
(Walling, 1974):
Fe2+ + H2O2 Fe
3+
+ HO + HO
(1.1)
In the absence of light and complexing ligands other than water, the most accepted
mechanism of H2O2 decomposition in acid homogeneous aqueous solution, involves the
formation of hydroxyperoxyl (HO2/O2-) and hydroxyl radicals HO (De Laat and Gallard,
H., 1999; Gallard and De Laat, 2000). The metal regeneration can follow different paths.
For Fe2+, the most accepted scheme is described in the equations below (Sychev and Isak,
1995).
Fe3+ + H2O2 Fe2+ + HO- + HO
(1.2)
Fe2+ + HO Fe3+ + HO-
(1.3)
HO + H2O2 HO2 + H2O
(1.4)
Fe3+ + HO2 Fe2+ + H+ + O2
(1.5)
Fe3+ + O2- Fe2+ + O2
(1.6)
Fe2+ + HO2 Fe3+ + HO2-
(1.7)
The Fenton reagent has been successfully used in the degradation of several
compounds such as chlorophenols (Kwon et al., 1999), surfactants (Lin et al., 1999), the
oxidation of the leaching of landfill waste (Kang and Hwang, 2000) and the degradation of
19
dyes, which was more advantageous than the hypochlorite, ozone and electrochemical
processes (Szpyrkowicz et al., 2001).
1.4.2 Photo-Fenton system
The Fenton process can be highlighted in their ability to oxidize refractory
compounds present in water and wastewater through the addition of ultraviolet radiation
(sunlight or artificial sources of UV radiation) to the classical Fenton reagent. Fenton
reaction rates are strongly increased by irradiation with UV/visible light (Ruppert et al.,
1993; Sun and Pignatello, 1993) (Figure 1.13). During the reaction, Fe3+ ions are
accumulated in the system and after Fe2+ ions are consumed, the reaction practically stops.
Photochemical regeneration (Eq 1.8) of ferrous ions (Fe2+) by photoreduction of ferric ions
(Fe3+) is the proposed mechanism (Faust and Hoign, 1990). The new generated ferrous
ions reacts with H2O2 generating a second HO radical and ferric ion, and the cycle
continues.
Fe(OH)2+ + h Fe2+ + HO
(1.8)
The research published by different authors shows that the combination of the
Fenton reaction with conventional radiation zone of the visible and near ultraviolet
(reaction of photo-assisted Fenton) gives a better performance in the degradation of
organic pollutants such as 4-chlorophenol (Bauer and Fallmann, 1997), nitrobenzene and
anisole (Zepp et al., 1992), herbicides (Sun and Pignatello, 1993) or ethyleneglycol
(McGinnis et al., 2000).
20
UV
End
products
CO2 + H2O
Fentons
reagent
UV
Figure 1.13 - Sequence of reactions occurring in the photo-Fenton system.
The hydroxylated ferric ion, Fe(OH)2+, the predominant complex of Fe2+ in acidic
conditions in aqueous solution, can be reduced to Fe2+ by ultraviolet or visible radiation.
The ion Fe(OH)2+ shows absorption bands between 290 and 400 nm. Thus, the reaction can
be developed efficiently for a wavelength higher than those involved in other AOP as
O3/UV or H2O2/UV which require a wavelength <300 nm (Huston and Pignatello, 1999).
However, the effectiveness of the training of the hydroxyl radical/iron ion decreases with
increase in wavelength where a quantum yield of formation of HO is 0.14 to 313 nm and
only 0.017 at 360 nm (Pignatello, 1992).
It also occurs to direct photolysis of H2O2 (reaction 1.9). However, in the presence
of iron complexes of strongly absorbing radiation, this reaction will contribute only in
small scale for the photodegradation of organic contaminants (Safarzadeh-Amiri et al.,
1997).
H2O2 + h 2HO
(1.9)
21
The pH optimum performance of the photo-Fenton process is considered to be pH = 3.0,

when the hydroxy-Fe3+ complexes are more soluble and when the species Fe(OH)2+ are
more photoactive, which is the predominant form of these complexes (Kim, 1999).
1.4.3 Photo-ferrioxalate process
Oxalic acid forms complexes with Fe(III) strongly absorb from 254 to 442 nm. The
absorption corresponds to a ligand to metal charge transfer band, with max values around
103-104 M1 cm1. Photolysis of trisoxalatoferrate(III) (ferrioxalate, FeOx) constitutes the
most used chemical actinometer; the quantum yield of Fe2+ formation is high ( = 1.0
1.2) and almost independent of the wavelength (Hatchard and Parker, 1956). If H2O2 is
added, the photochemical reduction of the Fe(III)-complex will be coupled with a Fenton
reaction (Eq. 1.1) (Zuo and Hoign, 1992; Safarzadeh-Amiri et al., 1997). Thus, the use of
illuminated mixtures of H2O2 and FeOx is very efficient for the photodegradation of
organic contaminants: the energy required to treat the same volume of a selected
wastewater is 20% of the energy required by the common photo-Fenton system
(Safarzadeh-Amiri et al., 1996; Safarzadeh-Amiri et al., 1997; Nogueira and Jardim, 1999).
The main reactions in the photo/FeOx/H2O2 system are described by the following
sequence of reactions (Lee et al., 2003). After light absorption, oxalyl radical (C2O4) is
produced through a ligand to metal charge transfer:
(Fe(C2O4)3)3- + h Fe2+ + 2C2O42- + C2O4-
(1.10)
Then, a rapid decarboxylation takes place from the oxalyl radical:

C2O4- CO2- + 2CO2
(1.11)
The fate of CO2 depends on the competitive reactions between dissolved oxygen and
ferrioxalate:
22
C2O4- + (Fe(C2O4)3)3- Fe2+ + 3C2O42- + 2CO2
(1.12)
C2O4- + O2 O2- + 2CO2
(1.13)
The superoxide radical (or its conjugate acid) has three reaction pathways,
depending on the oxidation state of iron or the H2O2 concentration and the pH:
HO2 (or O2) + Fe2+ + H+(2H+) Fe3+ + H2O2
(1.14)
HO2 (or O2) + (Fe(C2O4)3)3- Fe2+ + 3C2O42- + O2 + H+
(1.15)
HO2 (or O2) + Fe(OH)2+ Fe2+ + O2 + H2O
(1.16)
Equation (1.15) is the predominant one at high H2O2 concentration (in the mM
range) and acid pH, while at low H2O2 concentration (M range), equation (1.14) is the
preferred path. HO2 can produce H2O2 and O2:
HO2 + HO2 (or O2 + H+) H2O2 + O2
(1.17)
Then, the Fenton equation (1.1) takes place. The method is useful to treat waters
with high absorbance at < 300 nm, because of the high ferrioxalate absorption crosssection in the 200 to 400 nm range. Solar light can be used, which becomes the technology
very attractive from the economical point of view. As previously mentioned, the energy
required to treat the same volume of a wastewater is about 20% of the energy required by
the photo-Fenton system (Safarzadeh-Amiri et al., 1997), and this high efficiency is
attributed to the broad range of absorbance of the reagent, and the high quantum yield of
Fe2+ formation. The reagents are totally water soluble, and there are no mass transfer
limitations. The process is cheap and the oxidant is accessible. Ferrioxalate technology has
been used for the treatment of aromatic and chloroaromatic hydrocarbons, chlorinated
ethylenes, ethers, alcohols, ketones and other compounds.
1.4.4 Heterogeneous photocatalysis
The basis of photocatalysis is the photoexcitation of a semiconductor solid as a
result of the absorption of radiation, often but not exclusively in the near ultraviolet
spectrum. Under near UV irradiation, a suitable semiconductor material may be excited by
photons possessing energies of sufficient magnitude to produce conduction band electrons
and valence band holes. These charge carriers are able to induce reduction or oxidation,
respectively, and react with both water and organic compounds. The holes are extremely
23
oxidant and should thus be able to oxidize almost all chemicals, as well as water, resulting
in the formation of hydroxyl radicals (Munter et al., 2001). Many catalysts have been
tested, although TiO2 in the anatase form seems to possess the most interesting features,
such as high stability, good performance and low cost (Andreozzi et al., 1999). It presents
the disadvantage of the catalyst separation from solution, as well as the fouling of the
catalyst by the organic matter. Minero et al., (1994) studied the photocatalytic degradation
of nitrobenzene (NB) on TiO2 and ZnO, reporting that complete mineralization with TiO2
was achieved. Mathews (1990) also reported more than 90% of NB mineralization was
achieved with TiO2 and sunlight. Regarding 2,4-dichlorophenol (DCP), almost complete
mineralization was achieved in the study carried out by Ku and Hsieh (1992) with TiO2
and 6W 254 nm Hg lamp and showed to be faster in alkaline solutions. Gimnez et al.,
(1999) also tested the photocatalytic treatment of DCP by using TiO2 and solar light,
proving that reaction was first order with respect to DCP concentration and comparing the
efficiencies of two different photocatalytic reactors.
Heterogeneous photocatalysis is a process based on the direct or indirect absorption
of visible or UV radiant energy by a solid, normally a wide-band semiconductor. In the
interfacial region between the excited solid and the solution, destruction or removal of
contaminants takes place, with no chemical change in the catalyst.
Figure 1.14 - TiO2-semiconductor photocatalysis process. Representative scheme of some

photochemical and photophysical events that might take place in an irradiated semiconductor
particle.
24
Figure 1.14 shows a scheme of processes occurring in a particle of semiconductor

when it is excited by energy light higher than that of the band gap. Under these conditions,
electron-hole pairs are created, whose lifetime is in the nanosecond range; during this time
interval, electrons and holes migrate to the surface and react with adsorbed species,
acceptors or donors (Mills and Le Hunte, 1997). Electron-hole pairs that cannot separate
and react with surface species, recombine with energy dissipation. The net process is the
catalysis of the reaction between the oxidant and the reductant (for example, between O2
and organic matter).
Various materials are candidates to act as photocatalysts such as, for example,
TiO2, ZnO, CdS, iron oxides, WO3, ZnS, etc. These materials are economically available,
and many of them participate in chemical processes in nature. Besides, most of these
materials can be excited with light of a wavelength in the range of the solar spectrum ( >
310 nm), therefore increasing the interest in the possible use of sunlight. So far, the most
investigated photocatalysts are metallic oxides, particularly TiO2; given the fact that this
semiconductor presents a high chemical stability and it can be used in a wide pH range,
being able to produce electronic transitions by light absorption in the near ultraviolet range
(UV-A).
Heterogeneous photocatalysis over TiO2 can also be combined with other AOTs.
For example, addition of Fe(III) and H2O2 combines UV/TiO2 with photo-Fenton; in doing
this, the destruction of some resistant pollutants can be improved. For example, EDTA,
NTA and other oligocarboxylic acids are more rapidly mineralized in the presence of
Fe(III)/H2O2 than when using TiO2 alone (Babay et al., 2001). Similarly, the presence of
photochemical Fe(III) complexes such as Fe(III)-NTA helps the photocatalytic degradation
of 4-chlorophenol (Abida et al., 2004). In these cases, an important effect of the Fe(III)complexes formed with the initial compound or with possible degradation intermediates
takes place: these complexes can be photolyzed and even photocatalyzed in the reaction
medium, generating Fe(II) and other active radical species.
1.4.5 Ozonation
Ozone is a very powerful oxidizing agent, which is able to participate in a great
number of reactions with organic and inorganic compounds. Among the most common
oxidizing agents, it is only surpassed in oxidant power by fluorine and hydroxyl radicals
25
(Table 1.3). Since the beginning of the century the disinfectant power of ozone has been
known. However it has been mainly during the last two decades that this chemical agent
acquired notoriety in wastewater treatment. Thus, the ozonation of dissolved compounds in
water can constitute an AOP by itself, as hydroxyl radicals are generated from the
decomposition of ozone, which is catalyzed by the hydroxyl ion or initiated by the
presence of traces of other substances, like transition metal cations (Staehelin and Hoign,
1985). As the pH increases, so does the rate of decomposition of ozone in water. At pH 10,
for example, the half-life of ozone in water may be less than one minute. In an ozonation
process two possible pathways have to be considered: the direct pathway through the
reactions with molecular ozone, and the radical pathway through the reactions of hydroxyl
radicals generated in the ozone decomposition and the dissolved compounds (Figure 1.15).
The combination of both pathways for the removal of a compound will depend on
the nature of these, the pH of the medium and the ozone dose (Beltrn et al., 1997). Thus,
molecular ozone can directly react with dissolved pollutants by electrophilic attack of the
major electronic density positions of the molecule. This mechanism will take place with
pollutants such as phenols, phenolates or tiocompounds.
Reactions of molecular ozone normally take place through ozonolysis of a double
bond or attack of nucleophilic centers, where aldehydes, ketones or carboxylic acids are
obtained from double bonds; amides from nitriles; amine oxides from amines, etc (Bailey,
1972). The radical mechanism predominates in less reactive molecules, such as aliphatic
hydrocarbons, carboxylic acids, benzenes or chlorobenzenes (Hoign and Bader, 1979).
Usually under acidic conditions (pH<4) the direct pathway dominates, above pH 10
it changes to the radical. In ground and surface water (pH7) both pathways can be of
importance (Staehelin and Hoign, 1983). In special wastewaters, even at pH=2 the radical
oxidation can be of importance, depending much on the contaminants present (Gottschalk
et al., 2000). Both pathways should always be considered when developing a treatment
scheme.
26
Figure 1.15 - Scheme of reactions of ozone added to an aqueous solution (Hoign and Bader,
1983a).
The rate of attack by hydroxyl radicals is typically 106 to 109 times faster than the
corresponding reaction rate for molecular ozone. A great deal of studies have been
undertaken about the reactivity of ozone with many pollutants and reaction-rate constants
of several organic and inorganic compounds have been establish (e.g. Hoign and Bader,
1983a,b). Besides the oxidation process, ozone decreases colour and turbidity.
1.4.6 Ozone/UV
The O3/UV process is an effective method for the oxidation and destruction of toxic
and refractory organics in water. Basically, aqueous systems saturated with ozone are
irradiated with UV light of 253.7 nm. The extinction coefficient of O3 at 253.7 nm is 3300
M-1cm-1, much higher than that of H2O2 (18.6 M-1cm-1). The decay rate of ozone is about a
factor of 1000 higher than that of H2O2 (Guittoneau et al., 1991). The AOP with ozone and
UV radiation is initiated by the photolysis of ozone. The photodecomposition of ozone
leads to two hydroxyl radicals, which do not act as they recombine producing hydrogen
peroxide (Peyton and Glaze, 1988):
H2O + O3 + h 2 HO + O2
(1.18)
2HO H2O2
(1.19)
27
This system contains three components to produce OH radicals and/or to oxidize

the pollutant for subsequent reactions: UV radiation, ozone and hydrogen peroxide.
Therefore, the reaction mechanism of O3/H2O2 as well as the combination UV/H2O2 is of
great importance. Considering that hydrogen peroxide photolysis is very slow compared
with the rate at which ozone is decomposed by HO2-, it seems that a neutral pH reaction of
ozone with HO2- is the main pathway.
Figure 1.16 - Scheme of the degradation mechanism by means of the O3/UV process (Peyton and Glaze,
1988).
The efficiency of this process with different aromatic compounds has been studied by
several authors. Gurol and Vatistas (1987) studied the photolytic ozonation of mixtures of
phenol, p-cresol, 2,3-xylenol and catechol at acidic and neutral pH. Guittoneau et al.,
(1990) reported that the O3/UV process was found to be more efficient than the UV/H2O2
system for the degradation of p-chloronitrobenzene.
1.4.7 Ozone/UV/H2O2
The addition of H2O2 to the O3/UV process accelerates decomposition of ozone
resulting in increased rate of OH radicals generation. In processes targeted at pollutants
28
that are weak absorbers of UV radiation, it is more cost effective to externally add
hydrogenperoxide at reduced UV flux. This is a very powerful method that allows a
considerable reduction of the TOC. This process is the combination of the binary systems
O3/UV and O3/H2O2. The global equation for the O3/UV/H2O2 is obtained (1.20):
2 O3 + H2O2 + h 2 HO + 3 O2
(1.20)
Zeff and Barich (1990) studied the oxidation of different organic compounds
(methylene chloride, chlorobenzene, benzene, toluene, ethylbenzene) by means of this
system, which proved to be more efficient that the treatment of each oxidant alone or in
binary combinations. Mokrini et al., (1997) presented the degradation of phenol by means
of this process at different pHs, establishing the optimal H2O2 amount. A 40% of TOC
reduction was achieved by this method. Trapido et al., (2001) reported the combination of
ozone with UV radiation, and hydrogen peroxide was found to be more effective for the
degradation of nitrophenols than single ozonation or the binary combinations, increasing
the reaction rate and decreasing the ozone consumption when using low pH values. With
regard to NB and DCP, no articles have been found in the literature about the oxidation of
these compounds by means of this process.
References
Abdullah, E., Tzanov, T., Costa, S., Robra, K.H., Cavaco-Paulo, A., Gubitz, G.M. 2000.
Decolorization and detoxification of textile dyes with a laccase from Trametes hirsuta. Appl.
Environ. Microbiol. 66, 3357-3362.
Abida, O., Emlio, C., Quici, N., Gettar, R., Litter, M., Mailhot, G., Bolte, M. 2004. Wat. Sci.
Technol. 49, 123-128.
Airoldi, G., Balsari, P., Gioelli, F. 2004. Results of a survey carried out in Piedmont region winery
on slurry characteristics and disposal methods. Proceedings of the 3rd International Specialised
Conference on Sustainable Viticulture and Winery Wastes Management, Barcelona, 24-26 May,
335-338.
29
Andreotolla, G., Foladori, P., Ziglio, G. 2009. Biological treatment of winery wastewater an
overview. 5th International specialized conference on sustainable viticulture: winery waste and
ecologic impacts in management. Trento and Verona. Italy, 30th March 3rd April, pp. 35-42.
Andreozzi, R., Caprio, V., Insola, A., Marotta, R. 1999. Advanced Oxidation Processes (AOP) for
water purification and recovery. Catalysis Today 53, 51-59.
Ardern, E., Lockett, W.T. 1914. Experiments on the oxidation of sewage without the aid of filters.
J. Soc. Chem. Ind. 33, 1112.
Arnaiz, C., Buffiere, P., Lebrato, J., Moletta, R. 2007. The effect of transient changes in organic
load on the performance of an anaerobic inverse turbulent bed reactor. Chem. Eng. Proc. 46, 13491356.
Babay, P.A., Emilio, C.A., Ferreyra,, R.E., Gautier, E.A., Gettar, R.T., Litter, M.I. 2001. Int. J.
Photoenergy 3, 193-199.
Bailey, P.S. 1972. Ozone in water and wastewater treatment, Ann. Arbor Science Publishers,
Michigan.
Bauer, R., Fallmann, H. 1997. The photo-Fenton oxidation a cheap and efficient wastewater
teatment method. Res. Chem. Intermed. 23, 341-354.
Baxendale, J.H., Wilson, J.A. 1957. Photolysis of hydrogen peroxide at high light intensities.
Trans. Farad. Soc. 53, 344-356.
Beltrn, F.J., Gonzlez, M., lvarez, P. 1997. Tratamiento de aguas mediante oxidacin avanzada
(I): Procesos con ozono, radiacin ultravioleta y combinacin ozono/radiacin ultravioleta,
Ingeniera Qumica 331, 161-168.
Benitez, F., Beltran-Heredia, J., Real, F. Acero, J. 1999. Enhancement of the ozonation of wine
distillery wastewaters by an aerobic pretreatment. Bioprocess Engineering 21, 459464.
Bernardo, E.C., Egashira, R., Kawasaki, J., 1997. Decolorization of molasses wastewater using
activated carbon prepared from cane bagasse. Carbon 35, 12171221.
Brenes, M., Garcia, P., Romero, C., Garrido, A. 2000. Treatment of green table olive waste waters
by an activated-sludge process. J. Chem. Technol. Biotechnol. 75, 459463.
Brito, A.G., Peixoto, J., Oliveira, J.M., Oliveira, J.A., Costa, C., Nogueira, R., Rodrigues, A. 2007.
Brewery and winery wastewater treatment: Some focal points of design and operation in utilization
of by-products and treatment of waste in the food industry. Springer US, 109-131.
30
Brow, M.A., DeVito, S.C. 1997. Predicting azo dye toxicity. Crit. Rev. Environ. Sci. Technol.
36:65-72.
Brown, D., Hamburger, B. 1987. The degradation of dyestuffs Part III investigation of their
ultimate biodegradability. Chemosphere 16, 1539-1553.
Carliell, C.M., Barclay, S.J., Buckley, C.A. 1996. Treatment of exhausted reactive dye bath
effluent using anaerobic digestion: laboratory and full scale trials. Water S.A., 22, 225-233.
Carliell, C.M., Barclay, S.J., Naidoo, N., Buckley, C.A., Mulholland, D.A., Senior, E. 1994.
Anaerobic decolourisation of reactive dyes in conventional sewage treatment processes. Water
S.A., 20, 341-345.
Carliell, C. M., Barclay, S. J., Naidoo, N., Buckely, C. A., Mulholland, D. A., Senior, E. 1995.
Microbial decolourisation of reactive azo dye under anaerobic conditions. Water S.A. 21, 61.
Chandra, R., Pandey, P.K., 2000. Decolorization of anaerobically treated distillery effluent by
activated charcoal adsorption method. Indian J. Environ. Protect. 21, 134137.
Chung, K.T., Stevens, S.E.J., Cerniglia, C.E. 1992. The reduction of azo dyes by the intestinal
microflora. Crit. Rev. Microbiol. 18, 175-197.
Chung, K.T., Stevens, S.E.J. 1993. Degradation of azo dyes by environmental microorganisms and
helmints. Environ. Toxicol Chem. 54, 435-441.
Cisneros, R.L., Espinoza, A.G., Litter, M.I. 2002. Photodegradation of an azo dye of the textile
industry. Chemosphere 48, 393-399.
Colour Index International. 2002. Society of Dyes and Colourists and American Association of
Textile Chemists and Colorists, 4th Ed., www.colour-index.org.
Correia, V.M., Stephenson, T., Judd, S.J. 1994. Characterization of textile wastewaters a review.
Environ. Technol. 15, 917-929.
De Laat, J., Gallard, H. 1999. Catalytic decomposition of hydrogen peroxide by Fe(III) in
homogeneous aqueous solution: mechanism and kinetic modeling, Environ. Sci. & Technol. 33,
2726-2732.
Domnech, X., Jardim, W.F., Litter, M.I. 2001. Procesos Avanzados de oxidacin para la
eliminacin de contaminantes. In: CYTED. Eliminacin de Contaminantes por Fotocatlisis
Heterognea.
31
El-Dein, A.M., Libra, J.A., Wiesmann, U. 2003. Mechanism and kinetic model for the
decolorization of the azo dye Reactive Black 5 by hydrogen peroxide and UV radiation.
Chemosphere 52, 1069-1077.
EU-European Parliament. Directive 2000/60/EC of the European Parliament and of the Council of
23th October establishing a framework for Community action in the field of water policy. Official
Journal L 327/1 22.12.2000.
Faust, B., Hoigne, J. 1990. Photolysis of Fe(III) - hydroxy complexes as sources of OH radicals in
clouds, fog and rain. Atmos. Environ, 24A, 79-89.
Fenton, H.J.H. 1894. Oxidation of tartaric acid in the presence of iron. J. Chem. Soc., 65, 899-910.
Figueiredo, S.A.R.C. 2002. Remoo de corantes txteis em soluo aquosa usando materiais
naturais contendo quitina. PhD Dissertation, FEUP.
Forgacs, E., Cserhti, T., Oros, G. 2004. Removal of synthetic dyes from wastewaters: a review.
Environ. Int. 30, 953-971.
van der Zee, F. P., Villaverde, S. 2005. Combined anaerobic-aerobic treatment of azo-dyes. A short
review of bioreactor studies. Water Res. 39, 1425-1440.
Gallard, H., De Laat, J. 2000. Kinetic modelling of Fe(III)/H2O2 oxidation reactions in dilute
aqueous solution using atrazine as a model organic compound, Wat. Res. 34, 3107-3116.
Gimnez, J., Curc, D., Queral, M.A. 1999. Photocatalytic treatment of phenol and 2,4dichlorophenol in a solar plant in the way to scaling-up. Catalysis Today 54, 229-243.
Glaze, W.H., Kang, J.W. 1989. Advanced oxidation processes. Test of a kinetic model for the
oxidation of organic compounds with ozone and hydrogen peroxide in a semibatch reactor. Ind.
Eng. Chem. Res. 28, 1580-1587.
Glaze, W.H., Kang. J.W., Chapin, D.H. 1987. The chemistry of water treatment processes
involving ozone, hydrogen peroxide and ultraviolet radiation, Ozone Sci. & Eng. 9, 335-342.
Gomes da Silva, C., Faria, J. L. 2003. Degradation of an azo dye in aqueous solution by UV
irradiation. J. Photochem. Photobiol. A: Chem. 155, 133-143.
Gottschalk, C., Libra, J.A., Saupe, A. 2000. Ozonation of water and waste water. A practical guide
to understanding ozone and its application. Wiley-VCH, Weinheim, Germany.
Grau, P. 1991. Textile industry wastewater treatment. Wat. Sci. Technol. 24, 97-103.
32
Guittonneau, S., De Laat, J., Duguet, J.P., Bonnel, C., Dor, M. 1990. Oxidation of
Parachloronitrobenzene in dilute aqueous solution by O3+UV: a comparative study. Ozone Sci. &
Eng. 12, 73-94.
Gurol, M.O., Vatistas, R. 1987. Oxidation of phenolic compounds by ozone and ozone + UV
radiation: a comparative study. Wat. Res. 21, 895-900.
Haber, F., Weiss, J. 1934. The catalytic decomposition of hydrogen peroxide by iron salts. Proc.
Roy. Soc. A, 147, 332-351.
Hatchard, C.G., Parker, C.A. 1956. Proc Roy Soc (London) A 235, 518.
Hoign, J., Bader, H. 1979. Ozonation of water: selectivity and rate of oxidation of solutes. Ozone
Sci. & Eng. 1, 73-85.
Hoign, J., Bader, H. 1983a. Rate constants of reaction of ozone with organic and inorganic
compounds in water. Part I. Non-Dissociating organic compounds. Wat. Res. 17, 173-183.
Hoign, J., Bader, H. 1983b. Rate constants of reaction of ozone with organic and inorganic
compounds in water. Part II. Dissociating organic compounds. Wat. Res. 17, 185-194.
Huston, P.L., Pignatello, J.J. 1999. Degradation of selected pesticide active ingredients and
commercial formulations in water by the photo-assisted Fenton reaction. Wat. Res. 33, 1238-1246.
Inanc, B., Ciner, F., Ozturk, I., 1999. Color removal from fermentation industry effluents. Wat. Sci.
Technol. 40, 331338.
Inglezakis, V.J., Poulopoulos, S.G. 2006. Adsorption, ion exchange and catalysis - Design of
operations and environmental applications. Elsevier B. V.
Kang, Y.W., Hwang, K.Y. 2000. Effects of reaction conditions on the oxidation efficiency in the
Fenton process. Wat. Res. 34, 27862790.
Katsiri, A., Dalou, F. 1994. Wine and distillery effluents in Greece: main results of the SPRINT
AQUANET program. In: Proceedings of international specialized conference on winery
wastewaters, 20 - 22 June, Narbonne, France. 25 - 30.
Kim, S.M., Geissen, S.U., Vogelpohl, A. 1997. Landfill leachate treatment by a photoassisted
Fenton reaction. Wat. Sci. Technol. 35, 239-248.
Ku, Y., Hsieh, C.B. 1992. Photocatalytic decomposition of 2,4-dichlorophenol in aqueous TiO2
suspensions. Wat. Res. 26, 1451-1456.
33
Kwon, B.G., Lee, D.S., Kang, N., Yoon, J. 1999. Characteristics of p-chlorophenol oxidation by
Fentons reagent. Wat. Res. 33, 21102118.
Lee, Y., Jeong, J., Lee, C., Kim, S., Yoon, J. 2003. Influence of various reaction parameters on 2,4D removal in photo/ferrioxalate/H2O2 process. Chemosphere 51, 901-912.
Legrini, O., Oliveros, E., Braun, A.M. 1993. Photochemical processes for water treatment. Chem.
Rev. 93, 671-698.
Lin, S.H., Lin, C.M., Leu, H.G. 1999. Operating characteristics and kinetic studies of surfactant
wastewater treatment by Fenton oxidation. Wat. Res. 33, 17351741.
Lorenzen, L., Hayward, D.J., Bezuidenhout, S., Barnardt, N., Prozesky, V., Trerise, M., et al. 2000.
The development of an integrated management plan for the handling, treatment and purification of
effluents in the wine, spirit and grape juice industries. Research report to Winetech, IRSOT.
Mane, J.D., Modi, S., Nagawade, S., Phadnis, S.P., Bhandari, V.M., 2006. Treatment of spentwash
using chemically modified bagasse and color removal studies. Bioresource Technol. 97, 1752
1755.
Mansilla, H.D., Yeber, M.C., Freer, J., Rodrguez, J., Baeza, J. 1997. Homogeneous and
heterogeneous advanced oxidation of a bleaching effluent from the pulp and paper industry. Wat.
Sci. Technol. 35, 273-278.
Matthews, R.W. 1990. Purification of water with near-UV illuminated suspensions of titanium
dioxide. Wat. Res. 24, 653-660.
McGinnis, B.D., Adams, V.D., Middlebrooks, E.J. 2000. Degradation of ethylene glycol in photo
Fenton systems. Wat. Res. 34, 2346-2354.
McMullan, G., Meehan, C., Conneely, A., Kirby, N., Robinson, T., Nigam, P., Banat, I.M.,
Marchant, R., Smyth, W.F. 2001. Microbial decolourisation and degradation of textile dyes. Appl.
Microbiol. Biotechnol. 56, 81-87.
Meri, S., Kaptan, D., lmez, T. 2004. Color and COD removal from wastewater containing
Reactive Black 5 using Fentons oxidation process. Chemosphere 54, 435-441.
Mills, A., Le Hunte, S. 1997. An overview of semiconductor photocatalysis. J. Photochem.
Photobiol. A: 108, 135
Minero, C., Pelizzetti, C., Piccini, P., Vinceti, M. 1994. Photocatalyzed transformation of
nitrobenzene on TiO2 and ZnO. Chemosphere 28, 1229-1244.
34
Mokrini, A., Oussi, D., Esplugas, S. 1997. Oxidation of aromatic compounds with UV
radiation/ozone/hydrogen peroxide. Wat. Sci. Technol. 35, 95-102.
Moletta, R. 2005. Winery and distillery wastewater treatment by anaerobic digestion. Wat. Sci.
Technol. 51, 137-144.
Mller, A.M. 1999. Government of South Africa gazette no. 20526.8, October, 1999. Government
notice, Department of Water Affairs and Forestry. Section 21.
Munter, R., Preis, S., Kallas, J., Trapido, M., Veressinina, Y. 2001. Advanced oxidation processes
(AOPs): Water treatment technology for the twenty-first century, Kemia-Kemi, 28, 354-362.
Nogueira, R.F.P., Jardim, W.F. 1999. Photodegradation of water contaminants using potassium
ferrioxalate. J. Adv. Oxid. Technol. 4, 1-4.
Oliveros, E., Legrini, O., Hohl, M., Muller, M., Braun, A.M. 1997. Industrial wastewater treatment:
large scale development of a light-enhanced Fenton reaction. Chem. Eng. Proc. 36, 397-405.
Ollis, D.F., Al-Ekabi, H. (Eds.) 1993. Photocatalytic purification and treatment of water and air.
Elsevier Sci. Pub. Amsterdam, The Netherlands.
Ollis, D.F., Pelizzetti, E., Serpone, N. 1989. Heterogeneous photocatalysis in the environment:
application to water purification in Photocatalysis: Fundamentals and Applications. Serpone N.
and Pelizzetti E. (eds.), Wiley, New York.
ONeill P. Environmental Chemistry. 1985. 1st ed. London, George Allen & Unwin Ltd.
Paar, A., Costa, S., Tzanov, T., Gudelj, M., Robra, K., Cavaco-Paulo, A., Gubitz, G.M. 2001.
Thermo-alkali-stable catalases from newly isolated Bacillus sp. for the treatment and recycling of
textile bleaching effluents. J. Biotechnol. 89, 147-153.
Peyton, G.R., Glaze, W.H. 1988. Destruction of pollutants in water with ozone in combination with
ultraviolet radiation. 3. Photolysis of aqueous ozone. Environ. Sci. Technol. 22, 761-767.
Pierce, J. 1994. Colour in textile effluents the origins of problem. J. Soc. Dyers Colour. 110:131134.
Pignatello, J.J. 1992. Dark and photoassisted Fe3+-catalyzed degradation of chlorophenoxy
herbicides by hydrogen peroxide, Environ. Sci. Technol. 26, 944-951.
Pinheiro, H.M., Tourad, E., Thomas, O. 2004. Aromatic amines from azo dye reduction: status
review with emphasis on direct UV spectrophotometric detection in textile industry wastewaters.
Dyes and Pigments 61, 121-139.
35
Pirra, A. 2005. Treatment of winery effluents from the Douro region (Port wine region). PhD
Thesis, University of Trs-os-Montes and Alto Douro. Vila Real, Portugal. 296 pp. (in Portuguese).
Rafols, C., Barcelo, D. 1997. Determination of mono- and disulphonated azo dyes by liquid
chromatographyatmospheric pressure ionization mass spectrometry. Journal of Chromatography
A, 777, 177.
Rai, H.S., Bhattacharyya, M.S., Singh, J., Bansal, T.K., Vats, P., Banerjee, U.C. 2005. Removal of
dyes from the effluent of textile and dyestuff manufacturing industry. A review of emerging
techniques with reference to biological treatment. Crit. Rev. Env. Sci. Tec., 35, 219-238.
Reife, A, Freeman, H.S. 1996. Environmental chemistry of dyes and pigments. John Wiley and
Sons, Inc., New York.
Robinson, T., McMullan, G., Marchant, R., Nigam, P. 2001. Remediation of dyes in textile
effluent: a critical review on current treatment technologies with a proposed alternative.
Bioresource Technol., 77, 247-255.
Rocha, E.O., Sousa, M.J., Ferreira, M.L. 2006. Como evoluram os clusters do txtil e vesturio em
portugal durante o perodo de desmantelamento do acordo multi-fibras (1995-2005)?. Universidade
Catlica Portuguesa.
Rochard, J. 1995. Nature et consquences de la pollution vinicole: rduction de la charge
pollutante, Ind. Bev. 24, 16.
Ruppert, G., Bauer, R., Heisler, G. 1993. The photo-Fenton reaction - an effective photochemical
wastewater treatment process. J. Photochem. Photobiol. A, 73, 75-78.
Safarzadeh-Amiri A, Bolton J.R., Cater, S.R. 1996. Ferrioxalate-mediated solar degradation of
organic contaminants in water. Solar Energy 56, 439-443.
Safarzadeh-Amiri, A., Bolton, J.R., Cater, S.R. 1997. Ferrioxalate-mediated photodegradation of
organic pollutants in contaminated water. Wat. Res. 31, 787-798.
Solozhenko, E.G., Soboleva, N.M., Goncharuk, V.V. 1995. Decolourization of azo dye solutions
by Fenton's oxidation. Wat. Res. 29, 2206-2210.
Staehelin, S., Hoign, J. 1983. Mechanism and kinetics of decomposition of ozone in water in the
presence of organic solutes. Vom Wasser, 61, 337.
Staehelin, S., Hoign, J. 1985. Decomposition of ozone in water in the presence of organic solutes
acting as promoters and inhibitors of radical chain reactions. Environ. Sci. Technol. 19, 1209-1212.
36
Stylidi, M., Kondarides, D.I., Verykios, X.E. 2003. Pathways of solar light-induced photocatalytic
degradation of azo dyes in aqueous TiO2 suspensions. Appl. Catal. B: Environ. 40, 271-286.
Sun, Y., Pignatello, J.J. 1993. Photochemical reactions involved in the total mineralization of 2,4-D
by Fe3+/H2O2/UV. Environ. Sci. Technol. 27, 304-310.
Sychev, A.Y., Isak, V.G. 1995. Iron compounds and the mechanisms of the homogeneous catalysis
of the activation of O2 and H2O2 and of the activation of organic substrates. Russ. Chem. Rev. 64,
1105-1129.
Szpyrkowicz, L., Juzzolino, C., Kaul, S.N. 2001. A comparative study on oxidation of disperse
dyes by electrochemical process, ozone, hypochlorite and Fenton reagent. Wat. Res. 35, 2129
2136.
Trapido, M., Veressinina, Y., Kallas, J. 2001. Degradation of aqueous nitrophenols by ozone
combined with UV-radiation and hydrogen peroxide. Ozone Sci. & Eng. 23, 333-342.
van der Zee FP. 2002. Anaerobic azo dye reduction. Doctoral Thesis. Wageningen University.
Wageningen, The Netherlands.
Vandevivere, P.C., Bianchi, R., Verstraete, W. 1998. Treatment and reuse of wastewater from the
textile wet-processing industry: review of emerging technologies. J. Chem. Technol. Biotechnol.
72, 289-302.
vanLoon, G.W., Duffy, S.L. 2000. Environmental chemistry, a global perspective, Oxford
University Press, Oxford.
Vasconcelos, E. Anlise da indstria txtil e do vesturio Estudo EDIT VALUE Empresa Jnior
N. 02 2006.
Vlyssides, A.G., Barampouti, E.M., Mai, S. 2005. Wastewater characteristics from Greek wineries
and distilleries. Wat. Sci. Technol. 51, 5360.
Wackernagel, M, Rees, W. 1996. Our ecological footprints. Gabriola Island, BC: New Press
Publishers.
Walling, C. 1974. Fenton's reagent revisited. Acc. Chem. Res. 8, 125-131.
WHO. 2005. Lack of water and inadequate sanitation. World Health Organization.
http://www.who.int/en
Zeff, J.D., Barich, J.T. 1990. Symposium on Advanced Oxidation Processes and Treatment of
Contaminated Water and Air: Wastewater Technologies, Center, Ontario (Canad).
37
Zepp, R.G., Faust, B.C., Hoign, J. 1992. Hydroxyl radical formation in aqueous reactions (pH 3-8)
of iron (II) with hydrogen peroxide: the photo-Fenton reaction. Environ. Sci. Technol. 26, 313-319.
Zollinger, H. 1991. Color chemistry. Syntheses, properties and applications of organic dyes and
pigments. VCH, 2nd Ed., New York, USA.
Zuo, Y., Hoign, J. 1992. Formation of hydrogen peroxide and depletion of oxalic acid in
atmospheric water by photolysis of iron(III)-oxalato complexes. Environ Sci Technol 26, 10141022.
38
Chapter 2 - Degradation of Reactive Black 5 by Fenton/UV-C and ferrioxalate/H2O2/solar light processes
CHAPTER 2 - DEGRADATION OF REACTIVE BLACK 5 BY FENTON/UV-C

AND FERRIOXALATE/H2O2/SOLAR LIGHT PROCESSES
Abstract
The feasibility of employing different photoxidation systems, like Fenton/UV-C and
ferrioxalate/H2O2/solar light in the decolorization and mineralization of an azo dye, has
been investigated. Batch experiments were carried out to evaluate, on the first stage, the
influence of different processes on Reactive Black 5 (RB5) decolourization. During the
second stage were investigated the optimal operational conditions of Fenton/UV-C and
ferrioxalate/H2O2/solar light processes, like pH, H2O2 dosage, iron dosage, RB5
concentration and source of light. The experiments indicate that RB5 can be effectively
decolorized using Fenton/UV-C and ferrioxalate/H2O2/solar light processes with a small
difference between the two processes, 98.1 and 93.2%, respectively, after 30 minutes.
Although there is lesser difference in dye decolourization, significant increment in TOC
removal was found with Fenton/UV-C process (46.4% TOC removal) relative to
ferrioxalate/H2O2/solar light process (29.6% TOC removal). This fact reveals that UV-C
low pressure mercury lamp although with its small effect on dye decolorization is
particularly important in dye mineralization, when compared to solar light. However,
ferrioxalate/H2O2/solar light system shows large potential on photochemical treatment of
textile wastewater with particular interest from the economical point of view.
* Adapted from: Lucas M.S., Peres J.A. Dyes and Pigments. 2007, 74, 622-629.
39
2.1 Introduction
Textile industry is one of the highest water consuming sectors, between 25 and 250
m3 per ton of product depending on the processes - and the largest consumer of colorants
for various dyeing, printing and finishing processes [1,2]. This water consumption, allied
to high dosages of dyes, originates effluents that are extremely colorized. The release of
these wastewaters to natural environments is described as very problematic to aquatic life
[3] and mutagenic to human [4].
The conventional treatment techniques applied in textile wastewaters, such as
chemical coagulation/flocculation, membrane separation (ultrafiltration, reverse osmosis)
or elimination by activated carbon adsorption, are not only costly, but also result in phase
transfer of pollutants. Biological treatment is not an efficient solution to these effluents due
to the complex structure of some dyes that provokes resistances to biodegradation. Hence,
the resource to Advanced Oxidation Processes (AOPs) could be a good alternative to treat
and remove textile dyes from the wastewaters.
The azo dyes, characterized by an azo group (-N=N-), are the largest class of dyes
used in textile industry for dyeing several natural and synthetic materials [1,5]. Between
the several azo dyes (acid, reactive, disperse, vat, metal complex, mordant, direct, basic
and sulphur) the most used are the reactive type. These dyes are the most problematic
pollutants of textile wastewaters. This fact occurs because, after the dyeing process, more
than 15% of the textile dyes are lost in wastewater stream [6]. Therefore, in this study was
selected the azo dye Reactive Black 5 (RB5) as a representative dye pollutant of textile
wastewaters.
Advanced Oxidation Processes offers a highly reactive, non-specific oxidant,
namely hydroxyl radicals (HO), capable of destroying a wide range of organic pollutants
in water and wastewater [7,8]. Fenton's reagent oxidation is a homogeneous catalytic
oxidation process using a mixture of hydrogen peroxide and ferrous ions. In an acid
environment if hydrogen peroxide is added to an aqueous system containing an organic
substrate and ferrous ions, a complex redox reaction will occur [9-11]. The overall reaction
is:
2+
H2O2 + Fe
40
Fe
3+
+ HO + HO
(2.1)
The ferrous ion initiates and catalyses the decomposition of H2O2, resulting in the
generation of hydroxyl radicals, HO [12-13]. Hydroxyl radicals are capable of rapidly
attacking organic substrates and causing chemical decomposition of these compounds by
H-abstraction and addition to C=C unsatured bonds [14].
The addition of UV radiation to Fentons reagent process could be an interesting
allied in dye decolorization due to its capacity in influencing direct formation of HO
radicals [15,16]. This AOP combination has gained progressive attention in recent years
due to its higher efficiency when compared to the dark process. In Fenton/UV-C process,
in addition to Eq. 2.1, the formation of hydroxyl radical also occurs by the following
reactions (Eq. 2.2 and 2.3):
H2O2 + UV HO + HO
Fe
3+
+ H2O + UV HO + Fe2+ + H+
(2.2)
(2.3)
Recently, other processes have been studied trying to use solar light instead of
artificial UV radiation. Ferrioxalate, used for decades as a chemical actinometer, has been
applied in the Fentons reagent process as iron source thus allowing further benefit from
solar radiation [17]. The use of ferrioxalate in the degradation of organic pollutants was
reported to be very effective, and using solar light was found to be an economic alternative
when compared to artificial UV radiation [18-20]. The photolysis of ferrioxalate generates
Fe(II) in acid solutions reported as follows [18,21]:
[Fe(C2O4)3]3- + h Fe2+ + 2C2O42- + C2O4-
(2.4)
C2O4- + [Fe(C2O4)3]3- Fe2+ + 3C2O42- + 2CO2
(2.5)
C2O4- + O2 O2- + 2CO2
(2.6)
The main objective of this study is to analyse the feasibility of decolorization and
mineralization of RB5 by Fenton/UV-C and ferrioxalate/H2O2/solar light processes. The
influence of different operational parameters (source and intensity of light, pH and H2O2,
iron and RB5 concentration) that affect the efficiency of Fenton/UV-C and
ferrioxalate/H2O2/solar light processes during the oxidation of Reactive Black 5 are
studied.
41
2.2 Experimental
2.2.1
Material
The azo dye, Reactive Black 5 (Color Index 20505), was kindly provided by DyStar
Anilinas Txteis Lda. (Portugal) and used as received without further purification. UV-vis
absorption spectra and molecular structure of RB5 in non-hydrolyzed form are illustrated
in Figure 2.1. The chemicals used in the experiments, FeCl3 (Riedel-de-Han), C2H2O4
(Fluka), FeSO4.7H2O (Panreac), H2O2 (Merck, Perhydrol, 30% w/w) and Na2SO3 (M&B)
were of reagent grade. All the solutions were prepared by dissolving requisite quantity of
dye in deionised water from a Millipore purification system. When appropriate, the pH of
the solution was adjusted using H2SO4 and NaOH solutions. Initial pH of solution was
monitored using a Basic pH Meter from Denver Instrument Company.
5
NaO3SOCH2CH2O2S
SO3Na
SO3Na
HO
Absorbance
H2N
N
NaO3SOCH2CH2O2S
0
200
300
400
500
600
700
800
Wavelenght (nm)
Figure 2.1 UV-visible absorption spectra and chemical structure of Reactive Black 5.
2.2.2
Photoreactor
Batch experiments for Fenton/UV-C oxidation, were performed in a Heraeus
photoreactor. The cylindrical reactor of 800 mL capacity was made of borosilicate glass
with ports, at the top, for sampling. For Fenton/UV-C oxidation was used a low-pressure
mercury vapor lamp, Heraeus TNN 15/32, placed in axial position inside the reactor. The
reaction temperature was kept at the desired value within 0.5 C by using a
thermostatically controlled outer water jacket. For every experiment performed, the reactor
42
was initially loaded with 500 mL of RB5 aqueous solution and continuous mixing was
maintained by means of a magnetic stirrer. Ferrioxalate/H2O2/solar light experiments were
carried out, in open air, at the University of Trs-os-Montes and Alto Douro campus,
Portugal (4118N; 745W) under clear sky conditions. All photocatalytic experiments
were carried out under similar conditions on sunny days of May August, between 11 AM
and 3 PM. Solar reactions were conducted in a glass reactor wrapped externally with
aluminium foil to avoid lateral penetration of irradiation through the sidewalls. During the
experiments solar light intensity was measured at 5-minutes intervals using a Macam Q102
PAR Radiometer (400-1000 nm). The measurements were standardized in the way that the
sensor was always set in the horizontal position. The average light intensity over the
duration of each experiment was calculated.
2.2.3
Analysis
For Fenton/UV-C process a desired quantity of dye/Fe2+/H2O2 solution was freshly
prepared from FeSO4.7H2O, H2O2 and the dye stock solution. Most of the experiments
were carried out at pH=5 of the solution. The required amount of Fe2+ was added into the
dye solution. In ferrioxalate/H2O2/solar light process the required amounts of Fe3+ and
oxalic acid were added simultaneously into the dye solution and mixed by means of a
magnetic stirrer. Finally, in both processes, the desired volume of H2O2 was injected into
the solution. In Fenton/UV-C process the reaction time was recorded when the UV lamp
was turned on, and in ferrioxalate/H2O2/solar light process when the solution was exposed
to solar irradiation. Samples of dye solution were withdrawn during the course of the
reaction, at periodic intervals, and analysed in a UV-vis scanning spectrum, 200-800 nm,
using a Jasco V-530 UV/vis (Tokyo, Japan) double-beam spectrophotometer. Na2SO3
solution was used to quench oxidation in samples before the spectrophotometric analysis.
The color of dye solution in the reaction mixture was obtained by the measure of
the absorbance at maximum wavelength (max = 595 nm) and computing the concentration
from calibration curve. Total Organic Carbon (TOC) measurements were carried out with a
Skalar Formacs TOC/TN analyser.
43
2.3 Results and Discussion

Absorption spectra of the dye solutions were recorded. The concentration of residual dye in
solution was calculated by Beer-Lambert law using the optical density and the molar
extinction observed at the characteristic wavelength (max = 595 nm):
A = l C
(2.7)
where A is the absorbance, l, the path length (cm), , the molar extinction coefficient
(Lmol-1cm-1), and C, the dye concentration at time t (mol/L). Dye decolorization was
calculated as follows:
Dye decolorization = (1 - Cdye,t /Cdye,0) x 100%
(2.8)
where Cdye,t and Cdye,0 are the concentrations of dye at reaction time t and 0, respectively.
2.3.1
Photochemical decolorization of Reactive Black 5

Initially, the photochemical degradability of the dye RB5 was carried out with
Fenton/UV-C and ferrioxalate/H2O2/solar light process to compare the decolorization

capacity of each one. From Figure 2.2 it is possible to verify that the decolorization of RB5
solutions was efficiently induced by both processes.
RB5 Decolorization (%)
100
80
Time Evolution:
Ferrioxalate/H2O2/Solar light
Fenton/UV-C
60
40
20
0
0
10
20
30
40
50
60
Time (min)
Figure
2.2
Reactive
Black
decolorization
evolution
during
Fenton/UV-C
and
ferrioxalate/H2O2/solar light processes. Experimental conditions: [RB5] = 1.0x10-4 mol/L; iron
44
concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x10-3mol/L; [H2O2] = 1.5x10-3 mol/L; pH = 5;

Solar light intensity average = 530 Wm-2; UV lamp = TNN 15/32 Heraeus; Reaction time = 60
min.
However, Fenton/UV-C process has a better decolorization capacity than

ferrioxalate/H2O2/solar light process. Although from the results it is not possible to
evaluate, for example, whether the higher decolorization of Fenton/UV-C process is due to
the source of iron or from the source of light. Therefore, to analyse the influence of each
parameter on dye decolorization several experiments were carried out that permits to
evaluate the employment of UV-C radiation, solar light and different sources of iron
(ferrous and ferrioxalate). In Table 2.1 are represented the results of that experiments.
Through this it is possible to observe that for a RB5 concentration of 1.0x10-4 mol/L, at pH
5, and with a solar light intensity average of 530 Wm-2, the dye decolorization is null after
60 minutes for the following processes: (1) RB5 + solar light; (3) RB5 + Fe2+ + solar light;
(7) RB5 + H2O2 + solar light and (11) RB5 + ferrioxalate + H2O2 + dark. In the process (2)
RB5 + UV-C was observed a small dye decolorization of about 11.4% in 30 minutes. In
process (7), where could be expected a significant decolorization due to the use of a
powerful oxidant - hydrogen peroxide (H2O2 = 1.78 V), the RB5 decolorization does not
happen. This result reveals that RB5 azo dye has a complex and resistant molecular
structure (Figure 2.1). Therefore, decolorization of Reactive Black 5 could be primarily
attributed to the hydroxyl radicals, with a higher redox potential (HO = 2.80 V), generated
from Fenton/UV-C and ferrioxalate/H2O2/solar light processes.
Comparing processes (1) and (2) results reveal a better RB5 decolorization capacity
of the UV-C radiation than solar light. The addition of Fe2+ to the UV-C radiation (process
4) promotes an increase in dye decolorization, compared to process 2, achieving the value
of 25.4%. However, the addition of Fe2+ to process (3) RB5 + solar light does not effect
positively to the dye decolorization.
45
Table 2.1 Reactive Black 5 decolorization efficiencies with different processes.
Process
Conditions
Reaction
Time (min)
RB5
Decolorization
(%)
1.
RB5 + solar light
sunny day
60
2.
RB5 + UV-C
UV lamp
30
11.4
60
30
25.4
30
16.4
30
53.5
60
30
97.4
30
97.5
30
98.1
60
30
93.2
30
98.7
3.
4.
Fe2+ =1.5x10-4 mol/L;
2+
RB5 + Fe + solar light
sunny day
Fe2+ =1.5x10-4 mol/L;
2+
RB5 + Fe + UV-C
UV lamp
Fe3+ =1.5x10-4 mol/L;
5.
RB5 + ferrioxalate + solar light

sunny day
6.
7.
8.
Fe3+ =1.5x10-4 mol/L;
RB5 + ferrioxalate + UV-C
UV lamp
H2O2=1.5x10-3 mol/L;
RB5 + H2O2 + solar light
sunny day
Fe2+ =1.5x10-4 mol/L;
2+
RB5 + Fe + H2O2 + dark
H2O2 =1.5x10-3 mol/L

Fe2+ =1.5x10-4 mol/L;
9.
RB5 + Fe2+ + H2O2 + solar light
H2O2=1.5x10-3 mol/L;
sunny day
Fe2+ =1.5x10-4 mol/L;
10. RB5 + Fe2+ + H2O2 + UV-C
H2O2=1.5x10-3 mol/L;
UV lamp
Fe3+ =1.5x10-4 mol/L;
11. RB5 + ferrioxalate + H2O2 + dark
H2O2 =1.5x10-3 mol/L

Fe3+ =1.5x10-4 mol/L;
H2O2=1.5x10-3 mol/L;
12. RB5 + ferrioxalate + H2O2 + solar light
sunny day
Fe3+ =1.5x10-4 mol/L;
H2O2=1.5x10-3 mol/L;
13. RB5 + ferrioxalate + H2O2 + UV-C
UV lamp
-4
-3
[RB5]0 = 1.0x10 mol/L; oxalic acid = 9.0x10 mol/L; pH = 5; solar light intensity average (sunny day) =
530 Wm-2; UV lamp = TNN 15/32 Heraeus.
46
By adding H2O2 to the processes (3) and (4) (processes (9) RB5 + Fe2+ + H2O2 +
solar light and (10) RB5 + Fe2+ + H2O2 + UV-C) it is visible that decolorization capacity
increases significantly for both processes, achieving a very similar decolorization
percentage of 97.5% and 98.1%, respectively. Process (8) RB5 + Fe2+ + H2O2 + dark
shows a decolorization of 97.4%. With a ferrioxalate iron source (processes (5) and (6)) the
UV-C radiation for a time reaction of 30 min, have a higher decolorization capacity than
solar light (53.5% and 16.4%, respectively). By comparing processes (11) (dark, 0 %) and
(12) (solar light, 93.2%), it is patent that light is absolutely necessary for processes
involving ferrioxalate. Processes (12) and (13) present a decolorization capacity of 93.2
and 98.7%, respectively, evidencing that artificial UV-C light leads to a better performance
than solar light.
The higher efficiency of processes (10) RB5 + Fe2+ + H2O2 + UV-C and (13) RB5
+ ferrioxalate + H2O2 + UV-C, achieving a decolorization of 98.1% and 98.7%, signifies
that the combination between UV-C lamp, ferrous ions and ferrioxalate has a sensible
increase on dye decolorization when compared to the experiments with solar light.
2.3.2
Kinetic analysis of ferrioxalate processes

For a better knowledge of decolorization processes with ferrioxalate were also
evaluated the reaction kinetics and the half-life time (t1/2). As show in Table 2.2 the
disappearance of dye during the first 30 min of oxidation could be described as a firstorder reaction kinetics with regard to dye concentration. Initial decolorization rate
constants were determined from the slope of -ln(C/C0) vs t (min) plots, where C0 and C are
dye concentrations at time zero and t, respectively.
Table 2.2 First order rate kinetics (k) and half-life (t1/2) of dye decolorization.
k (min-1)
t1/2 (min)
5. RB5 + ferrioxalate + solar light
0.0044
---
6. RB5 + ferrioxalate + UV-C
0.0264
27.2
---
---
12. RB5 + ferrioxalate + H2O2 + solar light
0.0772
5.4
13. RB5 + ferrioxalate + H2O2 + UV-C
0.0922
3.7
Oxidation Processes
11. RB5 + ferrioxalate + H2O2 + dark
47
As it can be seen in Table 2.1 and comparing k values and t1/2 in Table 2.2 it
follows that process (13) RB5 + ferrioxalate + H2O2 + UV-C process, when compared to
process (12) RB5 + ferrioxalate + H2O2 + solar light, presents an improved decolorization
capacity. This fact is due to the little effect of solar light radiation as can be seen for the
small k value process (5) RB5 + ferrioxalate + solar light. In process (6) RB5 + ferrioxalate
+ UV-C, although there is little power of the low-pressure mercury vapor lamp TNN
15/32, the k value is six times higher than that obtained in the process (5). This result
permits defined as more efficient, with these experimental conditions, the (13) RB5 +
ferrioxalate + H2O2 + UV-C process. However, to have a complete knowledge of optimal
conditions the next steps of this work are to assess the capacity of each principal process
(Fenton/UV-C and ferrioxalate/H2O2/solar light) that oxidizes the Reactive Black 5 azo
dye.
2.3.3
Effect of pH
The effect of pH on the RB5 decolorization by processes (10) RB5 + Fe2+ + H2O2 +
UV-C and (12) RB5 + ferrioxalate + H2O2 + solar light is shown in Figure 2.3. This figure
shows that pH significantly influences the conversion of RB5 in both processes. The
experiments were carried out at pH between 1 and 8. At low pH (1 and 2) was obtained a
very low decolorization in both processes. In the Fenton/UV-C process the decolorization
percentage, for a reaction time of 30 min, was 32% and 46% for pH 1 and 2, respectively.
For ferrioxalate/H2O2/solar light process the decolorization was minor than Fenton/UV-C
process at this pH, achieving a decolorization of 2% for pH 1 and 39% for pH 2. The low
decolorization at pH 1 and 2 is probably due to the hydroxyl radical scavenging by the H+
ions (Eq. 2.9) [16].
HO + H+ + e- H2O
(2.9)
By increasing the pH for 3 was obtained the highest decolorization for Fenton/UVC, 98.6%. For pH above 3 the Fenton/UV-C process decolorization capacity is very similar
to that for pH 3, achieving a color removal of about 98% for all pH. In the
ferrioxalate/H2O2/solar light process for pH 3 a color removal of 69% was achieved, with
increasing the decolorization capacity until the pH 5, the highest value for this process
48
being 90%. For pH above 5 the color removal capacity decreases until the value of 72% for
pH 8. This behavior could be explained by the formation of ferric hydroxo complexes
during the reaction, which blocks the decomposition of hydrogen peroxide catalyzed by the
ferrous iron [22].
100
80
60
pH Effect:
Fenton/UV-C
40
20
0
0
pH
Figure 2.3 Effect of pH on the decolorization of RB5 by Fenton/UV-C and
ferrioxalate/H2O2/solar light processes. Experimental conditions: [RB5] = 1.0x10-4 mol/L; Iron
concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x10-3mol/L; [H2O2] = 1.5x10-3 mol/L; UV lamp =
TNN 15/32 Heraeus; Reaction time = 30 min; Solar light intensity average = 530 Wm-2.
2.3.4
Effect of H2O2 dosage

Figure 2.4a and b shows the relationship between degradation of dye and initial
dosage of H2O2 in the Fenton/UV-C and ferrioxalate/H2O2/solar light processes. The

objective of this evaluation is to select the best operational dosage of H2O2 in both
processes. In Fenton/UV-C process, the addition of H2O2 between 0.5x10-3 and 2.0x10-3
mol/L increases the decolorization from 86% to 99%, respectively, at 20 minutes. For
ferrioxalate/H2O2/solar light process is achieved a RB5 decolorization of 78% to a H2O2
dosage of 1.5x10-3 mol/L. However, increasing the peroxide dosage to 2.0x10-3 mol/L, dye
decolorization decreases to 73 %, also for a reaction time of 20 minutes. This decrease is
probably due to the scavenging of HO radicals by the H2O2, which can be expressed by
Equations 2.10 and 2.11 [23,24]:
49
HO + H2O2 H2O + HO2
(2.10)
HO2 + HO H2O + O2
(2.11)
100
80
60
Peroxide Dosage:
Fenton/UV-C
40
20
0
0,5
1,0
1,5
2,0
-3
H2O2 (10 mol/L)

Figure 2.4a Effect of the peroxide dosage on the decolorization of RB5 by Fenton/UV-C and
concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x10-3mol/L; pH = 5; UV lamp = TNN 15/32
Heraeus; Reaction time = 20 min; Solar light intensity average = 530 Wm-2.
100
80
60
Peroxide Dosage:
Fenton/UV-C
40
20
0
0,5
1,0
1,5
2,0
-3
H2O2 (10 mol/L)

Figure 2.4b Effect of the peroxide dosage on the decolorization of RB5 by Fenton/UV-C and
50
concentration = 1.5x10-4 mol/L; Oxalic acid = 9.0x10-3mol/L; pH = 5; UV lamp = TNN 15/32

Although for a reaction time of 60 minutes the decolorization percentage achieved

for Fenton/UV-C and ferrioxalate/H2O2/solar light processes are similar to all peroxide
dosages. The difference between the two processes, for the same peroxide dosage, is minor
for a reaction time of 60 minutes than for 20 minutes. Ferrioxalate/H2O2/solar light process
increases its decolorization capacity with time, revealing that reaction time is very
important in RB5 decolorization. For a RB5 concentration of 1.0x10-4 mol/L, 1.5x10-3
mol/L of H2O2 could be defined as the optimum dosage.
2.3.5
Effect of iron dosage

The effect of adding iron on RB5 decolorization has been studied. The results are
shown in Figure 2.5a and b. The amount of iron is one of the main parameters that
influence the Fenton/UV-C and ferrioxalate/H2O2/solar light processes. The results indicate
that the extent of decolorization increases with a higher initial iron concentration.
In Fenton/UV-C process addition of Fe2+ from 0.5x10-4 to 2.0x10-4 mol/L increases
color removal from 89% to 96% for a reaction time of 20 minutes. From results it is
possible say that efficiency of RB5 destruction increases with a higher initial Fe2+
concentration. Although, by increasing the iron dosage from 1.5x10-4 to 2.0x10-4 mol/L
only a small decrease in decolorization is verified. It may be explained by redox reactions
that HO radicals may be scavenged either by the reaction with hydrogen peroxide present
or with another Fe2+ molecule as mentioned below (Eqs. 2.12 and 2.13) [25].
H2O2 + HO H2O + HO2
Fe
2+
+ HO HO + Fe
3+
(2.12)
(2.13)
In ferrioxalate/H2O2/solar light process, to the same reaction time, addition of Fe3+

from 0.5x10-4 to 2.0x10-4 mol/L increases color removal from 48% to 79%. The lower
decolorization capacity at small concentration of iron is probably due to the lowest HO
radicals production available for oxidation. But for a reaction time of 60 minutes a
51
significant increase in RB5 decolorization is observed in both processes. However, in the

ferrioxalate/H2O2/solar light process the enhancement in the decolorization is higher.
100
80
60
40
Iron Dosage:
Fenton/UV-C
20
0
0,0
0,5
1,0
1,5
2,0
-4
Iron Dosage (10 mol/L)

Figure 2.5a Effect of the iron dosage on the decolorization of RB5 by Fenton/UV-C and
ferrioxalate/H2O2/solar light processes. Experimental conditions: [RB5] = 1.0x10-4 mol/L; [H2O2] =
1.5x10-3 mol/L; Oxalic acid = 9.0x10-3mol/L; pH = 5; UV lamp = TNN 15/32 Heraeus; Reaction
100
80
Iron Dosage:
Fenton/UV-C
60
40
20
0
0,0
0,5
1,0
1,5
2,0
-4
Iron Dosage (10 mol/L)

Figure 2.5b Effect of the iron dosage on the decolorization of RB5 by Fenton/UV-C and
1.5x10-3 mol/L; Oxalic acid = 9.0x10-3mol/L; pH = 5; UV lamp = TNN 15/32 Heraeus; Reaction
52
The decolorization increases, for the same iron dosage, from 79 to 93% for the
ferrioxalate/H2O2/solar light process and from 96 to 99% for Fenton/UV-C process. This
reveals an important dependence of the ferrioxalate/H2O2/solar light process on the
reaction time. For both processes 1.5x10-4 mol/L of iron can be used as the optimum
dosage.
2.3.6
Effect of dye concentration

The
effect
of
initial
dye
concentration
on
the
Fenton/UV-C
and
ferrioxalate/H2O2/solar light processes was investigated, since pollutant concentration is an

important parameter in wastewater treatment. The influence of the concentration is shown
in Figure 2.6a and b. From these figures it is possible observe that the extent of degradation
decreases with the increase in the initial dye concentration. The increase of RB5
concentration from 0.5x10-4 mol/L to 1.5x10-4 mol/L decreases the decolorization from
99% to 93% for Fenton/UV-C and from 98% to 22% for ferrioxalate/H2O2/solar light
process in 20 minutes. A higher concentration increases the number of dye molecules, but
not the HO radical concentration, and so the removal rate diminishes. In both processes
the high color of dye concentration makes the penetration of photons difficult, even from
UV-C and from solar light into dye solution, thereby decreasing the hydroxyl radical
concentration [15]. After 60 minutes of reaction time the ferrioxalate/H2O2/solar light
process reveals a better performance achieved, even for the highest RB5 concentration
studied - an 83% color removal.
53
100
80
60
40
RB5 Concentration:
Fenton/UV-C
20
0
0,0
0,5
1,0
1,5
2,0
-4
Dye Initial Concentration (10 mol/L)

Figure 2.6a Effect of dye initial concentration on the decolorization of RB5 by Fenton/UV-C and
ferrioxalate/H2O2/solar light processes. Experimental conditions: Iron concentration = 1.5x10-4
mol/L; [H2O2] = 1.5x10-3 mol/L; Oxalic acid = 9.0x10-3mol/L; pH = 5; UV lamp = TNN 15/32
100
80
RB5 Concentration:
Fenton/UV-C
60
40
20
0
0,0
0,5
1,0
1,5
2,0
-4
Dye Initial Concentration (10 mol/L)

Figure 2.6b Effect of dye initial concentration on the decolorization of RB5 by Fenton/UV-C and
ferrioxalate/H2O2/solar light processes. Experimental conditions: Iron concentration = 1.5x10-4
mol/L; [H2O2] = 1.5x10-3 mol/L; Oxalic acid = 9.0x10-3mol/L; pH = 5; UV lamp = TNN 15/32
54
2.3.7
Effect of solar light intensity

The solar light intensity changes during the day and with the climatic conditions.
Therefore, to evaluate the effect of solar light intensity in the ferrioxalate/H2O2/solar light
process were performed several experiments at different weather conditions sunny day
and cloudy day at the same hour of the day. From the Figure 2.7 it is visible that RB5
decolorization is significantly different during the first minutes half an hour to
experiments with sunny or cloudy day. In the cloudy day the decolorization achieved at 30
minutes is 75 % and in the sunny day for the same reaction time it is 92 %. However for a
reaction time of 60 minutes the decolorization capacity of both experiments is the same
93 %. From these results it is possible to conclude that if the solar light intensity was minor
a higher retention time in the reactor could be sufficient to find the same color removal.
100
80
60
Sunny Day
Cloudy Day
40
20
0
0
10
20
30
40
50
60
Time (min)
Figure 2.7 Effect of solar light intensity on the decolorization of RB5 by ferrioxalate/H2O2/solar
light processes. Experimental conditions: Iron concentration = 1.5x10-4 mol/L; [H2O2] = 1.5x10-3
mol/L; Oxalic acid = 9.0x10-3 mol/L; pH = 5; Solar light intensity average: sunny day = 530 Wm-2;
cloudy day = 230 Wm-2.
2.3.8
Mineralization study
It is known that reaction intermediates can be formed during the oxidation of azo
dyes and some of them could be long-lived and even more toxic than the parent
compounds. Therefore, it is necessary understand the mineralization degree of the azo dye
55
RB5 to evaluate the degradation level applied by Fenton/UV-C and ferrioxalate/H2O2/solar

light processes. To quantitatively characterize the mineralization of azo dyes in the
solution, the TOC removal ratio is used in the study, which is defined as follows:
TOC removal ratio = (1-TOCt/TOC0) x 100%
where TOCt and TOC0 are the TOC values at reaction time t and 0, respectively.
Removal (%)
100
75
TOC
50
Color
25
0
Fenton/UV-C
Ferriox./H2O2/Solar light
Figure 2.8 Comparison between decolorization and TOC removal of RB5 after Fenton/UV-C and
1.5x10-3 mol/L; Oxalic acid = 9.0x10-3 mol/L; Iron concentration = 1.5x10-4 mol/L; UV lamp =
TNN 15/32 Heraeus; Solar light intensity average = 530 Wm-2; Reaction time = 1 hour; pH = 5.
Figure 2.8 presents the color degradation and TOC removal ratio of the azo dye
RB5 with Fenton/UV-C and ferrioxalate/H2O2/solar light processes. As could be seen, dye
decolorization is much higher than TOC removal even in Fenton/UV-C and also in
ferrioxalate/H2O2/solar light processes. Although, it is visible from this figure that
Fenton/UV-C process presents a TOC removal higher than ferrioxalate/H2O2/solar light
process, 46.4% and 29.6%, respectively. So, from this analysis it is evident that neither
Fenton/UV-C nor ferrioxalate/H2O2/solar light has the capacity of eliminate the RB5 dye.
However, the employment of the UV lamp benefits the azo dye mineralization when
compared to the solar light. Although from the economical point of view, the use of solar
light could be a good alternative in dye decolorization.
56
2.4 Conclusions
In this work was evaluated the decolorization and mineralization capacity of two
advanced photochemical processes: Fenton/UV-C and ferrioxalate/H2O2/solar light on
Reactive Black 5. From the results the following conclusions can be drawn:
- Fenton/UV-C and ferrioxalate/H2O2/solar light processes, within of the used
experimental conditions, lead to more than 90% of Reactive Black 5 decolorization in half
an hour.
- The experiments with RB5 + ferrioxalate follow a first-order kinetic law even
with UV-C or solar light alone and with hydrogen peroxide addition. However, when UVC lamp + H2O2 was employed the kinetic rate (k) was higher comparatively to the solar
light + H2O2 combination, achieving, consequently, a minor half-life time (t1/2).
- Optimal experimental conditions for both processes, with a RB5 concentration of
1.0x10-4 mol/L, can be summarized as: pH=5, hydrogen peroxide dosage = 1.5x10-3 mol/L
and iron dosage = 1.5x10-4 mol/L.
- The Fenton/UV-C and ferrioxalate/H2O2/solar light processes do not only
decolorize the dye solutions but also partially mineralize the azo dye RB5.
- Although the very similar decolorization is noted in both processes, the
employment of the UV lamp benefits the azo dye degradation. However, from the
economical point of view the employment of the natural resource solar light could be
an interesting option due to its low cost and the fact of being environmentally harmless.
References
[1] Chacn JM, Leal MT, Snchez M, Bandala ER. Solar photocatalytic degradation of azo dyes by
photo-Fenton process. Dyes and Pigments. 2006;69:144-150.
[2] Gonalves MST, Pinto EMS, Nkeonye P, Oliveira-Campos AMF. Degradation of C. I. Reactive
Orange 4 and its simulated dyebath wastewater by heterogeneous photocatalysis. 2005;64:135-139.
[3] Chung KT, Stevens SEJ. Degradation of azo dyes by environmental microorganisms and
helmints. Environ. Toxicol Chem. 1993;54:435-441.
57
[4] Chung KT, Stevens SEJ, Cerniglia CE. The reduction of azo dyes by the intestinal microflora.
Crit. Rev. Microbiol. 1992;18:175-197.
[5] van der Zee FP. Anaerobic azo dye reduction. Doctoral Thesis. Wageningen University.
Wageningen, The Netherlands, 2002,142 pages.
[6] Park H, Choi W. Visible light and Fe(III)-mediated degradation of Acid Orange in the absence
of H2O2. Journal of Photochemistry and Photobiology A: Chemistry 2003;159:241-247.
[7] Legrini O, Oliveros E, Braun AM. Photochemical processes for water treatment. Chem. Rev.
1993;93:671-698.
[8] Nogueira RFP, Silva MRA, Trov AG. Influence of the iron source on the solar photo-Fenton
degradation of different classes of organic compounds. Solar Energy. 2005;79:384-392.
[9]
Peres
JAS,
Carvalho
LHM,
Boaventura
RAR,
Costa
CAV.
Characteristics
of
p-hydroxybenzoic acid oxidation using Fenton's reagent. Journal of Environmental Science and
Health Part A Toxic. 2004;39:117.
[10] Kuo WG. Decolorizing dye wastewater with Fenton's reagent. Water Research
1992;26(7):881-886.
[11] Walling C. Intermediates in the reactions of Fenton type reagents. Accounts of Chemical
Research 1998;31(4):155-157.
[12] Venkatadri R, Peters RW. Chemical oxidation technologies: ultraviolet light/hydrogen
peroxide, Fenton's reagent, and titanium dioxide-assisted photocatalysis. Hazardous Waste &
Hazardous Materials 1993;10(2):107-149.
[13] Chen R, Pignatello J. Role of quinone intermediates as electron shuttles in Fenton oxidations
of aromatic compounds. Environmental Science Technologie 1997;31:2399-2406.
[14] Benitez FJ, Beltran-Heredia J, Acero JL, Rubio FJ. Contribution of free radicals to
chlorophenols
decomposition
by
several
advanced
oxidation
processes.
Chemosphere
2000;41:1271-1277.
[15] Feng J, Hu X, Yue PL, Zhu HY, Lu GQ. Discoloration and mineralization of Reactive Red
HE-3B by heterogeneous photo-Fenton reaction. Water Research 2003;37:3776-3784.
58
[16] Muruganandham M, Swaminathan M. Decolourisation of Reactive Orange 4 by Fenton and

photo-Fenton oxidation technology. Dyes and Pigments 2004;63:315-321.
[17] Safarzadeh-Amiri A, Bolton JR, Cater SR. Ferrioxalate-mediated photodegradation of organic
pollutants in contaminated water. Water Research. 1997;31:787798.
[18] Safarzadeh-Amiri A, Bolton JR, Cater SR. Ferrioxalate-mediated solar degradation of organic
contaminants in water. Solar Energy. 1996;56:439443.
[19] Nogueira RFP, Trov AG, Mod DF. Solar photodegradation of dichloroacetic acid and 2,4dichlorophenol using an enhanced photo-Fenton process. Chemosphere. 2002;48:385-391.
[20] Bauer R, Waldner G, Fallman H, Hager S, Klare M, Krutzler T. The photo-Fenton reaction
and the TiO2/UV process for wastewater treatment-novel developments. Catalysis Today.
1999;53:131-144.
[21] Selvam K, Muruganandham M, Swaminathan M. Enhanced heterogeneous ferrioxalate photoFenton degradation of reactive orange 4 by solar light. Solar Energy Materials & Solar Cells. 2005;
89: 61-74.
[22] Bigda RJ. Consider Fentons chemistry for wastewater treatment. Chem. Eng. Prog.
1995;91:62-66.
[23] Walling CH. Fentons reagent revisited. Acc. Chem. Res. 1975;8:125-131.
[24] Fernandez J, Bandara J, Lopez A, Buffar Ph, Kiwi J. Photo-assisted Fenton degradation of
nonbiodegradable azo dye (Orange II) in Fe-free solutions mediated by cation transfer membranes.
Langmuir 1999;15(1):185-192.
[25] Malik PK, Saha SK. Oxidation of direct dyes with hydrogen peroxide using ferrous
ion as catalyst. Separation and Purification Technology 2003;31:241-250.
59
Chapter 3 Degradation of a textile reactive azo dye by a combined chemical-biological process: Fentons reagent-yeast
CHAPTER 3 DEGRADATION OF A TEXTILE REACTIVE AZO DYE BY A

COMBINED CHEMICAL-BIOLOGICAL PROCESS:
FENTONS
REAGENT-
YEAST
Abstract
This work presents the results of our studies on the decolorization of aqueous azo dye
Reactive Black 5 (RB5) solution combining an Advanced Oxidation Process (Fentons
reagent) followed by an aerobic biological process (mediated by the yeast Candida
oleophila). Under our conditions, initial experiments showed that Fentons process alone,
as well as aerobic treatment by Candida oleophila alone, exhibited the capacity to
significantly decolorize azo dye solutions up to 200 mg/L, within about 1 and 24 hours
respectively. By contrast, neither Fentons reagent nor Candida oleophila sole treatments
showed acceptable decolorizing abilities for higher initial dye concentrations (300 and 500
mg/L). However, it was verified that Fentons reagent process lowered these higher azo
dye concentrations to a value less than 230 mg/L, which is apparently compatible with the
yeast action. Therefore, to decolorize higher concentrations of RB5 and to reduce process
costs the combination between the two processes was evaluated. The final decolorization
obtained with Fentons reagent process as primary treatment, at 1.0x10-3 mol/L H2O2 and
1.0x10-4 mol/L Fe2+, and growing yeast cells as a secondary treatment, achieves a color
removal of about 91% for an initial RB5 concentration of 500 mg/L.
* Adapted from: Lucas M.S., Peres J.A. Water Research. 2007, 41, 1103-1109.
61
3.1 Introduction
Textile wastewaters are strongly colored and contain high amounts of organic
matter depending on forms of dyes and auxiliary chemicals (Meri and Kaptan, 2004;
Muruganandham and Swaminathan, 2004). The traditional treatment techniques applied in
textile wastewaters, such as chemical coagulation/flocculation, membrane separation
(ultrafiltration, reverse osmosis) or activated carbon adsorption only does a phase transfer
of the pollutant. Moreover, conventional biological treatment such as activated sludge is
considered an unsatisfactory solution to these effluents due to the high content of dyestuffs,
surfactants and additives, which generally are organic compounds of complex structures,
that provokes resistance to biodegradation.
Among 20-30 different chemical or chromophore structure dye groups,
anthraquinone, phthalocyanine, triarylmethane and azo dyes are quantitatively the most
important groups. Azo dyes are synthetic organic compounds widely used in textile dyeing,
paper printing and other industrial processes such as the manufacture of pharmaceutical
drugs, toys and foods. Within the azo dyes wide types can by distinguished: acid, reactive,
disperse, vat, metal complex, mordant, direct, basic and sulphur dyes (van der Zee, 2002).
The reactive azo dyes are highly recalcitrant to conventional wastewater treatment
processes. In fact, as much as 90% of reactive dyes can remain unaffected after activated
sludge treatment (Pierce, 1994). Therefore, alternative methods should be implemented for
effective pollution abatement of dyed effluents.
Advanced Oxidation Processes offers a highly reactive non-specific oxidant called
hydroxyl radicals (HO), capable of destroying a wide range of organic pollutants in water
and wastewater (Legrini et al., 1993). Fenton's reagent is a homogeneous catalytic
oxidation process using a mixture of hydrogen peroxide and ferrous ions, in an acidic
environment resulting a complex redox reaction (Lipczynska-Kochany, 1991; Kuo, 1992;
Walling, 1998). The ferrous ion initiates and catalyses the decomposition of H2O2,
resulting in the generation of hydroxyl radicals, HO (Venkatadri and Peters, 1993; Chen
and Pignatello, 1997).
H2O2 + Fe
62
2+
Fe
3+
+ HO + HO
[3.1]
The Fentons reagent has the capacity to completely decolorize and partially
mineralize textile industry dyes in short reaction time, as reported by some studies
(Neamtu et al., 2001; Kang et al., 2002; Lucas and Peres, 2006). Also its capacity to
improve organic biodegradability of toxic or non-biodegradable wastewaters has been
described (Chamarro et al., 2001).
The biological treatment of wastewaters containing organic compounds, like azo
dyes, is not an easy process due to the refractory character of some of then. However, since
1990, several reports have clearly demonstrated the effectiveness of decolorization and
mineralization of dyes by white-rot basidiomycetous strains belonging to genera
Phanerochaete, Bjerkandera, Phlebia, Pleurotus, Pycnoporus and Trametes among others
(Cripps et al., 1990; Fu and Viraraghavan, 2001; Gill et al., 2002; Selvam et al., 2003;
Mximo et al., 2003). Fungal treatment of dyed effluents removes several chromoforic
groups and thus decreases its toxicity and esthetic impact in the receiving water bodies.
More recently it was observed that a few ascomycetous yeast species such as Candida
zeylanoides (Martins et al., 1999; Ramalho et al., 2002), Candida oleophila (Lucas et al.,
2006), Candida tropicalis, Debaryomyces polymorphus (Yang et al., 2003) and
Issatchenkia occidentalis (Ramalho et al., 2004) perform a putative enzymatic
biodegradation and concomitant decolorization of azo dyes. However, the difficulties and
even failures in biological plant operation at high azo dye concentrations, strongly suggest
the use of pre-chemical process (Scott and Ollis, 1995). Therefore, the Fentons reaction
was employed in the current work as a pre-treatment for further aerobic treatment with the
yeast C. oleophila of Reactive Black 5. This work is, to the best of our knowledge, the first
study that combines Fentons reagent, as a pre-treatment, with yeasts as a secondary
treatment.
3.2 Experimental
3.2.1
Reagents and microbiological media

The azo dye, Reactive Black 5 (CI 20505), was kindly provided by DyStar Anilinas
Texteis Lda (Portugal) and used without prior purification. Molecular structure and UVvisible absorption spectra of RB5 was previously illustrated in Figure 2.1. FeSO4.7H2O
was purchased from Panreac, H2O2 (Perhydrol, 30% w/w) from Merck and yeast malt
(YM) agar from Difco. Other chemicals and medium components were at least analytical
63
grade reagents. Solutions were prepared by dissolving dye in deionised Millipore type
water accordingly to desired final concentrations (w/v). pH was monitored in initial and
treated samples (Denver Instrument Company).
3.2.2
Fentons reagent experiments

Batch experiments for Fenton oxidation were performed in a cylindrical
borosilicate glass reactor of 800 mL capacity, with sampling ports at the top. The reaction
temperature was kept at the desired value within 0.5 C using a thermostatically
controlled outer water jacket. For every experiment performed, the reactor was initially
loaded with 500 mL of RB5 aqueous solution and continuous mixing was maintained by
means of a magnetic stirrer. In all experiments a necessary quantity of dye/Fe2+/H2O2
solution was freshly prepared from FeSO4.7H2O, H2O2 and dye stock solution.
Experiments were carried out, at an initial pH=5.0 because the non-buffered
solutions used in used in the Fentons reactions suffer a pH decrease during the reaction
time to a pH range around 3.0-4.0. The required amounts of Fe2+ and H2O2 were added
simultaneously into dye solution. Na2SO3 solution was used to quench the Fentons reagent
oxidation.
3.2.3
Yeast (Candida oleophila) experiments

Batch cultures for biodegradation experiments with C. oleophila were conducted in
minimal medium containing (per litre): 5.0 g glucose, 1.0 g (NH4)2SO4, 1.0 g KH2PO4, 0.5
g MgSO4.7H2O, 0.1 g yeast extract, 0.1 g CaCl2.2H2O and different dyestuff amounts (100,
200, 300, 500 mg/L final concentrations). The minimal medium, dyestuff solutions and the
effluent treated by Fentons reagent were autoclaved at 121C for 15 min, to assure that no
other microrganism than Candida oleophila it will be present in the solution. One mL of
yeast suspension prepared from a recent grown culture in the same medium without dye
and aseptically adjusted to an Abs640 = 1.0 was used to inoculate 250 mL Erlenmeyer
flasks containing 100 mL of medium. Incubations were carried out on an orbital shaker set
at 120 rpm and 26C. Abiotic controls (without yeast inoculation) were always included.
Samples were periodically collected for determination of color removal. In the combined
64
experiments - Fentons reagent and Candida oleophila - it was not necessary to adjust the
pH of the reaction mixture due to the effect of the culture medium added.
3.2.4
Other analytical procedures

Both absorbance readings at visible maximum peak (595 nm) and UV-Vis spectrum
between
200-800
nm
were
performed
using
Jasco
V-530
double-beam
spectrophotometer. All values and data points presented are the means of at least three
independent assays unless otherwise stated. The observed standard deviation of
experimental data was always less than 6% of the reported value. The concentration of
residual dye in solution was calculated by Beer-Lambert law, after dilution when
necessary, using the optical density and the molar extinction coefficient observed at the
characteristic wavelength (max = 595 nm) and expressed as:
Dye decolorization = (1 - Cdye,t/Cdye,0) x 100%
[3.2]
where Cdye,t and Cdye,0 are the concentration of dye at reaction time t and 0, respectively.
3.3 Results and Discussion
3.3.1
Reactive Black 5 decolorization with Fentons reagent
The Fentons reagent decolorization capacity at different RB5 concentrations was

evaluated since pollutant concentration is an important parameter in wastewater treatment.
The concentrations used in this study were 100, 200, 300 and 500 mg/L. For this purpose it
was selected the hydrogen peroxide concentration of 1.5x103 mol/L and the ferrous iron
concentration of 1.5x10-4 mol/L for above-mentioned RB5 concentrations. The initial
molar ratio between hydrogen peroxide and ferrous iron was maintained at 10:1 during this
work in Fentons reagent process (Lucas and Peres, 2006). In Figure 3.1 it is possible to
observe that the extent of RB5 decolorization decreases with increasing initial dye
concentrations. For a reaction time of 60 minutes, Fentons decolorization capacity
decreases from 98.0% to 62.6% when dye concentration varied from 100 and 500 mg/L.
65
Dye Concentration:
100
-4
Remaining RB5 (%)
5.0x10 mol/L
80
-4
3.0x10 mol/L
-4
2.0x10 mol/L
60
-4
1.0x10 mol/L
40
20
0
0
10
20
30
40
50
60
Time (min)
Figure 3.1 Effect of RB5 concentration on decolorization by Fentons reagent process.
Experimental conditions: [Fe2+] = 1.5x10-4 mol/L; [H2O2] = 1.5x103 mol/L; Temperature = 20C;
pH = 5.0.
Under these hydrogen peroxide and ferrous iron dosages, Fentons reagent was
unable to completely decolorize RB5 solutions at initial concentrations of 300 and 500
mg/L.
3.3.2
Reactive Black 5 decolorization with Candida oleophila

Almost full decolorization (95-100%) was observed in batch cultures of C.
oleophila yeast cells containing RB5 up to 200 mg/L (Figure 3.2). It is worth noting that C.
oleophila achieves this performance within 20-24h in the presence of lower glucose
concentration (0.5% w/v) and without visible signs of dyestuff adsorption to yeast cells.
Since higher initial dye concentrations (300 and 500 mg/L) exhibited low decolorization
yields and yeast biomass growth was not significantly affected, an apparent dye inhibition
should have occurred as previously observed (Lucas et al., 2006). Furthermore yeast cells
remain colored, a phenomenon not observed with batch cultures containing initial dye
concentrations up to 200 mg/L.
66
RB5 Concentration (%)
100
80
60
40
20
0
0
10
20
30
40
50
60
Time (Hour)
Figure 3.2 Time course decolorization of RB5 at 100 mg/L (), 200 mg/L (), 300 mg/L ()
and 500 mg/L () initial concentrations in batch cultures of Candida oleophila.
3.3.3
Kinetic analysis
A comparative kinetic study was carried out for the chemical process with Fentons
reagent and for the biological process with C. oleophila cells. Initial decolorization rate
constants (k) were determined, for both processes, from the slope of -ln(C/C0) vs t (time)
plots where C0 and C are dye concentration at time zero and at time t, respectively. It is
also presented the half-life times (t1/2), i.e. the time necessary to reduce 50% of initial RB5
concentration for each process. The half-life times are determined by interpolation from
experimental data.
3.3.4
Fentons reagent process

In all experiments with Fentons reagent the disappearance of dye color during the
first two minutes of oxidation (Peres et al., 2004), using the initial-rate method, could be
described as a first-order reaction kinetics (Table 3.1).
67
Table 3.1 First-order rate constant (k), R2 values and half-life (t1/2) of RB5 decolorization by Fentons
reagent.
RB5 Concentration
k (min-1)
R2
t1/2 (min)
500 mg/L
0.135
0.996
21.2
300 mg/L
0.208
0.991
5.82
200 mg/L
0.558
0.987
0.52
100 mg/L
1.225
0.978
0.20
As it can be seen in Figure 3.1 and comparing k values and t1/2 presented in Table
3.1, Fentons process shows a better decolorization capacity, within these experimental
conditions, at low RB5 concentrations. The rate constant (k) for a RB5 concentration of
100 mg/L is approximately double in respect to the concentration of 200 mg/L, and 10
times higher than the RB5 concentration of 500 mg/L. The half-life time (t1/2) is one
hundred times higher for a concentration of 500 mg/L than to the concentration of 100
mg/L.
3.3.5
Candida oleophila process

The aerobic biological treatment with C. oleophila shows, as expected, minor
apparent first-order rate constants on RB5 decolorization (Table 3.2). On the contrary to
Fentons reagent, that can remove a significant amount of color only in few minutes,
decolorization in the presence of growing C. oleophila yeast cells occurs in hours. For this
biological process, after a lag phase period of 12 hours, were calculated the first-order rate
constants k that are less influenced by initial dye concentration than the chemical process.
For instance, to an initial dye concentration of 500 mg/L, the k value obtained is only three
times smaller than at an initial concentration of 100 mg/L.
68
Table 3.2 First-order rate constant (k), R2 values and half-life (t1/2) of RB5 decolorization by C. oleophila.
RB5 Concentration
k (h-1)
R2
t1/2 (h)
500 mg/L
0.005
0.968
ND
300 mg/L
0.009
0.931
ND
200 mg/L
0.014
0.918
16.3
100 mg/L
0.016
0.926
15.0
ND not determined
3.3.6
Optimization of Reactive Black 5 decolorization by Fentons reagent

From the results of Figure 3.1, it is observed that for RB5 concentrations above 200
mg/L the Fentons reagent is not efficient on decolorization. This happens due to the
influence of experimental conditions on the oxidation efficiency of Fenton process (Kang
and Hwang, 2000). Therefore, it was necessary to find the ferrous iron and the hydrogen
peroxide concentrations that efficiently decolorize high concentrations of RB5. In Figure
3.3 it is represented the RB5 color removal with an initial concentration of 500 mg/L to
evaluate the decolorization capacity of Fentons reagent using different dosage of
hydrogen peroxide and ferrous iron in a proportional molar ratio of 10:1. Between 1.0x10-3
and 7.0x10-3 mol/L of hydrogen peroxide were applied to find the optimal oxidant dosage.
For a hydrogen peroxide concentration of 1.0x10-3 mol/L a RB5 color removal of 54.4%
was achieved, however, increasing the peroxide dosage until 5.0x10-3 mol/L a higher
decolorization was reached (93.7%). An increase up to 7.0x10-3 mol/L does not
significantly improve the decolorization reaching the value of 94.7%. So, trough the
augment of hydrogen peroxide and ferrous iron dosages it is possible to decolorize higher
RB5 concentrations. However, the increase on dye decolorization leads to a more
expensive treatment cost particularly due to the enhancement in hydrogen peroxide
concentration. Therefore, to decrease the operational costs of Fentons reagent, its
combination with other processes must be evaluated.
69
H2O2 Concentration:
100
-3
7.0x10 mol/L
RB5 Concentration (%)
-3
5.0x10 mol/L
80
-3
3.0x10 mol/L
-3
2.0x10 mol/L
60
-3
1.0x10 mol/L
40
20
0
0
10
20
30
40
50
60
Time (min)
Figure 3.3 RB5 decolorization by Fentons reagent oxidation at different H2O2 concentrations.
Experimental conditions: [RB5] = 500 mg/L; Temperature = 20C; pH = 5.0.
Analysing these results in other perspective, Figure 3.3 presents also the remaining
concentration of Reactive Black 5 after the Fentons reagent. It was verified that for a
hydrogen peroxide concentration of 1.0x10-3 mol/L the RB5 remaining is about 228 mg/L
while for a hydrogen peroxide concentration of 7.0x10-3 mol/L it is about 24 mg/L. From
these results it should be underlined the fact that the remaining RB5 after a hydrogen
peroxide concentration of 1.0x10-3 mol/L probably is acceptable for Candida oleophila
treatment, once the Fenton-treated final effluent has a value next to 200 mg/L of RB5. For
all Fenton-treated final effluent, except for the hydrogen peroxide concentration of 3.0 and
7.0x10-3 mol/L, it was evaluated the benefit of applying C. oleophila as secondary
treatment.
The next step of this work was the study of the capacity of combining Fentons
reagent process and the yeast C. olephila to efficiently decolorize the RB5 dye at a high
concentration of 500 mg/L.
3.3.7
Combining Fentons reagent and Candida oleophila on RB5 decolorization

The major purpose of this integrated process was to reduce the operational costs,
particularly the hydrogen peroxide concentration used in Fentons reagent, to decolorize a
70
RB5 concentration of 500 mg/L. Theoretically, experiments with C. oleophila used as

primary treatment should be performed. However, as seen in Figure 3.2, for a RB5
concentration of 500 mg/L, C. oleophilas decolorization capacity has no significance due
to the high reaction time and irrelevant decolorization obtained. Therefore, the study was
conducted to evaluate the efficiency of Fentons reagent as pre-treatment during 60
minutes, performed at different hydrogen peroxide dosages. After that, each Fenton-treated
effluent was inoculated with 1 mL of C. oleophila suspension (Abs640 = 1.0) to remove the
remaining concentration of RB5. From Figure 3.4 it is seen that combining Fentons
reagent and C. oleophila yeast, a total color removal of 91% and 95% was achieved for an
initial hydrogen peroxide concentration of 1.0x10-3 and 2.0x10-3 mol/L, respectively.
100
A
B
C
RB5 Removal (%)
80
60
40
20
0
0
Time (Days)
Figure 3.4 Decolorization of a RB5 solution at 500 mg/L with a combined process; a) Fentons
reagent (1 hour shaded portion of the graph); b) Candida oleophila (7 days). Experimental
conditions in Fentons reagent: (A) = 5.0x10-3 mol/L H2O2; (B) = 2.0x10-3 mol/L H2O2; (C) =
1.0x10-3 mol/L H2O2. In all experiments molar ratio H2O2:Fe2+ = 10:1.
At an initial hydrogen peroxide concentration of 5.0x10-3 mol/L, remaining RB5

after Fentons reagent was too low (5%). Despite this Fenton-treated effluent exhibit a
putative high oxidative power, growth of C. oleophila yeast cells was not inhibited. Since
optimal hydrogen peroxide concentration could be selected and according to operational
costs, an effective RB5 color removal can be reached combining an AOP (Fentons
reagent) and aerobic biological treatment (C. oleophila). Accordingly with other works
(Chamarro et al., 2001), this study showed that Fentons reagent is an efficient process to
71
improve organic chemical biodegradability. Moreover, it should be pointed out that

doubling the initial hydrogen peroxide concentration only a minor impact was obtained in
the final dye decolorization (from 91% to 95%). Thus, the goal it is not the complete
decolorization of the azo dye in the chemical process, but the generation of a new
biocompatible effluent.
3.4 Conclusions
Esthetic and ecological impacts on water bodies arising from colored effluents face
increasingly restrictive policies of environmental protection around the world. Therefore,
measures should rapidly be adopted to stop this environmental aggression. This work
presents an alternative option to decolorize dyed textile effluents, through the sequential
use of an Advanced Oxidation Process (Fentons reagent) followed by an aerobic
biological process (yeast C. oleophila). Under our experimental conditions, a good
treatment could be purposed as follows: Fentons reagent using 1.0x10-3 mol/L H2O2,
1.0x10-4 mol/L Fe2+ at 20 C and pH 5.0, as primary treatment and then inoculation with
growing yeast cells as a secondary treatment. This combined process allows removing
about 91% of color for an initial RB5 concentration of 500 mg/L. It should be pointed out
that Fentons reagent alone requires 5 times more H2O2 and Fe2+ to achieve an identical
level of color removal.
References
Chamarro, E., Marco, A., Esplugas, S., 2001. Use of Fenton reagent to improve organic chemical
biodegradability. Water Res. 35, 1047-1051.
Chen, R., Pignatello, J., 1997. Role of quinone intermediates as electron shuttles in Fenton
oxidations of aromatic compounds. Environ. Sci. Technol. 31, 2399-2406.
Cripps, C., Bumpus, J.A., Aust, S.D., 1990. Biodegradation of azo and heterocyclic dyes by
Phanerochaete chrysosporium. Appl. Environ. Microbiol. 56, 1114-1118.
Fu, Y., Viraraghavan, T., 2001. Fungal decolorization of dye wastewaters: a review. Bioresource
Technol. 79, 251-262.
72
Gill, P.K., Arora, D.S., Chander, M., 2002. Biodecolorization of azo and triphenylmethane dyes by
Dichomitus squalens and Phlebia spp. J. Ind. Microbiol. Biotechnol. 28, 201-203.
Kang, S.F., Liao, C.H., Chen M.C., 2002. Pre-oxidation and coagulation of textile wastewater by
the Fenton process. Chemosphere 46, 923-928.
Kang, Y. W., Hwang, K-Y., 2000. Effects of reaction conditions on the oxidation efficiency in the
Fenton process. Water Res. 34,2786-2790.
Kuo, W.G., 1992. Decolorizing dye wastewater with Fenton's reagent. Water Res. 26, 881-886.
Legrini, O., Oliveros, E., Braun, A.M., 1993. Photochemical processes for water treatment.
Chemical Review. Chem. Rev. 93, 671-698.
Lipczynska-Kochany, E., 1991. Degradation of aqueous nitrophenols and nitrobenzene by means
of the Fenton reaction. Chemosphere. 22, 529-536.
Lucas, M.S., Amaral, C., Sampaio, A., Peres, J.A., Dias. A.A., 2006. Biodegradation of the diazo
dye Reactive Black 5 by a wild isolate of Candida oleophila. Enzyme Microb. Technol. 39,
51-55
Lucas, M.S., Peres, J.A., 2006. Decolorization of the azo dye Reactive Black 5 by Fenton and
photo-Fenton oxidation. Dyes Pigments. 71, 235-243.
Martins, M.A.M., Cardoso, M.H., Queiroz, M.J., Ramalho, M.T., Campos, A.M.O., 1999.
Biodegradation of azo dyes by the yeast Candida zeylanoides in batch aerated cultures.
Chemosphere 38, 2455-2460.
Mximo, C., Amorim, M.T.P., Costa-Ferreira, M., 2003. Biotransformation of industrial reactive
azo dyes by Geotrichum sp. CCMI 1019. Enzyme Microb. Technol. 32, 145-151.
Meri, S., Kaptan, D., lmez, T., 2004. Color and COD removal from wastewater containing
Reactive Black 5 using Fentons oxidation process. Chemosphere. 54, 435-441.
Muruganandham, M., Swaminathan, M., 2004. Decolourisation of Reactive Orange 4 by Fenton
and photo-Fenton oxidation technology. Dyes Pigments. 63, 315-321.
Neamtu, M., Yediler, A., Siminiceanu, I., Kettrup, A., J. 2001. Oxidation of commercial reactive
azo dye aqueous solutions by the photo-Fenton and Fenton-like processes. Photochem.
Photobiol A: Chem. 141, 247-254.
73
Pierce, J., 1994. Colour in textile effluents the origins of the problem. J. Soc. Dyers Colourists
110, 131134.
Peres, J.A., Carvalho, L., Boaventura, R., Costa, C., 2004. Characteristics of p-hydroxybenzoic
acid oxidation using Fentons reagent. J. Environ. Sci. Health A 39, 1-17.
Ramalho, P.A., Cardoso, M.H., Cavaco-Paulo, A., Ramalho M.T., 2004. Characterization of azo
reduction activity in a novel ascomycete yeast strain. Appl. Environ. Microbiol. 70, 22792288.
Ramalho, P.A., Scholze, H., Cardoso, M.H., Ramalho, M.T., Campos. A.M.O., 2002. Improved
conditions for the aerobic reductive decolourisation of azo dyes by Candida zeylanoides.
Enzyme Microb. Technol. 31, 848-854.
Scott, J., Ollis, D., 1995. Integration of chemical and biological oxidation processes for water
treatment: review and recommendations. Environ. Progr. 14, 88-103.
Selvam, K., Swaminathan, K., Chae, K-S., 2003. Microbial decolorization of azo dyes and dye
industry effluent by Fomes lividus. World J. Microbiol. Biotechnol. 19, 591-593.
van der Zee, F.P., 2002. Anaerobic azo dye reduction. Doctoral Thesis. Wageningen University.
The Netherlands.
Venkatadri, R., Peters, R.W., 1993. Chemical oxidation technologies: ultraviolet light/hydrogen
peroxide, Fenton's reagent, and titanium dioxide-assisted photocatalysis. Haz. Waste Haz.
Mater. 10, 107-149.
Walling, C., 1998. Intermediates in the reactions of Fenton type reagents. Acc. Chem. Res. 31, 155157.
Yang, Q., Yang, M., Pritsch, K., Yediler, A., Hagn, A., Schloter, M., Kettrup, A., 2003.
Decolorization of synthetic dyes and production of manganese-dependent peroxidase by new
fungal isolates. Biotechnol. Lett. 25, 709-713.
74
Chapter 4 Gallic acid photochemical oxidation as a model compound of winery wastewater
CHAPTER 4 GALLIC ACID PHOTOCHEMICAL OXIDATION AS A MODEL

*
COMPOUND OF WINERY WASTEWATER
Abstract
Winery wastewaters (WW) are characterized by their high organic load and by the
presence of non-biodegradable compounds such as phenolic compounds. This study was
undertaken to evaluate the capacity of different Advanced Oxidation Processes (AOP)
combined with several radiation sources to degrade the phenolic compound Gallic Acid
(GA). A toxicological assessment was also carried out to evaluate the subproducts
harmful effect generated during the most efficient AOP in the GA photoxidation. Through
the course of the study it was verified that the UV radiation lamp TNN 15/32 showed the
capacity to degrade 34.7% of GA, the UV radiation lamp TQ 150 achieved a value of
20.2% and the solar radiation presented only a value of 2.3% in 60 minutes. The
combination of different advanced oxidation processes (Fentons reagent, ferrioxalate and
heterogeneous photocatalysis) were evaluated with the previously studied sources of
radiation. From the experiments conducted it was possible to suggest that the AOP in
combination with Fe2+ + H2O2 + UV TNN 15/32 (photo-Fenton process) was the most
efficient process thereby achieving the GA degradation value of 95.6% in 7.5 minutes and
resulting in a total elimination of toxicity.
* Adapted from: Lucas M.S., Dias A.A., Bezerra R.M., Peres J.A. Journal of Environmental Science and
Health, Part A. 2008, 43, 1288-1295.
75
4.1 Introduction
Wine production processes generate different kinds of pollution mostly associated
with solid wastes and liquid effluents. Wastewater from the wine-producing, named as
winery wastewaters, mainly originate from various washing operations during the crushing
and pressing of grapes, as well as during the rinsing of fermentation tanks, barrels, bottles
and other equipments or surfaces.[1-4] The volumes and pollution loads significantly vary in
relation to the working period (vintage, racking, bottling) and to the winemaking
technologies used (e.g. in the production of red, white and special wines).[5] It is estimated
that a cellar produces around 1.3 - 1.5 kg of residues per liter of wine produced, 75% of
which are winery wastewaters.[6] These wastewaters are characterized for being rich in
organic substances (polyphenols, organic acids, sugars), high COD values (3-30 g O2/L),
and a remarkable recalcitrant character due to the presence of phenolic compounds.
Various natural phenols and their condensation products, such as tannins or lignins, are
present in several types of agro-industrial wastes. Gallic acid is a common polyphenol
present in several agro-wastewaters, like olive oil factories, boiling cork and wine
processing industries, and can be also considered as one of the simplest models of natural
organic matter.[7,8]
Several physical and chemical processes are available to winery wastewater
treatment but its major action is a phase transfer of pollutants. Biological waste treatment
methods have been recognized as a possible way for a significant degradation of
wastewater with high organic content, such as those coming from wineries in particular.
However, the presence of toxic compounds for the microorganisms together with the high
operational costs and large quantities of waste sludge generated reduces the treatment
usability.[7,9]
Advanced Oxidation Processes (AOP) offer a highly reactive, non-specific oxidant,
namely hydroxyl radicals (HO), capable of destroying a wide range of organic pollutants
in water and wastewater.[10-13] Fenton's reagent oxidation is a homogeneous catalytic AOP
using a mixture of ferrous salts and hydrogen peroxide.[14-16] The overall reaction is:
Fe
76
2+
+ H2O2 Fe
3+
+ HO + HO
(4.1)
generation of hydroxyl radicals, HO.[17,18] Adding UV radiation to Fentons reagent
process, creating a photo-Fenton process, could be an interesting allied in the wastewater
treatment due to its capacity in influencing direct formation of HO radicals.[19-21] In
photo-Fenton process, in addition to the Equation 1, the formation of hydroxyl radical also
occurs by the following reactions (Equations 4.2 and 4.3):
H2O2 + UV HO + HO
Fe
3+
+ H2O + UV Fe2+ + HO + H+
(4.2)
(4.3)
Ferrioxalate, used for decades as a chemical actinometer, has also been applied in
the Fentons reagent process as iron source allowing further benefit mediated by ultraviolet
radiation.[22] The photolysis of ferrioxalate generates Fe2+ in acidic solution reported as
following:[23-26]
[Fe(C2O4)3]3- + h Fe2+ + 2C2O42- + C2O4-
(4.4)
C2O4- + [Fe(C2O4)3]3- Fe2+ + 3C2O42- + 2CO2
(4.5)
C2O4- + O2 O2- + 2CO2
(4.6)
Heterogeneous photocatalysis is a technology based on the irradiation of a catalyst,

usually a semiconductor (e.g. TiO2), which can be photoexcited to form electron-donor
sites (reducing sites) and electron-acceptor sites (oxidising sites), providing great scope as
redox agents. In the interfacial region between the excited solid particle and the solution,
destruction or removal of contaminants takes place, with no chemical change in the
catalyst.
Hence, the main objective of this study is to evaluate the performance of Advanced
Oxidation Processes, specifically the processes Fentons reagent, ferrioxalate and
heterogeneous photocatalysis (TiO2) combined with different UV radiation sources, in the
degradation of one of the most representative phenolic compounds present in the winery
wastewaters: gallic acid. Finally, a toxicological assessment carried out with the marine
bacteria Vibrio fischeri was also realized to evaluate the influence of each AOP studied in
the gallic acid detoxification.
77
4.2 Materials and methods

4.2.1
Chemicals
The phenolic compound, Gallic Acid (GA) analytical grade, was provided by
Sigma and used as received without further purification. Molecular formula, molecular
structure and molar weight of GA are illustrated in Table 4.1.
Table 4.1. Molecular formula, molecular structure and molar weight of gallic acid.
Molecular Formula
Molecular Structure
Molar weight
(g/mol)
COOH
C6H2(OH)3COOH
170.0
HO
OH
OH
3,4,5-trihydroxybenzoic acid
Other chemicals used in the experiments, FeCl3 (Riedel-de-Han), C2H2O4 (Fluka),

TiO2 (Degussa P-25), FeSO4.7H2O (Panreac), H2O2 (Merck, Perhydrol, 30% w/w) were
applied as reagent grade. All the solutions were daily prepared in ultra-pure water from a
Millipore purification system. The pH of the solution was monitored using a Basic pH
Meter from Denver Instrument Company. In the experiments with heterogeneous
photocatalysis the TiO2 was separated by centrifugation and filtration (through 0.2 m
membrane filters) before analysis of gallic acid.
4.2.2
Experiments and analysis

Batch experiments with solar radiation were realized at the campus of UTAD -
University of Trs-os-Montes and Alto Douro (4118' N; 745' W) in days of clear sky,
between May and August (11 AM and 3 PM), in a 1000 mL reactor. The solar radiation
intensity was monitored in intervals of 5 minutes using a radiometer Macam Q102 PAR
(400-1000 nm). The average light intensity over the duration of each experiment was
calculated.
78
In the processes with ultraviolet lamps as source of radiation, a UV Heraeus

photoreactor was used equipped with a low-pressure mercury vapor lamp (Heraeus TNN
15/32); and the other UV experiments were conducted with a medium-pressure mercury
lamp (Heraeus TQ 150). The concentration of hydrogen peroxide was measured by the
iodometric method. Hydrogen peroxide present in the samples from the AOP experiment
was removed using catalase (2500 U/mg; 100 mg/L) acquired from Sigma. Experiments
were conducted in the absence of any buffer solution.
Samples of gallic acid solution were withdrawn during the course of the reaction, at
periodic intervals, and analyzed by high performance liquid chromatography (HPLC)
carried out on a Gilson system (two pumps, dynamic mixer and UV/VIS detector) fitted
with a column EC Nucleosil 120-5 C18 (Macherey-Nagel). The HPLC analysis was
performed in a gradient mode with two solutions, solution A: water, methanol, acetic acid
(88:10:2 v/v) and solution B: water, methanol (70:30 v/v). The elution flow rate was
1 mL/min and the injection volume was 20 L in all samples. Detection of gallic acid was
done at 260 nm with a retention time of 5.8 minutes.
Toxicity assessment was performed using a commercial assay marketed: the
luminometer Aboatox 1253 and the Biotox kit. The biological agent is a freeze-dried
preparation of the marine bacterium Vibrio fischeri (formerly known as Photobacterium
phosphoreum, NRRL number B-11177). To monitor the inhibition of the bacterial
luminescence, different samples of gallic acid, made with a specially prepared non-toxic
2% sodium chloride solution, were mixed with the bacterial suspension, to provide optimal
living conditions for the marine test organism. The light emission was measured after a
contact period of 15 min at 15 C. Hydrogen peroxide present in the samples was removed
prior to toxicity analysis using catalase (2500 U/mg; 100 mg/L). All the samples were
analysed after adjusting the pH to 7. Careful control of temperature was essential because
light emission is sensitive to temperature. For example, for P. phosphoreum the light
intensity changes about 10% for every C variation in temperature. The inhibition effect of
the samples was compared with a toxicant-free control to obtain the percent of inhibition
(INH %) determined as described in the following formula:
% INH = {1- (T15/T0)/(C15/C0)} x 100
(4.7)
79
where T0 = light in sample vial at 0 minutes; T15 = light in sample vial at 15 minutes; C0 =
light in control vial at 0 minutes and C15 = light in control vial at 15 minutes. All the
experiments were carried out in duplicate and average values are presented.
4.2.3
TiO2 characterization
Titanium dioxide (TiO2 Degussa P25) was characterized by X-ray diffraction
(XRD) in order to have a better knowledge of the material used in this study. XRD
measurements were performed at room temperature with a PW 3040/60 XPert Pro
diffractometer system, using CuK radiation ( = 1.54 A) and Bragg-Bentano /2
geometry. The system includes the ultra-fast XCelerator detector PW3015/20 and a
secondary monochromator. The measurements were performed over the 2 range of 10100. An acquisition step of 0.017 was used with an acquisition time of 100 s/step. Phase
quantification and particle size determination were performed using Rietveld refinements
PowderCell 2.4 software[27]. It is verified that the TiO2 used shows, in volume, 87% of
anatase and 13% of rutile phase with a particle size 40 nm and 70 nm, respectively.
4.3 Results and discussion
4.3.1
Gallic acid photoxidation

The present study aimed to evaluate the capacity of different AOP in the
degradation of the gallic acid. The action of each process was increased using different
sources of radiation - solar light and ultraviolet radiation (Heraeus UV lamps 15/32 TNN
and TQ 150). Figure 4.1 shows the individual performances of the different sources of
radiation in the decrease of gallic acid concentration as a function of irradiation time. It is
possible to verify that, after 60 minutes of irradiation, the UV lamp TNN 15/32 shows the
capacity to degrade 34.7% of gallic acid, a superior value in relation to the UV lamp TQ
150 (20.2%) and highly superior one to the solar radiation (2.3%). This different
degradation capacity of the studied phenolic compound can be justified by the different
characteristics of each source of radiation. The UV lamp 15/32 is classified as a
monochromatic lamp and the UV lamp TQ 150 as a polychromatic lamp.
80
GA Concentration (%)
100
80
60
Solar Radiation
UV TQ 150
UV TNN 15/32
40
20
0
0
10
20
30
40
50
60
Time (min)
Figure 4.1. Gallic acid degradation in aqueous solution by different sources of radiation: solar and
ultraviolet radiation (Heraeus lamps TNN 15/32 and TQ 150). Experimental conditions: [GA]0 =
5.3x10-4 mol/L; Solar intensity (sunny day) = 545 Wm-2; Initial pH 4.0.
Therefore, it can be stated that the gallic acid photodegradation is more efficiently
achieved with the UV lamp TNN 15/32 since the main emission wavelength of this lamp
(253.7 nm) is very close to the main absorption wavelength of the phenolic acid (260 nm).
On the other side, the UV lamp TQ 150 presents large emission spectra from the ultraviolet
to the infrared wavelengths, being minor the effect in the gallic acid photodecomposition.
The gallic acid (GA) oxidation values obtained by solar light radiation are almost
insignificant, comparatively to the action of UV lamps. This probably occurs due to the
great dispersion/diffusion of the solar radiation, as well as to the fact that the solar UV
radiation that really acts in the gallic acid photodegradation constitutes only a value among
3.5-8% of the global solar radiation.[28]
The curves of GA concentration versus reaction time in these photoxidation
experiments suggest that the decomposition follow pseudo-first-order reaction kinetics.
Hence, the reaction rate could be determined by the integrated first order kinetics
expression:
ln [GA]0/[GA] = kPt
(4.8)
81
where [GA]0 and [GA] represent, respectively, the gallic acid concentration at time 0 and
time t; and kP the pseudo-first order rate constant. Therefore, according to Equation 4.8, a
plot of ln [GA]0/[GA] versus time should provide straight lines, and after linear regression
analysis, the kP values listed in Table 4.2 are deduced.
Table 4.2. Gallic acid photoxidation: conversions at 15 and 60 minutes and pseudo-first-order rate constant
(kP) using different sources of radiation.
X15 (%)
X60 (%)
kP x 10-3 (min-1)
R2
Solar radiation
0.88
2.30
0.40
0.981
UV TQ 150
6.57
20.2
3.9
0.987
UV TNN 15/32
13.3
34.7
7.7
0.984
Experiment
The determination coefficients are all greater than 0.98 which reinforce the trend
described above for the decomposition rate with the irradiation time. Table 4.2 also
summarises the conversions obtained at two selected reaction times, 15 and 60 min (X15
and X60, respectively). From the presented table it is possible to verify that solar radiation,
even after 60 minutes of reaction time, does not have significant influence on the gallic
acid photoxidation; as revealed by the kP value (0.40x10-3 min-1). The UV lamps show
significant changes along the oxidation reaction. At 15 and 60 minutes the UV lamp TNN
15/32 and the UV lamp TQ 150 present significant oxidation increase, from 6.57 to 20.2%
and 13.3 to 34.7%, respectively. The values of the constant rate kP highlights the high
oxidation capacity of these two lamps comparatively to the solar radiation; with special
attention to the UV lamp TNN 15/32 (7.7x10-3 min-1).
However, gallic acid photodegradation with UV radiation is a slow process and
must be followed by another AOP.[29] Hence, the work was conducted to combine different
UV radiation sources with several AOP processes such as hydrogen peroxide, Fentons
reagent, ferrioxalate and heterogeneous photocatalysis with TiO2.
4.3.2
Influence of H2O2 on gallic acid photoxidation

Hydrogen peroxide (H2O2) was added to the experiments presented in Figure 4.1 to
evaluate the combined action of this strong oxidant agent (1.78 V) with the different
82
sources of UV radiation. From the results presented in Figure 4.2 it is possible to see that
H2O2, de per si, and H2O2 plus solar radiation, can not significantly oxidise the phenolic
compound GA, achieving degradation values of 1.5% and 2.6%, respectively, after 60
minutes. However, the combination of hydrogen peroxide with the UV radiation lamps
TNN 15/32 and TQ 150 highly increases the gallic acid oxidation. The results obtained
were: to the UV lamp TQ 150 of 42.2% and to the UV lamp TNN 15/32 of 57.0%. These
values clearly demonstrate the positive influence of this combined system UV + H2O2 in
comparison to the single photodegradation process.
100
80
60
40
H2O2
H2O2+Solar Radiation
H2O2+UV TQ 150
H2O2+UV TNN 15/32
20
0
0
10
20
30
40
50
60
Time (min)
Figure 4.2. Gallic acid degradation in aqueous solution by different sources of radiation: solar and
ultraviolet radiation (Heraeus lamps TNN 15/32 and TQ 150) combined with hydrogen peroxide.
Experimental conditions: [GA]0 = 5.3x10-4 mol/L; [H2O2] = 2.7x10-3 mol/L; Solar intensity (sunny
day) = 545 Wm-2; Initial pH 4.0.
The combination of UV radiation with the H2O2 promotes the photolysis of this
oxidant agent generating two hydroxyl radicals (HO) for each H2O2 molecule (Equation
2). The hydroxyl radicals produced show a high oxidant potential (2.80 V) higher than
hydrogen peroxide increasing therefore the oxidation power of the UV lamps.[30] The
global oxidation of the gallic acid results from the combination of two phases: on the one
hand the direct photodegradation of the phenolic compound trough the UV radiation and,
on the other hand, with the hydroxyl radical reaction generated during the hydrogen
peroxide photolysis. The results obtained at this assay are directly related to the obtained in
83
the Figure 4.1. The major degradation capacity of the UV lamp TNN 15/32 also remains
even when combined with the H2O2.
The increased degradation by the combination of UV radiation and H2O2 are
confirmed through the evaluation of the pseudo-first order rate constants kT for this process
presented in Table 4.3. The kT value for Solar Radiation + H2O2 (0.4x10-3 min-1) is only
slightly higher comparatively to that obtained with H2O2 alone (0.3x10-3 min-1) and equal
to that achieved for the solar radiation alone. Thus, addition of hydrogen peroxide can not
increase the oxidation capacity of the solar radiation alone. This can be explained by the
low capacity of the solar radiation to promote the photolysis of the hydrogen peroxide and
therefore with no generation of hydroxyl radicals.
In the processes with the UV lamps TQ 150 and TNN 15/32 their combination with
H2O2 significantly increases the gallic acid oxidation. Hydrogen peroxide photolysis
induced by UV lamps is considerably superior to the solar radiation and different among
them; achieving kT values of 9.6x10-3 to the UV lamp TQ 150 and 14.5x10-3 to the UV
lamp TNN 15/32. These results reveal that gallic acid decay is improved in relation to the
single photodegradation by the HO generated trough the presence of H2O2.
Therefore, in this combined photoxidation, it is possible to evaluate the contribution of the
two main oxidation effects to the global degradation rate. The global reaction rate is the
accumulation of the rate corresponding to the direct photolysis (kP) and to the radical
reaction (kR). In Table 4.3 are presented the rate constants of the UV/H2O2 process (kT) and
of the radical reaction (kR).
Table 4.3. Gallic acid oxidation through the combination of different sources of radiation and hydrogen
peroxide: conversions at 15 and 60 minutes and pseudo-first-order rate constants (kT and kR).
X15 (%)
X60 (%)
kT x 10-3 (min-1)
R2
kR x 10-3 (min-1)
H2O2
0.20
1.46
0.30
0.983
Solar Rad. + H2O2
1.2
2.60
0.40
0.986
UV TQ 150 + H2O2
14
42.2
9.6
0.992
5.7
19.5
57.0
14.5
0.996
6.8
Experiment
UV TNN 15/32 + H2O2
84
The kr value was calculated taking into account that the global photodecomposition rate rT
can be expressed as the addition of the direct rP and radical rR reaction rates as previously
reported:[31]
- rT = [- dCGA/dt] = - (rP + rR) = (kP + kR) CGA = kTCGA
(4.9)
The rate constants for the radical reaction kR are deduced through the subtraction of the
determined kP from kT. Comparing kP (Table 4.2) and kR (Table 4.3) values it is visible that
the direct photolysis provides a minor contribution to the overall reaction in the experiment
with the lamp UV TQ 150. However, the contribution of direct photolysis is higher than
the radical reaction in the experiment with the lamp UV TNN 15/32.
4.3.3
Influence of Fentons processes on gallic acid photoxidation

Figure 4.3 presents the results of the assays of gallic acid degradation in aqueous
solution with Fentons reagent and its combination with several sources of radiation
(homogeneous photocatalysis). According to our results, all photo-Fenton processes
present a similar degradation capacity which is superior to the Fentons process carried out
in dark conditions (Equation 4.1). Although the small differences between the three photoFenton processes (solar, TQ 150 and TNN 15/32 radiations) the experiments with the lamp
TNN 15/32 reveal a high oxidation capacity of the gallic acid (95.6%) against the 93.8% of
oxidation obtained in the presence of TQ 150 lamp. Dark Fentons process presents a
90.8% of gallic acid degradation.
In contrast to dark Fenton reaction (without photo-activation), ferrous ion (Fe2+) is
recycled continuously by irradiation of Fe3+ (Equation 4.3) and therefore it is not depleted
during the course of the oxidation reaction. Hence, the production of hydroxyl radicals is
only limited by the availability of UV/Vis radiation and H2O2.
These small differences achieved among all Fentons processes can be explained by
the dosage of hydrogen peroxide used: ratio [H2O2]/[GA]=5:1 and [H2O2]/[Fe2+]=51:1. The
relatively low concentration of ferrous iron versus concentration of H2O2 was used being in
mind to reduce the iron dosage necessary for the organic compound oxidation; thus
minimizing the iron sludge formation in the Fentons process.
85
GA Removal (%)
100
90
80
70
No radiation
Solar radiation
UV TQ 150
UV TNN 15/32
Figure 4.3. Comparison of the gallic acid degradation with Fentons reagent after 7.5 min of
reaction using different radiation sources. [GA]0 = 5.3x10-4 mol/L; [Fe2+] = 5.3x10-5 mol/L; [H2O2]
= 2.7x10-3 mol/L; Solar intensity (sunny day) = 545 Wm-2; Initial pH 4.0.
In Figure 4.4 it is presented the GA oxidation by the ferrioxalate process (Equations

4-6). This process is considered as a Fenton-like process, since it also combines iron and
hydrogen peroxide. Its degradation capacity was studied comparatively to Fentons reagent
with and without radiation. In parallel to the results observed with Fentons process, the
ferrioxalate process presents similar GA oxidation capacity, independently of the radiation
source. In this case the quantum yield of Fe2+ photoproduction can be enhanced by
photolysis of the highly photosensitive ferrioxalate complex (Equation 4.4). The UV lamp
TQ 150, UV lamp TNN 15/32 and solar radiation conducted to a GA degradation of
87.8%, 89.9% and 91.1%, respectively. By contrast in the absence of a radiation source,
ferrioxalate was almost ineffective. The most significant difference among the two
processes (Fentons reagent and ferrioxalate) was achieved in the assay without a radiation
source. This result reveals that in the ferrioxalate process the generation of hydroxyl
radicals, which allow the oxidation of the phenolic compound, is highly dependent on a
radiation source.
86
100
GA Removal (%)
80
60
40
20
No radiation
Solar radiation
UV TQ 150
UV TNN 15/32
Figure 4.4. Comparison of the gallic acid degradation with ferrioxalate after 7.5 min of reaction
using different radiation sources. [GA]0 = 5.3x10-4 mol/L; [H2O2] = 2.7x10-3 mol/L; [Fe3+] =
5.3x10-5 mol/L; [Oxalic Acid.] = 1.7x10-4 mol/L; Solar intensity (sunny day) = 545 Wm-2; Initial
pH 4.0.
Comparing the combination of Fentons reagent and ferrioxalate processes with the
different sources of radiation, it is possible to verify that there are not significant
differences between the two processes. However, solar radiation and the UV lamp TNN
15/32 were defined as the best radiation sources for both ferrioxalate and Fenton processes,
respectively. Although the best choice should be solar radiation because the energy
required to treat the same solution of gallic acid is only 20% of the energy amount required
by the photo-Fenton system in the presence of UV lamps.[32]
4.3.4
Influence of TiO2 on gallic acid photoxidation

The gallic acid degradation by TiO2 (heterogeneous photocatalysis) was also
evaluated in this study. Figure 4.5 presents the results obtained in these experiments. It was
observed that the TiO2 (Degussa P25) itself can not oxidize the phenolic compound
studied, and that after 60 min of contact time no adsorption process occurs. The
combination of TiO2 with the UV lamps presents similar oxidation values (UV TNN 15/32
- 41.3% and UV TQ 150 - 42.6%) which are roughly superior to the assays with solar
87
radiation (37.2%). Hence, the influence of the UV radiation source observed on the gallic
acid degradation through the TiO2 photocatalysis is reduced.
Later the additions effect of H2O2 to the heterogeneous photocatalysis processes is
presented in Figure 4.6. In contrast to previous data (Figure 4.5), the UV lamps combined
with H2O2 present significant differences on its degradation capacities (UV TNN 15/32 38.5% and UV TQ 150 - 71.0%).
100
75
50
TiO2
TiO2+Solar Radiation
TiO2+UV TNN 15/32
TiO2+UV TQ 150
25
0
0
10
20
30
40
50
60
Time (min)
Figure 4.5. Gallic acid degradation in aqueous solution by heterogeneous photocatalysis using
different radiation sources: solar and ultraviolet radiation (lamps Heraeus TNN 15/32 and Heraeus
TQ 150). Experimental conditions: [GA]0 = 5.3x10-4 mol/L; [TiO2] = 0.5 g/L; Solar intensity
(sunny day) = 545 Wm-2; Initial pH 4.0.
The combination of H2O2 with TiO2 and solar radiation showed a degradation of
52.1%. These different degradation capacities can be justified through the polychromatic
radiation emitted by the UV lamp TQ 150 that promotes, at a higher level, the excitement
of the electrons from the valence band to the conduction band of the semiconductor (TiO2),
in contrast to the monochromatic radiation emitted by the UV lamp TNN 15/32 (Equations
4.10 and 4.11).[33,34]
88
TiO2 + h TiO2 (e- + h+)
(4.10)
TiO2 (e-) + O2 TiO2 + O2-
(4.11)
The presence of H2O2 increases the effect of polychromatic radiation favouring the
generation of hydroxyl radicals (Equation 4.12):
TiO2 (e-) + H2O2 TiO2 + HO- + HO
(4.12)
100
75
50
TiO2+H2O2+UV TNN 15/32

TiO2+H2O2+Solar Radiation
TiO2+H2O2+UV TQ 150
25
0
0
10
20
30
40
50
60
Time (min)
Figure 4.6. Gallic acid degradation by heterogeneous photocatalysis using different radiation
sources: solar and ultraviolet radiation (lamps Heraeus TNN 15/32 and Heraeus TQ 150) combined
with hydrogen peroxide. Experimental conditions: [GA]0 = 5.3x10-4 mol/L; [TiO2] = 0.5 g/L;
[H2O2] = 2.7x10-3 mol/L; Solar intensity (sunny day) = 545 Wm-2; Initial pH 4.0.
4.3.5
Toxicity assessment
After the degradation assays with the different AOP, the gallic acid detoxification
level achieved with each oxidation process was evaluated. For that purpose Biotox test was
performed, through which the bioluminescence of the marine photobacteria Vibrio fischeri,
allows the assessment of the gallic acid initial toxicity and the toxicity of the sub-products
formed along the AOP reaction.
Figure 4.7 shows the inhibition percentage of the bacteria Vibrio fischeri after 15
minutes of contact with aqueous solutions of gallic acid withdraw during the treatment
with three AOP: ferrioxalate + H2O2 + UV TNN 15/32; Fe2+ + H2O2 + UV TNN 15/32 and
TiO2 + H2O2 + UV TNN 15/32. These processes were selected due to the high degradation
capacity presented by the UV TNN 15/32 both with Fentons and ferrioxalate processes.
89
100
Inhibition (%)
75
50
Ferrioxalate+H2O2+UV TNN 15/32

TiO2+H2O2+UV TNN 15/32
25
2+
Fe +H2O2+UV TNN 15/32

0
0
10
20
30
40
50
60
Time (min)
Figure 4.7. Toxicity development assessment from gallic acid in aqueous solution through the
oxidation reaction during the different AOP processes. Values obtained by luminescence of the
bacteria Vibrio fischeri after 15 min of incubation, achieved with Biotox. Experimental conditions:
[GA]0 = 5.3x10-4 mol/L; [H2O2] = 2.7x10-3 mol/L; [TiO2] = 0.5 g/L.
V. fischeri showed high sensitivity to the presence of gallic acid in solutions of 100
mg/L. Analysing the luminescence inhibition of the bacteria Vibrio fischeri through the
course of the reaction several oscillations occur, mainly in the first few minutes of AOP
treatment. This result may be explained through the gallic acid subproducts generated
which could present different levels of toxicity to the marine bacteria.
Among the studied AOP, the photo-Fenton process using the lamp UV TNN 15/32
was the only that showed a total capacity to remove the toxicity of gallic acid. The process
TiO2 + H2O2 + UV TNN 15/32 reveals, under our experimental conditions, no capacity to
diminish the toxicity of the gallic acid. After 60 minutes of reaction with TiO2, the same
inhibition level is obtained, with the initial concentration of the phenolic compound. The
ferrioxalate + H2O2 + UV TNN 15/32 process after the first 10 minutes of oxidation,
removes 42.6% of Vibrio fischeri luminescence inhibition; although, until the end of
reaction time (60 min) the toxicity increases achieving a value equal to the initial
compound. In sum, only the AOP Fe2+ + H2O2 + UV TNN 15/32 can effectively reduce the
harmful effect of the gallic acid.
90
4.4 Conclusions
The photodegradation of the most representative phenolic compound present in the
winery wastewaters (gallic acid) using only monochromatic and polychromatic UV lamps,
cannot be achieved in great extension. However, combining radiation with advanced
oxidation processes, we can maximize the effect of the different radiation sources. From
the present study it is possible to conclude that the Fe2+ + H2O2 + UV TNN 15/32 (photoFenton process) could be proposed as the best advanced oxidation process for the
degradation of gallic acid in aqueous solutions. Therefore, this work shows a possible
treatment to remove or, at least, significantly diminish the problematic phenolic fraction of
winery wastewaters, in this case using gallic acid as compound reference, for biological
treatment, decreasing their concentration and toxicity.
Finally, although the less positive results of the AOP with solar radiation, a
particular attention should be given to these processes due to their special advantages from
economical and environmental viewpoints as an example of solar application.
References
Airoldi, G.; Balsari, P.; Gioelli, F. Results of a survey carried out in Piedmont region winery on
slurry characteristics and disposal methods. Proceedings of the 3rd International Specialised
Conference on Sustainable Viticulture and Winery Wastes Management, Barcelona, 2004, 24-26
May, 335-338.
Artiga, P.; Ficara, E.; Malpei, F.; Garrido, J.M.; Mndez, R. Treatment of two industrial
wastewaters in a submerged membrane bioreactor. Desalination 2005, 179, 161-169.
Bahnemann, D. Photocatalytic water treatment: solar energy applications. Solar Energy 2004, 77,
445459.
Bauer, R.; Waldner, G.; Fallman, H.; Hager, S.; Klare, M.; Krutzler, T. The photo-Fenton reaction
and the TiO2/UV process for wastewater treatment-novel developments. Catalysis Today 1999, 53,
131-144.
91
Beck, C.; Prades, G.; Sadowski, A-G. Activated sludge wastewater treatment plants optimisation to
face pollution overloads during grape harvest periods. Water Science and Technology 2005, 51, 8188.
Beltran-Heredia, J.; Torregrosa, J.; Dominguez, J.R.; Peres, J.A. Advanced oxidation processes for
the degradation of p hydroxybenzoic acid: 2. Photo-assisted Fenton oxidation. Journal of Chemical
Technology and Biotechnology 2001, 76 (12), 1243-1248.
Benitez, F.J.; Acero, J.L.; Real, F.J. Degradation of carbofuran by using ozone, UV radiation and
advanced oxidation processes. Journal of Hazardous Materials 2002, (B89), 51-65.
Benitez, F.J.; Beltran-Heredia, J.; Real, F.J.; Gonzalez, T. Aerobic and anaerobic purification of
wine distillery wastewater in batch reactors. Chem. Eng. Technol. 1999, 22, 165-172.
Benitez, F.J.; Real, F.J.; Acero, J.L.; Leal, A.I.; Garcia, C. Gallic acid degradation in aqueous
solutions by UV/H2O2 treatment, Fentons reagent and photo-Fenton system. Journal of Hazardous
Materials, 2005, 31-39.
Chen, R.; Pignatello, J. Role of quinone intermediates as electron shuttles in Fenton oxidations of
aromatic compounds. Environmental Science Technologie 1997, 31, 2399-2406.
Feng, J.; Hu, X.; Yue, P.L.; Zhu, H.Y.; Lu, G.Q. Discoloration and mineralization of Reactive Red
HE-3B by heterogeneous photo-Fenton reaction. Water Research 2003, 37, 3776-3784.
Galvez, JB., Malato, S. Solar detoxification. 2003. United Nations Educational, Scientific and
Cultural Organization (UNESCO).
Gernjak, W.; Krutzler, T.; Glaser, A.; Malato, S.; Cceres, J.; Bauer, R.; Fernndez-Alba, AR.
Photo-Fenton treatment of water containing natural phenolic pollutants. Chemosphere 2003, 50,
71-78.
Gimeno, O; Fernandez, L.A.; Carbajo, M.; Fernando Beltran, F.;Rivas, J. Photocatalytic Ozonation
of Phenolic Wastewaters: Syringic Acid, Tyrosol and Gallic Acid. Journal Environ. Sci. Health,
Part A, 2008, 43(1), 61-69.
Kraus,
W.;
Nolze,
G.;
PowderCell
for
Windows
version
2.3,
http://ccp14.minerals.csiro.au/ccp/web-mirrors/powdcell/av/v1/powder/e cell.html (accessed Sep

2007).
Kuo, W.G. Decolorizing dye wastewater with Fenton's reagent. Water Research 1992, 26, 881-886.
92
Legrini, O.; Oliveros, E.; Braun, AM. Photochemical processes for water treatment. Chem. Rev.
1993, 93, 671-698.
Litter, M.I. Introduction to Photochemical Advanced Oxidation Processes for Water Treatment.
Hdb. Env. Chem. Vol. 2, Part M, Springer-Verlag Berlin, Heidelberg, 2005, 325-366.
Lucas,
M.S.,
Peres,
J.A.
Degradation
of
Reactive
Black
by
Fenton/UV-C
and
ferrioxalate/H2O2/solar light processes. Dyes and Pigments 2007, 74, 622-629.

Malandra, L.; Wolfaardt, G.; Zietsman, A.; Viljoen-Bloom, M. Microbiology of a biological
contactor for winery wastewater treatment. Water Research 2003, 37, 4125-4134.
Mosteo, R.; Ormad, P.; Mozas, E.; Sarasa, J.; Ovelleiro, J.L. Factorial experimental design of
winery wastewaters treatment by heterogeneous photo-Fenton process. Water Research 2006, 40,
1561-1568.
Muruganandham, M.; Swaminathan, M. Decolourisation of Reactive Orange 4 by Fenton and
photo-Fenton oxidation technology. Dyes and Pigments 2004, 63, 315-321.
Nogueira, R.F.P.; Silva, M.R.A.; Trov, A.G. Influence of the iron source on the solar photoFenton degradation of different classes of organic compounds. Solar Energy 2005, 79, 384-392.
Parsons, S. Advanced Oxidation Processes for water and wastewater treatment. IWA Publishing,
London, 2004.
Peres, J.A.; Carvalho, L.M.; Boaventura, R.; Costa, C. Characteristics of p-hydroxybenzoic acid
oxidation using Fenton's reagent. Journal Environ. Sci. Health, Part A, 2004, 39 (11-12), 28972913.
Petruccioli, M.; Duarte, JC.; Federici, F. High rate aerobic treatment of winery wastewater using
bioreactors with free and immobilized activated sludge. J Biosci Bioeng. 2000, 90, 381-386.
Pirkanniemi, K.; Sillanp, M. Heterogeneous water phase catalysis as an environmental
application: a review. Chemosphere 2002, 48, 1047-1060.
Quici N.; Litter M.I.; Braun A.M., Oliveros E., Vacuum-UV photolysis of aqueous solutions of
citric and gallic acids, Journal of Photochemistry and Photobiology A: Chemistry. 2007,
doi:10.1016/j.jphotochem.2008.01.008.
93
Safarzadeh-Amiri, A.; Bolton, J.R.; Cater, S.R. Ferrioxalate-mediated photodegradation of organic

pollutants in contaminated water. Water Research 1997, 31, 787798.
Safarzadeh-Amiri, A.; Bolton, J.R.; Cater, S.R. Ferrioxalate-mediated solar degradation of organic
contaminants in water. Solar Energy 1996, 56, 439443.
Selvam, K.; Muruganandham, M.; Swaminathan, M. Enhanced heterogeneous ferrioxalate photoFenton degradation of reactive orange 4 by solar light. Solar Energy Materials & Solar Cells 2005,
89, 61-74.
Thiruvenkatachari, R.; Tae Ouk Kwon, T.O.; Moon, I.S. Degradation of Phthalic Acids and
Benzoic Acid from Terephthalic Acid Wastewater by Advanced Oxidation Processes. Journal
Environ. Sci. Health, Part A. 2006, 41(8), 1685-1697.
Venkatadri, R.; Peters, R.W. Chemical oxidation technologies: ultraviolet light/hydrogen peroxide,
Fenton's reagent, and titanium dioxide-assisted photocatalysis. Hazardous Waste & Hazardous
Materials 1993, 10, 107-149.
Walling, C. Intermediates in the reactions of Fenton type reagents. Accounts of Chemical Research
1998, 31, 155-157.
94
Chapter 5 Solar photochemical treatment of winery wastewater in a CPC reactor
CHAPTER 5 SOLAR
PHOTOCHEMICAL TREATMENT OF
WINERY
WASTEWATER IN A CPC REACTOR*
Abstract
Degradation of simulated winery wastewater was studied in a pilot-scale Compound
Parabolic Collector (CPC) solar reactor. Total organic carbon (TOC) reduction with
heterogeneous photocatalysis (TiO2) and homogeneous photocatalysis with photo-Fenton
was observed. The influence of TiO2 concentration (200 or 500 mg/L) and also of
combining TiO2 with H2O2 and Na2S2O8 on heterogeneous photocatalysis was evaluated.
Heterogeneous photocatalysis with TiO2, TiO2/H2O2 and TiO2/S2O82- is revealed to be
inefficient in removing TOC, achieving TOC degradation of 10%, 11% and 25%,
respectively, at best. However, photo-Fenton experiments achieved 46% TOC degradation
in simulated wastewater prepared with diluted wine (WV) and 93% in wastewater prepared
with diluted grape juice (WG), and if ethanol is previously eliminated from mixed wine
and grape juice wastewater (WW) by air stripping, it removes 96% of TOC. Furthermore,
toxicity decreases during the photo-Fenton reaction very significantly from 48% to 28%.
At the same time, total polyphenols decrease 92%, improving wastewater biodegradability.
* Adapted from: Lucas M.S., Mosteo R., Maldonado M. I., Malato S., Peres J.A. (Accepted to
Journal of Agricultural and Food Chemistry).
95
5.1 Introduction
Wine is the product of alcoholic fermentation of fresh grapes or of grape must.
Wastewater from wine production, called winery wastewater, comes mainly from washing
operations during grape crushing and pressing, and rinsing of fermentation tanks, barrels,
bottles and other equipment or surfaces (1-3). Discharge and biological treatment of this
type of effluent is a complex process due to the high concentration of organic matter,
mainly composed of organic acids, ethanol, glucose, fructose and polyphenols with COD
from 3 000-15 000 mg O2/L. Furthermore, winery wastewater is seasonal, fluctuating
widely in volume and composition.
Several physical and chemical processes are available for winery wastewater
treatment but the main one used is phase transfer of pollutants. Anaerobic treatments have
been recognized as a possible way to significantly degrade wastewater with high organic
content, such as winery effluents (4,5). However, the presence of compounds that are
refractory and even toxic to the microorganisms along with the large quantities of sludge
generated reduces the treatments usability (6-8).
Advanced Oxidation Processes (AOPs) are based on chemical oxidation with
hydroxyl radicals, which are very reactive short-lived oxidants. The radicals are produced
in an on-site reactor, where they are capable of destroying a wide range of organic
pollutants in water and wastewater (9, 10). Fenton's reagent oxidation is a homogeneous
catalytic AOP that combines hydrogen peroxide and ferrous iron, as the catalyst, to oxidize
contaminants or wastewaters. The overall reaction is:
Fe
2+
+ H2O2 Fe3+ + HO + HO
(R5.1)
The ferrous ion catalyses and triggers decomposition of H2O2, resulting in the generation
of hydroxyl radicals, HO (11,12). Addition of UV radiation to Fentons reagent allied in a
photo-Fenton process could be of interest for wastewater treatment, because it directly
influences the formation of HO radicals, (13). In photo-Fenton, in addition to Reaction 1,
then hydroxyl radicals are also formed through the following reactions (Reactions 5.2 and
5.3):
96
H2O2 + UV HO + HO
(R5.2)
Fe3+ + H2O + UV Fe2+ + HO + H+
(R5.3)
Heterogeneous photocatalysis is based on irradiation of a catalyst, usually a

semiconductor (e.g., TiO2), which can be photoexcited to form electron-donor sites
(reducing sites) and electron-acceptor sites (oxidising sites), providing them with wide
scope as redox agents. Destruction or removal of contaminants takes place in the interfacial
region between the excited solid particle and the solution, with no chemical change in the
catalyst. Reactions 5.4, 5.5 and 5.6 are the main reactions in heterogeneous photocatalysis
with TiO2 (14,15):
TiO2 + h TiO2 (e- + h+)
(R5.4)
TiO2 (e-) + O2 TiO2 + O2-
(R5.5)
TiO2 (e-) + H2O2 TiO2 + HO- + HO
(R5.6)
Winery wastewater treatment by photo-Fenton and heterogeneous photocatalysis

has been previously demonstrated (16,17). Mosteo et al. (18) report that heterogeneous
photo-Fenton, using natural sunlight as the radiation source, removed 50% TOC in 24
hours, suggesting that this process can be used as a pre-treatment for an aerobic biological
process.
The purpose of this paper is to evaluate the performance of solar photochemical
AOPs, such as heterogeneous photocatalysis (with TiO2, TiO2/H2O2 and TiO2/S2O82-) and
homogeneous photocatalysis with photo-Fenton, to treat winery wastewater in a
Compound Parabolic Collector (CPC) pilot-solar plant. This is, to the best of our
knowledge, the first study performed with winery wastewater in this type of solar collector.
5.2 Material and methods
5.2.1
Winery wastewater
Because of the seasonal character of winery wastewater, the effluents had to be
reproduced with synthetic samples prepared by diluting commercial grape juice (WG),
commercial red wine (WV), and a mixture of both (wine and grape juice - WW) in MilliQ water. WG is simulated wastewater characterized by its high sugar content that
reproduces winery wastewater during fermentation. WV is wastewater with high ethanol
content that attempts to imitate wastewater generated after fermentation. WW simulates the
97
combination of both of the above in a mixture similar to the equalization tank in some
wineries where all the effluents are mixed.
Table 5.1 shows the main characteristics of the three types of winery wastewater:
conductivity, pH, total organic carbon (TOC), chemical oxygen demand (COD) and total
polyphenol content.
Conductivity
TOC
COD
Total Polyphenols
(S/cm)
(mg/L)
(mg O2/L)
(mg Gallic Acid/L)
3.8
152
1155
4440
93
4.3
107
1185
4500
112
4.1
124
1165
4474
103
Wastewater
Synthetic Sample
pH
WV
Wine
WG
Grape Juice
WW
Wine + Grape Juice

(50:50)
5.2.2 Chemicals
Heterogeneous photocatalytic degradation was carried out using a slurry suspension
of Degussa (Frankfurt, Germany) P-25 titanium dioxide (surface area 51-55 m2/g) and
sodium persulfate (Na2S2O8) purchased from Panreac. The photo-Fenton experiments were
performed using ferrous iron sulphate (FeSO4.7H2O), hydrogen peroxide (30% w/w) and
sulphuric acid for pH adjustment (around 2.83.0), all supplied by Panreac.
The photo-treated solutions were neutralized by means of NaOH (reagent grade,
Panreac) for the toxicity test. Water used in the pilot plant was from the Plataforma Solar
de Almera (PSA) distillation plant (conductivity < 10 S/cm, Cl- = 0.7-0.8 mg/L, NO3- =
0.5 mg/L, organic carbon < 0.5 mg/L). Other chemicals used in these experiments were
reagent grade and used as received.
5.2.3 Analytical determinations
Organic matter concentration and mineralisation were monitored by measuring the
TOC by direct injection of filtered samples into a Shimadzu-5050A TOC analyser,
equipped with an ASI5000 autosampler, provided with an NDIR detector and calibrated
with standard solutions of potassium phthalate. The COD analysis was determined by
98
Merck Spectroquant cuvette tests. Samples were pre-filtered through 0.20 m syringe
nylon filters (25 mm, Millex GN, Millipore).
The COD and TOC are expressed in mg of O2/L and mg of C/L, respectively. The
initial hydrogen peroxide concentration was always 12 mM and controlled to avoid
complete disappearance by adding small amounts as consumed. Hydrogen peroxide
concentration was determined by the metavanadate method (19). Colorimetric
determination of total iron concentration with 1,10-phenantroline was used according to
ISO 6332. Ultra pure distilled-deionised water was from a Milli-Q (Millipore Co.) system.
The polyphenol content was measured in filtered samples by Folin-Ciocalteau reagent (20).
5.2.4 Toxicity measurements
Toxicity was assessed using the Biofix Lumi-10 luminometer and the Biofix
Lumi kit by Macherey-Nagel. The biological agent is a freeze-dried preparation of the
marine bacterium Vibrio fischeri (formerly known as Photobacterium phosphoreum,
NRRL number B-11177). Light emission was measured at 15C after a 15-min contact
period. Hydrogen peroxide in the samples was removed prior to the toxicity analysis using
catalase (2500 U/mg bovine liver; 100 mg/L) from Fluka Chemie AG. All the samples
were analysed after adjusting the pH to 7. Careful control of temperature was essential
because light emission is sensitive to temperature.
5.2.5 Experimental set-up
All experiments were carried out under sunlight, in a pilot plant installed at the
Plataforma Solar de Almera (latitude 37N, longitude 2.4W). Photo-Fenton and titanium
dioxide experiments were carried out in a Compound Parabolic Collector (CPC) pilot-solar
plant (21) able to treat up to 40 L of wastewater (3.1 m2 irradiated surface, 22 L irradiated
volume).
99
20 lmin
-1
CPC
CPCs (Vi = 22 l)
2
3 x 1.03 m
Tank
Pump
Figure 5.1 Photo and schematic drawing of the CPC reactor used in the photochemical
experiments.
The absorber tube has an internal diameter of 29.2 mm and an external diameter of
32.0 mm. Each experiment was repeated twice and the data used for kinetic calculations
(and drawing the figures) correspond to the average of two different tests. The pilot plant
(Figure 5.1) operates in batch mode. The solar collector is mounted on a fixed platform
tilted 37 (local latitude). Solar ultraviolet radiation (UV <400 nm) was measured by a
global UV radiometer (KIPP&ZONEN, model CUV 3), mounted on a platform tilted 37,
which provides data in terms of incident UV (W/m2). This gives an idea of the energy
reaching any surface in the same position with regard to the sun.
With Reaction (5.1), the combination of the data from several days experiments and the
comparison between photo-reactors installed at different emplacements are possible.
t30w,n = t30w,n-1 + tn
UV Vi
,
30 VT
tn = tn - tn-1
(Eq. 5.1)
where UV is the average solar ultraviolet radiation measured during tn and tn-1 (tn), tn is
the experimental time for each sample, VT is the total volume of water loaded in the pilot
plant (35 L), Vi is the total irradiated volume (22 L, glass tubes) and t30W is a normalized
illumination time. In this case, time refers to a constant solar UV power of 30 Wm-2
(typical solar UV power on a perfectly sunny day around noon). As the system is outdoors
and is not thermally controlled, the temperature inside the reactor is continuously recorded
by a PT-100 inserted in the tank. At the beginning of the process, the collectors were
covered, the pH was adjusted and the TiO2 or ferrous iron salt was added. After each
addition of reagents, the plant was well homogenised by recirculation. Finally, the first
100
amount of hydrogen peroxide was added and after 15 minutes of homogenization, a sample
was taken (time zero) and the collector was uncovered. The hydrogen peroxide was
measured frequently and consumed reagent was continuously replaced to maintain the
original concentration throughout the reaction.
5.3.Results and Discussions
5.3.1
Degradation of winery wastewater by TiO2

Figure 5.2 shows TOC/TOC0 values during solar photolysis and heterogeneous
photocatalysis (TiO2) of the simulated winery wastewater in the CPC reactor. The results
reveal that solar photolysis, by itself, produces a very small decrease in TOC in the two
studied samples of winery wastewater. However, in the synthetic sample with high sugar
content (WG sample) the TOC content decreases slightly faster than in the synthetic WV
sample.
1.00
0.95
TOC/TOC0
0.90
0.85
WG Photolysis
WV Photolysis
WG TiO2 200 mg/L
WV TiO2 200 mg/L
WV TiO2 500 mg/L
0.80
0.75
0.70
-100
-50
50
100
150
200
250
300
350
400
450
500
t30W
Figure 5.2 - Total organic carbon in winery wastewater (WV and WG) during solar photolysis and
heterogeneous photocatalysis (TiO2) in a CPC reactor. Experimental conditions: [TiO2]0 = 200
mg/L and 500 mg/L; initial pH = 3.8.
In the experiments performed with heterogeneous photocatalysis (TiO2),

degradation of two types of winery wastewater (WG or WV) was evaluated with two
different amounts of catalyst (200 and 500 mg/L). In the experiments with 200 mg/L of
TiO2, TOC decreased 8% in the WV sample and 10% in WG after a t30W of 400 minutes.
101
TOC removal from WV was not improved by increasing the amount of catalyst from
200 mg/L to 500 mg/L, which was again 10%. Thus, TiO2 alone is insufficient, even when
the amount of catalyst was more than doubled, to remove TOC present in the winery
wastewater. Therefore, a TiO2 concentration of 200 mg/L was selected as the best option
and was used in following experiments.
5.3.2
Degradation of winery wastewaters by TiO2/H2O2 and TiO2/S2O82Figure 5.3 shows experiments performed with TiO2 combined with hydrogen
peroxide and persulfate to evaluate the improvement in TOC removal generated by the
addition of these oxidants to TiO2. No significant changes are observed in the data with
either of the combinations (TiO2/H2O2 and TiO2/S2O82-). With TiO2/H2O2, TOC removal
was 11% after a t30W of 150 minutes, and with a single addition of 10 mM of S2O82- to
TiO2 at the beginning of the experiment, TOC degradation was 12% in both WV and WG
samples.
WV H2O2 12mM t=0
1.00
2-
WG S2O8 10mM t=0

0.95
2-
WV S2O8 10 mM t=0
TOC/TOC0
2-
WV S2O8 10 mM Cte
0.90
0.85
0.80
0.75
0.70
-50
50
100
150
200
250
300
350
400
450
500
t30W
Figure 5.3 Influence of hydrogen peroxide (H2O2) and sodium persulfate (Na2S2O8) in
heterogeneous photocatalysis (TiO2) treatment of winery wastewater (WV or WG) in a CPC
reactor. Experimental conditions: [TiO2]0 = 200 mg/L; initial pH = 3.8.
When the concentration of S2O82- (10 mM) in solution was kept constant throughout the
reaction in a TiO2/S2O82- experiment, TOC removal was 25% after a t30W of 440 minutes.
Therefore, as a final comment on the heterogeneous photocatalysis experiments, it may be
102
confirmed that no significant TOC degradation can be achieved with this process in either
WV or WG even when the amount of TiO2 is increased or H2O2 and S2O82- are added. The
effectiveness of photo-Fenton has previously been demonstrated using different sources of
radiation and different types of winery wastewater (16,18,22). So, the next step in this
study is to test the effectiveness of photo-Fenton in the treatment of a winery wastewater in
a CPC reactor.
5.3.3
Degradation of winery wastewater by photo-Fenton oxidation

Figure 5.4 shows the application of solar photo-Fenton to treatment of a sample of
WV, which has a high alcohol content simulated by a wine dilution. The photo-Fenton
experiments were done with a single dose of Fe2+ (55 mg/L) at pH3. The hydrogen
peroxide dose of 12 mM was maintained constant with successive additions throughout the
experiment. The solar photo-Fenton experiments started when the CPC reactor was
exposed to solar radiation. The results show that after a t30W of 500 minutes with an added
H2O2 concentration of 151 mM TOC removal was 54%.
1.0
160
140
0.8
120
100
0.6
80
0.4
60
0.8
0.6
Fe/Fe0
H2O2 (mM)
TOC/TOC0
1.0
0.4
40
0.2
0.2
20
0
0.0
-50
50
100
150
200
250
300
350
400
450
500
0.0
550
t30W (min)
Figure 5.4 Winery wastewater (WV) treatment by solar photo-Fenton using a CPC reactor. TOC
(), hydrogen peroxide () and iron () concentrations during reaction. Experimental conditions:
[Fe2+]0 = 55 mg/L; [H2O2]0 = 12 mM; initial pH = 3.0.
103
These results are not particularly exceptional since longer reaction time and higher
dose of H2O2 were used. A possible explanation could be the fast disappearance of iron
from the reaction media, probably because the iron forms complexes with compounds
present in the winery wastewater. Figure 5.4 shows how fast iron disappears from the
reaction media, especially in the first 100 minutes. So to find out whether this poor TOC
removal could be explained by the very low iron concentration in solution, the amount of
iron necessary to maximize solar photo-Fenton was specifically evaluated.
5.3.3.1 Influence of ferrous iron concentration

Photo-Fenton experiments were carried out at two different Fe2+ concentrations,
55 mg/L and 110 mg/L. Figure 5.5 shows a photo-Fenton experiment performed with
110 mg/L. From the data shown, it may be observed that no significant improvement was
achieved by increasing the iron concentration to double the experiment performed with
only 55 mg/L. In fact, contrary to what was expected, there is a small decrease in TOC
removed. In the experiment with 55 mg/L of iron and a t30w of 250 minutes, TOC
degradation was 21% whilst with 110 mg/L of iron degradation was only 11%.
1.0
60
0.8
40
0.4
0.6
0.4
Fe/Fe0
0.6
1.0
H2O2 (mM)
TOC/TOC0
0.8
80
20
0.2
0.2
0
0.0
0.0
-50
50
100
150
200
250
300
350
400
t30W(min)
Figure 5.5 Winery wastewater (WV) treatment by solar photo-Fenton in a CPC reactor. TOC (),
hydrogen peroxide () and iron () concentrations during reaction. Experimental conditions:
[Fe2+]0 = 110 mg/L; [H2O2]0 = 12 mM; initial pH = 3.0.
104
This reduction in TOC removal may be explained by redox reactions in which HO radicals
are scavenged by reaction with other Fe2+ molecules as displayed below (Reaction 5.7)
(23).
Fe
2+
(R5.7)
+ HO HO + Fe3+
Thus, the large amount of ferrous iron added decreases the strength of the photo-Fenton
reaction. It was also found that even with a large initial amount of iron, the concentration
in solution decreases very fast in the first minutes, just as it did in the experiment with
55 mg/L of iron.
Furthermore, the effect on TOC removal of several additions of iron during the
reaction in an attempt to keep the amount of iron in solution constant at around 55 or
110 mg/L was studied. Figure 5.6 shows the results of these experiments. In the
experiment started with 55 mg/L of iron, TOC degradation was 44% and in the experiment
started with 110 mg/L removal was 48% in around the same reaction time (400 minutes).
These results reveal an improvement in TOC degradation compared to the experiments
with single additions of iron, especially in the experiment started with 110 mg/L.
400
1.0
350
300
200
0.4
100
0.2
(mg/L)
150
2+
accumulated
250
0.6
Fe
TOC/TOC0
0.8
50
0.0
-50
50
100
150
200
250
300
350
400
0
450
t30W
Figure 5.6 Effect of several additions of iron on TOC removal and accumulated iron
concentration during photo-Fenton experiment. Experimental conditions: winery wastewater (WV);
[Fe2+]const. = 110 mg/L () and [Fe2+]const. = 55 mg/L (); [H2O2] = 12 mM; initial pH = 3.0.
Therefore, the continuous addition of ferrous iron throughout the reaction slightly
improves the solar photo-Fenton degradation capacity, however, with continuous addition,
105
the total amount of iron is obviously larger than with only one dose. Thus, in the
experiment started with 55 mg/L of ferrous iron, at the end of reaction, the cumulative total
of ferrous iron was 153 mg/L, and in the experiment started with 110 g/L, it was 323 mg/L.
Thus, around three times more ferrous iron was used than in the experiments with a single
dosage, but this increment in iron does not directly correspond to an increment in TOC
degradation, as the large amount of iron added in several additions does not lead to a clear
improvement in TOC removal, because the difference between 55 mg/L and 110 mg/L on
TOC degradation was only 4%. Therefore, the best ferrous iron dosage for solar photoFenton operation is a single dose of 55 mg/L. The next step in the study was an in-depth
analysis of application of photo-Fenton to simulated winery wastewater.
5.3.3.2 Influence of the winery wastewater composition
Figure 5.7 shows the results of several experiments performed with photo-Fenton
with different initial operating conditions. First, the effect of wastewater type (WV or WG)
on the photo-Fenton experiment with a single 55-mg/L dose of ferrous iron was evaluated,
and TOC removal was found to be higher in the WG sample than in the WV sample. TOC
removal was 46% in a t30W of 400 minutes in WV whilst in WG, degradation was 93%.
1,0
TOC/TOC0
0,8
0,6
0,4
0,2
0,0
-50
50
100
150
200
250
300
350
400
450
500
550
t30W
Figure 5.7 Influence of winery wastewater composition on TOC removal during photo-Fenton
oxidation. Experimental conditions: [H2O2]0 = 12 mM; original pH = 3.0. () WV with [Fe2+]0 = 55
mg/L; () WG with [Fe2+]0 = 55 mg/L; () WW with [Fe2+]0 = 55 mg/L; () WW with [Fe2+]0 =
20 mg/L; (*) WW without ethanol with [Fe2+]0 = 20 mg/L.
106
So photo-Fenton treatment of winery wastewater is observed to be significantly affected by

the composition of the wastewater, with a difference of up to 47%. The next step was
therefore to assess the application of photo-Fenton in wastewater containing a mixture of
WV and WG (WW).
This simulates real wastewater treatment in some wineries that have retention tanks
to store and equalize the seasonal effluent from the different stages of wine production
before further treatment in a wastewater treatment plant. Photo-Fenton treatment of the
wastewater with WG and WV was faster than with either WV or WG alone. TOC removal
in the mixture was 90% for a t30W of 150 minutes. This strong removal of the organic load
present in the wastewater means that photo-Fenton was more efficient in terms of the iron
dose applied. Therefore, another experiment was done with the mixture of wine and grape
juice, but with a single dose of ferrous iron of only 20 mg/L.
Figure 5.7 shows that there are no significant differences in TOC removal due to
the smaller iron dosage, as after a t30W of 150 minutes, degradation was 84%. Thus, for a
60% decrease in ferrous iron concentration, TOC removal is only 6% lower. Therefore, an
interesting option may be to store and equalize such wastewater before photo-Fenton
treatment, which would be significantly more economical in terms of ferrous iron
consumption and TOC degradation.
5.3.3.3 Influence of the ethanol presence in winery wastewaters
The main difference between the two types of wastewater (WV and WG) is that
WV has a large amount of ethanol and in WG there is a high concentration of sugars.
Therefore, to evaluate the effect of ethanol on the photo-Fenton process and consequently
on TOC removal, ethanol elimination from the winery wastewater was evaluated. Ethanol
was removed from the wastewater made with diluted wine (WV) by air stripping using
aquarium pumps and warming the solution to 35C for 24 hours. By removing ethanol, the
main volatile compound in the wastewater, the corresponding organic load, equivalent to
70% of the TOC present in the solution, was also removed, similar to other studies (24).
Although the experiment was done with the same original TOC as the other experiments, a
large volume of wine without ethanol was added so the initial TOC would be the same and
only the ethanol concentration changed.
107
Photo-Fenton degradation of this ethanol-free winery wastewater was 96% after a

t30W of 130 minutes. Based on this assay, it should be stressed that ethanol significantly
influences photo-Fenton efficiency. This can be explained by the ethanol degradation
pathways during photo-Fenton. Since ethanol is transformed during photoxidation, e.g., as
in photo-Fenton, into acetaldehyde and later into acetic acid (Reaction 5.8) (25):
CH3CH2OH
Ethanol
CH3CHO
Acetaldehyde
CH3COOH
(R5.8)
Acetic Acid
Acetic acid is a well-known hydroxyl radical scavenger, as can be observed in the

following reaction (Reaction 5.9):
CH3COOH + HO CH2COOH + H2O
(R5.9)
Therefore, the lower degradation capacity of the photo-Fenton process when applied to
WV is because of the action of acetic acid on the hydroxyl radicals. Thus, if the wastewater
contains a large amount of ethanol, an air stripping pre-treatment prior to photo-Fenton
significantly increases the efficiency of this advanced oxidation process.
5.3.3.4 COD, total polyphenols and toxicity evolution in photo-Fenton process
Winery wastewater contains significant concentrations of refractory and even toxic
compounds. Figure 5.8 shows COD, total polyphenols and toxicity during the photoFenton experiment. This experiment was performed with winery wastewater prepared with
ethanol-free WV and WG (curve * in Figure 5.7).
Photo-Fenton removes 98% of the COD load in the winery wastewater after a t30W
of 82 minutes. This confirms the previous finding of 96% TOC after a t30W of 130 minutes.
The total polyphenol content, measured as the reduction in the concentration of gallic acid,
was monitored during the photo-Fenton reaction. This model phenolic compound was
selected since it is the most representative phenolic acid present in winery wastewater (2628). Its concentration increases in the first t30W of 30 minutes due to aromatic ring
108
hydroxylation (7), but after that, during the rest of the reaction, it drops to 92% of the
original polyphenol content.
110
100
90
0,8
80
0,6
0,4
2
0,2
Inhibition(%)
COD/COD0
Total Polyphenols (GA/GA0)
1,0
Total Polyphenols
COD
Toxicity
70
60
50
40
30
0
0,0
0
10
20
30
40
50
60
70
80
20
90
t30W
Figure 5.8 Total polyphenols, COD and toxicity during photo-Fenton oxidation of winery
wastewater. Experimental conditions: [Fe2+]0 = 20 mg/L; [H2O2]0 = 12 mM; initial pH = 3.0.
The toxicity of the winery wastewater was measured with the luminescent bacteria
Vibrio fischeri, which verified that original toxicity decreases after photo-Fenton, making
the wastewater more acceptable for biological treatment. At first, after a tw30 of 15 minutes
of contact with the winery wastewater, Vibrio fischeri showed 48% inhibition, but at tw30
of 25 minutes, the percentage of inhibition decreased to 44%, although afterwards toxicity
increased again to 82%. This can be explained by the increased content in total
polyphenols, making the wastewater more toxic. Afterwards, as photo-Fenton progressed,
toxicity dropped to 28% when COD was reduced 98% and the total polyphenol content
92%.
As final remarks, this study shows that heterogeneous photocatalysis (TiO2,
TiO2/H2O2, TiO2/Na2S2O8) of simulated winery wastewater is inefficient in removing
TOC, with best performance of only 25% TOC degradation. Homogeneous photocatalysis
with solar photo-Fenton in the CPC reactor showed a TOC removal efficiency of 46% with
simulated wine (WV) wastewater and 93% with grape juice (WG) in a t30W of 400 minutes.
However TOC removal was 90% in a 50:50 WV and WG mixture after a t30W of 150
minutes.
109
If ethanol is previously removed from the winery wastewater mixture (WW) by air
stripping, TOC degradation is 96%. In addition to this high TOC degradation, toxicity also
decreases significantly from 48% to 28%, almost completely eliminating polyphenols
(92%) as well. So as a final remark, solar photo-Fenton may be considered an efficient
treatment for winery wastewater treatment, especially if air stripping is previously applied
to remove ethanol.
5.4 Conclusions
This
work
shows
that
heterogeneous
photocatalysis
(TiO2,
TiO2/H2O2,
TiO2/Na2S2O8) of a simulated winery wastewater reveals to be inefficient on TOC

removal, achieving in the best performance a TOC degradation of 25%. The obtained
results with homogeneous photocatalysis with solar photo-Fenton process in the CPC
reactor have shown that it can be reached a TOC removal efficiency of 46% with a
simulated wastewater carried out with wine (WV) and 93% with grape juice (WG) in a t30W
of 400 minutes. Mixing WV with WG in a ratio 50:50 a TOC removal of 90% was
achieved for a t30W of 150 minutes.
If an air stripping process is previously applied for ethanol removal from the winery
wastewater mixture (WW), a TOC degradation of 96% is obtained. Besides this high TOC
degradation a significant detoxification occurs, given the fact that the toxicity level
decreases from 48% to 28%, as well as almost total elimination of the total polyphenols
(92%). So, as a final remark solar photo-Fenton process can be defined as an efficient
treatment process to winery wastewater treatment, especially if air stripping is previously
applied for ethanol removal.
References
(1) Petruccioli, M.; Duarte, J.C.; Federici, F. High rate aerobic treatment of winery wastewater
using bioreactors with free and immobilized activated sludge. J. Biosci. Bioeng. 2000, 90, 381-386.
(2) Malandra, L.; Wolfaardt, G.; Zietsman, A.; Viljoen-Bloom, M. Microbiology of a biological
contactor for winery wastewater treatment. Water Res. 2003, 37, 4125-4134.
110
(3) Beck, C.; Prades, G.; Sadowski, A-G. Activated sludge wastewater treatment plants
optimisation to face pollution overloads during grape harvest periods. Water Sci. Technol. 2005,
51, 81-88.
(4) Di Berardino S.; Caetano L.; Converti. A. Characterization and anaerobic pretreatment of the
effluent from a wine cooperative. Eng. Life Sci. 2001, 3, 127-131.
(5) Brito, A.G.; Peixoto, J.; Oliveira, J.M.; Oliveira J.A.; Costa, C.; Nogueira, R.; Rodrigues, A.
Brewery and winery wastewater treatment: some focal points of design and operation in utilization
of by-products and treatment of waste in the food industry. Springer US, 2007, 109-131.
(6) Benitez, F.J.; Beltran-Heredia, J.; Real, F.J.; Gonzalez, T. Aerobic and anaerobic purification of
wine distillery wastewater in batch reactors. Chem. Eng. Technol. 1999, 22, 165-172.
(7) Gernjak, W.; Krutzler, T.; Glaser, A.; Malato, S.; Cceres, J.; Bauer, R.; Fernndez-Alba, A.R.
Photo-Fenton treatment of water containing natural phenolic pollutants. Chemosphere 2003, 50,
71-78.
(8) Lucas, M.S.; Peres, J.A.; Lan, Y.B.; Li Puma, G. Ozonation kinetics of winery wastewater in a
pilot-scale bubble column reactor, Water Res. 2009, 43, 1523-1532.
(9) Kuo, W.G. Decolorizing dye wastewater with Fenton's reagent. Water Res. 1992, 26, 881-886.
(10) Nogueira, R.F.P.; Silva, M.R.A.; Trov, A.G. Influence of the iron source on the solar photoFenton degradation of different classes of organic compounds. Solar Energy 2005, 79, 384-392.
(11) Chen, R.; Pignatello, J. Role of quinone intermediates as electron shuttles in Fenton oxidations
of aromatic compounds. Environ. Sci. Technol. 1997, 31, 2399-2406.
(12) Feng, J.; Hu, X.; Yue, P.L.; Zhu, H.Y.; Lu, G.Q. Discoloration and mineralization of Reactive
Red HE-3B by heterogeneous photo-Fenton reaction. Water Res. 2003, 37, 3776-3784.
(13) Muruganandham, M.; Swaminathan, M. Decolourisation of Reactive Orange 4 by Fenton and
photo-Fenton oxidation technology. Dyes and Pigments 2004, 63, 315-321.
(14) Pirkanniemi, K.; Sillanp, M. Heterogeneous water phase catalysis as an environmental
application: a review. Chemosphere 2002, 48, 1047-1060.
(15) Bahnemann, D. Photocatalytic water treatment: solar energy applications. Solar Energy 2004,
77, 445459.
111
(16) Mosteo, R.; Ormad, P.; Mozas, E.; Sarasa, J.; Ovelleiro, J.L. Factorial experimental design of
winery wastewaters treatment by heterogeneous photo-Fenton process. Water Res. 2006, 40, 15611568.
(17) Ormad, M.P.; Mosteo, R.; Ibarz, C.; Ovelleiro, Jos L. Multivariate approach to the photoFenton process applied to the degradation of winery wastewaters. Appl. Catal. B: Environ. 2006,
66, 5863.
(18) Mosteo, R.; Sarasa, J.; Ormad, M.P.; Ovelleiro, J.L. Sequential solar photo-Fenton-biological
system for the treatment of winery wastewaters. J. Agric. Food Chem. 2008, 56, 73337338.
(19) Nogueira, R.F.P.; Oliveira, M.C.; Paterlini, W.C. Simple and fast spectrophotometric
determination of H2O2 in photo-Fenton reactions using metavanadate. Talanta. 2005, 66, 86-91.
(20) Singleton, V. L.; Rossi, J. A.. Colorimetry of total phenolics with phosphomolybdicphosphotungstic acid reagents. Am. J. Enol. Vitic. 1965, 16, 144-158.
(21) Kositzi, M.; Poulios, I.; Malato, S.; Cceres, J.; Campos, A. Solar photocatalytic treatment of
synthetic municipal wastewater. Water Res. 2004, 38, 11471154.
(22) Rodrguez, E.; Mrquez, G.; Carpintero, J.C.; Beltrn, F.J.; lvarez, P. Sequential use of
bentonites and solar photocatalysis to treat winery wastewater. J. Agric. Food Chem. 2008, 56,
1195611961.
(23) Malik, P.K.; Saha, S.K. Oxidation of direct dyes with hydrogen peroxide using ferrous ion as
catalyst. Sep. Purification Technol. 2003, 31, 241-250.
(24) Colin, T.; Bories, A.; Sire, Y.; Perrin, R. Treatment and valorisation of winery wastewater by a
new biophysical process (ECCF). Water Sci. Technol. 2005, 51, 99-106.
(25) Nimlos, M.R.; Wolfrum, E.J.; Brewer, M.L.; Fennell, J.A. Gas phase heterogeneous
photocatalytic oxidation of ethanol: pathways and kinetic modelling. Environ. Sci. Technol. 1996,
30, 3102-3110.
(26) La Torre, G.; L., Saitta, M.; Vilasi, F.; Pellicano, T.; Dugo, G. Direct determination of
phenolic compounds in Sicilian wines by liquid chromatography with PDA and MS detection.
Food Chem. 2006, 94, 640650.
(27) Silva, M.N.B.S.; Coelho, A.V.; Vilas Boas, L.; Bronze, M.R.. Analysis of phenolic
compounds in Muscatel wines produced in Portugal. Analyt. Chemic. Acta 2006, 563, 84-92.
112
(28) Lucas, M.S.; Dias, A.A.; Bezerra, R.M.; Peres, J.A. Gallic acid photochemical oxidation as a
model compound of winery wastewaters. J. Environ. Sci. Health-A 2008, 43, 12881295.
113
Chapter 6 Ozonation kinetics of winery wastewater in a pilot-scale bubble column reactor
CHAPTER 6 OZONATION
KINETICS OF
PILOT-SCALE BUBBLE COLUMN REACTOR
WINERY WASTEWATER
IN A
Abstract
The degradation of organic substances present in winery wastewater was studied in a
pilot-scale, bubble column ozonation reactor. A steady reduction of chemical oxygen
demand (COD) was observed under the action of ozone at the natural pH of the wastewater
(pH 4). At alkaline and neutral pH the degradation rate was accelerated by the formation of
radical species from the decomposition of ozone. Furthermore, the reaction of hydrogen
peroxide (formed from natural organic matter in the wastewater) and ozone enhances the
oxidation capacity of the ozonation process. The monitoring of pH, redox potential (ORP),
UV absorbance (254 nm), polyphenols content and ozone consumption was correlated with
the oxidation of the organic species in the water. The ozonation of winery wastewater in
the bubble column was analysed in terms of a mole balance coupled with ozonation
kinetics modeled by the two-film theory of mass transfer and chemical reaction. It was
determined that the ozonation reaction can develop both in and across different kinetic
regimes: fast, moderate and slow, depending on the experimental conditions. The dynamic
change of the rate coefficient estimated by the model was correlated with changes in the
water composition and oxidant species.
* Adapted from: Lucas M.S., Peres J.A., Lan B.Y., Li Puma G. Water Research. 2009, 43, 15231532.
115
6.1 Introduction
The wine industry generates a seasonal effluent which is characterized by a high
organic load. The organic load and its composition depends on the stages used during the
production of the wine (e.g., vintage, racking, bottling) and on the winemaking technology
(e.g. production of red, white and special wines) (Malandra et al., 2003; Artiga et al.,
2005). These effluents usually referred to as winery wastewater originated from various
unit operations such as washing of the presses used to crush the grapes, rinsing of
fermentation tanks, barrels, bottles and other equipments or surfaces (Petruccioli et al.,
2000; Malandra et al., 2003; Beck et al., 2005; Mosteo et al., 2006).
Winery wastewater has a high concentration of polyphenols, organic acids and
sugars with typical COD values in the range from 3 to 30 g L-1 (Benitez et al., 1999a; Pirra,
2005), and it is toxic to the aquatic environment and needs treatment before discharge.
Current methods of treatment of winery wastewater include physical and chemical
processes. However, the high bio-recalcitrance and toxicity of phenolic contaminants in the
winery wastewater cause difficulties in the biological treatment of these wastewaters. The
presence of refractory compounds, in addition to the large quantities of waste sludge
generated, in practice limits the applicability and efficiency of such treatment methods
(Legrini et al., 1993; Benitez et al., 1999b).
Advanced oxidation processes (AOP) can be efficient methods for the treatment of
refractory wastewater characterized by a high organic load. AOP involve the generation of
highly reactive radical species, predominantly hydroxyl radical (HO) (Legrini et al., 1993;
Litter, 2005). The application of AOP to winery wastewater is usually limited to the
destruction of the refractory compounds (polyphenols) with the objective of rendering the
wastewater more viable to biological treatment (Beltran et al, 1999).
Ozone is a strong oxidizer having high reactivity towards organic compounds such
as polyphenols. Ozonation has been previously used for the treatment of polyphenols
loaded wastewater such as from the cork manufacturing industry (Benitez et al., 2003a;
Lan et al, 2008), the olive oil industry (Benitez et al., 1997; Beltran-Heredia et al., 2000)
and the wine distillery industry (Beltrn et al, 1999; Beltrn et al. 2001; Benitez et al.,
1999c; Benitez et al., 2003b; Monteagudo, 2005; Santos et al, 2003). Hydroxyl radicals
from ozone are generated from different pathways such as ozone decomposition at alkaline
116
pH, the reaction of ozone with hydrogen peroxide and the photolysis of ozone in aqueous
media (Sotelo et al., 1987).
The treatment of winery wastewater by ozonation and ozone related processes have
been demonstrated in small-scale laboratory studies. Gimeno et al., (2007) reported the
photocatalytic ozonation of winery wastewater in a 1 L reactor and the total mineralization
of the COD removed in the presence of UV-A ozone and titanium dioxide. Navarro et al.
(2005) investigated the degradation of winery industrial wastewater by photocatalytic
oxidation, UV-peroxidation and Fenton reaction over iron rich clays in 100 ml glass vials.
Ozonation has been successfully applied to the treatment of wine distillery wastewater
(Beltrn et al, 1999; Beltrn et al. 2001; Benitez et al., 2003a; Santos et al, 2003) in small,
laboratory scale reactors.
In this work, the kinetics of ozonation of winery wastewater is studied in detail in a
pilot-scale, semi-batch bubble column reactor previously employed for the treatment of
cork-processing water (Lan et al, 2008). The study investigates the relationship between
pH, ORP, COD, UV absorbance (254 nm), total polyphenol content and ozone
consumption as a function of time, as well as, the prevalent kinetic conditions (fast,
intermediate, and slow kinetic regime) for the reaction of ozone with the dissolved organic
species. Furthermore, a kinetic ozonation model is presented and used to estimate the
kinetic coefficients of the ozonation of winery wastewater under the prevailing
experimental conditions. In contrast with previous work carried out in laboratory scale
reactors, this study considers the ozonation of winery wastewater in a pilot-scale bubble
column reactor, which facilitate scale-up and practical application in the wine industry.
6.2.1
Winery wastewater
The winery wastewater was collected from a wine production unit located in the
Douro region in the north of Portugal. The pH, the absorbance at 254 nm, the total carbon
(TC) and inorganic carbon (IC) content, the COD and polyphenol content measured as
equivalent gallic acid content are presented in Table 6.1.
117

pH
4.0
6.2.2
Absorbance
TC
IC
COD
-1
Polyphenols
-1
(254 nm)
(mg L-1)
(mg L )
(mg O2 L )
(mggallic acid L-1 )
1.562
1255
1.11
4650
103
Ozonation
The ozonation experiments were conducted in a bubble-column semi-batch reactor
(internal diameter 0.1 m, height 1 m) made of QVF borosilicate glass. The reactor was
equipped with a liquid stream outlet at the bottom and an inlet at the top, connected to a
peristaltic pump (Masterflex 77200-62, Cole-Parmer, USA) to assist water recirculation in
the reactor. An in-line redox potential (ORP) sensor was installed in the water recirculation
tube. The gas stream enriched with ozone entered the reactor via a sintered stainless steel
porous disk S20 (Porvair Ltd., UK, mean pore size 15 m) at the bottom of the reactor. A
gas stream outlet at the top of the reactor led to a thermal ozone destructor. Liquid samples
were collected with a syringe through a sealed port in the reactor. The ozone concentration
at the gas inlet and outlet of the reactor were measured by redirecting the flows to a series
of Dreschel flasks containing a 2% potassium iodide solution.
High purity oxygen (99.999 %, BOC gases, UK) was fed to a silica drier to remove
trace water prior to entering the ozone generator (OZOMAX 8Vtt, Ozomax, Canada)
capable of producing up to 0.68 g ozone per minute. The hydrodynamic and operational
conditions used in this study are summarised in Table 6.2 with the symbols presented in
the nomenclature section.
Table 6.2. Hydrodynamic and operational conditions of the ozonation reactor.
Qg (L min-1)
Ug (m s-1)
Hg (%)
a (m-1)
PO3 ,inlet (kPa)
[O*3 ] a (mg L-1)
3.6
6.8 x 10-3
3.5
65.1
1.31
7.5
100.1
11.2
5.4
10 x 10-3
6.9
92.6
1.31
7.5
124.7
17.0
mO3 (mg min-1)
kLab x 10-3 (s-1)
Based on Henry constant 8400 kPa L mol-1 (Sander, 1999)
Calculated from the results on ozone physical sorption by pure water (Huang, 1995) and confirmed by the correlation of
Akita and Yoshida (1974).
118
Nine liters of winery wastewater were charged into the reactor and the degradation
experiments were performed with continuous ozone supply for various time periods. The
water was re-circulated at a flow rate of 1 L per minute in order to improve the mixing of
the liquid in the reactor, in addition to the mixing provided by the gas bubbles.
Water samples were withdrawn regularly and analysed. The pH was monitored at
regular intervals through the ozonation process and, if required, it was controlled using 0.1
M NaOH or 0.1 M H2SO4 solutions. All solutions and reagents were prepared in ultra-pure
water, supplied by a NANOpure Diamond UV water purification system that provides
bacteria free water with resistivity of 18.2 M cm-1 or higher and TOC < 1 ppb. All of the
oxidation experiments were performed in duplicate and the observed standard deviation
was always less than 7% of the reported value.
6.2.3 Analytical methods
The organic matter in the samples was characterised in terms of COD (HACH,
model 45600 coupled with a colorimeter HACH, ODYSSEY) and TOC (Shimadzu TOCVCPH). The absorbance of samples was determined by a UV/vis Spectrophotometer, UV
mini 1240 Shimadzu. The Folin-Ciocalteau method, using gallic acid as a standard, was
followed to evaluate the total polyphenol content in the samples (Singleton and Rossi,
1965). Peroxide concentration in the samples was measured by means of Merckoquant
Peroxide Test strips (0-25 mg H2O2 L-1). If required, the samples were diluted several
times in order to achieve an accurate measurement of the H2O2 concentration.
6.2.4 Ozone consumption
The instantaneous rate of ozone consumption (g L-1 s-1) was calculated by a
macroscopic material balance across the bubble column reactor as:
ro3 =
M o3 ( Po3 ,inlet Po3 ,oulet )
RT
(6.1)
where is the space time for the gas phase with the assumption that it does not vary with
column height. Other symbols are described in the nomenclature section.
119
6.2.5 Stoichiometric ratio

The stoichiometric ratio (z) on a mass basis was calculated from the instantaneous
rate of COD depletion and the rate of ozone consumption:
z=
d (COD) / dt
rCOD
=
ro3
d (Co3 ,inlet Co3 .outlet ) / dt
(6.2)
In a semi-batch reactor with continuous change of the composition of dissolved organics,

ozone consumption varies as a function of time.
6.3 Results and Discussions
6.3.1 Ozonation kinetics of winery wastewater

Ozonation experiments were carried out at the natural pH of the winery wastewater
(pH = 4) and at two other initial pH, 7 and 10, in order to investigate the effect of radical
formation on the rate of COD removal. The pH was not controlled by buffer during the
oxidation experiments. Figure 6.1 shows the evolution of pH during experiments carried
out at pH of 4, 7, and 10. A slight decrease in pH from 4 to 3.5 was observed in the
experiments performed at the natural pH. A sharp decrease in the pH of the solution was
observed in the experiments with initial pH of 7 and 10, and the final pH was observed to
be 3.8 and 4.2, respectively.
10
initial pH 4
initial pH 7
initial pH 10
9
8
pH
7
6
5
4
20
40
60
80
100
120
140
160
180
200
Ozonation time (min)
Figure 6.1 - Evolution of pH during the ozonation experiments. Experimental conditions: liquid
volume 9 L; Qg = 5.4 L min-1; ozone partial pressure 1.31 kPa; initial COD 4650 mg L-1; initial pH
4 (c), 7 (y) and 10 ().
120
The reduction in pH is attributed to the formation of dicarboxylic acids and small

molecule organic acids, as well as CO2 and carbonic acid from total mineralization. The
degradation of organic matter in the wastewater occurs by direct reaction with molecular
ozone at pH = 4. Conversely, ozone decomposition to highly reactive radical species (i.e.,
HO2, O2-, HO3, O3-, HO) takes place at pH 7 and pH 10 (Hoigne and Bader, 1976).
1.0
COD/COD0
0.9
0.8
pH 4
pH 7
pH 10
0.7
0.6
(a)
0.5
0
20
40
60
80
100
120
140
160
180
200
1.0
pH 4
pH 7
pH 10
0.8
A/A0
0.6
0.4
0.2
(b)
0.0
0
20
40
60
80
100
120
140
160
180
200
Figure 6.2 COD (a) and total aromatic content (A) (b) evolution during the ozonation carried out
at initial pH of 4, 7 and 10. Experimental conditions: liquid volume 9 L; Qg = 5.4 L min-1; ozone
partial pressure 1.31 kPa; initial COD 4650 mg L-1; initial pH 4 (), 7 (y) and 10 (c).
121
The self-decomposition of ozone to radicals lasted 5 min in the experiment starting at pH =

7 and 40 min in the experiment at pH = 10, since the decomposition of ozone to radicals
can be considered to be negligible at pH less than 5.5 (Hoigne and Bader, 1976).
Figure 6.2 shows the removal of COD during the ozonation process and the
evolution of the total aromatic content (A) in the wastewater measured by the absorbance
at 254 nm. The fastest removal rates were observed at alkaline pH as a result of the fast
reaction of the organic matter with radical species formed. A rapid decrease of the
absorbance was observed during the first 30 min, and this decrease was faster at pH 10 due
to the rapid reaction of organic matter with molecular ozone and with radicals. The
absorbance approached a plateau at longer times indicating the formation of refractory
intermediates as well as radicals scavenger species (e.g., carbonates). The UV/vis spectra
for the experiment at pH 10 are shown in Figure 6.3.
4.0
3.5
Time
(min):
0
2
4
10
20
30
60
120
180
Absorbance
3.0
2.5
2.0
1.5
1.0
0.5
0.0
200
300
400
500
600
700
Wavelength (nm)
Figure 6.3 UV/vis spectra evolution of the winery wastewater during the ozonation process
starting at pH 10, from 0 min to 180 min. Experimental conditions: liquid volume 9 L; Qg = 5.4 L
min-1; ozone partial pressure 1.31 kPa; initial COD 4650 mg L-1.
A decrease in absorbance was observed, in general, as the reaction proceeded. The

absorbance in the visible range of the spectrum decreased at a faster rate compared to the
absorbance in the UV region. As a consequence, a very rapid colour removal was observed
during the ozonation experiment and the colour changed from light brown to clear after 4
min of ozonation time.
122
The total polyphenol content, measured as the reduction in the concentration of

gallic acid, was monitored during the ozonation reaction (Figure 6.4). This model phenolic
compound was selected since it is the most representative phenolic acid present in winery
wastewaters (La Torre et al., 2006; Silva et al., 2006; Lucas et al., 2008). The removal of
polyphenols is required if the objective of the treatment is to render the water
biodegradable.
1.00
[GA] / [GA] 0
0.80
pH 4
pH 7
pH 10
0.60
0.40
0.20
0.00
0
20
40
60
80
100
120
140
160
180
Figure 6.4 Total polyphenol content evolution during ozonation expressed as equivalent gallic
acid concentration. Reaction conditions: liquid volume 9 L; Qg = 5.4 L min-1; ozone partial pressure
1.31 kPa; initial COD 4650 mg L-1; initial pH 4 (c), 7 (y) and 10 ().
In contrast with the results presented in Figure 6.2, the removal rate of polyphenol
at pH 10 and pH 7 was lower than at pH 4. At pH 4 molecular ozone alone reacts with the
wastewater constituents, however, at pH 10 the predominant reaction mechanism is by
radical oxidation. These results suggest that in a complex mixture of polyphenols and other
species reacting with the oxidant (ozone and/or reactive radicals), the selectivity of
molecular ozone towards attack of polyphenols is higher than the selectivity of the radicals
for polyphenols. In the presence of radicals the reaction of these with easily oxidizable
organic matter in the wastewater other than polyphenols is favoured, which is supported by
the preferential removal of substances absorbing visible radiation (Figure 6.3). Santos et al.
(2003) have reported similar results for the degradation of phenol in vinasse wastewater in
the presence of ozone. The degradation rate of phenol was found to be faster at acidic pH
123
than at alkaline pH. Furthermore, Gurol and Vatistas (1987) have shown that the selectivity
of ozone for phenolic compounds decreases as the pH was increased. The differences in
the selectivity of ozone and radicals for polyhenols are associated with the different
mechanism of oxidation by these species, with ozone following electrophilic attack of
electron rich sites of the target molecule (Gurol and Nekouinaini, 1984), and reactive
radicals reacting unselectively with all species in solution (e.g., the OH radical reacts by
either hydrogen abstraction, OH addition or substitution, or by electron transfer).
Therefore, it may be concluded that the ozonation at natural pH (acidic pH) should
be favoured over the same reaction at alkaline pH, if the purpose of the treatment of winery
wastewater is the removal of the phenolic compounds, such as the removal of toxicity prior
to further biological treatment.
The possibility of peroxide formation by reaction of ozone with natural organic
matter was monitored during the ozonation experiments. The results obtained for three
different experiments at different initial COD are plotted in Figure 6.5, assuming that the
peroxides species generated were mainly hydrogen peroxide.
-1
H2O2 (mgL )
80
COD load:
-1
70
4650 mgL
60
460 mgL
-1
230 mgL
-1
50
40
30
20
10
0
0
20
40
60
80
100
120
140
160
180
200
Time (min)
Figure 6.5 Hydrogen peroxide generated during the treatment of winery wastewater with ozone.
Experimental conditions: initial pH 4; ozone partial pressure 1.31 kPa; liquid volume 9 L; Qg = 5.4
L min-1 (for COD0 equal to 4650 mg L-1 and 230 mg L-1); Qg = 3.6 L min-1 (for COD0 equal to 460
mg L-1 and 230 mg L-1).
124
The amount of hydrogen peroxide generated by the reaction of organic matter with
ozone was found to vary with the initial organic load, and to follow a linear dependence on
time. The rate of hydrogen peroxide produced was found to be 0.44 mg L-1 min-1 for the
experiment with the highest initial COD load (4650 mg O2 L-1). Decreasing the initial
COD of the wastewater by 10 and 20 times the rate of H2O2 formed was 0.17 mg L-1 min-1
and 0.06 mg L-1 min-1, respectively. These results are in agreement with those reported by
others (Latifoglu and Gurol, 2003) who reported the production of H2O2 to be the result of
the reaction of ozone with natural organic matter (NOM) (R6.1) which is also present in
the winery wastewater.
O3 + NOM H2O2
(R6.1)
The formation of hydrogen peroxide during the ozonation of winery wastewater

enhances the oxidation capacity of the ozonation process through secondary reactions. The
interaction of H2O2 with O3 leads to the production of reactive radicals (HO, HO2 and
O3-) that present higher oxidation capacity (reactions 6.2-6.6) than hydrogen peroxide
and/or ozone (Legrini et al., 1993). This effect is more significant at later stages of the
ozonation reaction once hydrogen peroxide has accumulated in the system.
H2O2 + H2O HO2- + H3O+
O3 + H2O2 O2 + HO + HO2
(R6.2)
slow
(R6.3)
HO2- + O3 HO + O2- + O2
(R6.4)
O3 + O2- O3- + O2
(R6.5)
O3- + H2O HO + HO- + O2
(R6.6)

During the experiments the rate of ozone consumption was monitored through the
measurement of the ozone mass flow rate at the inlet and at the outlet of the reactor (Figure
6.6a). The mass flow rate at the reactor inlet was kept constant throughout each
experiment. The difference between the values at the inlet and outlet of the reactor defines
the rate of ozone consumed within the reactor. This includes the contribution from the
reaction of molecular ozone with the organic matter, and can also include the contribution
125
from ozone decomposition at alkaline pH and ozone consumption by the hydrogen

peroxide formed. It should be noted that the ozone flow rate at the reactor outlet was found
to be lower than that at the inlet suggesting that a certain degree of ozone decomposition
occurred even in those cases controlled by the reaction kinetics.
An experimental indication of the prevalent kinetic regime at various reaction times
is provided by the dynamic change of the ORP of the water and ozone consumption during
the ozonation experiments (Lan et al., 2008). Figure 6.6b shows the evolution of the ORP
during the same experiments. For the experiment at initial pH 10 there is a gradual increase
in ORP up to 40 min during which the pH of the solution varies from 10 to 5 (pH evolves
as shown in Figure 6.1). During the first 40 min there is a sharp reduction in UVC
absorbance (Figure 6.1) and a high rate of ozone consumption, which is clearly caused by
the very fast reaction of the organic matter with hydroxyl radicals formed at these pH
values. After 40 min, the pH < 5.5 and the ORP levels out and reaches values well below
those expected for water saturated with ozone (1100 mV). Although, ozone selfdecomposition is suppressed at these pH values, ozone continues to react with the
hydrogen peroxide formed (Figure 6.5) producing radical species that in turn, rapidly react
with the organic matter. Simultaneously, molecular ozone also reacts with the organic
matter. Overall, the reaction will be shown (see Section 6.3.4) to be in the fast kinetic
regime with the reaction occurring at the gas-liquid interface and with little or no ozone
dissolved in the bulk liquid.
At pH 7, there is a rapid increase in ORP and ozone mass flow rate at the reactor
outlet that lasts 10 min, corresponding to the period in which ozone self-decomposition
occurs. At longer reaction time the ORP and the rate of ozone consumption become
constant. The ozone mass flow rate at the reactor outlet is higher than in the experiment
performed at pH 10 due to the lower amount of hydrogen peroxide produced. Overall, the
reaction will be shown to be in the fast kinetic regime with the reaction occurring at the
gas-liquid interface and with little or no ozone dissolved in the bulk liquid.
126
140
-3
-1
Ozone (10 g O3 min )
120
pH 4
pH 7
pH 10
100
80
60
40
20
(a)
0
0
20
40
60
80
100
120
140
160
180

1200
1000
pH 4
pH 7
pH 10
ORP (mV)
800
600
400
200
(b)
0
0
20
40
60
80
100
120
140
160
180
200
Ozonation Time (min)

Figure 6.6 Evolution of the ozone mass flow rate (a) and ORP (b) during winery wastewater
ozonation of winery wastewater at different initial pH. The ozone mass rate at the reactor inlet is
constant and equal to 124.7 mg O3 min-1 (o). Experimental conditions: liquid volume 9 L; Qg = 5.4
L min-1; ozone partial pressure 1.31 kPa; initial COD 4650 mg L-1; initial pH 4 (), 7 (y) and 10
(c).
At pH 4, the ORP instantaneously reaches the level corresponding to the saturation

of the liquid with ozone. The ozone mass flow rate at the reactor outlet also rapidly
increases to a level closer to that at the inlet of the reactor. However, once the hydrogen
peroxide is formed at later stages of the reaction the ORP decreases, as well as, the ozone
127
flow rate at the reactor outlet. At this stage of the reaction, ozone is consumed by hydrogen
peroxide yielding radicals that in turn react with the organic matter. The above
observations suggest that the reaction is in the slow kinetic regime at the beginning of the
reaction time, indicating that the reaction of ozone with organic matter occurs in the bulk
liquid, however the kinetic regime (Hatta number) will increase at later stages of the
oxidation reaction due to the formation of hydrogen peroxide and, in consequence, of
highly reactive radicals.
After 1 hour of reaction the ORP values stabilise around 500 mV, independently of
the initial pH. This suggests that the oxidation of organic matter in the winery wastewater
may proceed following a similar reaction mechanism, involving the reaction with radicals
generated by the reaction of ozone with hydrogen peroxide (reactions R6.2-R6.6).
6.3.3 Ozonation kinetics model
COD was used as a global concentration parameter to describe the complex kinetics
of removal of organic matter and to derive the essential kinetic parameters needed for
reactor design and optimisation. A simplified kinetic model was developed to represent the
kinetics of degradation of winery wastewater in the bubble column reactor. The kinetics of
COD removal by molecular ozone was represented by a second order irreversible reaction
as follows:
O 3 + z1 COD products
(R6.7)
In the presence of ozone decomposition to radicals at alkaline pH, the following

stoichiometry can be approximated for the purpose of modeling the ozonation of winery
wastewater in the reactor:
5.5
O 3 pH
>
radicals
(R6.8)
radicals + z 2COD products
(R6.9)
In the presence of residual hydrogen peroxide formed by the reaction of natural

organic matter with ozone it follows:
128
O3 + z 3COD H 2 O2 + products
(R6.10)
O 3 + H 2O2 radicals
(R6.11)
radicals + z 3COD products
(R6.12)
Adding reactions (R6.7-R6.12) the global kinetics of COD removal by molecular

ozone can be represented by a second order irreversible reaction as follows:
O 3 + z COD products
(R6.13)
where the overall stoichiometric coefficient z (= z1 + z2 + z3) can be estimated from the
instantaneous rate of COD depletion and the rate of ozone consumption (Eq. 6.2). The
value of z was found to vary with reaction time and experimental conditions in the range
from 0.4 to 1.4 on a weight basis.
The model of the bubble column reactor was developed as follows. The gas phase
in the reactor was assumed to be in plug flow and the liquid phase was considered to be
well mixed under the action of the bubbles and of the external recirculation flow. The
ozone mole balance in the absence of the accumulation term, which can be safely
neglected, leads to:
V=
Qg
(1 H g ) RT
Po3 ,inlet
dPo3
Po3 , outlet
ro3
(6.3)
where V is the volume of the bubble column, Qg is the flow rate of gas, Po3,inlet and Po3,outlet
are the partial pressures of ozone respectively at the inlet and at the outlet of the column.
The overall rate of ozone consumption rO3 per unit volume of liquid depends on the
relative effect of gas-liquid ozone mass transfer and ozone reaction in the liquid phase.
Thus, the overall rate of ozone consumption may be controlled by either one or the other or
a combination of both. According to the two-film theory by Lewis and Whitman (1924) the
corresponding kinetic regimes can be discerned by calculating the Hatta number:
Ha =
k o3 Do3 COD
kL
(6.4)
129
where kO3 is the second order reaction rate coefficient for the ozonation reaction, DO3 is the
ozone diffusion coefficient in the liquid and kL is the ozone mass transfer coefficient to the
liquid.
If Ha << 0.03 (very slow kinetic regime) the liquid is saturated with ozone and the
overall rate of ozone consumption is controlled by the rate of reaction of ozone in the
liquid bulk with:
ro3 = k o3 COD Co*3
(6.5)
where
Co*3 =
Po3
(6.6)
is the fictional concentration of ozone in the liquid film in equilibrium with the bulk gas.
If 0.03 < Ha < 0.3 (slow reaction with respect to mass transfer) the liquid contains
dissolved ozone but at a lower concentration than the saturation level. As the value of
Hatta approaches 0.3 the dissolved ozone concentration in the bulk liquid approaches zero
and the overall rate of ozone consumption is controlled by mass transfer of ozone from the
bulk gas to the liquid. According to the two film theory, the overall rate of ozone
consumptions in the kinetic regions described above (Ha < 0.3) is determined from:
ro3 =
k L a k o3 COD Co*3
k L a + k o3 COD
(6.7)
for a slightly soluble gas (gas-film resistance negligible) such as is ozone in water. Note
that Eq. (6.7) reduces to Eq. (6.5) if the rate is controlled by the chemical reaction only.
If Ha > 0.3 (fast or moderate kinetic regime) there is effectively no ozone dissolved
in the liquid bulk and the overall rate of ozone consumption is totally controlled by the rate
of ozone mass transfer from the gas to the liquid film with:
ro3 = k L a C o*3 E
130
(6.8)
where
k L a Ha '
'
'
'
Ha
1 sinh( Ha ) cosh( Ha )
E=
'
k L a Ha '
tanh( Ha )
k
COD
+
o3
tanh( Ha ' )
E E
Ha = Ha i
E
1
0.5
'
Ei = 1 +
(6.9)
DCOD COD
zDo3 C o*3
(6.10)
(6.11)
E is the liquid film enhancement factor, defined as the ratio of the rate of ozone
consumption to the maximum rate of ozone physical sorption.
If 0.03 < Ha < 0.3, E 1 and Eq. (6.8) reduces to Eq. (6.7). Note that in a semibatch bubble column reactor the partial pressure of ozone and the rate of ozone
consumption vary with column height (see Eq. 6.8); therefore the analysis of the reactor
must follow a numerical calculation which discretises the column height in sufficiently
small elements in which the partial pressure of ozone can be considered to be constant.
6.3.4 Estimation of reaction rate coefficient and kinetic regimes
Since the COD of the winery wastewater varies with reaction time, the Hatta
number takes different values as the reaction proceeds and, as a result, several kinetic
regimes may be realised during the same experimental run. The implications are that the
reaction may initially occur at the gas-liquid interphase with no contribution from the bulk
liquid when Hatta is higher than 0.3, shifting towards the bulk liquid at later stages of the
ozonation reaction (Ha << 0.3).
An experimental indication of the prevalent kinetic regime at various reaction times
is provided by the dynamic change of the ORP of the water and ozone consumption during
the ozonation experiments as discussed in Section 6.3.2.
131
The Hatta number can change as a result of a change in the COD or in the reaction rate
coefficient, which is not unexpected since the ozonation reaction of complex water can be
considered to follow a series-parallel reaction scheme. More likely the rate coefficient
would be higher at the beginning of the ozonation since the easily oxidizable species can
react rapidly with ozone and/or with radical species.
The reaction kinetic coefficient kO3 (L of liquid s-1 g-1) as a function of reaction time
in each experiment was estimated by a numerical iterative process involving Eqs. (3) and
(7) when Ha < 0.3, and Eqs. (6.3) and (6.8) when Ha > 0.3. The algorithm developed for
this purpose has been presented by Lan et al., (2008). Since the pH varied during the
reaction time (Figure 6.1), the dependence of the Henry law constant H (kPa L mg-1) from
pH was included in the calculations. The equation of Roth and Sullivan et al. (1981) with
different units was used:
2428
H = 1464.85 (10 1410 pH ) 0.035 exp
(6.12)
which applies in the ranges of temperature (4 60C) and pH (1-10).

The diffusivity of ozone in water at 20C was taken to be 1.7610-9 m2 s-1 (Johnson
and Davis, 1996). The diffusivity of the organic species dissolved in water was assumed to
be DOM= 5x10-10 m2 s-1 (Reid et al., 1977). The gas-liquid interfacial area per unit of liquid
volume was estimated from:
a=
6H g
d bs
(6.13)
where dbs is the Sauter bubble diameter calculated from the correlation of Bouaifi et al,
(2001) and Hg is the gas-hold up which was measured experimentally in the reactor. Hg
was found to be within 3.6% from the value calculated from the correlation by Hikita et al.
(1980).
132
Rate coefficient k O3 (l mg-1min-1)
100
a)
10
Exp 1 (pH = 4.0)

Exp 2 (pH = 4.2)
0.1
Exp 3 (pH = 7.0)

Exp 4 (pH = 10.0)
0.01
0.001
0.0001
0
50
100
150
200
250
300

10
(b)
Moderate - fast
kinetic regime
Hatta number
Slow kinetic
regime with mass
transfer control
0.1
0.01
Very slow kinetic

regime - kinetic
control
0.001
0
50
100
150
200
250
300
Figure 6.7 The dynamic change of the global ozonation reaction rate coefficient (a) and of the
Hatta number (b) as a function of time for experiment at different initial pH and COD
concentrations. Experimental conditions: liquid volume 9 L; ozone partial pressure 1.31 kPa. Exp
1, Exp 3 and Exp 4: Qg = 5.4 L min-1; initial COD 4650 mg L-1. Exp 2: Qg = 3.6 L min-1; initial
COD 487 mg L-1.
The mass transfer coefficient kL was estimated from the ratio of kLa and the interfacial area
estimated from Eq. 6.13 (Table 6.2).
133
Figure 6.7 show the dynamic change of the reaction rate coefficients as a function
of time calculated from the model for experiments conducted at different ozone superficial
velocities and at different initial pH. Exp 1 and 2 were carried out at initial pH 4 and 4.2
but with different initial CODs differing by one order of magnitude and at different gas
flow rates. The dynamic change of the reaction rate coefficients of these experiments
overlaps suggesting that the reactor model and assumptions were satisfactory.
The ozonation reaction for the experiment quoted in Exp 1 begins in the moderate
kinetic regime with a Hatta number 1.1 but quickly reaches the region of slow kinetic
regime with mass transfer control (0.03 < Ha < 0.3). The Hatta number decreases since the
COD decreases, then it increases due to the accumulation of hydrogen peroxide (Figure
6.5) and its reaction with ozone and formation of radicals. These results corroborate with
the trend of ozone consumption and ORP observed in Figure 6.6. Conversely, when the
initial COD and gas flow rate were reduced (Exp 2) the reaction evolves exclusively in the
very slow kinetic regime (Ha < 0.03) indicating that the reaction is occurring in the bulk
liquid. An experimental observation for such behavior was provided by the measurement
of the ozone mass flow rate at the reactor outlet, which reached a level close to that at the
inlet of the bubble column (results not shown) suggesting the saturation of the liquid with
ozone.
The experiments performed at initial pH of 7 and 10 evolve entirely in the
moderate/fast kinetic regime (Ha > 0.3) in the time frame of the experiments. It should be
noted that in the first 5 min (Exp 3) and 40 min (Exp 4) of reaction time, the organic matter
would react with hydroxyl radicals in addition to the reaction with ozone, since the pH
remained above the value of 5.5 (Figure 6.1). As a result the value of the reaction rate
coefficients estimated from the kinetic model can take very large values. Typical reaction
rate constants for the reaction of organics with hydroxyl radicals are reported to be of the
order of 109 L mol-1s-1 (Hoigne and Bader, 1976). However, despite such high values of the
reaction rate coefficient, the rate of COD removal is limited by the rate of ozone mass
transfer from the gas bubble to the liquid film. Once the pH descends below 5.5 the
reaction of organic matter occurs with molecular ozone alone and with radical species
formed through reactions (R6.2-R6.6). As a result, the reaction rate coefficients remain
relatively high compared to those in experiments 1 and 2. Beltrn et al., (1999) reported the
ozonation of wine distillery wastewater (vinasse wastewater) to develop in the fast kinetic
regime with a reaction rate coefficient of 1 L mg-1 min-1, a value close to the results for
134
Exp 4. Benitez et al., (2003b) also reported the ozonation of vinasses and assumed the
reaction to be in the slow kinetic regime and estimated an average value of k03 of 3.80x10-3
L mg-1 min-1, which is of the same order as those found in Exp 1 and 2.
In contrast to the above studies carried out in laboratory scale reactors, our results
show that the ozonation of winery wastewater may develop both in and across different
kinetic regimes depending on the experimental conditions. They further show that, under
the present experimental conditions, the treatment of winery wastewater follows a dynamic
process which reflects the changes in composition of the wastewater during treatment.
6.4 Conclusions
The application of ozonation in a pilot-scale bubble column reactor was proven to

be effective in the degradation of organic substances present in winery wastewater. The
degradation of aromatics and polyphenol content was found to be significantly faster than
the decrease in COD. This suggests that ozonation may be considered as pre-treatment to
further biological treatment. The degradation rate of organic matter and aromatics
increases at alkaline pH, however, polyphenols are more efficiently removed at acidic pH.
At alkaline and neutral pH the degradation rate was accelerated by the formation of radical
species from the decomposition of ozone, however, the observed kinetics was limited by
mass transfer at the gas-liquid interface. Hydrogen peroxide, formed by the reaction of
ozone with natural organic matter in the wastewater, was found to enhance the oxidation
capacity of the ozonation process.
Monitoring of pH, ORP and the rate of ozone consumption gave insights into the
prevalent kinetic regimes during the ozonation process. The reaction was found to develop
in and across different kinetic regimes: fast, moderate and slow depending on the
experimental conditions. As a result, beside the use of bubble columns (large bulk volume)
which are recommended for gas-liquid reactions in the slow kinetic regime (reaction in the
bulk liquid), other gas-liquid ozonation contactors that offer large contact surface area to
volume ratios may be considered if the reaction develops predominantly in the fast or
moderate kinetic regime (reaction at the gas-liquid interface).
A kinetic model of the ozonation process occurring in the semi-batch bubble
column reactor was presented and was coupled with a second order irreversible reaction of
ozone with the dissolved organic matter. The dynamic change of the rate coefficient
135
estimated by the model was correlated with changes in the water composition and oxidant
species. The model presented and the rate coefficient determined can be used for design
and scale-up of ozonation bubble columns for the treatment of winery wastewater under
similar experimental conditions as in this work.
References
Akita, K., Yoshida, F., 1974. Bubble size, interfacial area, and liquid-phase mass transfer
coefficient in bubble columns. Ind. Eng. Chem. Process Des. Develop. 13 (1), 84-91.
Artiga, P., Ficara, E., Malpei, F., Garrido, J.M., Mndez, R., 2005. Treatment of two industrial
wastewaters in a submerged membrane bioreactor. Desalination 179, 161-169.
Beck, C., Prades, G., Sadowski, A-G., 2005. Activated sludge wastewater treatment plants
optimisation to face pollution overloads during grape harvest periods. Water Sci. Technol. 51, 8188.
Beltran, F.J., Garca-Araya, J.F., lvarez, P.M.,1999. Wine-distillery wastewater degradation. 1.
Oxidative treatment using ozone and its effect on the wastewater biodegradability. 2. Improvement
of aerobic biodegradation by means of an integrated chemical (ozone)-biological treatment. J.
Agric. Food Chem. 47, 3911-3924.
Beltrn, F.J., Garca-Araya, J.F., lvarez, P.M., 2001. pH sequential ozonation of domestic and
wine-distillery wastewaters. Water Res. 35, 929-936.
Beltran-Heredia, J., Torregrosa, J., Dominguez J.R., Garcia J., 2000. Ozonation of black-table-olive
industrial wastewaters: effect of an aerobic biological pretreatment. J. Chem. Technol. Biotechnol.
75, 561-568.
Beltran-Heredia, J., Torregrosa, J., Dominguez J.R., Peres J.A., 2001. Kinetic model for phenolic
compound oxidation by Fenton's reagent. Chemosphere 45, 85-90.
Benitez, F.J., Beltrn-Heredia, J., Torregrosa, J. 1997. Improvement of the anaerobic
biodegradation of olive mill wastewaters by prior ozonation pretreatment. Bioprocess Engineering,
17, 169-176.
136
Benitez, F.J., Beltran-Heredia, J., Real F.J., Acero J.L., 1999a. Enhancement of the ozonation of
wine distillery wastewaters by an aerobic pretreatment. Bioprocess Eng. 21, 459 464.
Benitez, F.J., Beltran-Heredia, J., Real, F.J., Gonzalez, T., 1999b. Aerobic and anaerobic
purification of wine distillery wastewater in batch reactors. Chem. Eng. Technol. 22, 165-172.
Benitez, F.J., Beltrn-Heredia, J., Torregrosa, J., Acero, J.L., 1999c. Treatment of olive mill
wastewaters by ozonation, aerobic degradation and the combination of both treatments. J. Chem.
Technol. Biotechnol. 74, 639-646.
Benitez, F.J., Acero, J.L., Garcia, J., Leal, A.I. 2003a. Purification of cork processing wastewater
by ozone, activated sludge system and by their two sequential applications. Water Res. 37, 40814090.
Benitez, F.J., Real, F.J., Acero, J.L., Garcia, J., Sanchez, M., 2003b. Kinetics of the ozonation and
aerobic biodegradation of wine vinasses in discontinuous and continuous processes. J. Haz. Mat.
B101, 203-218.
Bouaifi, M., Roustan, M., 1998. Bubble size and mass transfer coefficients in dual-impeller
agitated reactors. Can. J. Chem. Eng. 76, 390-397.
Gimeno, O., Rivas, F.J., Beltrn, F.J., Carbajo, M., 2007. Photocatalytic ozonation of winery
wastewaters. J. Agricul. Food Chem. 55, 9944-9950.
Gurol, M.D., Nekouinaini, S., 1984. Kinetic behaviour of ozone in aqueous solutions of substituted
phenols. Ind. Eng. Chem. Fundam. 23, 54-60.
Gurol, M.D., Vatistas, R., 1987. Oxidation of phenolic compounds by ozone and ozone + UV
radiation: a comparative study. Water Res. 21, 895-900.
Hikita, H., Asai, S., Tanigawa, K., Segawa, K., Kitao, M., 1980. Gas holdup in bubble columns.
Chem. Eng. J. Biochem. Eng. J. 20, 59-67.
Hoigne, J., Bader, H., 1976. The role of hydroxyl radical reactions in ozonation processes in
aqueous solutions. Water Res. 10, 377-386.
Huang, C. R. S., 1995. The reaction kinetics, decomposition pathways and intermediate formations
of phenol in ozonation, UV/O3 and UV/H2O2 processes. J. Hazard. Mat. 41, 47-64.
137
Johnson, P.N., Davis, R.A., 1996. Diffusivity of ozone in water. J. Chem. Eng. Data 41, 14851487.
La Torre, G., L., Saitta, M., Vilasi, F., Pellicano, T., Dugo, G., 2006. Direct determination of
phenolic compounds in Sicilian wines by liquid chromatography with PDA and MS detection.
Food Chemistry 94, 640650.
Lan, B.Y., Nigmatullin, R., Li Puma, G. 2008. Ozonation kinetics of cork-processing water in a
bubble column reactor. Water Res. 42, 2473-2482.
Latifoglu, A., Gurol, M.D., 2003. The effect of humic acids on nitrobenzene oxidation by
ozonation and O3/UV processes. Water Res. 37, 1879-1889.
Legrini, O., Oliveros, E., Braun, A.M., 1993, Photochemical processes for water treatment. Chem.
Rev. 93, 671-698.
Lewis, W.K., Whitman W.G., 1924. The two-film theory of gas absorption. Ind. Eng. Chem. 16,
1215-1224.
Litter, M.I., 2005. Introduction to Photochemical Advanced Oxidation Processes for Water
Treatment. Vol. 2, Part M, 325-366 Springer-Verlag, Berlin.
Lucas, M.S., Dias, A.A., Bezerra, R.M., Peres, J.A., 2008. Gallic acid photochemical oxidation as a
model compound of winery wastewaters. J. Environ. Sci Health-A 43, 12881295.
Malandra, L., Wolfaardt, G., Zietsman, A., Viljoen-Bloom, M., 2003 Microbiology of a biological
contactor for winery wastewater treatment. Water Res. 37, 4125-4134.
Monteagudo, J.M., Carmona, M., Durn, A., 2005. Photo-Fenton-assisted ozonation of p-coumaric
acid in aqueous solution. Chemosphere 60, 1103-1110.
Mosteo, R., Ormad, P., Mozas, E., Sarasa, J., Ovelleiro, J.L., 2006. Factorial experimental design
of winery wastewaters treatment by heterogeneous photo-Fenton process. Water Res. 40, 15611568.
Navarro, P., Sarasa, J., Sierra, D., Esteban, S., Ovelleiro, J.L., 2005. Degradation of wine industry
wastewaters by photocatalytic advanced oxidation. Water Sci. Technol. 51, 113-120.
Petruccioli, M., Duarte, J.C., Federici, F., 2000. High rate aerobic treatment of winery wastewater
using bioreactors with free and immobilized activated sludge. J Biosci Bioeng. 90, 381-386.
138
Pirra, A.J.D., 2005. Caracterizao e tratamento de efluentes vincolas da Regio Demarcada do

Douro. PhD thesis, Universidade de Trs-os-Montes e Alto Douro, Vila Real, Portugal.
Roth, J.A., Sullivan, D.E. 1981. Solubility of ozone in water. Ind. Eng. Chem. Fundam. 20, 137140.
Reid, R.C., Prausnitz, J.M., Sherwood, T.K., 1977. The Properties of Gases and Liquids. McGrawHill, New York, USA.
Sander, R., 1999. Compilation of Henrys law constants for inorganic and organic species of
potential importance in environmental chemistry (version 3). <http://www.henrys-law.org>.
Santos, M.A.M., Bocanegra, J.L.F., Martn, A.M., Garcia, I.G., 2003. Ozonation of vinasse in acid
and alkaline media. J. Chem. Technol. Biotechnol. 78, 1121-1127.
Silva, M.N.B.S., Coelho, A.V., Vilas Boas, L., Bronze, M.R., 2006. Analysis of phenolic
compounds in Muscatel wines produced in Portugal. Analyt. Chemic. Acta, 563, 84-92.
Singleton, V.L., Rossi, J.A., 1965. Colorimetry of total phenolics with phosphomolybdicphosphotungstic acid reagents. Amer. J. Enol. Viticult. 16, 144158.
Sotelo, J.L., Beltrn F.J., Bentez, F.J., Beltrn-Heredia, J., 1987. Ozone decomposition in water:
kinetic study. Ind. Eng. Chem. Res. 26, 39-43.
139
Chapter 7 Application of O3/UV and O3/UV/H2O2 processes to winery wastewater in a pilot bubble column reactor
CHAPTER 7 APPLICATION OF O3/UV AND O3/UV/H2O2 PROCESSES

TO WINERY WASTEWATER IN A PILOT BUBBLE COLUMN REACTOR
Abstract
The effectiveness of different ozone-based advanced oxidation processes (O3, O3/UV and
O3/UV/H2O2) on the treatment of winery wastewater was investigated in a pilot-scale,
bubble column reactor. At the natural pH of the wastewater (pH 4) the effectiveness of
each AOP followed the sequence: O3/UV/H2O2 > O3/UV > O3 > UV-C. The rate of
chemical oxygen demand (COD) and total organic carbon (TOC) removal were enhanced
further by operation at neutral (pH 7) and at alkaline pH (pH 10). The underlying
chemistry involved in each of the AOPs is discussed and correlated with the observed
reactivity. The rate of ozone consumption in the reactor with the O3/UV and O3/UV/H2O2
processes was in the region from 70-95% during the experiments, suggesting an effective
use of the ozone supplied to the system. In all the experiments the disappearance of the
winery wastewater organic load was described by pseudo-first order apparent reaction
kinetics. The faster rate constant (6.5x10-3 min-1), at the natural pH of the wastewater, was
observed with the O3/UV/H2O2 process under optimised oxidant dose (COD/H2O2 = 2). An
economical analysis on the operating costs of the AOPs processes investigated revealed the
O3/UV/H2O2 to be the most economical process (1.31 Euro m-3 g-1 of TOC mineralised
under optimised conditions) to treat the winery wastewater.
* Adapted from: Lucas M.S., Peres J.A., Li Puma G. Journal of Hazardous Materials (Submitted).
141
7.1. Introduction
Wine is an alcoholic beverage made of fermented grape juice. Producing wine
requires the implementation of several unit operations (grape reception, must production,
fermentation, decanting, maturation-stabilization, filtration and transportation-disposal)
(Brito et al., 2007; Strong and Burgess, 2008). In the unit operations performed in
wineries, distilleries and other grape processing industries, large volumes of waste streams
are generated annually. These include organic waste (solids, skins, pips, etc.), wastewater,
greenhouse gases (CO2, volatile organic compounds, etc.) and inorganic wastes
(diatomaceous earth, bentonite clay and perlite). It is estimated that a cellar produces
between 1.3 and 1.5 kg of residues per litre of wine produced, 75% of which is winery
wastewater (Arnaiz et al., 2007).
The organic content of winery wastewater consists of highly soluble sugars,
alcohols, acids and recalcitrant high-molecular-weight compounds (e.g., polyphenols,
tannins and lignans) not easily removable by physical or chemical means.
Advanced Oxidation Processes (AOPs) are known for their capability to mineralise
a wide range of organic compounds. AOPs involve the generation of highly reactive
radical species, predominantly the hydroxyl radical (HO) (Legrini et al., 1993; Litter,
2005). Ozone is a strong oxidizer having high reactivity and selectivity towards organic
compounds such as polyphenols. Among AOPs, ozonation and ozonation in combination
with UV-C radiation and/or peroxidation has been shown to be effective in the treatment of
wastewater with high polyphenols content such as from the cork manufacturing industry
(Benitez, Acero et al., 2003; Lan et al., 2008), the olive oil industry (Benitez et al., 1997;
Beltrn-Heredia et al., 2000) and the wine distillery industry (Beltrn et al., 1999; BeltrnHeredia et al., 2001; Benitez et al., 1999; Benitez, Real et al., 2003; Monteagudo et al.,
2005; Santos et al., 2003). One major advantage of the application of ozone-based AOPs
(O3, O3/UV and O3/UV/H2O2) in the treatment of complex wastewater, of polyphenols and
other species, rests in the higher selectivity of molecular ozone towards polyphenols when
compared to the reaction of these with radical species (e.g., the hydroxyl radical). The
differences in the selectivity of ozone and radicals for polyphenols are associated with the
different mechanism of oxidation by these species, with ozone following electrophilic
attack of electron rich sites of the target molecule (Gurol and Nekouinaini, 1984) and
142
reactive radicals reacting unselectively with all species in solution (e.g., the OH radical
reacts by either hydrogen abstraction, OH addition or substitution, or by electron transfer).
On the other hand, the oxidation potential of the hydroxyl radical (E0 = 2.80 mV) is
much higher than that of ozone (E0 = 2.07 mV), therefore, the combination of ozone with
UV and/or H2O2 which yields hydroxyl, peroxyl and superoxide radicals should
synergistically accelerate the removal of organic matter from complex wastewater
matrices.
The treatment of winery wastewater by ozonation and ozone related AOPs
processes have been demonstrated in small and pilot scale studies. Gimeno et al. (2007)
reported the photocatalytic ozonation of winery wastewater in a 1 L reactor and the total
mineralization of the COD removed in the presence of UV-A, ozone and titanium dioxide.
Navarro et al. (2005) investigated the degradation of wine industry wastewater by
photocatalytic oxidation, UV-peroxidation and Fenton reaction over iron rich clays in 100
mL glass vials.
In our previous work (Lucas et al., 2009), we have investigated the kinetics of
ozonation of winery wastewater in detail in a pilot-scale (9 L), semi-batch bubble column
reactor under alkaline, neutral and acidic conditions. We have concluded that ozonation
prior to biological treatment could be beneficial to remove the toxicity (polyphenols) from
the wastewater. The degradation of aromatics and polyphenols was found to be
significantly faster than the decrease in COD.
In this work, we investigate the effectiveness of different ozone-based AOP (O3,
O3/UV and O3/UV/H2O2) on the treatment of winery wastewater, in a pilot-plant scale
reactor, with the objective of suggesting the most efficient process for implementation by
the industry. The effect of initial pH, organic load of winery wastewater and hydrogen
peroxide concentration were investigated in the same pilot scale reactor. The effect of each
AOP on the reduction of chemical oxygen demand (COD) and total organic carbon (TOC)
was evaluated and operating costs were estimated.
7.2.1
Winery wastewater
The winery wastewater was collected from a wine production unit located in the
Douro region in the north of Portugal. The pH, the absorbance at 254 nm, the total carbon
143
(TC), inorganic carbon (IC), the COD and polyphenols content measured as equivalent
gallic acid content are presented in Table 7.1.
Abs254 nm
pH
4.0
7.2.2
TC
-1
IC
-1
COD
-1
Polyphenols
-1
(cm )
(mg L )
(mgL )
(mg O2 L )
(mggallic acid L-1)
1.562
1255
1.11
4650
103
Ozonation
The ozonation and the ozone-based AOPs (O3/UV and O3/UV/H2O2) experiments
were conducted in a bubble-column semi-batch reactor (internal diameter 0.1 m, height 1

m) made of QVF borosilicate glass equipped with a quartz UV lamp tube (external
diameter 40 mm) mounted in the axial position which houses the lamp (Figure 7.1). The
UV-C lamp used (Philips TUV36W, bulb dimensions: 1.156 m long, 28 mm diameter)
emits predominantly monochromatic radiation at 253.7 nm.
8
13
3
10
4
12
7
6
2
2
14
9
11
Figure 7.1 Schematic representation of the pilot plant used in this study. The plant consists in:
[1]. Oxygen Cylinder; [2]. Silica Filter; [3]. Ozone Generator; [4]. Flowmeter; [5]. Dreschel Bottle
(In); [6]. Ozonation Reactor; [7]. UVC Lamp; [8]. Variable Power Transformer; [9]. Recirculation
Pump; [10]. Ozone Monitor; [11]. Dreschel Bottle (Out); [12]. Ozone Destructor; [13] Extractor;
[14] Ozone Detector.
144
The reactor was equipped with a liquid stream outlet at the bottom and an inlet at
the top, connected to a peristaltic pump (Masterflex 77200-62, Cole-Parmer, USA) to
assist water recirculation in the reactor. An in-line redox potential (ORP) sensor was
installed in the water recirculation tube. The gas stream enriched with ozone entered the
reactor via a sintered stainless steel porous disk S20 (Porvair Ltd., UK, mean pore size 15
m) at the bottom of the reactor. A gas stream outlet at the top of the reactor led to a
thermal ozone destructor. Liquid samples were collected with a syringe through a sealed
port in the reactor. The ozone concentration at the gas inlet and outlet of the reactor were
measured by redirecting the flows to a series of Drechsel flasks containing a 2% potassium
iodide solution.
High purity oxygen (99.999 %, BOC gases, UK) was fed to a silica drier to remove
trace water prior to entering the ozone generator (OZOMAX 8Vtt, Ozomax, Canada)
capable of producing up to 0.68 g ozone per minute. The hydrodynamic and operational
conditions used in this study are summarised in Table 7.2 with the symbols presented in
the nomenclature section.
Table 7.2 Hydrodynamic and operational conditions of the ozonation reactor
Qg (L min-1)
U g (ms-1)
H g (%)
a (m-1)
3.6
6.8 x 10-3
3.5
65.1
PO3
(kPa)
1.31
* 1
[ O3 ]
mO3 (mg min-1)
7.5
100.1
kLa2
x 10-3 (s-1)
11.2
-1
Based on Henrys constant 8400 k Pa L mol (Sander, 1999).
Calculated from the results on ozone physical sorption by pure water (Huang, 1995) and confirmed by the
correlation of Akita and Yoshida (1974).
Nine liters of winery wastewater were charged into the reactor and the degradation
experiments were performed with continuous ozone supply for various time periods. The
water was re-circulated at a flow rate of 1 L per minute in order to improve the mixing of
the liquid in the reactor, in addition to the mixing provided by the gas bubbles.
In the O3/UV/H2O2 process, the required amount of H2O2 was added to the reactor
as a single dose at time zero in order to reach COD/H2O2 ratios of 1, 1.3, 2 and 4. All
samples withdrawn from the experiments involving H2O2 were treated with a saturated
solution of NaOH to quench the reaction of residual H2O2 in the samples.
Water samples were withdrawn regularly and analysed. The pH was monitored at
regular intervals through the ozonation process and, if required, it was controlled using 0.1
145
M NaOH or 0.1 M H2SO4 solutions. All solutions and reagents were prepared in ultra-pure
water, supplied by a NANOpure Diamond UV water purification system that provides
bacteria free water with resistivity of 18.2 M cm-1 or higher and TOC < 1 ppb. All of the
oxidation experiments were performed in duplicate and the observed standard deviation
was always less than 6% of the reported value.
7.2.3 Analytical methods

The organic matter in the samples was characterised in terms of COD (HACH,
model 45600 coupled with a colorimeter HACH, ODYSSEY) and TOC (Shimadzu TOCVCPH). The absorbance of samples was determined by a UV/Vis Spectrophotometer, UV
mini 1240 Shimadzu. The Folin-Ciocalteau method, using gallic acid as a standard, was
followed to evaluate the total polyphenols content in the samples (Singleton and Rossi,
1965). Hydrogen peroxide concentration in the samples was measured by means of
Merckoquant Peroxide Test strips (0-25 mg H2O2 L-1). If required, the samples were
diluted several times in order to achieve an accurate measurement of the H2O2
concentration.
7.3.1. AOP comparison

Experiments were carried out with UV radiation, ozone only, O3/UV and
O3/UV/H2O2 at the natural pH of the winery wastewater (pH = 4), in order to investigate
the influence of each process on the rate of COD removal. The pH was not controlled by
buffer during these oxidation experiments. Figure 7.2 presents the results achieved on
COD reduction of winery wastewater and the comparison of the four treatment processes.
The direct photolytic action of UV-C radiation on the compounds dissolved in the winery
wastewater was insignificant. Ozonation reduced the initial COD by 12% and the
combination of UV-C radiation and ozonation reached a COD removal of 21%, after 180
minutes of reaction. An enhancement of the COD removal was achieved by adding
hydrogen peroxide to the solution in the O3/UV/H2O2 process. With a COD/H2O2 (w/w)
ratio equal to 4, the COD removal was 35% after 180 min. The UV light intensity and
ozone dose were kept constant in the above experiments. The low COD reduction by the
146
ozone alone process at pH 4 is due to the fact that the ozone molecule is too stable at this
acidic condition to produce reactive radical species. However, both the O3/UV and
O3/UV/H2O2 processes were capable of oxidizing winery wastewater faster than ozone on
its own showing a photochemical adding up oxidation effect. This is principally due to the
photolysis of ozone, the enhanced mass transfer of ozone and the generation of hydroxyl
radicals that react rapidly with the organic matter in the winery wastewater (Beltrn, 2003).
The underlying chemistry is well known.
1,0
COD/COD0
0,9
0,8
UV
Ozone
Ozone/UV
Ozone/UV/H2O2
0,7
0,6
0,5
0
50
100
150
200
Time (min)
Figure 7.2 COD evolution during the UV, O3, O3/UV and O3/UV/H2O2 treatment of winery
wastewater. Experimental conditions from Tables 7.1 and 7.2. Liquid volume 9 L; COD/H2O2
(w/w) = 4, initial pH 4.
The photodecomposition of ozone by UV-C radiation leads to formation of H2O2 and

hydroxyl radicals as shown by the following reactions (Legrini et al., 1993; Litter, 2005):
O3 + H2O + h H2O2 + O2
(7.1)
O3 + H2O2 HO2 + OH + O2
k = 6.5 10-2 (M-1 s-1) very slow (7.2)
In addition, the photolysis of H2O2 by UVC radiation yields two hydroxyl radicals
from each molecule of hydrogen peroxide:
H2O2 + h 2OH
(7.3)
147
In the presence of H2O2 in addition to photolysis (7.3) the following equilibrium

occurs:
H2O2 + H2O H3O+ + HO2-
pK = 11.65
(7.4)
Both ozone and hydrogen peroxide react with the hydroxyl radicals to form the
peroxyl and the superoxide radical (7.5-7.6):
OH + O3 O2 + HO2
k = 1.1 108 (M-1 s-1)
(7.5)
OH + H2O2 O2 - + H2O + H+
k = 2.7 107 (M-1 s-1)
(7.6)
which in turn they react further with the hydroxyl radical and ozone in a propagation
reaction scheme to yield hydroxyl radicals:
OH + O2 - OH-+ O2
k = 1 1010 (M-1 s-1), pH = 7.9
(7.7)
OH + OH- H2O + O -
k = 1.3 1010 (M-1 s-1)
(7.8)
O3 + O2 - O3 - + O2
k = 1.6 109 (M-1 s-1)
(7.9)
-1
O3 + H2O OH + OH + O2
k = 9.4 10 (s ) at alkaline pH
(7.10)
O3 + HO2- O2 - + OH + O2
k = 5.5 106 (M-1 s-1)
(7.11)
Hydroxyl, peroxyl and superoxide radical recombination (7.12-7.13) produce

hydrogen peroxide which can be photolyzed again (7.3).
HO2 + HO2 H2O2 + O2
k = 8.3 105 (M-1 s-1)
(7.12)
OH + OH H2O2
k = 4.2 109 (M-1 s-1)
(7.13)
HO2 + O2 - + H2O H2O2 + O2 + OH-
k = 9.7 107 (M-1s-1)
(7.14)
Under an excess of H2O2 the scavenging reaction (7.6) may become predominant
followed by:
OH + HO2 H2O + O2 k = 8.0 x 109 (M-1 s-1)
148
(7.15)
As the highest degradation capacity was showed by the O3/UV and O3/UV/H2O2
processes, the effects of the operational conditions, such as, pH, initial organic load (TOC)
and hydrogen peroxide concentration COD/H2O2 (w/w) ratio, were studied in the treatment
of winery wastewater.
7.3.2 Ozone/UV
O3/UV experiments were carried out at the natural pH of the winery wastewater
(pH = 4) and at two other initial pH, 7 and 10, in order to investigate the effect of radical
formation on the rate of COD removal. Figure 3 presents results of COD removal and pH
evolution. The fastest COD removal was observed at pH 10 as a result of the fast reaction
of the organic matter with the radical species (i.e., OH , HO2, O2-, O3). At alkaline pH
ozone self-decomposition to radicals occurs as a result of the initiation reaction (Tomiyasu
et al., 1985):
O3 + OH- HO2- + O2
k = 40 (M-1 s-1)
pH = 10
(7.16)
with a half life reported to be 20 s (Hoigne and Bader, 1976) (Figure 7.3a). In addition, the
H2O2 is deprotonated preferentially to water to give the hydroperoxide anion HO2- which
then reacts in a chain mechanism. However, once the pH reached values close to neutral
and below (Figure 7.3b) the COD removal rates were identical in the three experiments.
During this stage the removal of COD was controlled by the generation of radical
species by the reaction scheme presented above (in which reactions 7.4, 7.10, 7.11 and
7.15 become less important).
Figure 7.3b shows the evolution of pH for the above experiments. A slight decrease
in pH from 4 to 3.7 was observed in the experiments performed at the natural pH. A sharp
decrease in the pH of wastewater was observed in the experiments with initial pH of 7 and
10, and the final pH was 3.8 and 4.0, respectively, which indicates that a strong oxidation
took place. The reduction in pH is attributed to the formation of dicarboxylic acids and
small molecule organic acids, as well as, CO2 and carbonic acids from total mineralization.
149
1,0
COD/COD0
0,8
0,6
Ozone/UV:
initial pH 4
initial pH 7
initial pH 10
0,4
0,2
a)
0,0
0
50
100
150
200
250
300
Time (min)
10
b)
Ozone/UV:
initial pH 4
initial pH 7
initial pH 10
pH
8
7
6
5
4
50
100
150
200
250
300
Time (min)
Figure 7.3 (a) COD evolution during the O3/UV treatment of winery wastewater. (b) Evolution
of pH. Experimental conditions from Tables 7.1 and 7.2. Liquid volume 9 L; Initial pH 4 (), 7
(y) and 10 (c).
7.3.3 Ozone/UV/H2O2
Experiments in the presence of ozone, UV radiation and hydrogen peroxide
(O3/UV/H2O2 process) were found to increase the degradation of the organic matter in the
winery wastewater further. Figure 7.4 shows the effect of pH in the removal of COD as a
function of reaction time and the pH evolution during the experiments. The removal
150
efficiency is slightly higher at pH 10 (57%) than pH 4 (49%) and pH 7 (40%) after 300
minutes. In the O3/UV/H2O2 process the production of hydroxyl radicals by reaction (7.3)
becomes highly significant due to the supplementary H2O2 added to the solution, as well as
reaction (7.6) under an excess of peroxide. In addition, the reaction of ozone with H2O2
(7.2) also produce hydroxyl radicals although at a slower rate.
1,0
COD/COD0
0,8
0,6
0,4
Ozone/UV/H2O2:
initial pH 4
initial pH 7
initial pH 10
0,2
a)
0,0
0
50
100
150
200
250
300
Time (min)
11
b)
10
9
Ozone/UV/H2O2:
initial pH 4
initial pH 7
initial pH 10
pH
8
7
6
5
4
3
0
50
100
150
200
250
300
Time (min)
Figure 7.4 (a) COD evolution during the O3/UV/H2O2 treatment of winery wastewater. b)
Evolution of pH. Experimental conditions from Tables 7.1 and 7.2. Liquid volume 9 L; COD/H2O2
(w/w) = 4; initial pH 4 (), 7 (y) and 10 (c).
The evolution of pH in these experiments followed the same trends as in the

experiments carried out in the absence of H2O2, although the experiments at pH 10 showed
151
a slower rate of pH decay, which also explain partially the faster rates observed with the
O3/UV/H2O2 in comparison to the other AOPs.

During the experiments the rate of ozone consumption was monitored through the
measurement of the ozone mass flow rate at the inlet and at the outlet of the reactor (Figure
7.5). The mass flow rate at the reactor inlet was kept constant throughout each experiment.
The difference between the values at the inlet and outlet of the reactor defines the rate of
ozone consumed within the reactor. This includes the contribution from the reaction of
molecular ozone with the organic matter, and can also include the contribution from ozone
decomposition at alkaline pH and ozone consumption by the hydrogen peroxide formed or
added to the reactor.
The evolution of the ozone mass flow rate at the reactor outlet of the bubble column
reactor with the O3/UV and O3/UV/H2O2 processes at different pH, is shown in Figure 7.5.
In contrast with the results for ozonation alone presented in Lucas et al. (2009) a much
higher rate of ozone consumption, in the region from 70-95% was observed in these
experiments, suggesting a more effective use of the ozone supplied to the system.
Ozone Mass Flow Rate
100
Ozone/UV:
Initial pH 4
Initial pH 7
Initial pH 10
Ozone/UV/H2O:
Initial pH 4
Initial pH 7
Initial pH 10
80
60
40
20
0
0
50
100
150
200
250
300
Time (min)
Figure 7.5 Evolution of the ozone mass flow rate at different initial pH for the treatment of
winery wastewater with O3/UV (open symbols) and O3/UV/H2O2 (filled symbols). The ozone mass
rate at the reactor inlet is constant and equal to 100.1 mg O3 min-1 (o) in all cases. Experimental
conditions from Tables 7.1 and 7.2. Liquid volume 9 L; COD/H2O2 (w/w) = 4.
152
At pH 4, a lower rate was observed with O3/UV compared to the O3/UV/H2O2 process as a
result of lower contribution of reactions (7.2-7.4) since H2O2 can only be produced by
reaction (7.1) in the first instance and by radical recombination reactions (7.12-7.14).
Conversely, at pH 7 and 10 ozone consumption was found to be very similar
(> 85%) in both the O3/UV and the O3/UV/H2O2 processes. However in the experiment at
pH 10 with O3/UV/H2O2 a significant reduction of the rate of ozone uptake was observed
after 120 min, possibly due to the lower level of COD reached (Figure 7.4a) and the
decomposition of H2O2 (reaction 7.4) at alkaline conditions, which in turns reduces the
amount of hydroxyl radicals formed by H2O2 photolysis (reaction 7.3).
7.3.5 Reaction kinetics

A rigorous kinetic study of the ozonation of winery wastewaters is difficult to be
performed due to the presence of multiple and unknown reactions. However, COD and
TOC can be used to describe the global kinetics of organic matter removal and to derive
the essential kinetic parameters needed for reactor design and optimisation (Preis et al.,
1988). The removal of COD form the winery wastewater by the different AOPs was fitted
by an apparent first-order rate equation. The pseudo-first order rate constants at pH 4, 7
and 10 and the %TOC removed after 300 min are presented in Table 7.3. The removal of
TOC was found to follow the trend of COD removal. The COD/TOC ratio was found to
decrease during treatment other than in the experiments carried out in the presence of
H2O2. The decrease of COD/TOC ratio in both the O3 and the O3/UV processes indicates
the increase of the average oxidative state of carbon in the organic in solution and lower
reactivity toward ozone (Hsu et al., 2005). On the contrary, the increase in the COD/TOC
ratio in the experiments carried out with the O3/UV/H2O2 process indicates either an
increase of the H2O2 concentration in solution as the reaction proceeds through radical
recombination (reactions 7.12-7.14) and/or a degradation pathways driven primarily by
radical oxidation leading to different reaction intermediates. The rate constants and TOC
removal with the O3/UV/H2O2 process were the highest, and significantly higher at pH 4
(the natural pH of winery wastewater) compared to the other AOPs. These results suggest
the importance of combining ozone, UV radiation and hydrogen peroxide as a potential
method for the treatment of winery wastewater.
153
Table 7.3 Initial pseudo-first order rate constants (k') obtained from COD removal, R2 and TOC values
after a reaction time of 300 minutes with ozone and ozone related AOPs at different initial pH.
COD/TOC
COD/TOC
(0 min)
(300 min)
% TOC
removed
after 300 min
k ' (min )
O3 (pH 4)
1.1x10-3
0.994
4.13
3.99
4.4
O3 (pH 7)
1.1x10-3
0.986
3.83
3.29
5.4
O3 (pH 10)
1.4x10-3
0.989
3.84
3.23
7.9
O3/UV (pH 4)
1.5x10-3
0.997
4.15
3.04
8.5
O3/UV (pH 7)
1.8x10-3
0.986
3.00
2.60
13
O3/UV (pH 10)
1.9x10-3
0.966
3.76
3.21
26
O3/UV/H2O2 (pH 4)
2.2x10-3
0.983
3.24
3.99
49
O3/UV/H2O2 (pH 7)
2.2x10-3
0.969
3.74
5.92
49
O3/UV/H2O2 (pH 10)
2.9x10-3
0.979
3.68
4.40
64
Process
-1
7.3.6 Effect of initial hydrogen peroxide concentration and organic load

Figure 7.6 shows the influence of hydrogen peroxide concentration on the treatment
of winery wastewater by the O3/UV/H2O2 process at pH 4, the natural pH of the winery
wastewater (Table 7.1). The COD/H2O2 (w/w) ratio was varied: 1; 1.3; 2 and 4. It shows
that almost complete mineralisation can be achieved (88% TOC removal) under optimised
oxidant dose (COD/H2O2 = 2). At COD/H2O2 = 4 there is insufficient supplementary
peroxide, at COD/H2O2 = 1.3 the TOC removal is slightly lower than at the optimum
COD/H2O2 ratio, and at COD/H2O2 = 1 there is excess peroxide which scavenges hydroxyl
radicals (reactions 7.6 and 7.15). Figure 7.6 (inset) shows the apparent first-order rate
constant of TOC removal to be significantly affected by the COD/H2O2 ratio. The highest
rate constant (6.5x10-3 min-1 with COD/H2O2 = 2) is six-fold higher than the rate constant
with O3 process alone.
154
1,0
-1
k (min ) x 10
-3
0,8
TOC/TOC0
0,6
0,4
COD/H2O2
COD/H2O2:
4
2
1.3
1
0,2
0,0
50
100
150
200
250
300
Time (min)
Figure 7.6 Influence of initial hydrogen peroxide dosage in the mineralization of winery
wastewater with the O3/UV/H2O2 process. Inset shows the apparent first-order rate constant of
TOC removal. Experimental conditions from Tables 7.1 and 7.2. Liquid volume 9 L; initial pH 4,
COD/H2O2 (w/w) = 1, 1.3, 2 and 4.
1,0
Dilutions:
1:1 (TOC = 1255 mg/L)
1:2 (TOC = 628 mg/L)
1:10 (TOC = 125 mg/L)
TOC/TOC0
0,8
0,6
0,4
0,2
0,0
0
50
100
150
200
250
300
Ozonation Time (min)
Figure 7.7 - Effect of initial TOC on the treatment of winery wastewater by the O3/UV/H2O2
process. Experimental conditions from Table 7.2. Liquid volume 9 L; COD/H2O2 (w/w) = 2; initial
pH = 4.
Further experiments were carried out at COD/H2O2 (w/w) = 2 (fastest TOC

removal), pH = 4 (natural pH of the winery wastewater), and varying the initial TOC of the
water by dilution of the original wastewater by 1:2 and 1:10. Figure 7.7 shows slower TOC
155
removal rates (mg L-1 min-1), at higher initial TOC concentrations in accordance with the
observed apparent first-order kinetics.
7.3.7 Operating costs

The adoption of the optimal treatment process in the industrial environment would
depend on favourable process economics. In the case of the AOPs studied, the process
economics are primarily dependent on the costs of electricity (for ozone generation and to
power the UV-lamp), in-situ oxygen generation to feed the ozone generator, UV lamp
replacement, and added chemicals. An estimation of the operating costs of the, O3, O3/UV
and O3/UV/H2O2 processes based on the experiments carried out in the pilot-scale reactor
was performed. The analysis exclude capital, maintenance, labour and depreciation costs
since these will be common to all AOPs investigated. Table 7.4 shows the costs for
electricity, oxygen production, lamp replacement and H2O2 to operate the pilot plant.
Table 7.4 Operating costs for the 9 L pilot scale bubble column reactor operated for 5 hours under the
hydrodynamic conditions in Table 7.2.
Operating Costs
Euro
Cost of oxygen supplya
0.03536
Cost of electricity for ozone generationb
0.03942
Cost of electricity for UV lamp operationc
0.01971
Cost of UV lamp replacementd
0.01250
Cost of H2O2 added (COD/H2O2 = 4)
0.00837
Pilot plant operating cost for each AOPs
Euro/m3
O3 (1+2) Euro / 9L * 1000 L
8.31
O3/UV (1+2+3+4) Euro / 9L * 1000 L
11.89
O3/UV/H2O2 (1+2+3+4+5) Euro / 9L * 1000 L
12.82
@ 0.025 Euro/kg O2; b@ 0.1095 Euro/KWh, ozonator consumes 12 Wh/g ozone when fed with oxygen; c 36
W nominal power;
20 Euro/lamp, 8000 hrs lifetime; e@ 0.24 Euro/kg;
(COD/H2O2 = 1.3), 12.85 (COD/H2O2 = 1).
156
12.83 (COD/H2O2 = 2), 12.84
Table 7.5 shows the operating costs (Euro m-3 g-1 of TOC mineralised) for the
conditions in each of the experiments. The lowest operating cost was found to be 1.31 Euro
m-3 g-1 of TOC mineralised for the experiment carried out with the O3/UV/H2O2 process at
pH 4 and COD/H2O2 ratio of 2. Taking as a basis the operating costs of ozonation alone, a
significant reduction of 25-56% and 80-86% in the treatment costs were obtained with the
O3/UV and O3/UV/H2O2 processes, respectively. Dilution of the wastewater should not be
carried out since it increases treatment costs.
Table 7.5 Operating costs (Euro m-3 g-1 of TOC mineralised) for each experiment.
TOC0
(mgL-1)
COD/H2O2
(w/w)
TOC
removed in
pilot plant (9
L after 300
min (g)
O3 (pH 4)
1254
0.50
16.73
O3 (pH 7)
1254
0.61
13.63
O3 (pH 10)
1254
0.89
9.32
O3/UV (pH 4)
1254
0.95
12.39
O3/UV (pH 7)
1254
1.47
8.10
O3/UV (pH 10)
1254
2.93
4.05
O3/UV/H2O2 (pH 4)
1254
5.53
2.32
O3/UV/H2O2 (pH 7)
1254
5.53
2.32
O3/UV/H2O2 (pH 10)
1254
7.22
1.77
O3/UV/H2O2 (pH 4)
1254
9.82
1.31
O3/UV/H2O2 (pH 4)
1254
1.3
9.14
1.40
O3/UV/H2O2 (pH 4)
1254
7.11
1.81
O3/UV/H2O2 (pH 4)
628
5.54
2.31
O3/UV/H2O2 (pH 4)
125
1.10
4.93
Experiment
Operating
costs
(Euro m-3 g-1 of
TOC
mineralised)
After 150 min.
157
7.4. Conclusions
The overall results of this study carried out in a pilot-scale bubble column reactor
indicate that the O3/UV and O3/UV/H2O2 processes are feasible methods for the treatment
of winery wastewaters. These processes, comparatively to UV radiation and ozonation
alone at natural pH (pH 4), involve the formation of highly reactive radicals in solutions
resulting in faster degradation rates. O3/UV and O3/UV/H2O2 allowed significant COD and
TOC removals and reveal to be highly dependent on the initial pH of the wastewater.
The rate of ozone consumption in the reactor was in the region from 70 95%
during the experiments, suggesting an effective use of the ozone supplied to the system. In
all the experiments the disappearance of the winery wastewater organic load was described
by pseudo-first order apparent reaction kinetics useful for the design of industrial reactors.
The faster rate constant (6.5 x 10-3 min-1), at the natural pH of the wastewater, was
observed with the O3/UV/H2O2 under optimised oxidant dose (COD/H2O2 = 2). Water
dilution resulted in lower TOC removal rates. An economical analysis on the operating
costs of the AOPs processes investigated revealed the O3/UV/H2O2 to be the most
economical process (1.31 Euro m-3 g-1 of TOC mineralised under optimised conditions).
References
Akita, K., Yoshida, F. (1974) Bubble size, interfacial area, and liquid-phase mass transfer
coefficient in bubble columns. Industrial & Engineering Chemistry Process Design and
Development 13, 8491.
Arnaiz, C., Buffiere, P., Lebrato, J., Moletta, R. (2007) The effect of transient changes in organic
load on the performance of an anaerobic inverse turbulent bed reactor. Chemical Engineering and
Processing 46, 1349-1356.
Beltrn, F.J., Garca-Araya, J.F., lvarez, P.M. (1999) Wine-distillery wastewater degradation. 1.
Oxidative treatment using ozone and its effect on the wastewater biodegradability. 2. Improvement
of aerobic biodegradation by means of an integrated chemical (ozone)-biological treatment. Journal
of Agricultural and Food Chemistry 47, 3911-3924.
Beltrn, F.J. (2003) Ozone reaction kinetics for water and waste water systems. Boca Raton, Fla.:
Lewis Publishers, London, New York, Washington.
158
Beltrn-Heredia, J., Torregrosa, J., Dominguez, J.R., Garcia, J. (2000) Ozonation of black-tableolive industrial wastewaters: effect of an aerobic biological pre-treatment. Journal of Chemical
Technology & Biotechnology 75, 561-568.
Beltrn-Heredia, J., Torregrosa, J., Dominguez, J.R., Peres, J.A. (2001) Kinetic model for phenolic
compound oxidation by Fenton's reagent. Chemosphere 45, 85-90.
Benitez, F.J., Beltrn-Heredia, J., Torregrosa, J. (1997) Improvement of the anaerobic
biodegradation of olive mill wastewaters by prior ozonation pre-treatment. Bioprocess Engineering
17, 169-176.
Benitez, F.J., Beltrn-Heredia, J., Torregrosa, J., Acero, J.L. (1999) Treatment of olive mill
wastewaters by ozonation, aerobic degradation and the combination of both treatments. Journal of
Chemical Technology & Biotechnology 74, 639-646.
Benitez, F.J., Acero, J.L., Garcia, J., Leal, A.I. (2003) Purification of cork processing wastewater
by ozone, activated sludge system and by their two sequential applications. Water Research 37,
4081-4090.
Benitez, F.J., Real, F.J., Acero, J.L., Garcia, J., Sanchez, M. (2003) Kinetics of the ozonation and
aerobic biodegradation of wine vinasses in discontinuous and continuous processes. Journal of
Hazardous Materials 101, 203-218.
Brito, A.G., Peixoto, J., Oliveira, J.M., Oliveira, J.A., Costa, C., Nogueira, R., Rodrigues, A.
(2007) Brewery and winery wastewater treatment: Some focal points of design and operation in
utilization of by-products and treatment of waste in the food industry. Springer US, pp. 109-131.
Gimeno, O., Rivas, F.J., Beltrn, F.J., Carbajo, M. (2007) Photocatalytic ozonation of winery
wastewaters. Journal of Agricultural and Food Chemistry 55, 9944-9950.
Gurol, M.D., Nekouinaini, S. (1984) Kinetic behaviour of ozone in aqueous solutions of substituted
phenols. Industrial and Engineering Chemistry Fundamentals 23, 5460.
Hoigne, J., Bader, H. (1976) The role of hydroxyl radical reactions in ozonation processes in
aqueous solutions. Water Research 10, 377-386.
Hsu, Y. C., Yang, H. C., Chen J. H. (2005) The effects of preozonation on the biodegradability of
mixed phenolic solution using a new gas-inducing reactor. Chemosphere 59, 1279-1287.
159
Huang, C.R.S. (1995) The reaction kinetics, decomposition pathways and intermediate formations
of phenol in ozonation, UV/O3 and UV/H2O2 processes. Journal of Hazardous Materials 41, 4764.
Lan, B.Y., Nigmatullin, R., Li Puma, G. (2008) Ozonation kinetics of cork-processing water in a
bubble column reactor. Water Research 42, 2473-2482.
Legrini, O., Oliveros, E., Braun, A.M. (1993) Photochemical processes for water treatment.
Chemical Reviews 93, 671-698.
Litter, M.I. (2005) Introduction to photochemical advanced oxidation processes for water
treatment. Springer-Verlag, Berlin, Vol. 2, Part M, pp. 325-366.
Lucas, M.S., Peres, J.A., Lan, Y.B., Li Puma, G. (2009) Ozonation kinetics of winery wastewater
in a pilot-scale bubble column reactor. Water Research 43, 1523-1532.
Monteagudo, J.M., Carmona, M., Durn, A. (2005) Photo-Fenton-assisted ozonation of p-coumaric
acid in aqueous solution. Chemosphere 60, 1103-1110.
Navarro, P., Sarasa, J., Sierra, D., Esteban, S., Ovelleiro, J.L. (2005) Degradation of wine industry
wastewaters by photocatalytic advanced oxidation, Water Science and Technology 51, 113-120.
Preis, S., Munter, R., Siirde, E. (1988) Kinetic description of industrial wastewater ozonation
processes. Ozone Science & Engineering 10, 379-392.
Sander, R. (1999) Compilation of Henrys law constants for inorganic and organic species of
potential importance in environmental chemistry (version 3). http://www.henrys-law.org.
Santos, M.A.M., Bocanegra, J.L.F., Martn, A.M., Garcia, I.G. (2003) Ozonation of vinasse in acid
and alkaline media. Journal of Chemical Technology & Biotechnology 78, 1121-1127.
Singleton, V.L., Rossi, J.A. (1965) Colorimetry of total phenolics with phosphomolybdicphosphotungstic acid reagents. American Journal of Enology and Viticulture 16, 144158.
Strong, P.J., Burgess, J.E. (2008) Treatment methods for wine related and distillery wastewaters: A
review. Bioremediation Journal 12, 70-87.
Tomiyasu, H., Fukutomi, H., Gordon, G. (1985) Kinetics and mechanism of ozone decomposition
in basic aqueous solution. Inorganic Chemistry 24, 2962-2966.
160
Chapter 8 Winery wastewater treatment by a combined process: long term aerated storage and Fentons reagent
CHAPTER 8 WINERY WASTEWATER
TREATMENT BY A COMBINED
*
PROCESS: LONG TERM AERATED STORAGE AND FENTONS REAGENT
Abstract
The degradation of the organic pollutants present in winery wastewater was carried out by
the combination of two successive steps: an aerobic biological process followed by a
chemical oxidation process using Fentons reagent. The main goal of this study was to
evaluate the temporal characteristics of solids and chemical oxygen demand (COD) present
in winery wastewater in a long term aerated storage bioreactor. The performance of
different air dosage daily supplied to the biologic reactor, in laboratory and pilot scale,
were examined. The long term hydraulic retention time, 11 weeks, contributed remarkably
to the reduction of COD (about 90%) and the combination with the Fentons reagent led to
a high overall COD reduction that reached 99.5% when the mass ratio (R=H2O2/COD)
used was equal to 2.5, maintaining constant the molar ratio H2O2/Fe2+=15.
* Adapted from: Lucas M.S., Mouta M., Pirra A., Peres J.A. Water Science and Technology. 2009,
60, 1089-1095.
161
8.1. Introduction
Wine production processes generate organic and inorganic pollution mostly
associated with solid wastes and liquid effluents. The liquid effluents usually referred as
winery wastewater are mainly originated from various unit operations such as washing
of the presses used to crush the grapes, rinsing of fermentation vats, rakings, barrels,
bottles and other equipments or surfaces (Pirra, 2005; Mosteo et al. 2006).
Winery wastewaters contain large amounts of biodegradable organics in addition to
relatively small concentrations of recalcitrant compounds: polyphenols, organic acids and
sugars with typical COD values in the range from 3 to 30 gL-1. The disposal of winery
effluents in streams, creeks, rivers and on soils involves unacceptable environmental risks.
Hence, a responsible management of these effluents requires that their potential
environmental impacts be minimal and within an acceptable range (Petruccioli et al., 2000;
Malandra et al., 2003; Beck et al., 2005; Lucas et al., 2009).
Several physical and chemical processes are available to winery wastewater
treatment but its major action is a phase transfer of pollutants. Biological waste treatment
methods have been recognized as a reasonable alternative way for a significant degradation
of wastewater with high organic content, such as those coming from wineries in particular.
However, the presence of recalcitrant compounds for the microorganisms frequently makes
impossible the complete treatment of a winery wastewater. Combination of biological
treatment followed by chemical processes may prove useful in this situation (Beltran de
Heredia et al., 2005; Lucas et al., 2007). Biological treatment mineralizes the large
biodegradable portion, effectively reducing the residual COD of the wastewater. A
chemical polishing treatment (Fenton reagent) is then applied to degrade the persistent
compounds. The primary biological step reduces the number and concentration of
compounds that may compete for the chemical oxidant, thus increasing overall efficiency
and lowering costs.
Advanced Oxidation Processes offer a highly reactive, non-specific oxidant,
namely hydroxyl radical (HO), capable of destroying a wide range of organic pollutants in
water and wastewater (Legrini et al., 1993; Nogueira et al., 2005; Mosteo et al., 2007;
Lucas et al., 2008). Fenton reagent is a mixture of hydrogen peroxide (H2O2) solution and
ferrous iron, which generates hydroxyl radicals according to a complex mechanism in an
aqueous solution that could be resumed by the following reaction:
162
Fe
2+
+ H2O2 Fe
3+
+ HO + HO
(8.1)
generation of HO (Chen and Pignatello, 1997; Feng et al., 2003).
High-intensity aeration processes commonly require excessive energy input,
leading to prohibitive operative cost. Therefore, it is important to seek a cost-effective
treatment method. In this paper, the main objective is to evaluate the capacity of treating
winery wastewater in a long term biologic aerated storage, with different aeration schemes,
combined with Fentons reagent. This chemical oxidation process, that uses low-priced
reactants, was used as a secondary chemical treatment step for the oxidation of the
recalcitrant organic compounds or metabolites that could not be oxidized biologically.
8.2.1 Winery wastewater
The original winery wastewater used in this study resulted from the mixture of
different effluents collected from a Portuguese winery (Adega Cooperativa de Vila Real)
located in the Douro region (northeast of Portugal), representing the total annual
production of the winery. Table 8.1 summarizes the average values obtained after two
analyses for each parameter of the main physico-chemical characteristics of the winery
wastewater.
Table 8.1. Winery wastewater characteristics.
pH
3.9
Total polyphenols
TSS
VSS
COD
BOD5
Nt
(g caffeic acid /L)
(g/L)
(g/L)
(g O2/L)
(g/L)
(mg/L)
(mg/L)
(mg/L)
0.68
8.9
6.2
20
11
208
28
1111
8.2.2 Chemicals
The Fenton experiments were performed using ferrous iron sulfate (FeSO4.7H2O),
hydrogen peroxide (H2O2, 30% w/w), sulphuric acid (H2SO4) and sodium hydroxide
(NaOH) for pH adjustment all provided by Panreac. Other chemicals used in these
163
experiments were of reagent grade and used as received. Ultra pure distilled-deionised
water obtained from a Milli-Q (Millipore Co.) system.
8.2.3 Analytical determinations
The COD, TSS, VSS, Nt, P and K were determined according to Standard Methods
(APHA, 1992). COD analysis was done in a COD reactor from HACH Co., and a HACH
DR2010 spectrophotometer was used for colorimetric measurement. Biological oxygen
demand (BOD5) was evaluated by the respirometric method. In Fenton reagent
experiments before the COD analysis, the samples were conditioned removing the H2O2
excess by addition of NaOH. Hydrogen peroxide concentration was controlled during and
after the treatments using Merck Peroxide Test (0 to 25 mg H2O2/L and 0 to 100 mg
H2O2/L). pH evolution was determined by means of a pH-meter (CRISON 507). Total
polyphenols were evaluated by Folin-Ciocalteau method.
8.2.4 Aerobic biodegradation
The aerobic biodegradation experiments of winery wastewater were conducted in
completely mixed biological batch reactors consisting of a 4 L cylindrical Pyrex glass
(laboratory scale) and 60 L (pilot scale). These vessels, at environmental temperature, were
provided with covers containing inlets for bubbling the gas feed and stirring, and outlets
for sampling and venting. The activated sludge used as inoculum of the aerated storage
was directly obtained from aerobic stage of a full-scale urban wastewater treatment plant
located nearby Vila Real (Portugal) and applied with a two days acclimatization period.
The initial Volatile Suspended Solids (VSS) content of the sludge was 5 gL-1.
The air flow was fed to the reacting medium through a bubble gas sparger at a
constant flow rate of 125 L h-1 at room conditions and with four different aeration periods
2.4 h/day, 4 h/day, 8 h/day and 12 h/day. In this process, the bioreactors were initially
loaded with the above mentioned inoculum and the reaction medium was completed with a
load of winery wastewater containing an initial substrate concentration around 20 g
COD/L, and then the bioreactor was aerated and stirred during an hydraulic retention time
(HRT) of 11 weeks. During the experiment several samples were withdrawn at regular
times to analyze the COD, TSS, VSS and pH of the reacting medium.
164
8.2.5 Oxidation by Fentons reagent

The winery wastewater from the biological treatment (supernatant after natural
sedimentation) was further treated using Fentons reagent. The oxidation experiments were
conducted in a 1 L stirred glass batch reactor. Typical experiments were carried out with
500 mL of the effluent biologically pre-treated to which a weighed amount of FeSO47H2O
was added and dissolved under stirring. pH was adjusted to 3.5 by adding sulphuric acid
solution. The Fenton oxidation began with the addition of hydrogen peroxide solution
(30% w/w). Different concentrations of H2O2 and Fe2+ were tested. Before the
determination of final COD the total consumption of H2O2 was verified with Merckoquant
strips.
8.3 Results and discussions
8.3.1 Aerobic biodegradation
8.3.1.1 Lab scale.
Figure 8.1 shows the COD removal obtained with the biologic aerated storage
during 11 weeks of experiment at different aeration periods. In Figure 8.1a) are presented
the COD evolution along time and in Figure 8.1b) the final degradation rate achieved from
the initial organic load (20 g O2 L-1) with the aerobic treatment for the different aeration
periods.
The COD conversion (XCOD) obtained in each experiment is defined as follows:
X COD =
COD0 CODf
100
COD0
(8.2)
where COD0 and CODf are the initial and final concentrations of COD, respectively.
165
4 L 12 h/da y
4L 8h/d ay
4L 4h/day
4 L 2.4 h/da y
4L w ith s ludge
4L w ithout s lu dge
20
-1
COD removal (gL )
25
15
10
5
0
a)
2ndW eek
4thW eek
6
We e k
6thW eek
9thW eek
10
11
12
11thW eek
C ODremoval(% )
100
80
60
40
20
0
b)
4L 12h/day
4L 8h/day
4L 4h/day
4L 2.4h/day
4L with
s ludge
4L without
s ludge
Figure 8.1. COD removal a) evolution along time and b) final degradation rate achieved in
laboratory scale experiments with biological treatment of a winery wastewater supplied with
different aeration periods.
The COD decreases rapidly in the initial 2 weeks during the course of all
experiments. The experiment performed with an air supply of 12h/day achieves a high
degradation level in a short reaction time, for example after 4 weeks reaches a COD
removal of 87%, while the 8h/day obtained 77%, the 4h/day 76% and finally for 2.4h/day
61%.
However, since the 9th week it is possible to verify that COD removal is almost
similar for all the experiments. For example, increasing the HRT to 11 weeks the COD
removal percentage improves to a similar level for all experiments and corresponding
aeration periods. Therefore for 11 weeks reaction and aeration time of 12h/day achieves a
COD degradation of 88%, to 8h/day was obtained 89%, for 4h/day 96% and to 2.4h/day
95%. Thus, even for small aeration period, high COD removal could be achieved with a
166
long aeration time. As a final analysis it is possible highlight that a gradual reduction of the
substrate occurs during the 11 weeks until it reaches a residual value of non-biodegradable
organic matter (among 5 and 10%).
In addition to the experiments performed with different aeration periods, there were
also performed experiments without any aeration: with winery wastewater plus inoculum
(with sludge) and winery wastewater without inoculum (without sludge) to evaluate the
influences of the aeration and of the inoculum sludge. The results reveal a less degradation
capacity throughout the experiment, though at the end they presented a similar depuration
capacity. This means that in the experiment without any inoculum added, the natural
microorganisms present in the winery wastewater showed the capacity to decompose the
biodegradable organic matter. Another remark is that without aeration the degradation
reached is very similar to the assays with aeration. However, this situation produces
harmful bad odours as result of the anaerobic biodegradation. Therefore, experiments with
aeration are always preferable even with small aeration times (e.g. 2.4h/day) to reduce
these odours production.
4L 12h/day
4L 8h/day
4L 4h/day
4L 2.4h/day
4L with sludge
4L without sludge
7
6
VSS (gL-1)
5
4
3
2
1
0
0
10
11
12
Week
Figure 8.2. VSS evolution in laboratory scale experiments during biologic treatment of a winery
The volatile solids fraction generally represents the organic component of the TSS,
which is more biodegradable than the rest of solids that are mainly associated with the
coarse material in the slurry and effectively inert in a typical aerobic treatment process
(Figure 8.2). In all the experiments biomass achieves values different than zero after the
167
stage of decay. This can be explained due to the methodology adopted to measure the
biomass (VSS) once death or inactivated cells are also accounted.
Figure 8.3 shows the pH evolution during the experiments performed at laboratory
scale. The pH is a key factor on the microorganisms growth, once they can not support
values higher than 10 and less than 4. The experiments started all at an acidic pH (among 4
and 6). However, along the experiments the pH changes to basic values achieving the
higher value at 9.6. This fact happens due to the adaptation and type of microorganisms
naturally occurring along time, which clearly prefer higher pH values.
4L 12h/day
4L 8h/day
4L 4h/day
4L 2.4h/day
4L with sludge
4L without sludge
12
10
pH
8
6
4
2
0
10
11
12
Week
Figure 8.3. pH evolution in laboratory scale experiments during biologic treatment of a winery
8.3.1.2 Pilot scale.

After the laboratory scale, experiments were done at pilot scale. This
scale-up was performed to evaluate if the behaviour showed at the laboratory scale (4L)
would be similar to the observed in a 60 L pilot reactor. Figure 8.4 shows the COD
removal results obtained in the pilot reactor. In general, these data reveal that,
comparatively to lab scale data (Figure 8.1) the COD removal efficiency of the pilot scale
is lower than the obtained at the laboratory scale.
Figure 8.4a) presents the COD evolution along time in the pilot scale reactors and
Figure 8.4b) the final degradation rate achieved from the initial organic load (20 g O2 L-1)
with the different aerobic treatments. It is shown that the experiment performed with an air
supply period of 12h/day follows the same behaviour verified in laboratory scale,
168
achieving a high degradation level in a short reaction time. For example after 4 weeks it
was reached a COD removal of 85%, whereas the 8h/day obtain 76%, for 4h/day 47% and
finally to 2.4h/day 45%. However, increasing the HRT to 11 weeks the COD removal rate
improves for all aeration periods. For 11 weeks of reaction a 12h/day and aeration period
achieves 96% COD removal, for 4h/day 75% and to 2.4h/day 64%.
Figure 8.5 shows the evolution of VSS in pilot scale experiments. A gradual
decrease with some oscillations was observed throughout the 11 weeks experiment, being
more significant for the experiment with an aerated period of 12 and 8h/day. This fact can
be justified by the natural evolution of the microorganisms along their life cycle.
60 L 12h/day
60L 8h/day
60 L 4h/day
60L 2.4h/day
60 L with sludge
60L without sludge
-1
COD removal (gL )
25
20
15
10
5
0
0
a)
10
11
12
Week
2ndW eek
4thW eek
6thW eek
9thW eek
11thW eek
100
C ODrem oval(% )
80
60
40
20
0
b)
60L 12h/day
60L 8h/day
60L 4h/day
60L 2.4h/day
60L with
s ludge
60L whitout
s ludge
Figure 8.4. COD removal a) evolution along time and b) final degradation rate achieved in pilot
scale experiments with biologic treatment of a winery wastewater supplied with different aeration
periods.
Once the biomass is already acclimatized in these experiments the exponential

growth phase does not exist and the stationary phase occurs during a very short time. After
169
which a decrease in the biomass value occurs due to lack of nutrients and cellular death
(endogenous decayment).
60L 12h/day
60L 8h/day
60L 4h/day
60L 2.4h/day
60L with sludge
60L without sludge
7
6
-1
VSS (gL )
5
4
3
2
1
0
0
10
11
12
Week
Figure 8.5. VSS evolution in pilot scale experiments during biologic treatment of a winery
Figure 8.6 shows the pH evolution followed during the experiments performed at
pilot scale. As in laboratory scale, the experiments started at an acidic pH, however along
the experiments the pH changes to basic values.
60 L 12h/day
60 L 8h/day
60 L 4h/day
60L 2.4 h/day
60L with sludge
60L without sludge
10
9
8
pH
7
6
5
4
3
2
0
10
11
12
Week
Figure 8.6. pH evolution in pilot scale experiments during biologic treatment of a winery
170
8.3.2 Oxidation by Fentons reagent
As
described
previously,
winery
wastewaters
biodegraded
by
aerobic
microorganisms were then treated with Fentons reagent, in a group of experiments where
the initial concentration of hydrogen peroxide was modified, maintaining constant the
molar ratio H2O2/Fe2+=15. Table 8.2 presents the characteristics of the winery wastewater
after the biologic aerated treatment.
Table 8.2. Characterization of the winery wastewater after biologic pre-treatment.
pH
9.2
TSS
VSS
COD
(mg/L)
(mg/L)
(mg O2/L)
3600
2800
1560
Chemical oxidation with Fentons process was analyzed in order to test further
reduction in COD concentration to minimize the impact of winery wastewater discharge on
natural water courses and/or municipal wastewater treatment plants.
In the experiments carried out with Fenton reagent, they have had as reference the
mass ratio between the hydrogen peroxide and COD, R = H2O2/COD. Hence, the value of
R was changed from 0.25 to 2.5, remaining constant the initial pH (corrected after biologic
treatment to 3.5), the initial temperature (30C) and the molar ratio constant
(H2O2/Fe2+=15) (Peres et al., 2004) evaluating mainly the final COD removal.
Table 3 shows the COD removal at different R values after 4 hours of experiment.
From the data presented it is visible that COD removal increases from 17.4% to 93.2%
when the R value (H2O2/COD) increases from 0.25 to 2.5, respectively.
As expected, the increase in H2O2 concentration has a positive effect on the COD
reduction. For the maximum R value studied (R = 2.5), the COD removal reaches 93.2%
after 4 hours. This demonstrates the ability of Fenton reagent to degrade a large part of
recalcitrant organic matter present in winery wastewater. The reason for the increase in
COD conversion with the increase of R is related to the generation of a greater amount of
hydroxyl radicals and, therefore, a greater extent of oxidation reactions. One way to
generally express the reaction of the Fenton system (H2O2 + Fe2+) to the reduction of COD
can be summarized as follows:
171
Step 1:
COD + H2O2 + Fe2+
species partially oxidized
(8.3)
Step 2:
species partially oxidized + H2O2 + Fe2+ CO2 + H2O + inorganic salts (8.4)
The extent of oxidation (and consequently the degree of COD removal) depends
directly on the amount of H2O2 used.
Table 8.3. COD conversion (%) obtained for different R=H2O2/COD values, after chemical oxidation of
winery wastewater with Fenton reagent. Operational conditions: initial T = 30C, initial pH = 3.5, molar ratio
H2O2/Fe2+=15.
Mass ratio (R)
CODinitial
CODfinal
XCOD
(H2O2/COD)
(mg O2/L)
(mg O2/L)
(%)
WW-1
0.25
1560
1289
17.4
WW-2
0.50
1560
1072
31.3
WW-3
0.75
1560
877
43.8
WW-4
1.0
1560
699
55.2
WW-5
1.5
1560
515
67.0
WW-6
2.0
1560
239
84.7
WW-7
2.5
1560
106
93.2
Experiment
8.4 Conclusions
The combined process aerobic degradation followed by Fentons reagent oxidation

was employed to treat winery wastewater, leading to good performances. The results
indicate that aerobic biological treatment reaches a very high COD removal, corresponding
to the biodegradable fraction acting Fenton reagent like a final polishing step. The main
conclusions are: aerobic biological degradation rates reaches among 76% and 96% COD
removal in laboratory scale, and between 64% and 96% at pilot scale. It is preferable
applying a biological process as a first treatment step of a winery wastewater rather than
chemical oxidation, since the most fraction of the original effluent is biodegradable.
172
Depending of the discharge objectives and hurry, different aeration periods can be
applied. Therefore, for small wineries, long term aerated storage can be performed (e.g.
ponds, old cement vats, etc.) followed by a Fenton reagent treatment as a final polish with
relatively low investment and operation costs.
As a final remark, the results obtained starting with a typical winery effluent (20 g
COD/L) have demonstrated that this combined process (long term aeration plus Fenton
reagent) can lead to COD removal efficiency higher than 99%, with final effluents that can
be reused, rejected in the water streams or in the soil, according to the Portuguese law.
References
APHA-AWWA-WPCF. (1992). Standard Methods for the examination of water and wastewater.
17th edition, Washington DC, USA.
Beck, C., Prades, G. and Sadowski, A-G. (2005). Activated sludge wastewater treatment plants
optimisation to face pollution overloads during grape harvest periods. Water Sci. Technol., 51,
81-88.
Beltran de Heredia, J., Torregrosa, J., Dominguez, J.R. and Partido, E. (2005). Degradation of wine
distillery wastewaters by the combination of aerobic biological treatment with chemical
oxidation by Fentons reagent. Water Sci. Technol., 51, 167-174.
Chen, R. and Pignatello, J. (1997). Role of quinone intermediates as electron shuttles in Fenton
oxidations of aromatic compounds. Environ. Sci. Technol., 31, 2399-2406.
Feng, J., Hu, X., Yue, P.L., Zhu, H.Y. and Lu, G.Q. (2003). Discoloration and mineralization of
Reactive Red HE-3B by heterogeneous photo-Fenton reaction. Water Res., 37, 3776-3784.
Legrini, O., Oliveros, E. and Braun, A.M. (1993). Photochemical processes for water treatment.
Chem. Rev. 93, 671-698.
Lucas M.S., Albino A:A., Bezerra R., Peres J. A. (2008). Gallic acid photochemical oxidation as a
model compound of winery wastewaters. J. Environ. Sci. Health, A43:1288-1295.
Lucas M.S., Dias A.A., Sampaio A., Amaral C., Peres J.A. (2007) Degradation of a Textile
Reactive Azo Dye by a Combined Chemical-Biological Process: Fentons Reagent-Yeast.
Water Res. 41,1103-1109.
173
Lucas, M.S., Peres, J.A., Lan, Y.B. and Li Puma, G. (2009). Ozonation Kinetics of Winery
Wastewater in a Pilot-Scale Bubble Column Reactor, Water Res., 43, 1523 - 1532.
Malandra, L., Wolfaardt, G., Zietsman, A. and Viljoen-Bloom, M. (2003). Microbiology of a
biological contactor for winery wastewater treatment. Water Res., 37, 4125-4134.
Mosteo, R., Ormad, M.P. and Ovelleiro, J.L. (2007). Photo-Fenton processes assisted by solar light
used as preliminary step to biological treatment applied to winery wastewaters. Water Sci.
Technol., 56, 89-94.
Nogueira, R.F.P., Oliveira, M.C. and Paterlini, W.C. (2005) Simple and fast spectrophotometric
determination of H2O2 in photo-Fenton reactions using metavanadate. Talanta. 66, 86-91.
Nogueira, R.F.P., Silva, M.R.A. and Trov, A.G. (2005). Influence of the iron source on the solar
photo-Fenton degradation of different classes of organic compounds. Solar Energy, 79, 384392.
Peres, J.A., Carvalho, L.M., Boaventura, R. and Costa, C. (2004). Characteristics of
p-hydroxybenzoic acid oxidation using Fentons reagent. J. Environ. Sci. Health, A39, 28972913.
Petruccioli, M., Duarte, J.C. and Federici, F. (2000). High rate aerobic treatment of winery
wastewater using bioreactors with free and immobilized activated sludge. J Biosci Bioeng. 90,
381-386.
Pirra, A. (2005). Treatment of winery effluents from the Douro region (Port wine region). PhD
Thesis, University of Trs-os-Montes and Alto Douro. Vila Real, Portugal. 296 pp. (in
Portuguese).
174
Chapter 9 - Conclusions and suggestions of future work
CHAPTER 9 - CONCLUSIONS AND SUGGESTIONS OF FUTURE WORK
9.1 Conclusions
The main conclusions of this thesis are divided in two sections; in the first one are
mentioned those concerning the textile industry wastewaters, where an azo dye (Reactive
Black 5) was used as a model compound. In the second section are reported the main
conclusions concerning a deep study about the treatment of winery wastewater with:
Fentons reagent, photo-Fenton with solar light (CPC reactor), heterogeneous
photocatalysis (TiO2), ozone, ozone/UV, ozone/UV/H2O2 and the combination of aerobic
biological processes with Fentons reagent.
Chapter 2 and 3
In a first stage was evaluated the Reactive Black 5 decolourization and
mineralization capacity with two advanced photochemical processes: Fenton/UV-C and
ferrioxalate/H2O2/solar light. From the results it is possible conclude that Fenton/UV-C and
ferrioxalate/H2O2/solar light processes achieves a Reactive Black 5 decolourization higher
than 90% in half an hour. It was found that the experiments with ferrioxalate follow a first
order kinetic law even with UV-C or solar light alone and with hydrogen peroxide
addition. Although, when UV-C lamp + H2O2 were employed the kinetic rate (k) was
higher comparatively to the solar light + H2O2 combination, achieving, consequently, a
minor half-life time (t1/2). For both AOP, the optimal experimental conditions for a RB5
concentration of 1.0x10-4 mol/L, are: pH=5, hydrogen peroxide dosage = 1.5x10-3 mol/L
and iron dosage = 1.5x10-4 mol/L. Besides the very similar decolourization in both
processes, the employment of the UV lamp benefits the azo dye degradation. However,
from the economical point of view the employment of the natural resource solar light
could be an interesting option due to its low cost and the fact of being environmentally
harmless.
Further, an alternative option to decolourize dyed textile effluents was used
sequentially an Advanced Oxidation Process (Fentons reagent) followed by an aerobic
biological process (yeast C. oleophila). Under our experimental conditions, a good
175
treatment could be purposed as follows: Fentons reagent at 1.0x10-3 mol/L of H2O2 and
1.0x10-4 mol/L of Fe2+ as primary treatment and then inoculation with growing yeast cells
as a secondary treatment. This combined process allows removing about 91% of colour for
an initial RB5 concentration of 500 mg/L. It should be pointed out that Fentons reagent
alone requires five times more H2O2 and Fe2+ to achieve an identical level of colour
removal.
Therefore, the employment of AOPs like photo-Fenton and ferrioxalate/H2O2/solar
light could be an interesting way to treat coloured wastewaters like textile effluents. The
combination of Fentons reagent with the Candida oleophila yeast can be particularly
useful especially in the treatment of high coloured wastewaters and also to reduce the
operational treatment costs mainly associated to the chemical processes.
Chapter 4
In the second part of this thesis are reported the main conclusions concerning the
treatment of winery wastewaters. First, it was verified that photodegradation of the most
representative phenolic compound present in the winery wastewaters (gallic acid) using
only monochromatic and polychromatic UV lamps, can not be achieved in great extension.
However, combining radiation with AOPs it is possible maximize the effect of the different
radiation sources. From the presented study it is possible to conclude that Fe2+ + H2O2 +
UV TNN 15/32 (photo-Fenton process) could be proposed as the best AOP for the
degradation of gallic acid in aqueous solutions. Therefore, this work shows a possible
treatment to remove or, at least, significantly diminish the problematic phenolic fraction of
winery wastewaters once decreases their concentration and toxicity.
Chapter 5
Afterwards, the application of heterogeneous photocatalysis (TiO2, TiO2/H2O2,
TiO2/Na2S2O8) and homogeneous photocatalysis (photo-Fenton) to winery wastewaters
were performed in a CPC reactor. It was verified that applying heterogeneous
photocatalysis to a simulated winery wastewater reveals to be inefficient on TOC removal,
achieving in the best situation a TOC degradation of 25%. Using homogeneous
photocatalysis, solar photo-Fenton process, have shown that it can be reached a TOC
176
removal efficiency of 46% with a simulated wastewater carried out with wine (WV) and
93% with grape juice (WG) in a t30W of 400 minutes. Mixing WV with WG in a ratio 50:50
a TOC removal of 90% was achieved for a t30W of 150 minutes.
Further, if an air stripping process is previously applied for ethanol removal from
the winery wastewater mixture (WW), a TOC degradation of 96% is obtained. Besides this
high TOC degradation a significant detoxification occurs, given the fact that the toxicity
level decreases from 48% to 28%, as well as almost total elimination of the total
polyphenols (92%).
Chapter 6
Another AOP tested with winery wastewaters was ozone. The application of
ozonation in a pilot-scale bubble column reactor was proven to be effective in the
degradation of organic substances present in winery wastewater. The degradation of
aromatics and polyphenols content was found to be significantly faster than the decrease in
COD. This suggests that ozonation may be considered as pre-treatment to further
biological treatment. The degradation rate of organic matter and aromatics increases at
alkaline pH, however, polyphenols are more efficiently removed at acidic pH. At alkaline
and neutral pH the degradation rate was accelerated by the formation of radical species
from the decomposition of ozone, however, the observed kinetics was limited by mass
transfer at the gas-liquid interface.
Monitoring of pH, ORP and the rate of ozone consumption gave insights into the
prevalent kinetic regimes during the ozonation process. The reaction was found to develop
in and across different kinetic regimes: fast, moderate and slow kinetic regime depending
on the experimental conditions. As a result, beside the use of bubble columns (large bulk
volume) which are recommended for gas-liquid reactions in the slow kinetic regime
(reaction in the bulk liquid), other gas-liquid ozonation contactors that offer large contact
surface area to volume ratios may be considered if the reaction develops predominantly in
the fast or moderate kinetic regime (reaction at the gas-liquid interface).
A kinetic model of the ozonation process occurring in the semi-batch bubble
column reactor was presented and was coupled with a second order irreversible reaction of
ozone with the dissolved organic matter. The dynamic change of the rate coefficient
estimated by the model was correlated with changes in the water composition and oxidant
177
species. The model presented and the rate coefficient determined can be used for design
and scale-up of ozonation bubble columns for the treatment of winery wastewater under
similar experimental conditions as in this work.
Chapter 7
The next step of the work was evaluate, in the same pilot-scale bubble column
reactor used in chapter 6, the feasibility of O3/UV and O3/UV/H2O2 processes treat winery
wastewaters. These processes, comparatively to UV radiation and ozonation alone at
natural pH (pH 4), involve the formation of highly reactive radicals in solutions resulting
in faster degradation rates. O3/UV and O3/UV/H2O2 allowed significant COD and TOC
removals and reveal to be highly dependent on the initial pH of the wastewater. The rate of
ozone consumption in the reactor was in the region from 70 95% during the experiments,
suggesting an effective use of the ozone supplied to the system. In all the experiments the
disappearance of the winery wastewater organic load was described by pseudo-first order
apparent reaction kinetics useful for the design of industrial reactors. The faster rate
constant (6.5x10-3 min-1), at the natural pH of the wastewater, was observed with the
O3/UV/H2O2 under optimised oxidant dose (COD/H2O2 = 2). Water dilution resulted in
lower TOC removal rates. An economical analysis on the operating costs of the AOPs
processes investigated revealed the O3UV/H2O2 to be the most economical process (1.31
Euro m-3 g-1 of TOC mineralised under optimised conditions).
Chapter 8
The final component of this work presents the combination of an aerobic biological
process followed by Fentons reagent oxidation to treat a winery wastewater. The results
indicate that aerobic biological treatment reaches a very high COD removal, corresponding
to the biodegradable fraction, acting Fenton reagent as a final polishing step. It is
preferable applying a biological process as a first treatment step of a winery wastewater
rather than chemical oxidation once the main fraction of the original effluent is
biodegradable.
Depending of the discharge objectives, different aeration periods can be applied.
Therefore, for small wineries, long term aerated storage can be performed (e.g. ponds, old
178
cement vats, etc.) followed by a Fentons reagent treatment for final polish. The results
obtained starting with a typical winery effluent (20 g COD/L) have demonstrated that this
combined process (long term aeration plus Fenton reagent) can lead to COD removal
efficiency higher than 99%, with final effluents that can be reused, rejected in the water
streams or in the soil, according to the Portuguese law.
As final comment, it is possible say that the treatment of winery wastewaters largely
depends of the initial wastewaters organic load and of the reaching goals. Therefore, the
selection of an appropriated treatment process depends of local and economical variables
that should be object of a deep analysis between the technician proposal and the cellar
owners.
9.2 Suggestions of future work

Several topics related to the above treatment processes remain to be explored. Thus, in
this page are mentioned future research developments that can be followed in a near
opportunity:
Textile wastewaters:
Evaluate textile wastewaters treatment by photo-Fenton and ferrioxalate/H2O2 with

solar radiation in a CPC reactor;
Application of Fentons reagent process followed by the Candida oleophila yeast to

real textile wastewaters.
Winery wastewaters:
Test the degradation of organic compounds present in winery wastewaters (such as

tannins, antocianins, phenolic acids) by AOPs;
Treatment of winery wastewaters by ferrioxalate/H2O2 in a CPC reactor;
Combine an aerobic biological treatment with photo-Fenton system in a CPC

reactor;
179
Assess the ozone/H2O2 system to the treatment of winery wastewaters;
Combine ozonation with biological treatment. As ozonation reveals to be efficient

in removing the phenolic content present in winery wastewaters in the first reaction
minutes, the application of a further biologic process could be feasible and
economically interesting.
Finally, an economical analysis and a life cycle assessment of all the treatment
processes studied either with textile or winery wastewaters could be made. These analyses
will assess the economical and environmental impacts of a treatment process over the
entire life cycle from cradle to grave.
180
Publications related with this work
PUBLICATIONS RELATED WITH THIS WORK

I. Papers published in SCI journals
1. Lucas M.S., Peres J.A. Degradation of Reactive Black 5 by Fenton/UV-C and
ferrioxalate/H2O2/solar light processes. Dyes and Pigments. 2007, 74, 622-629.
(IF 2008 = 2.507; NC = 13)
2. Lucas M.S., Dias A.A., Sampaio A., Amaral C., Peres J.A. Degradation of a textile
reactive
azo
dye
by
combined
chemical-biological
process:
Fentons
reagent-yeast. Water Research. 2007, 41, 1103-1109. (IF 2008 = 3.587; NC = 11)
3. Lucas M.S., Albino A.A., Bezerra R., Peres J. A. Gallic acid photochemical oxidation
as a model compound of winery wastewaters. Journal of Environmental Science and
Health, Part A. 2008, 43, 1288-1295. (IF 2008 = 1.002; NC = 3)
4. Lucas M.S., Peres J.A., Lan B.Y., Li Puma G. Ozonation kinetics of winery
wastewater in a pilot-scale bubble column reactor. Water Research. 2009, 43, 15231532. (IF 2008 = 3.587; NC = 3)
5. Lucas M.S., Mouta M., Pirra A., Peres J.A. Winery wastewater treatment by a
combined process: long term aerated storage and Fentons reagent. Water Science and
Technology. 2009, 60, 1089-1095. (IF 2008 = 1.005).
6. Lucas M.S., Mosteo R., Maldonado M.I., Malato S., Peres J.A. Solar photochemical
treatment of winery wastewater in a CPC reactor. Journal of Agricultural and Food
Chemistry. (Accepted, IF = 2.562).
7. Lucas M.S., Peres J.A., Li Puma G. Treatment of winery wastewater by ozone-based
advanced oxidation processes (O3, O3/UV and O3/UV/H2O2) in a pilot-scale bubble
column reactor and process economics. (Submitted).
181
II. Communications in international conferences

8. Lucas M.S., Peres J.A. Oxidation of Reactive Black 5 by Fenton/UV-C and
ferrioxalate/H2O2/solar light processes. 4th Conference on Oxidation Technologies for
Water and Wastewater Treatment. Goslar, Germany, 15-17 May 2006, A. Vogelpohl,
M. Sievers, S.U. Geiben (Eds.), Proceedings book ISBN 3-89720-860-1, pp. 397-402
(Poster communication).
9. Lucas M.S., Amaral C., Sampaio A., Dias A.A., Peres J.A. Degradation of a textile
reactive azo dye by a combined process Fentons reagent-Candida oleophila.
IWC 2006 International Water Conference. Instituto Superior de Engenharia do
Porto, Portugal, 12-14 June 2006. V. Beleza (Ed.), pp. 138-144 (Oral communication).
10. Lucas M.S., Peres J.A. Comparative oxidation of Reactive Black 5 by solar light and
UV artificial processes, e-Proceedings of 1st European Conference on Environmental
Applications of Advanced Oxidation Processes, Chania, Crete, Greece, 7-9 September
2006 (CD of proceedings 8 pp, Poster communication).
11. Lucas M. S., Dias A. A., Bezerra R. M., Fraga I., J. A. Peres. Gallic acid degradation
in aqueous solutions by photochemical oxidation processes. II International Congress
of Energy and Environment Engineering and Management, Badajoz, Spain, 6-8 June
2007, Abstracts book ISBN 978-84-96560-45-1, pp. 244 (Poster communication).
12. Lucas M.S., Lan B.Y., Peres J.A., Li Puma G. Treatment of Industrial Winery
Wastewater by Advanced Oxidation in a Pilot-Scale Bubble Column Reactor. 14th
International Conference on Advanced Oxidation Technologies for Treatment of
Water, Air and Soil. San Diego, California, USA, 22-25 September 2008 (Oral
communication).
13. Lucas M.S., Maldonado M.I., Gernjak W., Sirtori C., Zapata A., Peres J.A. Solar
Photo-Fenton Treatment of Winery Wastewater. Solar Chemistry and Photocatalysis:
182
Environmental Applications (SPEA5). Sicilia, Italy, 4-8 October 2008 (Poster

communication).
14. Lucas M.S., Peres J.A., Li Puma G. Treatment of winery wastewater with ozone,
ozone/UV and ozone/UV/H2O2. 5th International specialized conference on sustainable
viticulture: winery waste and ecologic impacts in management. Trento and Verona,
Italy, 30 March 3 April 2009. Proceedings book ISBN 978-88-8443-284-1, pp. 429432 (Poster communication).
15. Lucas M.S., Mosteo R., Maldonado M.I., Malato S., Peres J.A. Photochemical
treatment of a winery wastewater in a solar pilot plant. 5th International specialized
conference on sustainable viticulture: winery waste and ecologic impacts in
management. Trento and Verona, Italy, 30 March 3 April 2009. Proceedings book
ISBN 978-88-8443-284-1, pp. 109-115 (Oral communication).
16. Lucas M.S., Mosteo R., Maldonado M.I., Malato S., Peres J.A. solar treatment and
detoxification of a winery wastewater in a CPC reactor. 1st International Edition Photocatalytic Products and Technologies Conference - PPTC09. Guimares,
Portugal, 1113 May 2009 (Oral communication).
17. Lucas M.S., Penela M., Peres J.A. Degradation of Reactive Black 5, Reactive Orange
16 and Acid Yellow 49 by advanced oxidation processes. 1st International Edition Photocatalytic Products and Technologies Conference - PPTC09. Guimares,
Portugal, 11- 13 May 2009 (Poster communication).
18. Lucas M.S., Penela M., Peres J.A. Photochemical degradation of three commercial azo
dyes used in the textile industry. 1st International Edition - Photocatalytic Products and
Technologies Conference - PPTC09. Guimares, Portugal, 11-13 May 2009 (Oral
communication).
19. Lucas M.S., Peres. J.A., Li Puma G. Ozonation and advanced oxidation of winery
wastewater in a pilot-scale bubble column reactor. 2nd European Conference on
Environmental Applications of Advanced Oxidation Processes (EAAOP2). Nicosia,
Cyprus, 9-11 September, 2009 (Oral communication).
183
20. Lucas M.S., Peres J.A., Li Puma, G. Pilot-scale treatment of winery wastewater by
ozonation and advanced oxidation. 1st International Workshop on Application of Redox
Technologies in the Environment (Arte'2009), Istanbul, Turkey, 14-15 September,
2009 (Poster communication).
21. Pirra A., Brs R., Lucas M.S., Peres J.A. Tratamento de efluentes vincolas por
processos de coagulao/floculao qumica. 3rd International Congress of Energy and
Environment Engineering and Management. Polytechnic Institute of Portalegre,
Portugal. 25-27 November, 2009 (Accepted for poster).
III. Communications in national conferences
22. Lucas M.S., Dias A.A., Bezerra R.M., Fraga I., Peres J.A. Foto-degradao do cido
glico por processos de oxidao avanada. 9 Conferncia Nacional do Ambiente,
Universidade de Aveiro, Aveiro, 18-20 April 2007. Borrego C., Miranda A. I.,
Figueiredo E., Martins F., Arroja L., Fidlis T. (Eds) Vol. 2, Proceedings book ISBN
978-972-789-230-3, pp. 608-614 (Oral communication).
IV. Patents
23. Lucas M.S., Peres J.A., Amaral C., Sampaio A., Dias A.A. Processo biolgico aerbio
de tratamento de efluentes agro-industriais com elevado teor em compostos aromticos
baseado na aplicao de microrganismos da espcie Candida oleophila. Portuguese
Patent n 103 738, assigned at 13th August 2009.
184

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APPLICATION OF ADVANCED OXIDATION PROCESSES TO WASTEWATER TREATMENT

APPLICATION OF ADVANCED OXIDATION PROCESSES

Dissertation presented for the

APPLICATION OF ADVANCED OXIDATION PROCESSES TO

Dissertation presented for the

MARCO PAULO GOMES DE SOUSA LUCAS

Supervisor: Prof. Dr. Jos Alcides Silvestre Peres

CQVR - Chemistry Centre of Vila Real

My deepest gratitude to them all!

1.1. The water resource

1.2. Textile industry

1.2.2. Dyes and the environment

1.2.3. Textile wastewater treatment processes

1.3. Winery wastewater

1.3.1. Production process and sources of wastes

1.3.2. Winery wastewater treatment processes

1.4. Advanced oxidation processes

1.4.1. Fentons reagent

1.4.2. Photo-Fenton system

1.4.4. Heterogeneous photocatalysis

2. DEGRADATION OF REACTIVE BLACK 5 BY FENTON/UV-C AND

2.3. Results and Discussion

2.3.1. Photochemical decolorization of Reactive Black 5

2.3.2. Kinetic analysis of ferrioxalate processes

2.3.4. Effect of H2O2 dosage

2.3.5. Effect of iron dosage

2.3.6. Effect of dye concentration

2.3.7. Effect of solar light intensity

2.3.8. Mineralization study

3. DEGRADATION OF A TEXTILE REACTIVE AZO DYE BY A COMBINED

Reagents and microbiological media

3.2.2. Fentons reagent experiments

3.2.3. Yeast (Candida oleophila) experiments

3.2.4. Other analytical procedures

3.3.1. Reactive Black 5 decolorization with Fentons reagent

3.3.2. Reactive Black 5 decolorization with Candida oleophila

3.3.3. Kinetic analysis

3.3.4. Fentons reagent process

3.3.5. Candida oleophila process

3.3.6. Optimization of Reactive Black 5 decolorization by Fentons reagent

3.3.7. Combining Fentons

4. GALLIC ACID PHOTOCHEMICAL OXIDATION AS A MODEL COMPOUND OF WINERY

4.2. Materials and methods

4.2.2. Experiments and analysis

4.2.3. TiO2 characterization

4.3. Results and discussion

4.3.1. Gallic acid photoxidation

4.3.2. Influence of H2O2 on gallic acid photoxidation

4.3.3. Influence of Fentons processes on gallic acid photoxidation

4.3.4. Influence of TiO2 on gallic acid photoxidation

4.3.5. Toxicity assessment

5. SOLAR PHOTOCHEMICAL TREATMENT OF WINERY WASTEWATER IN A CPC

5.2. Material and methods

5.2.1. Winery wastewater

5.2.3. Analytical determinations

5.2.4. Toxicity measurements

5.2.5. Experimental set-up

5.3. Results and Discussions

5.3.1. Degradation of winery wastewaters by TiO2

5.3.2. Degradation of winery wastewaters by TiO2/H2O2 and TiO2/S2O82-

5.3.3. Degradation of winery wastewaters by photo-Fenton oxidation

Influence of ferrous iron concentration

Influence of the winery wastewater composition