The Handbook of Environmental Chemistry 67

Series Editors: Damià Barceló · Andrey G. Kostianoy

Antonio Gil · Luis Alejandro Galeano 
Miguel Ángel Vicente Editors

Applications of
Advanced Oxidation
Processes (AOPs)
in Drinking Water
Treatment
The Handbook of Environmental Chemistry

Founded by Otto Hutzinger

Editors-in-Chief: Dami

a Barceló • Andrey G. Kostianoy

Volume 67

Advisory Board:
Jacob de Boer, Philippe Garrigues, Ji-Dong Gu,
Kevin C. Jones, Thomas P. Knepper, Alice Newton,
Donald L. Sparks
More information about this series at http://www.springer.com/series/698
Applications of Advanced
Oxidation Processes (AOPs)
in Drinking Water Treatment

Volume Editors: Antonio Gil
Luis Alejandro Galeano

Miguel Ángel Vicente

With contributions by
M. Antonopoulou
M. Brienza
B. R. Contesini

A. P. B. R. de Freitas
L. V. de Freitas
B. M. Esteves

P. Fernández-Ibá~nez
L. A. Galeano
A.-M. Garcı́a
A. Gil

F. M. Gomes
M. Guerrero-Flórez
J. Hofman
R. Hofman-Caris

H. J. Izário Filho
S. Jafarinejad
H. K. Karapanagioti
K. Katsanou

I. Konstantinou
G. Li Puma
C. C. A. Loures
L. M. Madeira

B. K. Mayer
S. Nahim-Granados
A. M. Nasser
C. B. Özkal

A. Pintar
M. I. Polo-López
J. H. Ramı́rez
C. E. R. Reis

C. S. D. Rodrigues
D. R. Ryan
C.-A. Sánchez
M. B. Silva

S. Sorlini
T. Tišler
R. A. Torres-Palma
M. Á. Vicente
Editors
Antonio Gil Luis Alejandro Galeano
Department of Sciences Department of Chemistry
Public University of Navarra University of Nari~
no
Pamplona, Spain Pasto, Nari~
no
Colombia

Miguel Ángel Vicente

Department of Inorganic Chemistry
University of Salamanca
Salamanca, Spain

ISSN 1867-979X ISSN 1616-864X (electronic)

The Handbook of Environmental Chemistry
ISBN 978-3-319-76881-6 ISBN 978-3-319-76882-3 (eBook)
https://doi.org/10.1007/978-3-319-76882-3

Library of Congress Control Number: 2018946685

© Springer International Publishing AG, part of Springer Nature 2019

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or
information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt
from the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors, and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
editors give a warranty, express or implied, with respect to the material contained herein or for any errors
or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims
in published maps and institutional affiliations.

Printed on acid-free paper

This Springer imprint is published by the registered company Springer International Publishing AG part
of Springer Nature.
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Editors-in-Chief
Prof. Dr. Dami
a Barceló Prof. Dr. Andrey G. Kostianoy
Department of Environmental Chemistry P.P. Shirshov Institute of Oceanology
IDAEA-CSIC Russian Academy of Sciences
C/Jordi Girona 18–26 36, Nakhimovsky Pr.
08034 Barcelona, Spain 117997 Moscow, Russia
and [email protected]
Catalan Institute for Water Research (ICRA)
H20 Building
Scientific and Technological Park of the
University of Girona
Emili Grahit, 101
17003 Girona, Spain
[email protected]

Advisory Board
Prof. Dr. Jacob de Boer
IVM, Vrije Universiteit Amsterdam, The Netherlands

Prof. Dr. Philippe Garrigues

University of Bordeaux, France

Prof. Dr. Ji-Dong Gu

The University of Hong Kong, China

Prof. Dr. Kevin C. Jones

University of Lancaster, United Kingdom

Prof. Dr. Thomas P. Knepper

University of Applied Science, Fresenius, Idstein, Germany

Prof. Dr. Alice Newton

University of Algarve, Faro, Portugal

Prof. Dr. Donald L. Sparks

Plant and Soil Sciences, University of Delaware, USA
The Handbook of Environmental Chemistry
Also Available Electronically

The Handbook of Environmental Chemistry is included in Springer’s eBook

package Earth and Environmental Science. If a library does not opt for the whole
package, the book series may be bought on a subscription basis.
For all customers who have a standing order to the print version of The Handbook
of Environmental Chemistry, we offer free access to the electronic volumes of the
Series published in the current year via SpringerLink. If you do not have access, you
can still view the table of contents of each volume and the abstract of each article on
SpringerLink (www.springerlink.com/content/110354/).
You will find information about the
– Editorial Board
– Aims and Scope
– Instructions for Authors
– Sample Contribution
at springer.com (www.springer.com/series/698).
All figures submitted in color are published in full color in the electronic version on
SpringerLink.

Aims and Scope

Since 1980, The Handbook of Environmental Chemistry has provided sound

and solid knowledge about environmental topics from a chemical perspective.
Presenting a wide spectrum of viewpoints and approaches, the series now covers
topics such as local and global changes of natural environment and climate;
anthropogenic impact on the environment; water, air and soil pollution; remediation
and waste characterization; environmental contaminants; biogeochemistry; geo-
ecology; chemical reactions and processes; chemical and biological transformations
as well as physical transport of chemicals in the environment; or environmental
modeling. A particular focus of the series lies on methodological advances in
environmental analytical chemistry.

vii
Series Preface

With remarkable vision, Prof. Otto Hutzinger initiated The Handbook of Environ-
mental Chemistry in 1980 and became the founding Editor-in-Chief. At that time,
environmental chemistry was an emerging field, aiming at a complete description
of the Earth’s environment, encompassing the physical, chemical, biological, and
geological transformations of chemical substances occurring on a local as well as a
global scale. Environmental chemistry was intended to provide an account of the
impact of man’s activities on the natural environment by describing observed
changes.
While a considerable amount of knowledge has been accumulated over the last
three decades, as reflected in the more than 70 volumes of The Handbook of
Environmental Chemistry, there are still many scientific and policy challenges
ahead due to the complexity and interdisciplinary nature of the field. The series
will therefore continue to provide compilations of current knowledge. Contribu-
tions are written by leading experts with practical experience in their fields. The
Handbook of Environmental Chemistry grows with the increases in our scientific
understanding, and provides a valuable source not only for scientists but also for
environmental managers and decision-makers. Today, the series covers a broad
range of environmental topics from a chemical perspective, including methodolog-
ical advances in environmental analytical chemistry.
In recent years, there has been a growing tendency to include subject matter of
societal relevance in the broad view of environmental chemistry. Topics include
life cycle analysis, environmental management, sustainable development, and
socio-economic, legal and even political problems, among others. While these
topics are of great importance for the development and acceptance of The Hand-
book of Environmental Chemistry, the publisher and Editors-in-Chief have decided
to keep the handbook essentially a source of information on “hard sciences” with a
particular emphasis on chemistry, but also covering biology, geology, hydrology
and engineering as applied to environmental sciences.
The volumes of the series are written at an advanced level, addressing the needs
of both researchers and graduate students, as well as of people outside the field of

ix
x Series Preface

“pure” chemistry, including those in industry, business, government, research

establishments, and public interest groups. It would be very satisfying to see
these volumes used as a basis for graduate courses in environmental chemistry.
With its high standards of scientific quality and clarity, The Handbook of Environ-
mental Chemistry provides a solid basis from which scientists can share their
knowledge on the different aspects of environmental problems, presenting a wide
spectrum of viewpoints and approaches.
The Handbook of Environmental Chemistry is available both in print and online
via www.springerlink.com/content/110354/. Articles are published online as soon
as they have been approved for publication. Authors, Volume Editors and
Editors-in-Chief are rewarded by the broad acceptance of The Handbook of Envi-
ronmental Chemistry by the scientific community, from whom suggestions for new
topics to the Editors-in-Chief are always very welcome.

Dami
a Barceló
Andrey G. Kostianoy
Editors-in-Chief
Foreword

Safe and readily available water is crucial for public health, and thus, the purification
of drinking water is of such vital importance. Advanced oxidation processes (AOPs)
are among the most promising methods to replace or integrate with conventional
drinking water purification technologies. AOPs are rarely applied alone, but in
combination with other treatment methods to obtain optimal removal rates.
All AOPs involve the generation of highly reactive oxygen species. These
methods are of interest to public health, as they have the potential for complete
mineralization of recalcitrant compounds, but at high concentrations of organic
compounds, their application is more limited due to the high energy and oxidant
consumption.
AOPs are efficient in natural organic matter (NOM) reduction and mitigation of
disinfection by-product (DBP) formation, though the use of AOPs for disinfection
is less studied in comparison to chemical degradation. Also, they can be used for the
removal of taste and odor causing components from water as well as for the
elimination of the emerging contaminants, such as pharmaceuticals. Importantly,
the selection of a specific AOP depends strongly on the physicochemical properties
of the water to be treated.
Full-scale applications of AOPs are still limited. This book offers major devel-
opments in recent research to put AOPs in practice. It provides a unique, holistic
perspective on basic and applied research issues regarding the application of AOPs
in drinking water purification. The reader finds up-to-date information and solutions
on AOPs from many leading experts in the field. The 15 chapters of the book form a
most useful, structured, and timely contribution to our understanding of the appli-
cation of AOPs in drinking water purification.

Lappeenranta University of Technology Mika Sillanpää

Lappeenranta, Finland

Florida International University

Miami, FL, USA

xi
Preface

Drinking water treatment plants worldwide are mostly based on simple physi-
cochemical and disinfecting technologies very well known from over a century.
Perhaps this is why recent challenges coming from more variable and complex
water supplies raised along the past 30 years still remain unsolved. Although
developed countries have in general adopted highly effective solutions, they are
usually energy expensive and then not cost-effective for application in the real
context of developing and more populated countries. On the other hand, within
the same timeframe, advanced oxidation processes (AOPs) have emerged as
alternative technologies for the treatment of quite dissimilar polluted streams;
though undoubtedly stressed in wastewaters, drinking water has remained some-
what ignored. This has motivated this revision about most up-to-date studies
dedicated to devise most promising process conditions, like AOPs, for simulta-
neous oxidation of chemicals and inactivation of microorganisms, as well as
types of water supplies feasible for production of drinking water. Moreover,
special attention has also been paid to most critical concerns that have prevented
more decided application of AOPs in this field, including potential formation of
disinfection by-products (DBPs), formation of intermediates of different molec-
ular sizes and polar character, challenging analytical techniques in recording
NOM substrates and by-products, pH close to neutral in most available supplies,
presence of inorganic ions acting as radical scavengers, and simultaneous role as
disinfection technologies, among others.
Accordingly, this book series volume in The Handbook of Environmental
Chemistry reviews the most typical sources of drinking water, namely, ground
and surface waters, not only from a purely technical approach but also taking
into account some influencing social factors. It is followed by a revision about
the most critical limitations of conventional technologies in the treatment of the
water supplies currently available. Second big topic is covered by the chapters
“Natural Organic Matter: Characterization and Removal by AOPs to Assist
Drinking Water Facilities,” “Natural Organic Matter Removal by Heterogeneous

xiii
xiv Preface

Catalytic Wet Peroxide Oxidation (CWPO),” “Separation and Characterization

of NOM Intermediates Along AOPs Oxidation,” and “Photo (Catalytic) Oxida-
tion Processes for the Removal of Natural Organic Matter and Contaminants of
Emerging Concern from Water” devoted to natural organic matter (NOM)
separation, fractionation, characterization, and removal by several AOPs includ-
ing photo-assisted and other catalyzed processes under either homogeneous or
heterogeneous regimes. Special attention has been given to analytic challenges
that should be faced in the short term in order to get more specific insights
regarding molecular size distributions and polar nature along a plethora of
AOPs, whereas the most important expected limitations for every given family
of technologies are also stressed. Just on the border of this and a novel and
exciting field, the removal of taste and odor compounds by AOPs is compre-
hensibly depicted in the chapter “AOPs Methods for the Removal of Taste and
Odor Compounds,” where the most critical aspects to get it more feasible in the
future are openly established.
Third even more promising but also challenging topic is the inactivation/
disinfection of a diversity of microorganisms that could be seriously enhanced
by AOPs in drinking water facilities in comparison to more conventional
chlorine or UV-based techniques. This part starts with those more thoroughly
studied homogeneous Fenton and photo-Fenton variants, where a gradient of
microorganism’s susceptibilities, main involved oxidizing species, and interfer-
ences are clearly stated (chapter “Homogeneous Fenton and Photo-Fenton Dis-
infection of Surface and Ground Water”), followed by a more comprehensive
chapter devoted to revise AOP’s mechanisms of inactivation aimed at reporting
foremost and more hazardous waterborne pathogens as well as particular inter-
actions with other AOPs including heterogeneous solid (photo)-catalysts and
electrocatalysts (chapter “Disinfection by Chemical Oxidation Methods”).
Finally, the actual potential of AOPs treating more resistant to disinfection
protozoan Cryptosporidium gets enclosed in the chapter “Inactivation of Cryp-
tosporidium by Advanced Oxidation Processes”. Last but not least, this
interesting section finishes with the chapters “Impact on Disinfection Byproducts
Using Advanced Oxidation Processes for Drinking Water Treatment” and “Evo-
lution of Toxicity and Estrogenic Activity Throughout AOP’s Surface and
Drinking Water Treatment” dedicated to analyze the impact of AOPs on disin-
fection by-products as target final pollutants of special concern in the context of
drinking water and the evolution of toxicity along the treatments, respectively.
Finally, within a kind of miscellaneous topics, cost-effective materials for
heterogeneous AOPs (chapter “Cost-Effective Catalytic Materials for AOP-
Treatment Units”), regime change of heterogeneous Fenton-like processes
toward continuous reactors (chapter “Wastewater Treatment by Heterogeneous
Fenton-Like Processes in Continuous Reactors”), and application of
chemometric methods, namely, statistical tools of process optimization, are
also critically exposed in the volume.
Preface xv

We hope this work to encourage not only scientists but also decision makers at
industrial and public health levels to embrace AOPs in the ultimate goal of
practically applying such a helpful family of technological alternatives
supplementing drinking water treatment plants in the short future.

Pamplona, Spain Antonio Gil

Pasto, Colombia Luis Alejandro Galeano
Salamanca, Spain Miguel Ángel Vicente
Contents

Surface Water and Groundwater Sources for Drinking Water . . . . . . . 1

Konstantina Katsanou and Hrissi K. Karapanagioti
Limitations of Conventional Drinking Water Technologies
in Pollutant Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Roberta Hofman-Caris and Jan Hofman
Natural Organic Matter: Characterization and Removal by AOPs
to Assist Drinking Water Facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
S. Sorlini
Natural Organic Matter Removal by Heterogeneous Catalytic Wet
Peroxide Oxidation (CWPO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
José Herney Ramı́rez and Luis Alejandro Galeano
Separation and Characterization of NOM Intermediates Along AOP
Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Ana-Marı́a Garcı́a, Ricardo A. Torres-Palma, Luis Alejandro Galeano,
Miguel Ángel Vicente, and Antonio Gil
Photo(Catalytic) Oxidation Processes for the Removal
of Natural Organic Matter and Contaminants of Emerging
Concern from Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Monica Brienza, Can Burak Özkal, and Gianluca Li Puma
Homogeneous Fenton and Photo-Fenton Disinfection
of Surface and Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Marı́a Inmaculada Polo-López, Samira Nahim-Granados,
and Pilar Fernández-Ibá~nez
AOPs Methods for the Removal of Taste and Odor Compounds . . . . . . 179
M. Antonopoulou and I. Konstantinou

xvii
xviii Contents

Wastewater Treatment by Heterogeneous Fenton-Like Processes

in Continuous Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
Bruno M. Esteves, Carmen S.D. Rodrigues, and Luis M. Madeira
Disinfection by Chemical Oxidation Methods . . . . . . . . . . . . . . . . . . . . 257
Luis-Alejandro Galeano, Milena Guerrero-Flórez, Claudia-Andrea
Sánchez, Antonio Gil, and Miguel-Ángel Vicente
Inactivation of Cryptosporidium by Advanced Oxidation Processes . . . . 297
Abidelfatah M. Nasser
Cost-Effective Catalytic Materials for AOP Treatment Units . . . . . . . . 309
Shahryar Jafarinejad
Impact on Disinfection Byproducts Using Advanced Oxidation
Processes for Drinking Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . 345
Brooke K. Mayer and Donald R. Ryan
Evolution of Toxicity and Estrogenic Activity Throughout
AOP’s Surface and Drinking Water Treatment . . . . . . . . . . . . . . . . . . . 387
Tatjana Tišler and Albin Pintar
Chemometric Methods for the Optimization of the Advanced
Oxidation Processes for the Treatment of Drinking and Wastewater . . . 405
Messias Borges Silva, Cristiano Eduardo Rodrigues Reis, Fabrı́cio Maciel
Gomes, Bruno dal Rovere Contesini, Ana Paula Barbosa Rodrigues de
Freitas, Hélcio José Izário Filho, Leandro Valim de Freitas,
and Carla Cristina Almeida Loures

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
Surface Water and Groundwater Sources
for Drinking Water

Konstantina Katsanou and Hrissi K. Karapanagioti

Abstract Raw water is groundwater, surface water, or rainwater that has not received
any treatment in order to be suitable for drinking. Its quality must be good enough to
produce when treated a safe and acceptable drinking water, and it must come from a
source that can consistently provide sufficient required quantity.
Polluted or contaminated water sources can contain chemical or microbiological
hazards which can lead to sickness and require treatment before consumption. In
many cases it is better to protect the quality of the raw water providing sustainable
management than to treat it after it has become deteriorated.

Keywords Aquifer, Artificial recharge, Municipal water supply, Protection,

Quality deterioration, Water treatment

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Water Cycle and Climate Change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3 Drinking Water Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1 Surface Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2 Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4 Deterioration Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1 Surface Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2 Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5 Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.1 Surface Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.2 Groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

K. Katsanou
Laboratory of Hydrogeology, Department of Geology, University of Patras, Patras, Greece
e-mail: [email protected]
H.K. Karapanagioti (*)
Department of Chemistry, University of Patras, Patras, Greece
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 1

Water Treatment, Hdb Env Chem (2019) 67: 1–20, DOI 10.1007/698_2017_140,
© Springer International Publishing AG 2017, Published online: 6 December 2017
2 K. Katsanou and H.K. Karapanagioti

6 Water Resource Management and Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

6.1 European Regulations-Legislation and Protection Measures . . . . . . . . . . . . . . . . . . . . . . . . . 15
6.2 Artificial Recharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7 Discussion and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

1 Introduction

The saline water of the oceans comprises approximately 97% of the global water
supply. The remaining 3% is freshwater, out of which nearly 69% is captured in
glaciers, 30% is hosted in karst and porous aquifers, and the rest is in surface water
reservoirs such as lakes, rivers, streams, and marshes.
Freshwater is the basic substance of life on earth and is increasingly in short
supply. According to [1], 75% of the European and 33% of the global population
use groundwater as their primary source of drinking water. Yet, in many countries,
both the quantity and quality of this resource have been compromised by human
activities. Nowadays, water scarcity affects 88 developing countries that are home
to half of the world’s population [2].
Surface water is any source of water that is open to the atmosphere and is subject
to run off from the land. Hence, it is very likely to contain microorganisms that can
cause sickness and in some cases more serious, even fatal, illnesses. In some areas,
a substantial portion of the surface drinking water is derived from bank filtration
that carries a diverse chemicals’ and pathogens’ load [3] and requires purification.
On the other hand, groundwater is covered by soils and sediments and is
considered to be less vulnerable than surface water. Its abstraction though requires
drilling and pumping equipment that is not always available or sustainable espe-
cially in developing countries.
As the population increases, the groundwater abstraction is expected to rise in
the coming century, while available sites for surface reservoirs become limited.
The most important step in providing an area with safe drinking water is the
selection of the best available source water. The more protected source waters are
the easier and the cheaper to be transformed into safe drinking water [4].
The availability of freshwater varies both spatially and temporarily. The renew-
able fraction of the earth freshwater is usually found in the form of surface water and
displays an uneven distribution. Groundwater is more evenly distributed, though
much of it is nonrenewable, fossil water.
The water use in a particular region is determined not only by the natural
groundwater availability but also by the population and the land use of an area, as
well as economical factors.
In the developed countries, the municipality is obliged by law to supply the
consumers with high-quality water, while in the developing countries, this is not
always valid. Hence, the economy of a community defines attitudes and funding
toward water development and treatment.
The local climate also plays a significant role due to influences on evaporation
rates and practices such as lawn watering and cooling requirements. Additionally,
Surface Water and Groundwater Sources for Drinking Water 3

cultural values, actions, policies, and laws of national governments also have an
impact on water use. Finally, the issue of ownership of the resource which is linked
to government influences can be an important factor.
Municipal water supply systems include facilities for storage, transmission,
treatment, and distribution. The design of these facilities depends on the quality
of the water, the particular needs of the user or consumer, and the quantities of
water that must be processed. In certain cases, seawater can also be used as a
drinking water source through the process of desalination.
The objective of this chapter is to present the drinking water sources, their
characteristics, conventional treatment schemes, and protection with respect to
sustainable use.

2 Water Cycle and Climate Change

The only naturally renewable source of freshwater globally is precipitation (about

110,000 km3/year). Out of the precipitation occurring over land, a large fraction
(70,000 km3/year) moves back to the atmosphere through evaporation and tran-
spiration from plants [5]. Infiltration rates vary depending on land use, the char-
acter, and the moisture content of the soil, as well as the intensity and duration of
precipitation.
In case that the rate of precipitation exceeds the rate of infiltration, overland
flow occurs. About 26% of this part of the cycle (18,000 km3/year) can be used by
humans.
Worldwide, the total annual runoff, including soil infiltration and groundwater
replenishment, is estimated to be 41,000 km3/year. Geographical remoteness and
seasonal issues such as floods limit the total annual accessible runoff to 12,500 km3/
year [6].
Therefore, it is estimated that about 54% of the accessible runoff and 23% of the
total renewable resource (precipitation over land) are currently appropriate for
human use in some form.
Although globally groundwater is not very significant in volume, it is a critical
source of water that can cover the human needs, because it is part of the limited
budget of freshwater. From the perspective of long-term sustainability, it is the
renewable resource that is most critical. However, it can also be viewed as a
nonrenewable resource because the rate that may be withdrawn can be higher than
the rate that it is replenished.
Climate change leads to atmosphere warming, which in turn alters the hydro-
logic cycle. This, depending on the area, results in changes to the amount, timing,
form, and intensity of precipitation, the water flow in watersheds, as well as the
quality of aquatic and marine environments.
Climate change can also change groundwater level and temperature and poses
another risk to groundwater and water supply that is not yet well understood, though
it needs attention to find solutions for adaptation.
4 K. Katsanou and H.K. Karapanagioti

Although several scenarios have been developed to predict the potential impact
of climate change, there is still no general consensus on the quantitative effects.
However, it is broadly accepted that many semi- or even arid areas will become
drier, resulting in less groundwater recharge. In humid zones, recharge is expected
to increase due to a higher number of extreme precipitation events. Efforts are being
undertaken so as to better understand the climate change mechanisms on a regional
and even local scale and hence to be able to determine mitigating measures.

3 Drinking Water Sources

The freshwater drinking sources are summarized in Fig. 1. Although water is a

single resource, to understand the quality and the accessibility of the different
formations, each geological water occurrence will be discussed separately. Thus,
surface water will be discussed as lake water and river water and groundwater as
springwater and well water.

3.1 Surface Water

Surface water is accumulated on the ground or in a stream, river, lake, reservoir, or

ocean. The total land area that contributes surface runoff to a lake or river is called
catchment area (Fig. 2). The volume of water depends mostly on the amount of
rainfall but also on the size of the watershed, the slope of the ground, the soil type
and vegetation, and the land use. Any changes in the water level of a lake are
controlled by the difference between the input and output compared to the total
volume of the lake.

Fig. 1 Freshwater drinking sources

Surface Water and Groundwater Sources for Drinking Water 5

Fig. 2 The occurrence of rivers, springs, and boreholes in a catchment area

Surface water is often used for large urban water supply systems, as rivers and
lakes can supply a large, regular volume of water. For small community supplies,
other forms of water supply, such as wells or spring-fed gravity systems, are
generally preferred to surface water. This is because the cost of treatment and
delivery of surface water is likely to be high and operation and maintenance less
reliable.
The advantages of the use of surface water as a resource for domestic water
supply are many. Surface water, among others, is easy to be abstracted by direct
pumping and can be treated after use and put back into a river. However, surface
water is seasonal and will always need treatment.

3.1.1 Lakes

Lakes have numerous features, such as catchment area, inflow and outflow, nutrient
content, dissolved oxygen, pollutants, pH, sedimentation, type, etc. The most
significant inputs are precipitation onto the lake surface, the runoff carried by
streams from the lake catchment area, the aquifers, and artificial sources from
outside the catchment area. The most significant outputs are evaporation from the
lake surface, surface water and groundwater flows, and any water extraction for
human activities. The water level of a lake displays fluctuations related to climate
and water abstraction variations.
The majority of lakes globally contain freshwater. Their water composition
varies depending on many factors. Freshwater lakes are important natural resources
that, among others, also serve as drinking water sources. However, they face
various water-quality deterioration problems due to the impact of human activities,
i.e., pollution, agriculture and fishery activities, and climate change [7, 8].
Based on their type, lakes can be classified into tectonic, landslide, saline,
volcanic, glacial, and others such as karst lakes, while based on their nutrient content,
they can be classified into oligotrophic, mesotrophic, eutrophic, and hypertrophic.
6 K. Katsanou and H.K. Karapanagioti

Oligotrophic lakes are characterized by clear waters that display low concentra-
tions of plant life, while hypertrophic ones are characterized by waters excessively
enriched in nutrients, poor clarity, and algal blooms due to an over-enrichment of
nutrients. Such lakes are of little use to humans and have a poor ecosystem due to
decreased dissolved oxygen. Variations in nutrient enrichment are influenced by
environmental changes and anthropogenic activities.

3.1.2 Rivers and Streams

Rivers are part of the hydrological cycle. Their flow is a function of many factors
including precipitation, runoff, interflow, groundwater flow, and pumped inflow
and outflow. The discharge of a river varies seasonally and among the years. In
many countries, rivers and streams have a wide seasonal variation in flow which
affects their water quality.
The chemical composition of the river water is complex and depends on the
inputs from the atmosphere, the geology of the catchment area, and the human
activities. It has a large effect on the ecology, and it also affects the uses of the river
water. In order to determine the river water chemistry, a well-designed sampling
and analysis is required.
During dry seasons and drought periods, springs feeding small watercourses in
river headwater areas are the main source of downstream waters [9]. When the
average discharge of a river cannot serve the water supply throughout the year, a
dam is built to block the flow of water. Gradually with time, an artificial lake is
formed. The construction of a dam for its abstraction is expensive and environ-
mentally damaging that may trigger earthquakes. Moreover it requires sufficient
precipitation and large river catchment while such reservoirs will eventually silt up.

3.2 Groundwater

Groundwater is a major source of drinking water worldwide and is hosted in aquifers.

Hydrological recharge of aquifers hugely varies geographically and strongly depends,
among other factors, on climate, geology, soil type, vegetation, and land use [10]. Ground-
water is recharged from precipitation, which is complemented by natural infiltration by
surface water or by artificial recharge. On a global scale, 20% of the irrigation water and
40% of the water used in industry are derived from groundwater [11].
Groundwater within an unconsolidated rock moves only a few centimeters a day,
i.e., about 10 m/year. Its velocity largely depends on the steepness of the aquifer
slopes and the permeability of the rocks. In consolidated rocks the water velocity
can be many times higher. A typical example is the karst formations.
Groundwater occurs in aquifers under two different conditions, the unconfined
and the confined. In an unconfined aquifer, the water only fills the aquifer partly,
and its upper surface of the saturated zone may rise and decline. On the other hand
Surface Water and Groundwater Sources for Drinking Water 7

in a confined aquifer, the water completely fills the aquifer that is overlain by a
confining bed. The recharge of the saturated zone occurs by percolation of water
from the land surface through the unsaturated zone.
The advantages of the use of groundwater as a resource for domestic water
supply are many. In most inhabited parts of the world, there is a large amount of
groundwater, and despite that the abstracted volumes are huge, they are often
readily supplemented. Another advantage is that the upper soil layers act as a filter
against physical, chemical, and biological deterioration which is effective both in
terms of quality and cost. Finally, groundwater use often brings great economic
benefits per unit volume compared to surface water because of ready local avail-
ability, high drought reliability, and a generally good quality requiring only minimal
treatment [12].
The movement of pollutants in an aquifer is defined by the hydraulic character-
istics of the hosting soils and rocks. Substances dissolved in water move along with it
unless they are tied up or delayed by adsorption. Thus, the movement of pollutants
tends to be through the most permeable zones; the farther their point of origin from a
groundwater discharge area, the deeper they penetrate into the groundwater system
and the larger the area that is ultimately affected [13].
Groundwater exploration utilizes hydrogeological mapping, hydrogeophysical
prospecting, investigation drilling, pumping tests, and groundwater regime obser-
vation, but also remote sensing, isotopic studies, shallow seismic prospecting, and
velocity logging are also being applied in groundwater exploration [14].

3.2.1 Springs

The physical outlets of an aquifer are known as springs. Springs occur mainly in
mountainous or hilly terrains, in locations where the water table meets the ground
surface (Fig. 2).
In the past, the community water supplies were often based on springs, and they
still comprise a source of water, because springwater usually displays a high natural
quality and its intake is relatively easy (Fig. 3). Springs can be classified as artesian,
gravity, perennial, intermittent, tubular, seepage, and thermal springs.

3.2.2 Boreholes and Wells

Groundwater can be obtained from an aquifer by drilling a well or a borehole below

the water table. The water level in boreholes or wells drilled into unconfined
aquifers stands in the same position as the water table in the surrounding aquifer.
The water level in boreholes drilled into confined aquifers stands at some height
above the top of the aquifer but not necessarily above the land surface. If the water
level in a borehole stands above the land surface, the well displays artesian flow,
where water rises to the surface without pumping (Fig. 4). Pumping water out of an
aquifer lowers the water level near the well.
8 K. Katsanou and H.K. Karapanagioti

Fig. 3 Intake of water from a spring in a remote mountainous area in Greece

The “safe yield” of an aquifer is the volume of water that can be withdrawn
without depleting the aquifer, i.e., the water that is renewable. In case that a higher
volume is withdrawn, a number of undesirable effects can occur (see Sect. 4). A
groundwater source of drinking water, such as a borehole, can be used as safe water
supply after no or very little treatment. Even a dug well that pumps shallow water and
is subject to weather can be treated effectively with relatively simple equipment.

4 Deterioration Issues

As already mentioned, freshwater ecosystems are important natural resources for

the survival of living organisms of the biosphere and are under pressure from a
range of stressors, including changes in land use, pollution, agriculture, climate
change, and human activities [15, 16]. In many regions, the increasing economic
development and human migration also stress water resources and water quality.
More than half of the world’s population live adjacent to water bodies and carry
out activities that increase aquatic stressors such as anthropogenic eutrophication
and algal blooms [17]. The problems most frequently encountered in the operation
of supply wells are related either to declines in yield or to deterioration in the
quality of water (Fig. 5).
Surface Water and Groundwater Sources for Drinking Water 9

Fig. 4 A borehole with artesian flow

Groundwater overexploitation has caused large and continuous decline of

groundwater levels, which in many cases results in the arrival of water from
different directions to a well or borehole that may contain a large concentration
of any substance.
In urban areas, groundwater overexploitation leads to land subsidence. In coastal
areas, the intensive groundwater use is not simply limited to subsidence. It can also
lead to the deterioration of groundwater quality. When freshwater heads are
declined by withdrawals through boreholes, the freshwater-saltwater interface
shifts until a new balance is established. Seawater can migrate kilometers toward
the inland [18]. Since seawater intrusion takes a long time to remedy and often is
irreversible, immediate actions should be taken for its prevention or mitigation.
Intensive overexploitation of groundwater globally has already created serious
environmental problems. Therefore, the analysis of the influence of exploited
groundwater on the environment and the allowable withdrawal of a well field should
be determined beforehand.
In aquifers, water moves slower than in surface water systems, and the time for
contaminant infiltration depends on the type of the contaminant, the characteris-
tics of the aquifer, and the length of the flow path. This can last from a number of
years up to centuries. As a consequence, there is a great deal of time for intimate
10 K. Katsanou and H.K. Karapanagioti

Fig. 5 Deterioration issues

contact between the water and soil and rock material, which results in changes of
the chemical composition of water that may involve almost any substance soluble
in water.
The arrival of water containing dissolved chemicals, which are naturally occur-
ring or human-introduced ones, in an undesirably large concentration will deterio-
rate the water quality of a borehole. The most commonly observed increases in
concentration involve NaCl and NO3
. Additionally, the growing number of
chemicals that is applied in manufacturing processes increases water-related risks.
Hazardous substances include herbicides, pesticides, and inorganic and complex
organic substances. Deterioration in physical quality has to do with changes in
appearance, taste, and temperature of water that may originate from rock particles
of variable sizes.
Deterioration in biological quality is related to the appearance of bacteria and/or
viruses associated with human, animal, and food processing wastes. It normally
indicates a connection between the land and the water surface.
Each water source has a unique set of contaminants. Groundwater contains
pesticides, chemicals, and nitrates, while surface water mostly contains bacteria
and other microorganisms as well as other suspended particles. Groundwater and
surface water recharge each other, and this interconnection between the two sources
of drinking water may lead to exchange of contaminants.
Human health can be harmed in case that contaminants and pathogens end up
in drinking water. The World Health Organization has estimated that contami-
nated drinking water causes 502,000 diarrheal deaths each year [19]. The deteri-
oration in water quality does not only impact human health but also has economic
consequences [20].
Groundwater from deep aquifers is protected from pathogen contamination by
the covering soil layers. Although groundwater is better protected than surface
water, shallower groundwater sources, or groundwater that can be influenced by
surface water, are still vulnerable to fecal contamination [21].
Surface Water and Groundwater Sources for Drinking Water 11

4.1 Surface Water

4.1.1 Lakes

Eutrophication has become a worldwide environmental problem [22, 23]. Recently,

studies have shown that lake eutrophication could accelerate in response to the
effects of anthropogenic activities and climate change [24]. Water in lakes, bogs,
and swamps may gain color, taste, and odor from decaying vegetation and other
natural organic matters.
It can also be polluted by (a) runoff of soils and farm chemicals from agricultural
lands, (b) waste from cities, (c) discharges from industrial areas, (d) leachate from
disposal sites, and (e) direct atmospheric pollutants such as rain, snow, or dust.
The interaction between lakes and groundwater systems has been studied with
numerical models and on the field [25], with attention paid to the place of a lake
within a local, intermediate, or regional groundwater system.

4.1.2 Rivers and Streams

Chemical composition of rivers in higher topographical areas where the water

volume is smaller is affected by fewer rock types and can reflect the local geology,
and in particular cases, their quality can be poor. In the absence of any pollution
source, the river water quality is similar to the rain and springwater.
However, as a river flows to lower topographic areas, its water accumulates fine
soil particles, microbes, organic material, and soluble minerals. In populated areas,
the quality of surface water as well as groundwater is directly influenced by land use
and human activities. According to Environmental Protection Agency (EPA) [26],
the most common source of river pollution is agriculture.
In wet periods, especially at their beginning, there is a high risk of fecal contam-
ination, as feces are washed into the river. However, along with the increase in flow,
there is a higher dilution rate, and thus, wastewater will be diluted, so the health risk
decreases [4]. In dry periods, the silt load is often lower than in wet ones, but the
dissolved solids are much more concentrated.

4.2 Groundwater

Nowadays, groundwater resources are facing qualitative and quantitative problems.

In many cases, the groundwater abstraction rates for many large aquifers worldwide
significantly exceed the natural renewal rate [27–29].
Growing industrialization, waste deposition, and the exponentially increasing
production and use of synthetic chemicals, which are often released into the envi-
ronment, put groundwater resources under growing pressure [30].
12 K. Katsanou and H.K. Karapanagioti

The chemical composition of groundwater also reflects the geology of the area
that has been in contact. If the groundwater is in contact with limestone, then, the
water is expected to be hard and to contain high concentrations of calcium and
carbonates. In general though, the water quality does not differentiate significantly
enough to be a concern to humans or any other living organisms and ecosystems.
The human activities are mainly responsible for groundwater quality degradation.
Groundwater pollution most often results from overuse of fertilizers and pesticides,
improper disposal of wastes on land, industrial and household chemicals, garbage
landfills, wastewater from mines, oil field brine pits, leaking of oil storage tanks,
sewage sludge, septic systems, etc.
Groundwater can be also contaminated by overpumping in coastal regions that
triggers seawater intrusion, a widespread and serious problem in many parts of the
world, especially in the Mediterranean region.
There are cases though where pollution sources are absent, while groundwater
does not lie within the potable regulations. These waters are mostly found in areas
with recent volcanic activity, where groundwater displays higher temperatures than
the groundwater of the surrounding watershed area and higher residence time and
salt content than the freshwaters. Moreover, in many coastal areas worldwide,
particularly in karst areas, natural seawater intrusion may exist.

4.2.1 Springs

The most vulnerable water supplies are those hosted in unconfined and karst
aquifers, where pollutants can readily diffuse into groundwater supplies. In case
that springs are used for water supply, special attention should be paid to any
variation of their water temperature during the day and coloration of their water
shortly after rain, which indicate that the aquifer layer is not deep enough or that
there is direct infiltration of surface water through the topsoil, and thus, the spring is
extremely vulnerable to contamination.

4.2.2 Boreholes and Wells

Deterioration in water quality may result either from changes in the biological,
chemical, or physical quality of water in the aquifer or changes in the well. The
monitoring of the biological and chemical quality of water of wells that supply
domestic needs is important, in order to spot any differentiations in their water
quality. Especially before using a new well for public supply, it should be clarified
first that its water quality meets the potability standards. Otherwise treatment is
required.
Surface Water and Groundwater Sources for Drinking Water 13

5 Treatment

In all cases, drinking water should be free of microbes or be disinfected before it is

consumed. In addition, surface water should be treated for the removal of suspended
solids and algae. Groundwater may not need additional treatment if it is springwater.
Springwaters often do not even need disinfection. However, depending on the
formations groundwater passes through, it may need softening or iron and manga-
nese removal or removal of other substances such as arsenic or chromium. The
following sections describe the conventional treatment methods that are mostly
described in [31]. Recent advances in disinfection are critically reviewed and
presented in [32].

5.1 Surface Water

If drinking water originates from surface water, it requires treatment that needs
substantial infrastructure, i.e., water treatment plants.

5.1.1 Lake Conventional Treatment

The most common treatment for lake or dam water is a combination of coagulation,
flocculation, sedimentation, sand filtration, and disinfection. Coagulation, floccu-
lation, and sedimentation are complimentary processes needed for the removal of
stable colloid particles that are light enough to be suspended and will take a long
time to settle due to gravity only. If these suspended solids are microalgae, more
sophisticated treatment is necessary, and expensive membranes are employed.
Coagulation is a chemical process that requires the addition of coagulants which
are usually salts in the form of powders. They are used to neutralize the surface of
colloids, in other words to destabilize their solution and allow their flocculation.
Colloids repulse each other due to common surface charge since they usually
originate from the same geological formation. Once their surface charge is neutral-
ized, then, they flocculate due to gravity forces forming bigger particles that settle
much faster by gravity. Sand filtration usually follows the sedimentation tank and is
used to remove the finer flocs that did not settle or the destabilized particles if no
sedimentation tank is present.
Disinfection is used to deactivate microorganisms in water and keep the water
supply safe throughout the pipelines of the municipality. In some countries for
surface water, sand filtration is mandatory before disinfection since attached
microbes to suspended particles are more persistent than suspended microbes.
Thus, disinfection would not be as effective in the presence of suspended particles.
Some industries use pressure filters, ion exchange, and ultraviolet radiation to
remove solids and alkalinity and to disinfect. This way they avoid the addition of
14 K. Katsanou and H.K. Karapanagioti

any chemicals that could create a taste and odor problem. However, these processes
are more expensive and more energy intensive.

5.1.2 River and Stream Conventional Treatment

River water follows similar treatment schemes as lake water for the removal of
suspended solids and for disinfection. Although river water is most commonly
pumped from the river sources or from the river banks, it still requires treatment
for suspended solids.

5.2 Groundwater

If drinking water originates from groundwater, it is usually treated on site of the

point it is collected, e.g., on the well.

5.2.1 Spring Conventional Treatment

If the spring is protected, springwater can be of high quality and may not require
any treatment, not even disinfection. However, in order to be safe, usually munic-
ipalities disinfect springwater in order to keep it safe during transportation through
the pipelines of the distribution system.

5.2.2 Borehole and Well Conventional Treatment

For groundwater originating from boreholes or wells, the most common treatment
scheme is a combination of softening, aeration, and disinfection.
Softening is a chemical process used for the removal of hardness that is due to
calcium and magnesium carbonate minerals dissolved in groundwater. Hardness is
associated with scaling in the pipelines or in machines that heat water.
Aeration is also a chemical process used for oxidation and, thus, formation of
less soluble species and precipitation of iron and manganese. It is also possible to
use an oxidation medium such as potassium permanganate or chlorine to help metal
precipitation.
Disinfection, also a chemical process, is used to deactivate microorganisms in
water and keep the water supply safe throughout the pipelines of the municipality.
The most common disinfection method is chlorination that requires the mixing of
water with chlorine gas or with sodium hypochlorite. Chlorine is hydrolyzed and
hypochlorite acid is formed. Chlorine is effective for the disinfection from bacteria
and is also persistent in the supply pipeline without requiring the addition of another
disinfectant. Ozone and UV are also used and are effective disinfectants. However,
Surface Water and Groundwater Sources for Drinking Water 15

they require the addition of chlorine in water before it is transported through

pipelines. The use of chlorine as a disinfectant could be a problem since chlorine
has strong taste and odor.
Other methods to get water free from salts are distillation, ion exchange, and
membrane filtration. Conventional distillation requires high amounts of power and
wasting lots of water for cooling. Solar distillation is friendlier to the environment
but requires space and sun shining. Ion exchange requires the use of specific resins
that remove both anions and cations. They still require water softening to avoid fast
consumption of the resins by hardness and frequent regeneration of resins. Mem-
brane filtration requires high pressure to push water through the membrane.
If water is polluted, it may require additional treatment before it can be con-
sumed. Toxic metals present in groundwater due to pollution or to natural minerals
can be removed by sorbent materials that will strongly bind them. However, in
many countries, it is considered preferable to change water supply than try to treat a
polluted one. In places where water supplies are scarce, in-house water filters are
commonly used employing ceramic pots and sorbent filtering media (e.g., activated
carbon, zeolites, biosorbents, bone chars, etc.).

6 Water Resource Management and Protection

Although water sources, mostly the surface ones, are treated before entering the
households, their treatment costs and the risks posed to public health could be
reduced by investing on their protection.
In Europe, 20% of surface water is at serious risk from pollution; 60% of the cities
overexploit their groundwater resources, while 50% of wetlands are endangered
[33]. There is a constantly increased demand for water that has as consequence that
nearly half of the European population live in “water-stressed” countries, where
abstraction of freshwater is extremely high.
The trends of deterioration of water quality and decrease of urban groundwater
supplies are being corrected by water allocation projects and protection measures.
For urban water pollution control, urban sewage and industrial wastewater will be
treated and reused increasingly.

6.1 European Regulations-Legislation and Protection

Measures

In 1998, the Council Directive (98/83/EC) was introduced and included essential
potability standards [34]. This Directive requires member states to monitor the
quality of water intended for human consumption regularly, by using a “sampling
16 K. Katsanou and H.K. Karapanagioti

points” method, providing regular information to consumers, and reporting the

results every 3 years to the Commission.
In 2000, the European Union adopted the Water Framework Directive (WFD,
2000/60/EC). According to it, member states have had to build river basin man-
agement plans (RBMPs), which were finalized after extensive public consultation.
They are aiming to protect each 1 of the 110 river basin districts and are valid for
6 years. The overall targets of the RBMPs are to accelerate water-saving techniques
to alleviate the crisis of urban water shortage, to protect groundwater resources in
the overexploited areas, to improve the coordination between socioeconomic
development and environmental improvement, and to seek sustainable utilization
of groundwater resources.
According to the WFD, protection zones have been established for both surface
water and groundwater resources in important water supply regions. They comprise
of three different zones:
• An “immediate” proximity protection area: This area is generally small and
encloses the well itself. It belongs to the municipality or the utility and is fenced.
Its purpose is to protect the well itself from direct pollution.
• A proximity area: Its purpose is to protect the well, allowing a sufficient reaction
time in case of pollution from nearby point source pollution. The criterion of
50-day water transit is generally applied to define the limits of this area. Its size
varies according to the hydrogeological characteristics of the area and the
volume of abstraction. In this area there are limitations in the use of the soil,
such as banning of manure, pesticides, road construction, etc., which are derived
by hydrogeological study of the area.
• A distant area: Its purpose is to protect the catchment area of a water source. In
this area, whose extent may vary from place to place, the use of soil is only
subject to recommendations.
In 2006 a new directive aiming to protect groundwater from contamination
(GWD, 2006/118/EC) was published. It stems from the European Water Frame-
work Directive of 2000 [35] and sets Community Quality Standards for groundwa-
ter with respect to the major contaminants, nitrates and pesticides. It also creates the
framework for setting any other Groundwater Quality Standards.
The Groundwater Directive [36] is based on a mixed regime that is in compli-
ance with Groundwater Quality Standards and measures to prevent hazardous or
limit nonhazardous substance emissions to the groundwater.
According to it, the member states are responsible for the establishment of certain
Groundwater Quality Standards based on the local or regional conditions [37].
Moreover, in 2007 the Commission launched the Water Information System for
Europe (WISE), an instrument for the collection and exchange of data and infor-
mation within Europe and for the monitoring of pollutants released to surface
waters or within the aquatic environment [38].
Surface Water and Groundwater Sources for Drinking Water 17

6.2 Artificial Recharge

The overexploitation of groundwater is controlled by increased infiltration and

extensive use of artificial recharge. Artificial recharge can be used to increase the
availability of groundwater storage and reduce saltwater intrusion in coastal aqui-
fers, where pumping and droughts have severely affected the groundwater quality.
Stored water from artificial recharge can be used not only for drinking but also for
industrial and agricultural water supplies.
In coastal areas, it can protect groundwater from saltwater intrusion.
In certain areas, artificial recharge can be used to provide protection from land
subsidence caused by drought and aquifer overexploitation [39].

7 Discussion and Conclusions

Groundwater plays an important role for urban water supplies. Nowadays that there
is recognition of the vertical dimension of hydrologic connectivity [40] and consent
that many surface water ecosystems depend on groundwater at different levels,
conservation and management of this linked resource are even more important [41].
For the efficient and sustainable exploitation, management, and remediation of
groundwater resources, it is important to know the water and contaminant flow
patterns and the way they interact with the geological formations.
Assessment and monitoring of water resources and their quality are generally a
routine in developed countries. However, this is not always the case in developing
or in remote areas where vulnerable communities are hugely affected by poor water
quality [42]. Areas that suffer from limited availability or accessibility of water
resources may also be at greater water risk [43] especially if limited water resources
are undermined by natural and anthropogenic contamination, climate change, or
other factors as poverty, remoteness, insufficient water management, and lack of
treatment [44–46].
Certain measures for groundwater protection such as reduction in water con-
sumption, enhancement of artificial recharge use, pollution control, and holistic
management of groundwater resources are already taken [47].

References

1. Sampat P (2000) Deep trouble-the hidden threat of groundwater pollution. World Watch Paper
154. Worldwatch Institute, Washington, DC
2. Howard KWF, Gelo KK (2002) Intensive groundwater use in urban areas: the case of
megacities. In: Ramon Llamas M, Custodio E (eds) Intensive use of groundwater: challenges
and opportunities. A.A. Balkema Publishers, CRC Press, Rotterdam
18 K. Katsanou and H.K. Karapanagioti

3. Tufenkji N, Ryan JN, Elimelech M (2002) The promise of bank filtration. A simple technology
may inexpensively clean up poor-quality raw surface water. Environ Sci Technol 36:422A–
428A
4. Medema GJ, Shaw S, Waite M, Snozzi M, Morreau A, Grabow W (2003) Catchment
characterization and source water quality. In: Assessing microbial safety of drinking water;
improving approaches and methods. Chapter 4, World Health Organization, London
5. AbuZeid KM (2012) Mediterranean water outlook: perspective on policies and water man-
agement in Arab countries. In: Choukr-Allah R, Ragab R, Rodriguez-Clemente R (eds)
Integrated water resources management in the Mediterranean region: dialogue towards new
strategy. Springer Science & Business Media, Dordrecht
6. Postel SL, Daily GC, Ehrlich PR (1996) Human appropriation of renewable fresh water.
Science 271(5250):785–788
7. Mushtaq F, Nee Lala MG (2017) Remote estimation of water quality parameters of Himalayan
lake (Kashmir) using Landsat 8 OLI imagery. Geocarto Int 32(3):274–285
8. Zhou Y, Zhang Y, Shi K, Liu X, Niu C (2015) Dynamics of chromophoric dissolved organic
matter influenced by hydrological conditions in a large, shallow, and eutrophic lake in China.
Environ Sci Pollut R 22:12992–13003
9. Di Matteo L, Dragoni W, Maccari D, Piacentini SM (2017) Climate change, water supply and
environmental problems of headwaters: the paradigmatic case of the Tiber, Savio and
Marecchia rivers (Central Italy). Sci Total Environ 598:733–748
10. Scanlon B, Healy R, Cook P (2002) Choosing appropriate techniques for quantifying ground-
water recharge. Hydrgeol J 10:18–39
11. Millennium Assessment (2005) Millennium ecosystem assessment. Ecosystems and human
well-being: wetlands and water synthesis. World Resources Institute, Washington, DC
12. Burke JJ, Moench M (2000) Groundwater and society: resources, tensions and opportunities.
United Nations, New York
13. U.S. Environmental Protection Agency (1993) A review of methods for assessing aquifer
sensitivity and ground water vulnerability to pesticide contamination. U.S. EPA/813/R-93/
002, EPA, Washington, DC
14. Changping Y, Tingfang S, Liangyu J, Tingzuo W, Shaodu L (1993) Exploration and evaluation
of groundwater well field. Geological Publishing House, Beijing
15. Rashid I, Romshoo SA (2012) Impact of anthropogenic activities on water quality of Lidder
River in Kashmir Himalayas. Environ Monit Assess 185(6):4705–4719
16. Mushtaq F, Pandey AC (2014) Assessment of land use/land cover dynamics vis-a-vis hydro-
meteorological variability in Wular Lake environs Kashmir Valley, India using multitemporal
satellite data. Arab J Geosci 7:4707–4715
17. Torbick N, Hession S, Hagen S, Wiangwang N, Becker B, Qi J (2013) Mapping inland
lake water quality across the Lower Peninsula of Michigan using Landsat TM imagery.
Int J Remote Sens 34:7607–7624
18. Bear J (1972) Dynamics of fluids in porous media. American Elsevier, New York. https://pdfs.
semanticscholar.org/0000/f028e1fe064dd1ae4bd3f9bb19fcbe2f7adf.pdf
19. World Health Organization (2016) Drinking-water – fact sheet. Geneve. http://www.who.int/
mediacentre/factsheets/fs391/en/. Accessed 13 Jan 2017
20. Juntunen J, Meriläinen P, Simola A (2017) Public health and economic risk assessment of
waterborne contaminants and pathogens in Finland. Sci Total Environ 599–600:873–882
21. Bouchoucha M, Piquet JC, Chavanon F, Dufresne C, Le Guyader FS (2016) Faecal contam-
ination of echinoderms: first report of heavy Escherichia coli loading of sea urchins from a
natural growing area. Lett Appl Microbiol 62:105–110
22. Huang J, Zhan J, Yan H, Wu F, Deng X (2013) Evaluation of the impacts of land use on water
quality: a case study in the Chaohu Lake Basin. Sci World J 2013:329187
23. Wang L, Liang T (2015) Distribution characteristics of phosphorus in the sediments and
overlying water of Poyang Lake. PLoS One 10(5):e0125859
Surface Water and Groundwater Sources for Drinking Water 19

24. Li Y, Zhang Y, Shi K, Zhu G, Zhou Y, Zhang Y, Guo Y (2017) Monitoring spatiotemporal
variations in nutrients in a large drinking water reservoir and their relationships with hydrological
and meteorological conditions based on Landsat 8 imagery. Sci Total Environ 599–600:1705–1717
25. Roningen JM, Burbey TJ (2012) Hydrogeologic controls on lake level: a case study at
Mountain Lake, Virginia, USA. Hydrgeol J 20:1149–1167
26. EPA (2015) Water Quality Assessment and TMDL Information. https://ofmpub.epa.gov/
waters10/attains_nation_cy.control
27. Danielopol DL, Greber C, Gunatilaka A, Notenboom J (2003) Present state and future
prospects for groundwater ecosystems. Environ Conserv 30(2):104–130
28. Gleeson T, Wada Y, Bierkens MFP, van Beek LPH (2012) Water balance of global aquifers
revealed by groundwater footprint. Nature 488:197–200
29. Griebler C, Avramov M (2015) Groundwater ecosystem services: a review. Freshw Sci 34
(1):355–367
30. Zaisheng H (1998) Groundwater for urban water supplies in northern China – an overview.
Hydrgeol J 6:416–420
31. American Water Works Association (AWWA) (2011) Water quality and treatment: a hand-
book on drinking water, 6th edn. McGraw Hill, New York
32. Ngwenya N, Ncube EJ, Parsons J (2013) Recent advances in drinking water disinfection:
successes and challenges. In: Whitacre DM (ed) Reviews of environmental contamination and
toxicology, vol 222. Springer Science+Business Media, New York, pp 111–170
33. http://ec.europa.eu/environment/pubs/pdf/factsheets/water-framework-directive.pdf
34. EU Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human
consumption. http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri¼OJ:L:1998:330:0032:0054:
EN:PDF
35. Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000
establishing a framework for Community action in the field of water policy. http://eur-lex.
europa.eu/resource.html?uri¼cellar:5c835afb-2ec6-4577-bdf8-756d3d694eeb.0004.02/DOC_
1&format¼PDF
36. Directive 2006/118/EC of 12 December 2006 on the protection of groundwater against pollution and
deterioration. http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri¼OJ:L:2006:372:0019:0031:
EN:PDF
37. Quevauviller P (2006) Agreement on new EU groundwater directive. J Soil Sediment 6(4):254
38. WISE (2007) http://water.europa.eu/
39. Masciopinto C, Vurro M, Palmisano VN, Liso IS (2017) A suitable tool for sustainable
groundwater management. Water Resour Manag 31(13):4133–4147
40. Pringle C (2003) What is hydrologic connectivity and why is it ecologically important? Hydrol
Process 17(13):2685–2689
41. Boulton AJ (2005) Editorial: chances and challenges in the conservation of groundwaters and
their dependent ecosystems. Aquat Conserv 15:319–323
42. UNEP (2010) Africa Water Atlas. Division of Early Warning and Assessment (DEWA), United
Nations Environment Programme (UNEP), Nairobi, Kenya
43. World Health Organization (2011) Noncommunicable diseases country profiles. Geneve.
http://apps.who.int/iris/bitstream/10665/44704/1/9789241502283_eng.pdf
44. Cai WJ, Wang Y, Krest J, Moore WS (2003) The geochemistry of dissolved inorganic carbon
in a surficial groundwater aquifer in North Inlet, South Carolina, and the carbon fluxes to the
coastal ocean. Geochim Cosmochim Acta 67:631–639
45. Garrett V, Ogutu P, Mabonga P, Ombeki S, Mwaki A, Aluoch G, Phelan M, Quick RE (2008)
Diarrhoea prevention in a high-risk rural Kenyan population through point-of-use chlorination,
safe water storage, sanitation, and rainwater harvesting. Epidemiol Infect 136(11):1463–1471
46. Hanjra MA, Ferede T, Gutta DG (2009) Reducing poverty in sub-Saharan Africa through
investments in water and other priorities. Agr Water Manage 96(7):1062–1070
47. Ferrier RC, Jenkins A (2010) The catchment management concept. Handbook of catchment
management. Wiley-Blackwell
Limitations of Conventional Drinking
Water Technologies in Pollutant Removal

Roberta Hofman-Caris and Jan Hofman

Abstract This chapter gives an overview of the more traditional drinking water
treatment from ground and surface waters. Water is treated to meet the objectives of
drinking water quality and standards. Water treatment and water quality are there-
fore closely connected.
The objectives for water treatment are to prevent acute diseases by exposure to
pathogens, to prevent long-term adverse health effects by exposure to chemicals
and micropollutants, and finally to create a drinking water that is palatable and is
conditioned in such a way that transport from the treatment works to the customer
will not lead to quality deterioration.
Traditional treatment technologies as described in this chapter are mainly
designed to remove macro parameters such as suspended solids, natural organic
matter, dissolved iron and manganese, etc. The technologies have however only
limited performance for removal of micropollutants. Advancing analytical technol-
ogies and increased and changing use of compounds however show strong evidence
of new and emerging threats to drinking water quality. Therefore, more advanced
treatment technologies are required.

Keywords Conventional water treatment, Disinfection, Groundwater,

Micropollutants, Surface water

R. Hofman-Caris (*)
KWR Watercycle Research Institute, PO Box 1072, 3430 BB Nieuwegein, The Netherlands
e-mail: [email protected]
J. Hofman
Water Innovation and Research Centre, Department of Chemical Engineering,
University of Bath, Claverton Down, Bath BA2 7AY, UK
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 21

Water Treatment, Hdb Env Chem (2019) 67: 21–52, DOI 10.1007/698_2017_83,
© Springer International Publishing AG 2017, Published online: 27 September 2017
22 R. Hofman-Caris and J. Hofman

Contents
1 Safe Drinking Water Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.1 General Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.2 Microbiological Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.3 Chemical Water Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.4 Water Quality: Presence and Characterization of Natural Organic Matter . . . . . . . . . . 28
1.5 Water Quality: Conditioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2 Water Treatment: Drinking Water from Groundwater Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3 Water Treatment: Drinking Water from Surface Water Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.1 Coagulation, Floc Formation and Floc Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2 Application of Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.3 Disinfection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4 Water Treatment: Drinking Water from River Bank Filtrate or Dune Filtrate . . . . . . . . . . . . . 47
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

Abbreviations

D German degree
AC Activated carbon
AOC Assimilable organic carbon
BB Building block
BP Biopolymer
DAF Dissolved air flotation
DOC Dissolved organic carbon
E. coli Escherichia coli
E2 17-Beta-estradiol
EC European Commission
EDC Endocrine-disrupting compound
EE2 17-Alpha-ethinylestradiol
FEEM Fluorescence excitation emission matrix
GAC Granular activated carbon
HS Humic substance
LC-OCD Liquid chromatography – organic carbon detection
LMw Low molecular weight
LP Low pressure (UV lamp, 253.7 nm)
LRV Logarithmic reduction values
LSI Langelier saturation index
MP Medium pressure (UV lamp, 200–300 nm)
Mw Molecular weight
NOM Natural organic matter
PAC Powdered activated carbon
PACl Polyaluminium chloride
PCCPP Practical calcium carbonate precipitation potential
PRAM Polarity rapid assessment method
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 23

QMRA Quantitative microbial risk assessment

REACH Registration, evaluation, and authorization chemicals
SAX Strong anion exchanger
SDWA Safe Drinking Water Act
SEC Size exclusion chromatography
SI Saturation index
SMP Soluble microbiological product
SPE Solid phase extraction
SUVA Specific UV absorbance
TCCPP Theoretical calcium carbonate precipitation potential
TH Total hardness
TOC Total organic carbon
TTC Threshold of toxicological concern
UV Ultraviolet
UV-A 315–380 nm
UV-B 280–315 nm
UV-C 200–280 nm
VUV Vacuum ultraviolet (100–200 nm)
WHO World Health Organization
WWTP Wastewater treatment plant

1 Safe Drinking Water Quality

1.1 General Aspects

The availability of safe drinking water is of utmost importance for human health,
everywhere in the world. For centuries people have been aware of this, although
they didn’t always realize what caused the problems, and why the methods they
applied were effective. Sanskrit texts dating from about 2000 BC indicate that
drinking water should be irradiated by sunlight and afterwards filtrated over char-
coal. In case the source water was unclean, it should first be boiled, then a piece of
copper would have to be immersed for seven times, and finally the water would
have to be filtrated. It took until about 1700 AD until Antony van Leeuwenhoek
discovered microorganisms, although by that time no one yet understood the
importance of this finding for human health. In 1854 during a cholera epidemic in
London, John Snow, an English physician, realized that the source of the epidemic
was a public water pump on Broad Street. By disabling the pump, the outbreak was
stopped. Since this time, the importance of safe drinking water has become more
and more clear, and since the end of the nineteenth and beginning of the twentieth
century, distribution of safe drinking water has become an important task of
authorities. By the same time, measurements were taken to improve sewerage.
The combination of these two facts resulted in a significant increase in health and
average lifespan of people.
24 R. Hofman-Caris and J. Hofman

As becomes clear from the above, the microbiological safety of drinking water is
a very important parameter in drinking water treatment. However, it also became
clear that the chemical composition of the water may play an important role. Some
Roman emperors are notorious because of their mental health. This probably was
caused by the fact that they were rich enough to afford drinking cups containing
lead, as a result of which they obtained a very high dose of lead. Originally,
drinking water mains also contained high lead concentrations, but as became
clear this may cause problems for public health the mains have been replaced
by polyvinyl chloride or polyethylene materials. Nowadays in some areas, like
Bangladesh, high arsenic concentrations cause serious health problems. In 1989 in
the Netherlands, bentazon, a pesticide, was detected in drinking water. As during
the last quarter of the twentieth century analytical techniques were significantly
improved, it became clear that sources for drinking water often contained (too) high
concentrations of pesticides. And shortly after it also was observed that many other
organic micropollutants, like pharmaceuticals, personal care products, flame retar-
dants, solvents and many other industrial chemicals, may be present in sources for
drinking water.
Nowadays, the World Health Organization (WHO) forms an authoritative basis
for the setting of national regulations and standards for water safety in support of
public health. Because of the “precautionary principle”, in many cases these
regulations and standards are set lower than the WHO guidelines. The objective
of the EU Drinking Water Directive (98/83/EC) is to protect human health from
adverse effects of any contamination of water intended for human consumption by
ensuring that it is wholesome and clean. Member states of the European Union can
include additional requirements, e.g. regulate additional substances that are relevant
within their territory or set more stringent standards. In the USA drinking water has
to comply with the Safe Drinking Water Act (SDWA). Here standards are set and in
some cases treatment technology is prescribed. The number of compounds in water
seems to increase, partly because of the improvement of analytical techniques,
increasing the number of detectable compounds, and partly because the number
of chemicals used in practice is increasing. Although there already are numerous
standards set, it is likely that the number of standards will further increase. Water
treatment techniques aim at safe drinking water, which contains no pathogens or
toxic substances. Besides, the water has to be palatable, clear, colourless and
odourless. Furthermore, it should not be corrosive (for tanks and pipes) and have
a low organic content, in order to prevent biological growth in pipes and tanks.
Nowadays, for customer convenience and environmental reasons (decreased use of
detergents and energy requirements), water often is softened and conditioned.
Finally, all these requirements should be met at low costs, as drinking water is a
first necessity for life. In this way it is tried to ensure safe drinking water and to keep
customers trust.
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 25

1.2 Microbiological Standards

Microbiological standards are important because when drinking water contains

pathogens, exposure to these microorganisms can lead to acute infectious diseases
and illness, and in severe cases even to death. Symptoms are gastroenteritis,
diarrhoea, inflammations, etc. In more severe conditions, waterborne diseases like
typhoid fever, cholera or poliomyelitis can occur.
Roughly three categories of pathogens with a high health impact can be distin-
guished: bacteria, viruses and protozoa. Sometimes a fourth category is added:
helminths. Bacteria have in general a low resistance to chlorine or other disinfec-
tants, and persistence in water supply is moderate. Some bacteria may multiply in
drinking water and their infectivity is in general low to moderate. Viruses are
moderately resistant to chlorine and have a high infectivity. Protozoa are highly
infective and very resistant to chlorine [1].
For microbiological standards two approaches are used. The more traditional
approach is the use of faecal indicators in drinking water. The standards in the
European Drinking Water Directive are 0/100 mL for E. coli and Enterococci
[2]. However, for the more infective viruses and protozoa, this approach is insuf-
ficient, and a health-based quantitative microbial risk assessment (QMRA) is
required to determine the microbiological safety of drinking water. The QMRA
methodology requires information on exposure, expressed as the number of micro-
organisms ingested, and dose-response models to determine the infection probabil-
ity. Finally, epidemiological data can be used to determine the disease effects and
severity. Using these data, the QMRA can be used to determine the health effects of
drinking water at very low concentrations of pathogens. For viruses the acceptable
concentrations are extremely low (one microorganism in a few hundred to thou-
sands m3) and thus are not measurable. Instead, logarithmic reduction values (LRV)
for pathogens by individual treatment steps are used. These LRVs can be added for
all individual steps in a treatment. If the number of pathogens in the raw water is
known, it can be calculated by the LRV what the concentration in the treated water
will be and whether this imposes an acceptable health risk.

1.3 Chemical Water Quality

Chemical water quality relates to several organic and inorganic compounds, both
from natural and from anthropogenic origin, that may be present in drinking water.
Problems caused by the presence of heavy metals have been recognized for quite
some time now, and measurements have been taken to prevent these problems.
Drinking water mains are no longer made of lead, and the water is conditioned
(i.e. the pH is adjusted) in order to prevent dissolution of, e.g. copper or carbonate
from cement pipes. However, it is well known that in some parts of the world,
sources for drinking water contain too high concentrations of e.g. arsenic or
26 R. Hofman-Caris and J. Hofman

chromium, which still causes a lot of human health problems worldwide. Coagu-
lation/flocculation and adsorption, sometimes in combination with oxidation, can
be applied to remove these metals from drinking water, and new techniques are
being developed [3, 4]. For arsenic the WHO standard is 10 μg/L, but it is known
that this isn’t a “safe” concentration, as arsenic is a very toxic metal. However, in
some cases it is technically difficult or too expensive to further decrease the arsenic
concentration.
Pesticides (Fig. 1) are applied in both municipal and agricultural areas and end
up in sources for drinking water either by run-off to surface water or by penetration
into groundwater. They are organic compounds which have been designed to be
harmful for certain organisms. Therefore, in principle they shouldn’t be present in
drinking water. However, as analytical techniques are optimized to be able to detect
lower and lower concentrations, it is very difficult to ensure that “no” pesticides are
present. Because of this often the “threshold of toxicological concern” (TTC) is
applied, which gives a guideline for safe concentrations for certain compounds,
below which no negative effects on human health are expected. In the Netherlands a
standard has been set at 0.1 μg/L for individual pesticides, with a total concentration
<0.5 μg/L.
In the past decade, it has become known that sources for drinking water also may
contain pharmaceuticals. These too are compounds designed for their effect on
living organisms. The major part of these pharmaceuticals after use is excreted in
urine and faeces and thus is present in municipal wastewater. However, wastewater
treatment plants (WWTPs) in general have not been designed to deal with these

Fig. 1 Several pesticides

Limitations of Conventional Drinking Water Technologies in Pollutant Removal 27

compounds; as a result of which, only 60–70% of the total load of pharmaceuticals

and their metabolites is removed from WWTP effluent. The rest ends up in surface
water, which in turn is used to produce drinking water. Research in the Netherlands
has shown that WWTPs significantly contribute to the pharmaceutical concentra-
tions in small surface waters [5], which leads to the conclusion that the presence of
pharmaceuticals in surface water may become a problem for drinking water pro-
duction. At the moment more than 4,000 chemical compounds are being applied as
pharmaceuticals, and in a small country like the Netherlands (with approximately
17 million people), yearly 3.5 million kg of pharmaceuticals is used, 140,000 kg of
which end up in surface water. It is expected that these amounts will increase in the
coming years, as a result of the development of new pharmaceuticals and of ageing
of the people [6]. Besides, due to climate change, longer periods of draught are
expected to occur, resulting in lower river discharge and thus higher concentrations.
It already has been shown that some of these compounds, like diclofenac and hormone
disruptors, also have a negative effect on the aquatic environment. Recently, the EU
has put some of these compounds (17-beta-estradiol (E2), 17-alpha-ethinylestradiol
(EE2), and diclofenac) on a watch list, and it is expected that eventually standards will
be set for these compounds [7, 8].
A separate category of pharmaceuticals are the veterinary pharmaceuticals. As
these often are excreted with manure, they may enter the environment more
diffusely and may finally end up in groundwater [9]. This, however, may take
several years; as a result of which, it has to be kept in mind that even after a certain
type of pharmaceutical may have been banned, still it may be observed in ground-
water for many years.
Apart from the above-mentioned pesticides and pharmaceuticals, also industrial
compounds, originating from industrial wastewater treatment plants, can be found
in surface waters. Their relevance for drinking water production depends on their
concentrations and characteristics, which also determine their behaviour in water
treatment processes. Unfortunately, very often little is known about their presence
in wastewater or surface water.
Another category of pollutants are (micro)plastics. As in many cases this is
particulate matter, other techniques will be required to deal with these materials.
They cannot be degraded or adsorbed by common processes, and often the particles
are too small (micro- and nanoscale) for removal in regular filtration processes like
sand filtration. No standards have been set yet for water.
A recent trend observed, initiated by REACH registration, is that apolar
chemicals are replaced by more polar ones [10]. More polar chemicals are better
soluble in water, and therefore removal in a treatment process is often more
difficult.
28 R. Hofman-Caris and J. Hofman

1.4 Water Quality: Presence and Characterization of Natural

Organic Matter

Natural organic matter (NOM) is present in all surface ground and soil waters. It
affects biogeochemical processes (like metal complexation and redox conditions)
as well as water treatment processes through several mechanisms. Therefore, it is a
key parameter with respect to design and operation of water treatment processes. It
is responsible for colour, taste and odour problems and the major part of the
coagulant and disinfectant requirements; it hinders the removal of other contami-
nants (e.g. by competition for adsorption sites in activated carbon, by pore blocking
in filters and by interference with photochemical and oxidation processes); it acts a
as a precursor for unwanted (disinfection) byproducts during treatment with chlo-
rine and ozone; it contributes to membrane fouling, corrosion and the formation
of metal complexes; and it acts as a substrate for bacterial growth, resulting in
biologically unstable water and metal complexes [11–14].
NOM is a complex heterogeneous mixture of various organic molecules origi-
nating from the natural biological activity in water. Its composition varies
from largely aliphatic to highly coloured and aromatic, from highly charged to
uncharged, with a wide variety of chemical compositions and molecular weights,
depending on its origin [11, 15–17]. NOM originating from plant matter has a high
lignin content, with a predominant aromatic fraction [18]. It is suggested that
aromatic parts of wood and nonwoody plants are the precursors of soil humic
acids [19]. These authors describe that aromatic hydroxyl carboxylic acids and
aldehydes are formed during UV and sunlight irradiation of lake and river NOM.
Often NOM represents a family of polymeric chains resulting from the condensa-
tion of polyphenols [20]. Colour often is caused by the presence of fulvic acids,
humic acids and hymatomelanic acids.
The amount and character of NOM in water differ with climate and the hydro-
logical regime as well as with other environmental factors. NOM found in natural
waters consists of both hydrophobic and hydrophilic components. Approximately
50% of the total organic carbon (TOC) in water consists of hydrophobic acids:
humic acids, fulvic acids and humin. This fraction contains much aromatic carbon,
phenolic structures and conjugated double bonds. Hydrophilic NOM contains more
aliphatic carbon and nitrogenous compounds like carbohydrates, sugars and amino
acids. Dissolved organic carbon (DOC) content and TOC content often are used as
indicators for NOM, but they give no information on its composition. The compo-
sition of NOM can be characterized in various ways, for example, by dividing it in a
soluble (<0.45 μm, also containing cell fragments and macromolecules) and a
particulate (suspended) fraction (>0.45 μm). Soluble microbiological products
(SMPs) end up in the water during, e.g. biological treatment in municipal waste-
water treatment plants. They originate either from the conversion of organic
compounds by microorganisms or from dead microorganisms. The SMPs contain
humic acids, polysaccharides, proteins, amino acids, antibiotics, extracellular
enzymes, parts of microorganisms themselves and conversion products [21, 22].
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 29

A common method to characterize organic material is by means of LC-OCD

(liquid chromatography-organic carbon detection) techniques [23]. In this case the
following classification is applied:
• Biopolymers (BP) with molecular weight (MW) 20,000
• Humic substances (HS) with MW 1,000
• “Building blocks” (BB) with MW 300–500 (These are natural conversion
products of humic substances)
• Neutral components with MW <350
• Acidic components (Low MW-acids) with MW <350
Size exclusion chromatography (SEC) often also is applied to determine the
molecular weight distribution of the material.
Assimilable organic carbon (AOC) is a mixture of various fractions of organic
material, which differ per type of water [24]. Grefte concluded that per type of
water, a specific linear relation can be observed between the average AOC concen-
tration and the concentration of LMW acids.
Important parameters in the characterization of NOM are the aromaticity and the
hydrophobicity of the material. Both variables are related. In literature, the material
often is characterized by its specific UV absorbance (SUVA). Material with a high-
SUVA value in general contains much high molecular weight compounds, whereas
low SUVA value material contains hydrophilic, low molar mass and low charge
density compounds. Moreover, compounds with a high SUVA have a higher aroma-
ticity and more unsaturated carbon bonds. However, size distribution and SUVA
value are not necessarily related: it is possible that, e.g. coagulation largely affects the
SUVA value but at the same time hardly affects the molecular weight of the DOC.
Audenaert et al. [25] used the UV absorption at a wavelength of 310 nm to determine
the presence and amount of NOM.
Fluorescence (fluorescence excitation emission matrix; FEEM) too is applied
to characterize dissolved organic material from a biological treatment process
[26]. These authors studied a method to determine the polarity of various NOM
fractions by means of the “polarity rapid assessment method” (PRAM). In this
method water is extracted by means of various adsorbents (solid phase extraction,
SPE). Apart from the hydrophobic surface of the material (and its aromatic char-
acter), also the molecular weight and molecular weight distribution play an impor-
tant role. Column materials used for this technique are, e.g. C2, C8 and C18, which
show an increasing capacity for hydrophobic components. The most important
parameter to characterize the various fractions is the difference in hydrophobic
surface of the various components. Furthermore, dipole interactions and hydrogen
bridging are used for characterization, for example, by applying anion exchangers
with NH2 (a weak anion exchanger) and SAX (a strong anion exchanger). This
method is affected by the pH and ionic strength [26–30].
The PRAM method differs from the commonly applied extraction using a XAD
resin, as in the XAD method, a low pH is applied, and separation of the fractions is
carried out in series instead of in a parallel execution. In XAD different fractions
can be isolated and analysed. Thus, it is possible to determine a mass balance based
on the XAD method, whereas this cannot be done using the PRAM results [26, 29].
30 R. Hofman-Caris and J. Hofman

1.5 Water Quality: Conditioning

Carbon dioxide and carbonate, and as a result pH, play a very important role in the
characteristics of (drinking) water and water treatment.
Carbon dioxide dissolves in water according to Eq. (1):

CO2 þ H2 O ! H2 CO3 ð1Þ

Subsequently, carbonic acid dissociates into bicarbonate and carbonate,

according to Eqs. (2) and (3).

H2 CO3 þ H2 O ! HCO3  þ H3 Oþ ð2Þ

HCO3  þ H2 O ! CO3 2 þ H3 Oþ ð3Þ

The dissociation constant for reaction (2) (K1) is 4.5  107 mol/L, and the
dissociation constant for reaction (3) (K2) is 4.7  1011 mol/L at 25
C. From this it
follows that at equilibrium:
!
½H2 CO3 
pK 1 ¼ pH þ log
 ¼ 6:35 ð4Þ
HCO 3

!
HCO
pK 2 ¼ pH þ log
2  ¼ 10:33
3
ð5Þ
CO3

Ca2+ may react with CO32, forming CaCO3, which has a very limited
solubility:



K s ¼ Ca2þ ∙ CO2
3 ¼ 3:8  109 at 25
C ð6Þ

The degree of super or subsaturation of calcium carbonate is expressed as the

saturation index SI (also Langelier saturation index (LSI)) and is defined as (Eq. 7)


!
Ca2þ ∙ CO2
SI ¼ log 3
¼ pH  pHs ð7Þ
Ks

In Eq. (7) [Ca2+] is the Ca2+ concentration, [CO32] is the carbonate concentra-
tion, and Ks is the solubility constant for CaCO3. pHs is the equilibrium pH of water
containing identical concentrations of Ca2+ and HCO3.



pHs ¼ pK 2  pK s  log Ca2þ CO
3 ð8Þ

In general, in the Netherlands it is strongly recommended that the pH of drinking

water should be above 7.4 in order to prevent the dissolution of zinc from brass in
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 31

taps and of copper and iron from pipe materials. In this way also the dissolution of
lead will be decreased in places where still lead piping is applied. Furthermore, the
SI should be >0.2 in order to prevent the dissolution of calcium carbonate from
cement. This recommendation sometimes contradicts the pH requirements men-
tioned above [31]. For conditioning marble filtration may be applied. As many
organic micropollutants are salts, the pH controls their degree of dissociation and
thus not only their solubility in water but also their behaviour in adsorption,
photolysis and oxidation processes.
A way to describe the precipitation of calcium carbonate is by applying the total
hardness (TH), the theoretical calcium carbonate precipitation potential at 90
C
(TCCPP90) and the practical calcium carbonate precipitation potential (PCCPP).
The TH is defined as the total concentration of calcium and magnesium ions in
water (in mmol/L or in German degrees (
D), 1 mmol/L corresponding to 5.6
D). In
the Netherlands it is recommended to apply a TH <1.8 mmol/L, in order to increase
customer comfort and decrease the environmental impact (use of detergents and
energy requirements). Besides, in the Netherlands a minimum calcium concentra-
tion of 1 mmol/L is required, based on the fact that sufficient calcium uptake is
essential for human health [32]. However, there is no evidence that the presence of
calcium in drinking water would positively contribute to this [33–36].
Furthermore, it is recommended that TCCPP <0.6 mmol/L and PCCPP
<0.4 mmol/L, in order to prevent precipitation of calcium carbonate, which results
in higher maintenance costs and lower lifespan for apparatus like laundry machines
and dish washers.
Under these conditions most organic micropollutants are soluble; as a result of
which, they are relatively difficult to remove from the water. Another point of
attention are heavy metals. By applying milk of lime for softening or marble
filtration for conditioning, small concentrations of heavy metals may be introduced
into drinking water. Precipitation of CaCO3 does not contribute to the removal of
e.g. organic micropollutants.

2 Water Treatment: Drinking Water from Groundwater

Sources

In many countries, groundwater is used as a source for drinking water production.

Groundwater is in general relatively clean, although due to biogeochemical pro-
cesses a wide range of compounds can be dissolved. The compounds present in the
groundwater depend largely on the soil composition of the aquifer. Also, the well or
borehole conditions can have influence on the water quality of the abstracted water.
In specific circumstances, groundwater can be under influence of surface water.
This can be the case in karstic aquifers where cracks in rocks result in a direct
shortcut between the surface water and the groundwater. Sometimes, groundwater
is deliberately put under influence of surface waters by application of river bed
filtration.
32 R. Hofman-Caris and J. Hofman

In principle, groundwater can be aerobic, slightly anaerobic and deeply anaer-

obic. Aerobic groundwater is open to the atmosphere and thus contains oxygen.
Most dissolved compounds will be present in an oxidized state. Under these
conditions iron from the soil doesn’t dissolve in the water. In order to produce
drinking water, even aerobic groundwater is aerated to increase the oxygen con-
centration and simultaneously decrease the CO2 concentration. The most important
parameters that will have to be adjusted in this case are pH, calcium content,
bicarbonate concentration and saturation index (SI). This is called “conditioning”.
When the groundwater originates from sandy soil, it often is lime aggressive; as
a result of which, cement pipe material may be dissolved (SI < 0.2) or enhanced
corrosion of drinking water mains may occur. Due to several degradation processes,
carbon dioxide is present in the water, and as there is hardly any calcium present,
the CO2 concentration may be (much) higher than its equilibrium concentration.
This is reflected in a large negative value of the SI. Air stripping will remove CO2,
but the pH and HCO3 concentration still will have to be adjusted. For example,
marble filtration may be applied for this purpose, dissolving the marble pellets and
adding some hardness to bring the water near equilibrium.
Sometimes the groundwater contains a relatively high calcium concentration
(in calcium-rich aquifers). Hard waters are no threat for public health. Nevertheless,
hardness can be a nuisance as warm water devices have a shorter life and require
more maintenance due to scaling at higher temperatures (calcium carbonate solu-
bility decreases with increasing temperatures), and, for instance, higher concentra-
tions of detergents will be required. For these reasons water in many cases is
softened.
As mentioned before, there are three types of groundwater: aerobic, slightly
anaerobic and deeply anaerobic [37]. The treatment requirements for the three types
differ considerably. Figs. 2–12 shows block schemes for typical groundwater
treatment schemes.
The aerobic groundwater doesn’t contain dissolved iron, but the anaerobic
groundwater does. Besides, it contains ammonium and manganese. For slightly
anaerobic groundwater, aeration and stripping result in the removal of CO2 but
also in the oxidation of Fe2+ to Fe3+, of NH4+ to NO3 by biological processes and
of Mn2+ to MnO2, partly by chemical and partly by biological processes [38]. Fe3+
reacts with hydroxyl ions, forming Fe(OH)3 flocs, which slowly converts into iron
oxide (Fe2O3). Bacteria, Nitrosomonas and Nitrobacter are responsible for the
biological conversion of ammonium, which requires a relatively high amount of
oxygen.
Deeply anaerobic groundwater may contain high concentrations of iron, man-
ganese, ammonium, hydrogen sulphide and methane. Sometimes also chlorinated
compounds, originating from industrial contaminations and spills, are found. Aer-
ation and stripping are applied to remove the gasses and to oxidize iron, manganese
and ammonium. For the nitrate formation, “dry filtration” has to be carried out, in
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 33

Fig. 2 Typical groundwater treatment schemes: (a) aerobic groundwater; (b) anaerobic ground-
water, (c) deeply anaerobic groundwater. Orange blocks are optional, depending on the water
quality: softening for hard water, activated carbon filtration and UV for the presence of organic
micropollutants and disinfection

order to provide sufficient oxygen for the oxidation process. The removal of gasses
can be described by applying Henry’s law (Eq. 9):

Cw ¼ K H  Cg ð9Þ

In which Cw is the equilibrium concentration of a gas in water, Cg is the equilib-

rium concentration of a gas in air and KH is Henry’s constant or distribution
coefficient. Stripping may also be an effective method to remove volatile contami-
nants, like vinyl chloride and 1,2-dichloro ethane, which sometimes are encountered
in groundwater due to industrial pollution. However, most organic micropollutants
are soluble salts, which cannot be removed in this way.
Simultaneously, iron and manganese are oxidized, forming precipitates. Colloi-
dal particles, with a size <1 μm, are kept floating by the Brownian motion. In case
of neutral particles, stirring will result in collisions of the particles, upon which
London-van der Waals forces will keep them together, forming larger flocs. These
flocs may also include other species, like heavy metals (arsenic) and NOM/DOC.
They precipitate the rate depending on their size and composition. Rapid sand
filtration then can be applied to remove the flocs from the water. Thus, also colour,
which originates from DOC, may be removed from the water.
34 R. Hofman-Caris and J. Hofman

Organic micropollutants, like pesticides and pharmaceuticals, resemble NOM in

certain ways and thus also may be included into the flocs. However, often these
compounds are more hydrophilic and polar; as a result of which, flocculation is
not a very efficient process for the removal of these compounds. During the last
decades, more and more filtration over activated carbon (AC) has been applied
to remove these compounds. AC is very effective for the removal of organic and
preferably hydrophobic compounds. As a result, serious competition is observed by
NOM in the removal of micropollutants. Other problems that are encountered are
pore blocking by NOM; as a result of which, micropollutants cannot reach the pores
anymore, and the effective surface for adsorption is reduced, and displacement
of already adsorbed compounds by less soluble and more hydrophobic NOM
compounds occurs.

3 Water Treatment: Drinking Water from Surface Water

Sources

Surface water has a much more dynamic behaviour than groundwater. Water
quality can vary quite rapidly, and river discharge flows can vary, in bigger rivers
sometimes up to three orders of magnitude. Moreover, surface water contains a
much wider variety of pollutants, as it is under direct anthropogenic influence by
discharging of municipal and industrial wastewaters, surface run-off, atmospheric
deposition and incidental spills and calamities. It is therefore also impossible
to control water quality. This puts additional pressure on a treatment system to
produce safe drinking water.
Surface water treatment exists in a wide variety of systems, and in recent years
innovation in this area is accelerating. Nevertheless, a number of general treatment
objectives have to be met: removal of suspended solids and disinfection, removal of
taste and odour compounds and removal of a wide variety of micropollutants.
Figure 3 shows a number of more traditional surface water treatment schemes.
Suspended solids are mostly removed by application of coagulation, flocculation
and sedimentation. Often these steps are followed by a rapid filtration. Disinfection
traditionally was done chemically by adding chlorine. However, because of the
detrimental health effects of the byproducts, these systems are mostly abandoned
nowadays. Other disinfection systems and multi-barrier approaches have been
introduced. Many surface water treatment works also contain improved barriers
against micropollutants often in combined processes for oxidation and disinfection
like ozone and activated carbon filtration. Below the removal of suspended solids,
disinfection and activated carbon filtration will be discussed.
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 35

Fig. 3 Typical surface water treatment schemes. (a) Traditional, (b) advanced, (c) advanced
including soil passage

3.1 Coagulation, Floc Formation and Floc Removal

An important step in producing clean water is the removal of suspended matter.

Suspended matter can consist of a large variety of materials and a wide range of
particle sizes, e.g. clay and silt, organic debris, plastics and engineered nanoparticles.
Part of the suspended matter may be stable in water, whilst other fractions may settle
or float. This depends on the water chemistry, the density of the particulate matter
relative to water, the temperature and viscosity of the water, flow and mixing, etc.
These conditions often vary hourly, daily and over the seasons.
Suspended matter causes turbidity in water, which is not only an aesthetic
problem but also leads to poor treatment and disinfection performance. When the
suspended matter content is relatively low, the particles can often be removed by
filtration. However, if the concentration increases or if the particles are too small, a
filtration step is in many cases insufficient or hindered by operational problems such
as filter blocking. In that case, it is necessary to utilize other particle removal
techniques like coagulation, flocculation and clarification. The suspended solid
concentration that determines whether filtration or coagulation should be applied
depends largely on the characteristics of the particulate matter and the water
composition and is therefore difficult to predict.
36 R. Hofman-Caris and J. Hofman

Although coagulation, flocculation and clarification are different processes from

a physico-chemical perspective, in practice they always are connected and taking
place in the same unit operation. Coagulation is a process of destabilizing the
suspended particles by reducing the repulsive forces between them. This can be
done by adding a salt or metal ion solution. The effect is that the particles start to
form agglomerates. The agglomerate now starts to grow further into larger flocs.
This process, called flocculation, needs gentle stirring to create collisions between
the particles. Often a flocculant or flocculation aid, such as a polymer solution, is
added to increase the stability of the flocs. Once the flocs are large enough, the
suspension can be clarified by sedimentation or floatation.

3.1.1 Colloid Stability

Suspended particles in water can span a large size range. The smallest particles are
often a few nanometres and can have a natural origin (minerals, clays) or can be
man-made (e.g. TiO2, n-Ag, ZnO, n-C60), whilst the larger particles can be a few
hundred micrometres. The latter can be of organic origin or larger sand grains. The
smaller size particles or colloids are often quite stable in water, which means that
the particles remain in suspension if the water is stagnant. They have a typical
diameter of a few micrometres or less. Only larger particles or the heavier ones will
sink in a stagnant water body. Particles with a lower density than water, e.g. organic
materials, oils and fats, will float on the surface.
Colloids in water can be stabilized by two independent physical principles. The
first one is steric stabilization (Fig. 4). Steric stabilization occurs if the water

Fig. 4 Steric stabilization

Limitations of Conventional Drinking Water Technologies in Pollutant Removal 37

contains water soluble polymers or large molecules like humic substances. These
materials can adsorb on the particle surfaces. The length of the polymers prevents
that the particles can approach each other at a sufficient short distance to form an
agglomerate. However, depending on the polymer chain length and/or particle
concentrations, the materials can start to form a stable network in the water.
The second form of stabilization can occur if the particle surface is charged. If a
surface charge is present at the particle surface, an electrical double layer will occur
around the particle (Fig. 5). This is caused by adsorption of ions from the water
phase or ionization of molecules at the particle surface. Ions of an opposite charge
are attracted by this charge, thus forming an electric double layer [39]. In most
cases particles in water, partly being clay minerals, are negatively charged. Only at
very acidic pH positive surface charges may occur.
Also significant parts of the NOM, the humic acids, are negatively charged.
Upon mixing, the colloidal particles and compounds will repel each other; as a
result of which coagulation will not occur. In this case the electrolyte content of the
water can be increased. In this way, the double layer surrounding the colloidal
particles may be compressed, decreasing the zeta potential of the surface [40]. It is
also possible to include positively charged particles in the flocs by adsorption of
highly charged counter ions, which also decrease the zeta potential. Thus, the
repelling Coulomb forces can be decreased until they become smaller than the
London-van der Waals forces.

Fig. 5 Electric double layer

38 R. Hofman-Caris and J. Hofman

3.1.2 Destabilization and Floc Formation

Suspended colloids can be destabilized by reducing the repulsive forces between

the particles. Adding positively charged ions will reduce the electrostatic repulsive
forces between the particles, because the positive ions will interact with negatively
charged particle surface. Divalent ions appear to be about eight times as effective as
a monovalent ion in causing coagulation, whereas a trivalent ion is even 600 times
as effective [41]. For this purpose, in practice often Fe(III) or Al(III) salts are added
to the water.
All metal cations are hydrated to some extend in water. In the primary hydration,
shell water molecules are in direct contact with the metal ion. The bonding of the
water in the secondary hydration shell is more loose. For Al3+ and Fe3+ ions, the
primary hydration shell consists of six water molecules in an octahedral coordina-
tion. Due to the high charge on the metal ion, the water molecules in this shell are
polarized. This may lead to a loss of one or more protons, depending on the solution
pH. As a result, the water molecules in the hydration shell are progressively
replaced by OH ions, lowering the positive charge, according to Eq. (10):

Me3þ ! MeðOHÞ2þ ! MeðOHÞ2 þ ! MeðOHÞ3 ! MeðOHÞ4  ð10Þ

In Eq. (10) Me is the metal (iron of aluminium). However, Eq. (10) is a

simplified scheme, as in practice various polynuclear forms are observed
[42]. Examples are Al2(OH)24+ and Al3(OH)45+, but equivalent species can be
found for iron. Furthermore, also polynuclear hydrolysis products exist, like
Al13O4(OH)247+. This is known as polyaluminium (PACl), and its chloride salt is
a very effective flocculant.
At about neutral pH, both Al(III) and Fe(III) salts show a limited solubility. As a
result, amorphous hydroxide precipitates, which plays a very important role in the
coagulation and flocculation processes. Positively charged precipitate particles may
deposit on colloidal particles (heterocoagulation), resulting in charge neutralization
and thus destabilization [42]. In order to obtain effective coagulation, a very short
mixing time is beneficial, which means often high mixing intensity is required. This
can be realized by, e.g. dosing in a cascade (Fig. 6) or utilizing a high-shear turbine
mixer. In the Netherlands mainly Fe-salts are applied, whereas in other countries
Al-salts are preferred, sometimes combined with active silica [43]. An aspect which
requires some attention is the pH of the salt solutions. Often they have a pH value
2. By administering the solutions at one injection point, pH gradients may occur,
with locally very low pH values. At these values certain hydrates can be formed,
which are relatively stable, are ineffective adsorbents and cause turbidity in the
water. A high mixing rate is required to prevent the formation of such hydrates, and
addition should take place at different locations. In practice the process starts at a
relatively high mixing rate, which later is reduced in order not to destroy the already
formed flocs by too high-shear rates (tapered coagulation).
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 39

Fig. 6 Dosing of ferric

chloride in a cascade

Another way to form larger particles is by adsorption and bridging of macro-

molecules and polyelectrolytes. This process is known as “flocculation”. For this
purpose both natural and synthetic flocculants (mainly polyelectrolytes) can be
applied. Anionic, nonionic and cationic polymer can be used. When the concentra-
tion of flocculant is too low, bridging cannot occur, and the floc size remains small.
At too high flocculant concentrations, the flocculant will cover the total particle
surface; as a result of which bridging also cannot occur. In practice the addition of
Fe3+ or Al3+ is often combined with the addition of a polyelectrolyte, thus enhanc-
ing flocculation. The use of polymers results in the formation of larger and stronger
flocs with an open structure. The higher the molecular weight of the polymer, the
more effective the flocculant will be. However, in this case too care should be taken
not to apply a too high polymer concentration, as this would shield the colloidal
particles or may cause so much steric hindrance that bridging of particles would be
hindered. Sometimes addition of a salt will increase the adsorption of polymers by
decreasing the electrical double layer. Addition of more particles, like clay parti-
cles, may also enhance flocculation, as it facilitates collisions between particles.
Examples of flocculation tanks are shown in Fig. 7.
40 R. Hofman-Caris and J. Hofman

Fig. 7 Top, Tapered flocculation tanks; Centre, mixing device in flocculation tank; Bottom,
flocculation tank in Wuppertal (Germany)
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 41

When this process occurs at a high rate, other compounds or contaminants may
be included in the flocs, which is called “sweep coagulation”. This process is more
effective than for contaminant removal than only applying charge destabilization.
Characteristics of the sweep coagulation process are that flocs form more rapidly
and can become much larger. Figure 8 shows the working areas for pH and metal
ion dose for the different modes of coagulation, such as sweep coagulation,
adsorption destabilization and charge neutralization.
When excess coagulant is used, more than would be required for baseline
coagulation, this is called enhanced coagulation. The effect can be increased by
changing the pH, the order of chemical addition or by using alternative coagulant
chemicals. In this way TOC and NOM removal may be improved [11].
The time required to transport colloidal particles and flocculants is in the order of
104 s, whereas very high molecular weight polymers would require a few seconds.
As a result good mixing is required to obtain optimum flocculation. pH may be an
important parameter in this respect. Often it is found that within a certain pH range,
in general pH 8, a minimum flocculant dosage is required. In case this is a narrow
range, it is difficult to maintain the right pH during the process. This also depends
on the colour of the water: in general it is found that the more colour there is
present, the lower the optimum pH will be. In order to remove fulvic acids, a higher
dose of flocculant is required than for the removal of humic acids, which probably is
caused by the lower molecular mass of the fulvic acids.
During coagulation and flocculation iron(hydr)oxides are formed, which precip-
itate (see Fig. 9). It is known that these compounds can react with phosphate. As a
result, during flocculation also phosphate is removed from the aqueous phase. The
same principle is encountered for arsenic, which also can (partly) be removed by
flocculation in this way. However, for other heavy metals, the method is less
effective.

Fig. 8 Coagulation diagrams alum and ferric (adapted from [44] and equilibrium constants from [45])
42 R. Hofman-Caris and J. Hofman

Fig. 9 Horizontal sedimentation

3.1.3 Pollutant Removal

Organic micropolllutants may be removed by flocculation, but only if they have

been adsorbed to some other, high molecular weight compounds. This will,
amongst others, depend on pH, which determines the charge of the molecules and
thus their ability to be adsorbed. In general, removal of organic micropollutants by
flocculation is very limited, as was demonstrated by van der Horst et al. [46] for
pharmaceuticals and endocrine disrupting compounds (EDC’s) and by Saraiva
Soares et al. [47] for pesticides and their metabolites (endosulfan, ethylenethiourea
(ETU) and 1,2,4-triazole). This mainly is due to the solubility and hydrophilicity of
the micropollutants.
Microorganisms like bacteria and algae may be removed by sweep coagulation
and by bridging. For viruses removal may occur by complexation with aluminium
and iron. However, the level of removal in general is insufficient to obtain safe
drinking water [48].
Recently, in a case of an industrial contamination of river water, used for the
production of drinking water in the Netherlands, it has been found that in a rapid
sand filter (Fig. 10), micropollutants may be removed by means of biodegradation.
However, the effectiveness of this biodegradation strongly depends on circum-
stances (like temperature) and the presence of certain types of microorganisms.
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 43

Fig. 10 Rapid sand filtration in the Netherlands (left) and in Germany (right)

3.1.4 Floc Removal

Once the flocs are formed, they have to be separated from the water stream. In most
cases this is done by sedimentation or gravity settling. In practice, many different
forms of sedimentation tanks exist. The simplest form is the long rectangular
sedimentation pond as shown in Fig. 9. The length of the tanks should be such
that under the low flow conditions, the residence time is sufficient for particles to
settle to the bottom of the tank. Periodically the sludge is removed from the tanks by
dredging. As these horizontal tanks need a large surface area, other engineering
solutions such as lamellae separators and circular clarifiers have been designed.
Instead of applying sedimentation to remove suspended matter, also flotation can be
applied, especially in case of low-density particles or, e.g. oil droplets or algae
(dissolved air flotation; DAF; see Fig. 11). In this case air is dissolved under
pressure, and then by means of nozzles, it is released in a tank at atmospheric
pressure. As a result small bubbles (10–100 μm, on the average 40 μm) will be
formed. In order to ensure the formation of such small bubbles, the pressure
differences should be 400–600 kPa [49]. These bubbles may adsorb surfactants
and/or NOM and thus obtain a negative charge. Bubbles may adsorb hydrophobic
particles. By dosing a coagulant like polyaluminium chloride or ferric chloride,
particles will be destabilized, promoting the adherence of the bubbles to the
particles, causing them to float to the surface, where they can be removed by
means of skimming. Care should be taken not to overdose the coagulant, as this
will result in charge restabilization of the positively charged particles and bubbles.
It is possible that organic micropollutants also will be removed in this way, but the
method is not very effective, as these compounds often have a high solubility.
As a final step to remove residual suspended solids but also to remove excess
coagulants, a rapid filter step is applied. These filters also contribute to a multi-
barrier disinfection.
44 R. Hofman-Caris and J. Hofman

Fig. 11 Dissolved air flotation in Norway

3.2 Application of Activated Carbon

Activated carbon often is used to improve the water quality by removing natural
organic matter and organic micropollutants. Two types of activated carbon can be
applied:
• Powdered activated carbon (PAC)
The particle size of this material is <0.05 mm. It is added to the water, where it
can adsorb organic compounds, like NOM but also organic micropollutants. As
it has a high surface area, due to its small particle diameter, filtration requires a
short contact time of about 10–15 min. Afterwards the activated carbon has to be
removed by means of filtration.
• Granular activated carbon (GAC)
The granules have a diameter of 0.3–3 mm and have a porous character. The
pores contribute to the adsorption capacity of the material. However, pore size
(micropores <1 nm, mesopores 1–25 nm and macropores >25 nm) determines
which compounds can enter the pores. Another aspect of the pores is that they
may be blocked by NOM which adsorbs at the surface. After the GAC has been
loaded, it can be reactivated, by heating under an inert atmosphere, followed by
activation, e.g. by an acid. GAC is applied in filter beds (Fig. 12).
The adsorption properties of the activated carbon strongly depend on the phys-
ical characteristics of the carbon (pore volume and size, surface area) and the
chemical characteristics (surface composition, which depends on the activation
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 45

Fig. 12 GAC filter at Leiden (the Netherlands)

method applied). Furthermore, in GAC filters microorganisms may develop; as

a result of which, biodegradation also will take place inside the column. This
improves the removal of organic compounds by the filter and results in a longer
time to reactivation of the GAC.
Whether organic micropollutants can be efficiently removed by activated carbon
strongly depends on the micropollutant characteristics. In general, it can be
assumed that the more hydrophobic the compounds are, the higher the adsorption
capacity of the carbon will be. However, NOM may act as a competitor. Other
parameters that may affect the effectiveness of activated carbon are temperature,
pH and the presence of salts. Small, hydrophilic compounds in general are very
difficult to remove by means of activated carbon.
After some time, the activated carbon will be saturated and adsorption will stop.
For powdered activated carbon, an equilibrium between the adsorbed and dissolved
compounds will occur quickly after dosing it. The PAC can therefore be used only
once and has to be removed after dosing. For granular activated carbon, the
adsorbing compounds will gradually saturate the filter column. During operation,
a mass transfer zone will exist in the filter that slowly moves down in the flow
direction in the filter bed. After some time, the compound will break through and
the filter column has to be taken out of operation and the activated carbon has to be
regenerated.
46 R. Hofman-Caris and J. Hofman

3.3 Disinfection

In the nineteenth century, it was discovered that some compounds, like chlorine,
can be used as a disinfectant. Since the beginning of the twentieth century,
disinfectants were applied by drinking water companies. However, since the
1970s it became clear that by adding chlorine (toxic) disinfection, byproducts
may be formed by the reaction of chlorine with humic acids [50]. Because of this
ozone became more popular as a disinfectant. However, also ozone appeared to
give harmful byproducts, as it reacts with bromide to form bromate.
Membrane filtration also can be applied but also appeared to have some disad-
vantages: fouling of the membrane surface may occur and sometimes leakage is
observed, decreasing the disinfection effectiveness.
In Marseille in 1901, UV was applied for disinfection purposes, but it took about
50 years until it was applied on a larger scale in Switzerland, Austria and Norway.
Since the last quarter of the twentieth century, application of UV for water disin-
fection has become quite common.
The photochemical active part of the electromagnetic spectrum can be divided
into four regions: vacuum UV (VUV; 100–200 nm), UV-C (200–280 nm), UV-B
(280–315 nm) and UV-A (315–380 nm). This division is based on physical,
biological or medical parameters.
UV-C radiation appears to be absorbed by DNA and RNA in cells of organisms.
This may result in the death of these cells or will prevent their reproduction. The
term “inactivation” can be applied to either a cell or its single subsystem. UV
irradiation has been shown to be a powerful tool in inactivation of both microor-
ganisms and cells such as bacteria, viruses, protozoan parasites, some spores, living
cells and subsystems such as enzymes, amino acids and lipids [51]. One of the main
advantages of UV inactivation is that no chemicals have to be added, since
irradiation is a physical process. The germicide effect of UV light on bacteria and
viruses is primarily due to the formation of thymine, thymine-cytosine (pyrimidine)
and cytosine dimers in polynucleotide chains of DNA (they are listed in prevalence
of order). It seems that radiation at wavelengths in the range of 200–295 nm
(so-called bactericide or germicide range) exerts the most effective action. The
absorption spectrum of DNA of viruses and bacteria shows a maximum at about
260 nm. However, also at wavelengths between 115 and 160 nm, the absorption
coefficient of DNA is high [52].
For killing microorganisms it is not always necessary to change the DNA of the
cells. It may also be enough to damage the cell membrane, allowing other com-
pounds to enter the cell and damage or kill it. (V)UV photons with a wavelength
below 275 nm can break C–C (3.8 eV) or C–H (4.5 eV) bonds, thus damaging the
cell membrane or proteins in the cell. Furthermore, photo desorption producing
species eroding the outer coat of the spore may lead to cell death during germina-
tion. Cells can be destroyed by etching [53]. Sosnin et al. also distinguish between
two different disinfection methods: the inactivation of microorganisms by UV
irradiation or their total VUV-induced photo mineralization.
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 47

Bacterial spores, which are the most resistant form of living microorganisms,
often are used as model microorganisms in studies [52]. The reason that spores are
10–50 times more resistant to 254 nm UV light than their corresponding growing
cells is the presence of a unique UV photoproduct of the spore DNA (called SP)
[54]. Finally, spore DNA is protected by multiple layers, which surround the core,
namely, a germ cell wall, cortex, inner and outer spore coats and sometimes an
exosporium. In B subtilis spores, these form a 150–200-nm-thick proteinous bar-
rier, which can shield the core from the effects of (V)UV photons. It is possible that
UV radiation can also kill spores by modifying these outer layers of the spores, but
the importance of this second pathway is not yet fully known.
Templeton et al. [55] have shown that humic acid flocs and particles <2 μm may
shield viruses from UV radiation, thus decreasing the disinfection effectiveness of a
UV process.
In order to inactivate microorganisms, it has been established that it is not
necessary to kill them. As a result, UV doses applied for disinfection have been
decreased in the past years, in order to decrease the energy demand of the process.
At the moment in general, a UV dose of 20–70 mJ/cm2 is applied in order to obtain
effective disinfection of drinking water. In principle, photolysis by UV irradiation
can also degrade organic micropollutants. This depends on the wavelength, i.e. the
energy of the UV photon that can be absorbed by the molecule. In practice two types
of mercury containing UV lamps are being used: low pressure (LP) UV lamps, which
emit a single wavelength of 253.7 nm, and medium pressure (MP) UV lamps, which
emit a much broader spectrum between 200 and 300 nm. Obviously, MP lamps will
be more effective in causing photolysis of micropollutants because of this broader
spectrum. However, it has been shown that for effective photolysis, much higher
doses will be required than is common for disinfection purposes [56, 57]. Therefore, it
can be concluded that UV disinfection in general will contribute very little to the
degradation of organic micropollutants.

4 Water Treatment: Drinking Water from River Bank

Filtrate or Dune Filtrate

Sometimes river bank filtrate is used instead of groundwater. By filtration through

soil, the water quality can significantly be improved, partly by adsorption to soil
particles, partly as a result of biodegradation by subsoil microorganisms. In this
way also some micropollutants may be removed, depending on the local conditions
(like the type of soil and water, presence of microorganisms, molecular properties
of the micropollutants, etc.). However, not all micropollutants appear to be removed
in this way. Because of this the treatment process may be simpler than the treatment
process required for surface water treatment. In general aeration, in order to increase
the oxygen content, sand filtration, conditioning and disinfection will be applied, but,
depending on the water quality, other techniques, like filtration over activated carbon,
also may be necessary.
48 R. Hofman-Caris and J. Hofman

A type of treatment typical for the Netherlands is dune filtration. This resembles
river bank filtration, but in general the residence time is longer. Dune filtration
significantly contributes to the removal of pathogens but also of other compounds.
To make dune filtration possible, the high water quality is already required to
protect the dune ecosystem. Especially organic micropollutants have to be removed
before infiltration. For the final treatment, similar processes as in case of river bank
filtrate will be necessary.

5 Conclusions

Water is treated to meet the objectives of drinking water quality and standards.
These objectives are to prevent acute diseases by exposure to pathogens, to prevent
long-term adverse health effects by exposure to chemicals and micropollutants and
finally to create a drinking water that is palatable and is conditioned in such a way
that transport from the treatment works to the customer will not lead to quality
deterioration.
Traditional treatment technologies are mainly designed to remove macro param-
eters such as suspended solids, natural organic matter, dissolved iron and manga-
nese, etc. Which kinds of technologies are required depends on the drinking water
source. For groundwater in general aeration, filtration, conditioning and disinfec-
tion will be required, whereas for surface water coagulation/flocculation, sedimen-
tation, several filtration processes, conditioning and disinfection will be necessary.
These technologies have however only limited performance for removal of micro-
pollutants. Advancing analytical technologies and increased and changing use of
compounds show strong evidence of new and emerging threats to drinking water
quality. Therefore, more advanced treatment technologies are required, in order to
guarantee the production of safe drinking water.

References

1. WHO (2017) Guidelines for drinking-water quality4th edn. WHO, Gutenberg. First addendum
to the fourth edition
2. European Commission (1998) Drinking Water Directive; Council Directive 98/83/EC on the
quality of water intended for human consumption. http://eur-lex.europa.eu/LexUriServ/
LexUriServ.do?uri¼OJ:L:1998:330:0032:0054:EN:PDF
3. Ahmad A, Kools S, Schriks M, Stuyfzand P, Hofs B (2015) Arsenic and chromium concen-
trations and their speciation in groundwater resources and drinking water supply in the
Netherlands. Nieuwegein, KWR Watercycle Research Institute
4. Ahmad A, Richards LA, Bhattacharya P (2016) Arsenic remediation of drinking water: an
overview. In: Bhattacharya P, Jovanovich D, Polya D (eds) Best practice guide on control of
arsenic in drinking water. IWA Publishing, London, pp 120–138
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 49

5. Coppens LJC, van Gils JAG, ter Laak TL, Raterman BW, van Wezel AP (2015) Towards
spatially smart abatement of human pharmaceuticals in surface waters: defining impact of
sewage treatment plants on susceptible functions. Water Res 81:356–365
6. Van Der Aa NGFM, Kommer GJ, Van Montfoort JE, Versteegh JFM (2011) Demographic
projections of future pharmaceutical consumption in the Netherlands. Water Sci Technol 63
(4):825–831
7. European Commission (2015) Commission implementing decision (EU) 2015/495 of 20 March
2015 establishing a watch list of substances for union-wide monitoring in the field of water policy
pursuant to Directive 2008/105/EC of the European Parliament and of the Council. http://eur-lex.
europa.eu/legal-content/EN/TXT/PDF/?uri¼CELEX:32015D0495&from¼EN
8. Carvalho RN, Ceriani L, Ippolito A, Lettieri T (2015) Development of the first watch list under
the environmental quality standards directive. EC Joint Research Centre, Ispra
9. ter Laak TL, van der Aa M, Houtman CJ, Stoks PG, van Wezel AP (2010) Relating environ-
mental concentrations of pharmaceuticals to consumption: a mass balance approach for the
river Rhine. Environ Int 36(5):403–409
10. Schoeps P, Schriks M (2010) The effect of REACH on the log Kow distribution of drinking
water contaminants. KWR Watercycle Research Institute, Nieuwegein
11. Matilainen A, Vepsäläinen M, Sillanpää M (2010) Natural organic matter removal by coag-
ulation during drinking water treatment: a review. Adv Colloid Interf Sci 159(2):189–197
12. Westerhoff P, Mezyk SP, Cooper WJ, Minakata D (2007) Electron pulse radiolysis determi-
nation of hydroxyl radical rate constants with Suwannee river fulvic acid and other dissolved
organic matter isolates. Environ Sci Technol 41(13):4640–4646
13. Cooper WJ, Mezyk SP, Peller JR, Cole SK, Song W, Mincher BJ, Peake BM (2008) Studies in
radiation chemistry: application to ozonation and other advanced oxidation processes. Ozone
Sci Eng 30(1):58–64
14. Cooper WJ, Song W, Gonsior M, Kalnina D, Peake BM, Mezyk SP (2008) Recent advances in
structure and reactivity of dissolved organic matter in natural waters. Water Sci Technol Water
Supply 8:615–623
15. Lakretz A, Ron EZ, Harif T, Mamane H (2011) Biofilm control in water by advanced oxidation
process (AOP) pre-treatment: effect of natural organic matter (NOM). Water Sci Technol 64
(9):1876–1884
16. Lamsal R, Walsh ME, Gagnon GA (2011) Comparison of advanced oxidation processes for the
removal of natural organic matter. Water Res 45(10):3263–3269
17. Matilainen A, Sillanpää M (2010) Removal of natural organic matter from drinking water by
advanced oxidation processes. Chemosphere 80(4):351–365
18. Metz DH, Reynolds K, Meyer M, Dionysiou DD (2011) The effect of UV/H2O2 treatment on
biofilm formation potential. Water Res 45(2):497–508
19. Thomson J, Parkinson A, Roddick FA (2004) Depolymerization of chromophoric natural
organic matter. Environ Sci Technol 38(12):3360–3369
20. Sarathy SR, Stefan MI, Royce A, Mohseni M (2011) Pilot-scale UV/H2O2 advanced oxidation
process for surface water treatment and downstream biological treatment: effects on natural
organic matter characteristics and DBP formation potential. Environ Technol 32(15):1709–1718
21. Azami H, Sarrafzadeh MH, Mehrnia MR (2012) Soluble microbial products (SMPs) release in
activated sludge systems: a review. J Environ Health Sci Eng 9(1):30
22. Xie WM, Ni BJ, Seviour T, Yu HQ (2013) Evaluating the impact of operational parameters
on the formation of soluble microbial products (SMP) by activated sludge. Water Res 47
(3):1073–1079
23. Huber SA, Balz A, Abert M, Pronk W (2011) Characterisation of aquatic humic and
non-humic matter with size-exclusion chromatography – organic carbon detection – organic
nitrogen detection (LC-OCD-OND). Water Res 45(2):879–885
24. Grefte A (2013) Removal of natural organic matter fractions by anion exchange; impact on
drinking water treatment processes and biological stability. Civil engineering. Delft University
of Technology, Delft
50 R. Hofman-Caris and J. Hofman

25. Audenaert WTM, Vermeersch Y, Van Hulle SWH, Dejans P, Dumoulin A, Nopens I (2011)
Application of a mechanistic UV/hydrogen peroxide model at full-scale: sensitivity analysis,
calibration and performance evaluation. Chem Eng J 171(1):113–126
26. Rosario-Ortiz FL, Snyder S, Suffet IH (2007) Characterization of the polarity of natural organic
matter under ambient conditions by the Polarity Rapid Assessment Method (PRAM). Environ
Sci Technol 41(14):4895–4900
27. Rosario-Ortiz FL, Mezyk SP, Doud DFR, Snyder SA (2008) Quantitative correlation of
absolute hydroxyl radical rate constants with non-isolated effluent organic matter bulk prop-
erties in water. Environ Sci Technol 42(16):5924–5930
28. Rosario-Ortiz FL, Mezyk SP, Wert EC, Devin FRD, Singh MK, Xin M, Baik S, Snyder SA
(2008) Effect of ozone oxidation on the molecular and kinetic properties of effluent organic
matter. J Adv Oxid Technol 11(3):529–535
29. Rosario-Ortiz FL, Snyder SA, Suffet IH (2007) Characterization of dissolved organic matter in
drinking water sources impacted by multiple tributaries. Water Res 41(18):4115–4128
30. Rosario-Ortiz FL, Wert EC, Snyder SA (2010) Evaluation of UV/H2O2 treatment for the
oxidation of pharmaceuticals in wastewater. Water Res 44(5):1440–1448
31. Slaats PGG, Meerkerk MA, Hofman-Caris CHM (2013) Conditionering: de optimale
samenstelling van drinkwater; Kiwa-Mededeling 100 –Update 201
32. WHO (2005) Nutrients in drinking water; water, sanitation and health protection and the
human environment. WHO, Geneva
33. Leurs LJ, Schouten LJ, Mons MN, Goldbohm RA, Van Den Brandt PA (2010) Relationship
between tap water hardness, magnesium, and calcium concentration and mortality due to
ischemic heart disease or stroke in the Netherlands. Environ Health Perspect 118(3):414–420
34. Momeni M, Gharedaghi Z, Amin MM, Poursafa P, Mansourian M (2014) Does water hardness
have preventive effect on cardiovascular disease? Int J Prev Med 5(2):159–163
35. Rylander R (2014) Magnesium in drinking water – a case for prevention? J Water Health 12
(1):34–40
36. Rapant S, Fajčı́ková K, Cvečková V, Ďurža A, Stehlı́ková B, Sedláková D, Ženišová Z (2015)
Chemical composition of groundwater and relative mortality for cardiovascular diseases in the
Slovak Republic. Environ Geochem Health 37(4):745–756
37. De Moel PJ, Verberk JQJC, Van Dijk JC (2006) Principles and practices. Sdu Editors, Delft
University of Technology, Delft
38. Bruins JH, Petrusevski B, Slokar YM, Huysman K, Joris K, Kruithof JC, Kennedy MD (2015)
Biological and physico-chemical formation of Birnessite during the ripening of manganese
removal filters. Water Res 69:154–161
39. Verwey EJW, Overbeek JTG, van Nes K (1948) Theory of the stability of lyophobic colloids;
the interaction of sol particles having an electric double layer. Elsevier, New York
40. Verwey EJW, Overbeek JTG (1955) Theory of the stability of lyophobic colloids. J Colloid Sci
10(2):224–225
41. Meijers AP (1974) De theorie van de vlokvomring. Rijswijk, Kiwa
42. Duan J, Gregory J (2003) Coagulation by hydrolysing metal salts. Adv Colloid Interf Sci
100–102(Suppl):475–502
43. van Melick MJ (1975) Tweede rapport van de commissie Vlokvomring en vlokverwijdering
44. Amirtharajah A, Mills KM (1982) Rapid-mix design for mechanisms of alum coagulation.
J Am Water Works Ass 74(4):210–216
45. Crittenden JC, Rhodes Trussell R, Hand DW, Howe KJ, Tchobanoglous G (2012) Water
treatment principles and design3rd edn. Wiley, Hoboken
46. Van Der Horst W, Ijpelaar GF, Scholte-Veenendaal P, Rietveld LC, Van Dijk JC (2006)
Occurrence and removal of pharmaceuticals and Endocrine Disrupting Compounds (EDCs)
from drinking water. In: American Water Works Association – water quality technology
conference and exposition 2006: taking water quality to new heights
47. Saraiva Soares AF, Le~ao MMD, Vianna Neto MR, Da Costa EP, De Oliveira MC, Amaral NB
(2013) Efficiency of conventional drinking water treatment process in the removal of endo-
sulfan, ethylenethiourea, and 1,2,4-triazole. J Water Supply Res Technol 62(6):367–376
Limitations of Conventional Drinking Water Technologies in Pollutant Removal 51

48. Gale P, Pitchers R, Gray P (2002) The effect of drinking water treatment on the spatial
heterogeneity of micro-organisms: implications for assessment of treatment efficiency and
health risk. Water Res 36(6):1640–1648
49. Edzwald JK (1995) Principles and applications of dissolved air flotation. Water Sci Technol 31
(3–4):1–23
50. Rook JJ (1974) Formation of haloforms during chlorination of natural water. Water Treat
Exams 23(2):234–243
51. Sosnin EA, Oppenländer T, Tarasenko VF (2006) Applications of capacitive and barrier
discharge excilamps in photoscience. J Photochem Photobiol C: Photochem Rev 7(4):145–163
52. Lerouge S, Fozza AC, Wertheimer MR, Marchand R, Yahia LH (2000) Sterilization by
low-pressure plasma: the role of vacuum-ultraviolet radiation. Plasmas Polym 5(1):31–46
53. Halfmann H, Denis B, Bibinov N, Wunderlich J, Awakowicz P (2007) Identification of the
most efficient VUV/UV radiation for plasma based inactivation of Bacillus atrophaeus spores.
J Phys D Appl Phys 40(19):5907–5911
54. Wang D, Oppenländer T, El-Din MG, Bolton JR (2010) Comparison of the disinfection effects
of vacuum-UV (VUV) and UV light on Bacillus subtilis spores in aqueous suspensions at
172, 222 and 254 nm. Photochem Photobiol 86(1):176–181
55. Templeton MR, Andrews RC, Hofmann R (2005) Inactivation of particle-associated viral
surrogates by ultraviolet light. Water Res 39(15):3487–3500
56. Wols BA, Harmsen DJH, Beerendonk EF, Hofman-Caris CHM (2014) Predicting pharmaceu-
tical degradation by UV (LP)/H2O2 processes: a kinetic model. Chem Eng J 255:334–343
57. Wols BA, Harmsen DJH, Beerendonk EF, Hofman-Caris CHM (2015) Predicting pharmaceu-
tical degradation by UV (MP)/H2O2 processes: a kinetic model. Chem Eng J 263:336–345
Natural Organic Matter: Characterization
and Removal by AOPs to Assist Drinking
Water Facilities

S. Sorlini

Abstract The water sources of drinking water generally contain natural organic
matter (NOM) as a result of the interactions between the hydrologic cycle and the
environment. The amount, character, and properties of NOM vary considerably
according to the origins of the waters and depend on the biogeochemical cycles of
their surrounding environments. NOM can negatively influence water quality in
drinking water supply systems, and it can significantly influence the performance of
drinking water treatment processes. Hence, NOM removal is an important issue in
order to optimize drinking water treatment operation and to reduce the risks of
water alteration in the distribution systems. Several treatment processes can be
applied for NOM removal depending on water quality, the nature of NOM, and the
treatments already existing in the supply system. Among the most effective con-
ventional solutions coagulation/flocculation, filtration, and carbon adsorption are
available. An interest has recently increased toward nonconventional solutions
based on membrane filtration and advanced oxidation processes (AOPs). An over-
view on the AOPs will be presented and discussed. Moreover, the AOP with ozone
and UV radiation, with two low pressure UV lamps, at 254 and 185 nm wavelength,
was experimented on a surface water in order to study the removal of odorous and
pesticide, organic compounds (UV absorbance and THMs precursors) and bromate
formation. Different batch tests were performed with ozone concentration up to
10 mg L
1, UV dose up to 14,000 J m
2, and a maximum contact time of 10 min.
The main results show that metolachlor can be efficiently removed with ozone
alone while for geosmin and MIB a complete removal can be obtained with the
advanced oxidation of ozone, with concentration of 1.5–3 mg L
1 and contact time
of 2–3 min, with UV radiation (with doses of 5,000–6,000 J m
2). As concerns the
influence of the organic precursors, all the experimented processes show a medium

S. Sorlini (*)
Department of Civil, Environmental, Architectural Engineering and Mathematics, University
of Brescia, Brescia, Italy
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 53

Water Treatment, Hdb Env Chem (2019) 67: 53–68, DOI 10.1007/698_2017_159,
© Springer International Publishing AG 2017, Published online: 30 December 2017
54 S. Sorlini

removal of about 20–40% for UV absorbance and 15–30% for THMFP (trihalo-
methane formation potential).

Keywords Advanced oxidation processes, Characterization, Natural organic

matter, Removal

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2 NOM Characteristics and Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3 Impact of NOM on Drinking Water Supply Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4 AOPs for the Removal of NOM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.1 Ozone-Based Treatments (O3/H2O2, O3/UV, and O3/H2O2/UV) . . . . . . . . . . . . . . . . . . . . . 58
4.2 UV Light-Based Treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.3 Photocatalytic Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.4 Fenton’s Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5 Case Study: Effect of the O3/UV Process on Organic Matter Removal and Influence
on DBPs Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5.1 Raw Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5.2 Experimental Plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.3 Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.4 Results: Removal of Organic Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.5 Results: Removal of Geosmin, MIB, and Metolachlor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.6 Results: Bromate Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6 General Considerations About the Application of AOPs for NOM Removal in Drinking
Water Treatment Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

Abbreviations

AOPs Advanced oxidation processes

DBPFP Disinfection by-products formation potential
DBPs Disinfection by-products
DOC Dissolved organic carbon
FAs Fulvic acids
GC Gas chromatography
HAAFP Haloacetic acid formation potential
HAAs Haloacetic acids
HAs Humic acids
HMM High molar mass
LMM Low molecular mass
NMR Nuclear magnetic resonance
NOM Natural organic matter
SUVA Specific UV absorbance
THMFP Trihalomethane formation potential
Natural Organic Matter: Characterization and Removal by AOPs to Assist. . . 55

THMs Trihalomethanes
TOC Total organic carbon
TOX Total organic halide
UV–Vis Ultraviolet and visible
VUV Vacuum ultraviolet

1 Introduction

Natural organic matter (NOM) is ubiquitous in water as it comes from the degra-
dation of plants, bacteria, algae, and vegetal organisms in general. NOM is defined
as a complex matrix of organic materials, present in all natural water. Water systems
often have multiple sources of NOM, thus different organic carbon fractions [1]. The
amount, character, and properties of NOM vary considerably according to the
origins of the waters and depend on the biogeochemical cycles of their surrounding
environments [2]. Concentrations of TOC in the ground water are typically in the
range of 0.1–2.0 mg L
1 and 1–20 mg L
1 in surface water [3, 4] although several
dozens of mg L
1 of TOC are not uncommon [5]. The factors that determine the
composition of NOM are location dependent and include the source of organic
matter, the water chemistry, temperature, pH, and biological processes. Moreover,
the range of organic components in NOM can vary seasonally at the same location
[6], for example, due to rainfall, snowmelt runoff, floods, or droughts. NOM found
in natural waters consists of both hydrophobic and hydrophilic components, of
which the largest fraction is generally hydrophobic acids, making up approximately
50% of the total organic carbon (TOC) in water [7].
NOM has a significant impact on many aspects of water treatment, including the
performance of unit processes, necessity for and application of water treatment
chemicals, and the biological stability of the water. Once the composition and
quantity of NOM in the water source has been examined, suitable methods for
efficient NOM removal can be applied. No single process alone can be used to treat
NOM due to its high variability. Among the suitable solutions, the following treat-
ment processes can be efficiently applied for NOM removal: adsorption, biological
treatments, coagulation/flocculation, electrochemical methods, ion exchange, mem-
brane technology, and AOP [8]. An increasing interest in drinking water treatment
has recently been shown for the AOPs due to several advantages: low chemical
consumption in some AOPs, complete mineralization of pollutant, oxidation of
disinfection by-product (DBP) rapid reaction, unselective oxidants, harmful to micro-
organisms, and easily implemented in existing water treatment plants.
This chapter presents an overview on AOPs applied for the NOM removal
during drinking water treatments. Moreover, the main results of an experimental
study on the O3/H2O2 process for NOM and micropollutant removal will be
presented.
56 S. Sorlini

2 NOM Characteristics and Characterization

NOM compounds are complex mixtures possessing unique combinations of various

functional groups, including esteric, phenolic, quinine, carboxylic, hydroxyl,
amino, and nitroso, which are usually negatively charged at neutral pH. NOM
found in natural waters consists of both hydrophobic and hydrophilic components,
of which the largest fraction is generally hydrophobic acids, making up approxi-
mately 50% of the total organic carbon (TOC) in water [7]. These hydrophobic
acids can be described as humic substances comprising (1) humic acids (HAs),
which are soluble in alkali, but insoluble in acid; (2) fulvic acids (FA), which are
soluble in both alkali and acid; and (3) humins, which are insoluble in both alkali
and acid. FAs constitute a major fraction of these humic substances, which vary in
molecular size and functional group content [9]. Hydrophobic NOM is rich in
aromatic carbon, phenolic structures, and conjugated double bonds, while hydro-
philic NOM contains more aliphatic carbon and nitrogenous compounds, such as
carbohydrates, sugars, and amino acids.
The amount of NOM in water can be predicted with parameters including
ultraviolet and visible (UV–Vis) detected compounds, TOC, and SUVA. TOC
and dissolved organic carbon (DOC) are the most convenient parameters for
analyzing the NOM removal of treatment processes. DOC is the organic carbon
in a water sample filtered through a 0.45 μm filter [10]. TOC is the sum of the
particulate and DOC when existing inorganic carbon is removed by acidification.
UV–Vis absorption spectroscopy is a semiquantitative method to determine
humic substances in natural waters. Any wavelength from 220 to 280 nm is
appropriate for NOM measurements: absorbance at 220 nm is associated with
both the carboxylic and aromatic chromophores, whereas absorbance at 254 nm
is typical for aromatic groups, and it has been identified as a potential surrogate
measure for DOC [11].
Specific UV absorbance (SUVA) is calculated as the ratio of a UV absorbance at
a specific wavelength (e.g., UV254 absorbance) and the TOC concentration. A high
SUVA value indicates that the organic matter is largely composed of hydrophobic,
high-MM organic material. A low SUVA value indicates that the water contains
organic compounds that are mainly hydrophilic, with a low MM and charge
density [6].
Several methods can be used for the characterization of NOM including resin
adsorption, size exclusion chromatography, nuclear magnetic resonance (NMR)
spectroscopy, and fluorescence spectroscopy. More precise methods for determin-
ing NOM structures have been developed recently: pyrolysis gas chromatography
mass spectrometry, multidimensional NMR techniques, and Fourier transform ion
cyclotron resonance mass spectrometry.
A detailed description of the methods used to characterize various features of
natural organic matter (NOM) is reported in literature [12].
Natural Organic Matter: Characterization and Removal by AOPs to Assist. . . 57

3 Impact of NOM on Drinking Water Supply Systems

Significance of NOM for drinking water quality and stability is represented by the
impact on several aspects of its treatment [13]:
• NOM greatly affect organoleptic properties of the water (taste, color, and odor)
[4, 14].
• NOM influence chemical properties in terms of mostly negative reactions and
interferences with other chemicals used for oxidation and disinfection by low-
ering their effectiveness and thus increasing their consumption to achieve the
treatment goal [4, 14].
• NOM can form complexes with the toxic heavy metals and synthetic organic
chemicals, making them more soluble and more difficult to remove by the
treatment [14].
• NOM are involved in formation of undesired and detrimental DBPs with an
increase in bioavailability of organic matter for microorganisms in the water
supply systems, enabling their proliferation.
NOM can cause several problems in drinking water treatment and distribution
systems. It can affect the performance of unit processes, the necessity for applica-
tion of water treatment chemicals, and the biological stability of the water. NOM
increases the reagent dose necessary during water treatment, especially for coagu-
lant and disinfectant. NOM can also interfere with the performance of unit opera-
tions, such as biofilm growth on media, causing rapid filter clogging and fast
saturation of activated carbon beds. NOM is also responsible for the fouling of
membranes.
During water treatment, NOM has generally been considered the main precursor
to DBPs, especially hydrophobic and high molar mass (HMM) NOM, with its high
aromatic carbon content [15, 16]. It has also been observed that hydrophilic and low
molar mass (LMM) NOM play a significant role in DBP formation [15]. Bromine
and iodine appear more reactive with hydrophilic and LMM fractions of NOM in
the formation of THMs and HAAs (haloacetic acids). Chlorine has been shown to
react more readily with HMM and hydrophobic NOM compounds [15].
NOM can impact also the water behavior in the distribution system as it affects
corrosion, is a source of nutrients for heterotrophic bacteria, and acts as a substrate
for bacterial growth in the pipes [17].

4 AOPs for the Removal of NOM

AOPs are obtained from the combination of several oxidants, radiation, and cata-
lysts: O3/H2O2, UV/H2O2, UV/O3, UV/TiO2, Fe2+/H2O2, Fe2+/H2O2 + hν, vacuum
ultraviolet (VUV) radiation, or ionizing radiation. All these processes involve the
generation of highly reactive radical intermediates, especially the OH• radical [18]
58 S. Sorlini

that is one of the most powerful known oxidants. The reaction rate of a compound in
OH• radical-mediated oxidation is usually several orders of magnitude higher than
that achieved by molecular ozone under the same conditions.
The reaction rate constants between OH• radicals and organic species are in the
range of 108–1010 M
1 s
1 [19].
OH• radicals are highly nonselective oxidants, enabling a very large number of
reactions. Once free radical reaction has been initiated (following photolysis,
ozone, hydrogen peroxide, or heat), a series of simple reactions will occur. The
reactions of OH• radicals with NOM proceed in three different ways:
• By the addition of OH• radicals to double bonds
• By H-atom abstraction, which yields carbon-centered radicals
• By the OH• radical gaining an electron from an organic substituent

4.1 Ozone-Based Treatments (O3/H2O2, O3/UV, and O3/

H2O2/UV)

Ozone reacts with NOM by an electrophilic addition to double bonds. This reaction
is very selective. In addition to the direct reaction of ozone with NOM, a non-
selective and fast reaction occurs with the OH• radicals formed when ozone
decomposes in water. The OH• radical formation potential is much lower during
ozonation than in AOPs. The combination of ozone with other systems, like UV
light or hydrogen peroxide, can promote OH• formation.
The influence of ozone on THM precursors depends on the kind and structures of
the organic material that can have different reactivities toward ozone and chlorine.
Some authors observed that ozonation produces a transformation of natural organic
matter from more reactive hydrophobic DOC, that reacts easily with chlorine to
produce THM, to a hydrophilic fraction, with a consequent lower THM formation
[20]. This finding is in agreement with other authors [21, 22].
The combination of O3 with H2O2 increases total THM concentrations than in
ozonated samples [23]. Similarly, other authors [24] did not observe any significant
gains in THM reduction after adding H2O2 or TiO2 to the ozone treatment.
Other authors [25] observed that TOC, THMFP, and TOX decreased with
O3/UV in comparison with ozone alone. Moreover, O3/UV results in significant
mineralization of DOC, reduction of trihalomethane formation potential (THMFP),
and haloacetic acid formation potential (HAAFP), according to [26].
The combined system O3/H2O2/UV was not remarkable more efficient than
O3/UV in HAA decomposition [27].
Natural Organic Matter: Characterization and Removal by AOPs to Assist. . . 59

4.2 UV Light-Based Treatments

Much research has focused on developing applications for UV/H2O2; little attempt
has been made to evaluate the impact of UV/H2O2 on NOM. Past studies have
demonstrated that substantial reduction of DBP formation potential (DBPFP) could
be achieved using UV/H2O2 [28–30]. But all these studies mainly focused on
strong advanced oxidation conditions made possible by very long UV exposures
(i.e., fluence) and/or high UV/H2O2 concentration. Under such conditions NOM is
mineralized leading to a reduction in the concentration of NOM [31].
Although the combination of UV irradiation at 254 nm and H2O2 treatment
increases the NOM reduction and promotes the OH• radical formation, a combina-
tion of high UV fluence and high peroxide concentration is required in order to
generate significant reduction of NOM [30]. Moreover, under fluence and H2O2
concentrations typically applied in drinking water treatment applications, UV
standard dose for disinfection is about 400 mJ cm
2 [26], and NOM is not removed.

4.3 Photocatalytic Oxidation

The photocatalytic oxidation combines the UV light with a heterogeneous photo-

catalysis in which several different semiconductors are employed (e.g., TiO2, ZnO,
ZnS, WO3, SrTiO3) for catalysis.
The TiO2/UV process was applied for controlling membrane fouling by NOM
[32]; even though the rate of TOC removal was relatively low, membrane fouling of
both an MF and a UF was completely eliminated after 20 min of treatment due to
the changes in NOM molecular characteristics.
The presence of hardness (Ca2+, Mg2+, Fe2+/Fe3+) and the accompanying com-
mon anions (e.g., Cl
, NO3
, SO42
, and HCO3
/CO32
) have considerable effects
on the degradation kinetics of NOM expressed as DOC or UV254 [33].
Little is known about the by-products formed during photocatalytic oxidation of
NOM. Some authors [34] reported that aldehydes and ketones were typical inter-
mediate products formed during photocatalytic oxidation of NOM in surface waters
and these compounds would be oxidized to form carboxylic acids as the reaction
proceeded. Photocatalytic oxidation may also form by-products that have different
reactivity with chlorine disinfectants [35].
NOM plays an important role as inhibitor of oxidation of target micropollutants
during AOPs; the degradation rates can decrease by one order of magnitude or more
in the presence of backgrounds such as NOM. Authors [36] provided a novel
analytical approach to select strategies to enhance the performance of AOPs,
even in systems with high levels of NOM or other background constituents.
60 S. Sorlini

4.4 Fenton’s Process

Fenton’s reagent is a catalytic oxidative mixture that contains iron ions and hydrogen
peroxide. In this process hydroxyl radicals are produced during the decomposition of
hydrogen peroxide in the presence of ferrous salts.
Fenton’s reagent, H2O2 with Fe(II)/Fe(III) ions, in water produces OH radicals.
Some authors [16] observed that UV/Fe(III) treatment was ineffective in NOM
removal, while the UV/Fe(III)/H2O2 system has the potential to remove organics
with a broad range of MMs. Even though high NOM removal rates were detected,
the remaining organic compounds appear fairly reactive to chlorine, thus resulting
in low reduction of THMFP.
Fenton and photo-Fenton’s processes were compared in order to assess their
potential to remove NOM from organic-rich waters [19]. The performance of both
processes was dependent on pH, Fe:H2O2 ratio, as well as Fe2+ dose. Under
optimum conditions both processes achieved greater than 90% removal of DOC
and UV254 absorbance. This removal leads to the THMFP of the water being
reduced from 140 to below 10 μg L
1.
A comparison of UV/H2O2, Fenton, and photo-Fenton for treating an upland
catchment reservoir (DOC ¼ 7.5 mg L
1) showed how both Fenton’s processes
could remove the excess of 90% of DOC and UV-absorbing species and are
significantly quicker than UV/H2O2 [37].

5 Case Study: Effect of the O3/UV Process on Organic

Matter Removal and Influence on DBPs Formation

This experimental research was addressed to compare the ozone conventional

oxidation with the advanced oxidation with ozone and UV radiation, as concerns
geosmin, MIB and metolachlor removal, the influence on DBPs organic precursors,
and bromate formation [38].

5.1 Raw Water

Raw water, collected from the river Secchia at the treatment plant of Tressano,
managed by AGAC of Reggio Emilia, in the North of Italy, showed the character-
istics indicated in Table 1: TOC ¼ 1.8 mg L
1; UV absorbance ¼ 0.36 cm
1;
THMFP ¼ 70–80 μg L
1; bromide ¼ 30 μg L
1.
During the experimental tests, water was artificially contaminated with
0.5 μg L
1 geosmin (trans-1,10-dimethyl-trans-9-decalol), 0.2–0.4 μg L
1 MIB
(2-methylisoborneol), and 7–10 μg L
1 metolachlor [2-chloro-N-(2-ethyl-6-
methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide].
Natural Organic Matter: Characterization and Removal by AOPs to Assist. . . 61

Table 1 Raw water characteristics

Parameter Average Maximum Minimum
pH (pH unit) 8.06 8.33 7.6
Alkalinity (mg HCO3 L
1) 173.84 263.2 136.44
Turbidity (NTU) 7.85 38.8 1.7
TOC (mg L
1) 1.80 3.35 0.61
UV absorbance 254 nm (cm
1) 0.36 0.9 0.058
Transmittance (%) 63.0 51.0 83.0
THMFP (μg L
1) 76.05 124.5 18
Bromide (μg L
1) 32.96 91 5
Ammonium (mg NH4 L
1) 0.05 0.14 <0.005

5.2 Experimental Plant

The experimental tests were performed in batch conditions on a laboratory-scale

plant (Fig. 1) (Q ¼ 10 L min
1) formed by a stainless steel reactor (volume of 20 L),
a pump, and an in-line ozone injection followed by a static mixer and a low pressure
mercury-vapor ultraviolet (UV) lamp. Ozone was generated by means of “Ozonia
Triogen Compact Ozone Generator” (Model TOGC2), with a capacity of 8 gO3 h
1.
Two UV lamps (Model TR-65) were applied separately with various nominal
wavelengths of maximum light intensity of 254 and 185 nm. Each lamp had about
80% of the radiation around the maximum wavelength, and the intensity was about
25 W m
2.
The experimental conditions tested on water samples were ozone concentrations
¼0–15 mg L
1, ozone contact time ¼ 0–14 min, and UV dose ¼ 0–14,000 J m
2.
Water samples were collected in an outlet from the UV chamber after 2, 4, 6, 8, and
10 min from the beginning of the test (the time required for one complete cycle in
the system is 2 min).

5.3 Analytical Methods

Geosmin, MIB, and metolachlor were analyzed with a capillary column gas
chromatography-mass spectrometry (GC/MS). Trihalomethane formation potential
(THMFP) was determined following [39]; THMs were determined with a gas
chromatograph (GC Perkin-Elmer 8600) with the static headspace method. TOC
was analyzed with a total carbon monitor (Model 1010), the UV absorbance with an
UV–visible spectrophotometer with a 1 cm quartz cell and turbidity with a 2100 AN
Hach turbidimeter. Ozone concentration was measured by means of an ozone
analyzer (BMT 961) that analyzes the flow of ozone production and that of ozone
outlet from the reactor; the difference between the second and the first term gives
the amount of ozone effectively transferred to water.
62 S. Sorlini

Fig. 1 Experimental plant

1 steel feed tank
5 2 ozone generator
6 3 static mixer
4 BMT 961
7 5 UV lamp
3 6 UV generator
1
2 7 sampling point

5.4 Results: Removal of Organic Matter

As concerns the influence on organic matter of the experimented treatments, ozone

alone and combined with UV radiation reduces the absorption of radiation at the
wavelength of 254 nm of about 10–20% with ozone/UV 254 nm and 10% with
ozone/UV 185 nm (Fig. 2). This is due to a removal of aromatic structures and
double bonds of natural organic matter.
As shown in Fig. 3, the removal of THM precursors with ozone and ozone/UV is
very different (from 0 to 40%), and no improvements are observed with increasing
ozone and UV dose and contact time. The partial THMFP reduction (10–30%)
observed in most of the trials is due to the degradation of humic substances into low
molecular weight compounds that are less reactive toward chlorine. However, at the
same time, bromide, whose concentration in raw water varies from 5 to 90 μg L
1,
is oxidized to hypobromite which further leads to brominated compounds [40], with
a consequent higher THM formation.
The combination of ozone with UV does not improve THM precursor removal
with respect to ozone alone, according to the results of other authors [25] that found
a significant reduction of total organic halide while no differences were shown for
chloroform.

5.5 Results: Removal of Geosmin, MIB, and Metolachlor

Molecular ozone has very different reaction rates with organic compounds (Fig. 4):
it reacts very fast with metolachlor, while the odorous compounds (MIB and
geosmin) are more persistent, and their complete removal can be obtained only
with ozone combined with UV radiation (Fig. 5).
The improvement in removal rates for taste and odor compounds obtained by the
advanced oxidation process (O3/UV) can be explained by the action of initiators
(UV rays) to introduce the decomposition of the ozone in water, thus generating
Natural Organic Matter: Characterization and Removal by AOPs to Assist. . . 63

UV ABSORBANCE
0.300 12,000

0.250 10,000

UV dose [J m-2]
0.200 8,000
[cm -1]

0.150 6,000

0.100 4,000
O3
O3+UV254
0.050 O3+UV185 2,000
UV dose

0.000 0
0 2 4 6 8 10 12 14 16 18 20
C x t [mg min L-1]

Fig. 2 UV absorbance removal with ozone, ozone/UV 254 nm and ozone/UV 185 nm

THMFP

50 12,000
40
10,000
30
Removal efficiency

20

UV dose [J m-2]
8,000
10
0 6,000
-10 0 20 40 60 80 100 120 140 160
4,000
-20
O3
-30 O3+UV254
2,000
O3+UV185
-40 UV dose
-50 0
C x t [mg min L-1]

Fig. 3 THMFP removal with ozone, ozone/UV 254 nm and ozone/UV 185 nm

hydroxyl radicals that are very reactive when the water has a low alkalinity (that
means low concentration of scavengers like HCO3
, CO32
, etc.).
The main results show that metolachlor can be efficiently removed with ozone
alone with C  t ¼ 8–10 mg min L
1 (ozone concentration ¼ 1 mg L
1 and 8–10 min
contact time); the same removal can be obtained with C  t ¼ 4 mg min L
1 for
ozone combined with UV (UV dose ¼ 4,000–6,000 J m
2). This means that, for
the same contact time, ozone concentration can be reduced from 1 mg L
1 to
0.2–0.4 mg L
1, whereas, for geosmin and MIB, a complete removal can be obtained
64 S. Sorlini

OZONE
100 METOLACHLOR

90
80
Removal efficiency [%]

GEOSMIN
70
60 MIB

50
40
30
GEOSMIN
20
MIB
10 METOLACHLOR
0
0 2 4 6 8 10 12 14 16 18 20
C x t [mg min L-1]

Fig. 4 Geosmin, MIB, and metolachlor removal with ozone

OZONE/UV 254 nm
METOLACHLOR
100 14,000
GEOSMIN
90
MIB 12,000
80
Removal efficiency [%]

UV dose [J m-2]
70 10,000
60 8,000
50
40 6,000

30 GEOSMIN 4,000
20 MIB
METOLACHLOR 2,000
10 UV dose
0 0
0 2 4 6 8 10 12 14 16
C x t [mg min L-1]

Fig. 5 Geosmin, MIB, and metolachlor removal with ozone/UV 254 nm

only with the combination of ozone (with concentration of 1.5–3 mg L
1 and contact
time of 2–3 min) with UV radiation, with doses of 5,000–6,000 J m
2.
Natural Organic Matter: Characterization and Removal by AOPs to Assist. . . 65

5.6 Results: Bromate Formation

As concerns bromate formation (Fig. 6), a significant reduction is shown in the

AOPs with ozone/UV with respect to conventional oxidation with ozone. UV
radiation, in the wavelength range of 180–300 nm, provides energy to reduce
bromate to hypobromite ion as intermediate and to bromide and oxygen as end
products [41] via complex reactions generated by the primary reaction of photol-
ysis. Ozone combined with UV lamp at 185 nm wavelength is about 10–20% lower
than ozone alone; the highest bromate destruction is obtained with ozone combined
with UV at 254 nm wavelength, for which bromate is about 40–50% lower than
ozone alone and its final concentration is generally lower than the 31/01 Italian
Legislative Decree Limit of 10 μg L
1.

5.7 Conclusions

The conventional and advanced oxidation tests performed on water contaminated

with geosmin, MIB and metolachlor show that the combination of ozone with UV
radiation, both at 254 nm and 185 nm wavelengths, improves the process efficiency
and offers a complete removal for all the analyzed contaminants with C  t of
4–10 mg min L
1 and UV doses of 4,000–6,000 J m
2. All the experimented
treatments offer a good removal of organic precursors, while a significant reduction
(below the limit of 10 μg L
1 of 31/01 Italian Legislative Decree) of bromate is
obtained only with ozone combined with UV 254 nm.

BROMATE

50.0 O3
14,000
O3+UV254
O3+UV185 12,000
40.0
Concentration [mg/L]

D.Lgs 31/01 Limit value

UV dose 10,000
UV dose [J m-2]

30.0 8,000

6,000
20.0

4,000
10.0
2,000

0.0 0
0 2 4 6 8 10 12 14 16
C x t [mg min L-1]

Fig. 6 Bromate formation during ozone, ozone/UV 254 nm and ozone/UV 185 nm
66 S. Sorlini

6 General Considerations About the Application of AOPs

for NOM Removal in Drinking Water Treatment Plants

AOPs are among the most studied and promising technologies for drinking water
purification and disinfection. Although total reduction of NOM has not been
achieved with AOPs, several studies have shown efficient NOM reduction and
mitigation of DBP formation.
The results of various studies dealing with NOM removal by AOPs are always
study specific depending on the water characteristics, such as the amount of organic
matter. Therefore, the characterization of NOM in water should be made before the
design and optimization of the AOP treatment. Furthermore, in order to assess its
influence on the downstream processes, it is important to determine the organic
characteristics of the treated water.
The implementation of an AOP process in a drinking water treatment plant can
be an interesting solution for the removal of NOM and DBP minimization in
drinking water systems. First, the objective of the AOP treatment needs to be
defined, whether it is to enhance biodegradability of organic matter or mineralize
organic compounds. Therefore, the optimal conditions for each case must be
determined according to the type and amount of organic compounds and the
interfering background compounds present in the water.
AOPs generally are not applied alone but may find better application in combi-
nation with other treatments, thus enhancing their efficiency for NOM removal. For
example, coagulation prior to oxidation removes most of the HMM NOM, thus
impacting on subsequent AOP treatment. The combination of AOP and BAC
treatment has been suggested to offer a more viable option for the reduction of
harmful DBPs than the AOP alone.
It should be emphasized that AOPs have site-specific effects, so pilot-scale and
full-scale tests must be conducted to define the optimal conditions for the process.
Experimental and pilot-scale studies are often conducted under conditions that are
not economically feasible in commercial applications. The full-scale application of
AOPs in drinking water treatment plants is still limited because of high cost, high
level of pretreatment required, a lack of experience, and operational difficulties.
Nevertheless, there is an increasing interest for AOPs that will take to an increase of
full-scale installation of these processes.

References

1. Rigobello E, Dantas A, Di Bernardo L, Vieira E (2011) Influence of the apparent molecular size of
aquatic humic substances on colour removal by coagulation and filtration. Environ Technol 32:
1767–1777
2. Fabris R, Chow C, Drikas M, Eikebrokk B (2008) Comparison of NOM character in selected -
Australian and Norwegian drinking waters. Water Res 42:4188–4196
Natural Organic Matter: Characterization and Removal by AOPs to Assist. . . 67

3. Rodrigues A, Brito P, Janknecht MF, Proença R, Nogueira R (2009) Quantification of

humic acids in surface water: effects of divalent cations, pH, and filtration. J Environ Monit
11:377–382
4. Crittenden JC (2012) MWH’s water treatment: principles and design. Wiley, Hoboken
5. Kokorite M, Klavins V, Rodinov G (2012) Trends of natural organic matter concentrations in
river waters of Latvia. Environ Monit Assess 184:4999–5008
6. Sharp E, Jarvis P, Parsons S, Jefferson B (2006) Impact of fractional character on the
coagulation of NOM. Colloids Surf A 286:104–111
7. Thurman E (1985) Organic geochemistry of natural waters. Martinus Nijhoff/Dr W. Junk
Publishers, Dordrecht
8. Shestakova M, Sillanpää M (2013) Removal of dichloromethane from ground and wastewater:
a review. Chemosphere 93:1258–1267
9. Snoeyink VL, Jenkins D (1980) Water chemistry. Wiley, New York
10. Danielsson L (1982) On the use of filters for distinguishing between dissolved and particulate
fractions in natural waters. Water Res 16:179–182
11. Korshin G, Chow C, Fabris R, Drikas M (2009) Absorbance spectroscopy-based examination of
effects of coagulation on the reactivity of fractions of natural organic matter with varying apparent
molecular weights. Water Res 43:1541–1548
12. Sillanpää M (2015) Natural organic matter in water. Characterization and treatment methods.
Elsevier, New York
13. Cehovin M, Medic A, Scheideler J, Mielcke J, Ried A, Kompare B, Gotvajn AZ (2017)
Hydrodynamic cavitation in combination with the ozone, hydrogen peroxide and the
UV-based advanced oxidation processes for the removal of natural organic matter from
drinking water. Ultrason Sonochem 37:394–404
14. Matilainen A, Sillanpää M (2010) Removal of natural organic matter from drinking water by
advanced oxidation processes. Chemosphere 80:351–365
15. Hua G, Reckhow D (2007) Characterization of disinfection byproduct precursors based on
hydrophobicity and molecular size. Environ Sci Technol 41:3309–3315
16. Sanly, Lim M, Chiang K, Amal R, Fabris R, Chow C, Drikas M (2007) A study on the removal of
humic acid using advanced oxidation process. Sep Sci Technol 42:1391–1404
17. Jacangelo J, DeMarco J, Owen D, Randtke S (1995) Selected processes for removing NOM:
an overview. J Am Water Works Assoc 87(1):64–77
18. Glaze W, Kang J, Chapin D (1987) The chemistry of water treatment processes involving
ozone, hydrogen peroxide and ultraviolet radiation. Ozone Sci Eng 9:335–352
19. Murray CA, Parsons SA (2004) Removal of NOM from drinking water: Fenton’s and photo-
Fenton’s processes. Chemosphere 54(7):1017–1023
20. Galapate R, Baes A, Okada M (2001) Transformation of dissolved organic matter during ozo-
nation: effects on trihalomethane formation potential. Water Res 35:2201–2206
21. Treguer R, Tatin R, Couvert A, Wolbert D, Tazi-Pain A (2010) Ozonation effect on natural
organic matter adsorption and biodegradation – application to a membrane bioreactor
containing activated carbon for drinking water production. Water Res 44:781–788
22. Molnar J, Agbaba J, Dalmacija B, Tubić A, Krčmar D, Maletić S, Tomašević D (2013) The
effects of matrices and ozone dose on changes in the characteristics of natural organic matter.
Chem Eng J 222:435–443
23. Irabelli A, Jasim S, Biswas N (2008) Pilot-scale evaluation of ozone vs. peroxone for trihalo-
methane formation. Ozone Sci Eng 30:356–366
24. Mosteo R, Miguel N, Martin-Muniesa S, Ormad M, Ovelleiro J (2009) Evaluation of trihalo-
methane formation potential in function of oxidation processes used during the drinking water
production process. J Hazard Mater 172:661–666
25. Kusakabe K, Aso S, Hayashi J, Isomura K, Morooka S (1990) Decomposition of humic acid and
reduction of trihalomethane formation potential in water by ozone with UV irradiation.
Water Res 24:781–785
68 S. Sorlini

26. Chin A, Bérube PR (2005) Removal of disinfection by-product precursors with ozone-UV
advanced oxidation process. Water Res 39(10):2136–2144
27. Wang GS, Liao CH, Chen HW, Yang HC (2006) Characteristics of natural organic matter
degradation in water by UV/H2O2 treatment. Environ Technol 27(3):277–287
28. Kleiser G, Frimmel F (2000) Removal of precursors for disinfection by-products (DBPs) –
differences between ozone- and OH-radical-induced oxidation. Sci Total Environ 256:1–9
29. Liu W, Andrews SA, Sharpless C, Stefan M, Linden KG, Bolton JR (2002) Bench-scale
investigations into comparative evaluation of DBP formation from different UV/H2O2 tech-
nologies. In: Proceedings of the AWWA water quality technology conference, Seattle
30. Toor R, Mohseni M (2007) UV/H2O2 based AOP and its integration with biological activated
carbon treatment for DBP reduction in drinking water. Chemosphere 66:2087–2095
31. Sarathy SR, Mohseni M (2009) UV/H2O2 treatment of drinking water: impacts on NOM char-
acteristics, vol 11. IUVA News
32. Huang X, Leal M, Li Q (2008) Degradation of natural organic matter by TiO2 photocatalytic
oxidation and its effect on fouling of low-pressure membranes. Water Res 42(4–5):1142–1150
33. Uyguner CS, Bekbolet M (2009) Application of photocatalysis for the removal of natural
organic matter in simulated surface and ground waters. J Adv Oxid Technol 12(1):2371–1175
34. Liu S, Lim M, Fabris R, Chow C, Drikas M, Amal R (2008) TiO2 Photocatalysis of
natural organic matter in surface water: impact on trihalomethane and haloacetic acid forma-
tion potential. Environ Sci Technol 42:6218–6223
35. Pichat P (2013) In: Pichat P (ed) Photocatalysis and water purification: from fundamentals to
recent applications. Wiley, New York
36. Brame J, Long M, Li Q, Alvarez P (2015) Inhibitory effect of natural organic matter or other
background constituents on photocatalytic advanced oxidation processes: mechanistic model
development and validation. Water Res 84:1–10
37. Parsons S, Byrne A (2004) Water treatment applications. In: Parsons S (ed) Advanced oxi-
dation processes for water and wastewater treatment. IWA Publishing, London, pp 329–34638
38. Collivignarelli C, Sorlini S (2004) AOPs with ozone and UV radiation in drinking water:
contaminants removal and effects on disinfection byproducts formation. Water Sci Technol
48(4):51–56
39. Standard methods for the examination of water and wastewater (1998) Front cover, 20th edn.
APHA – American Public Health Association
40. Camel V, Bermond A (1998) The use of ozone and associated oxidation processes in
drinking water treatment. Water Res 32(11):3208–3222
41. Siddiqui MS, Amy GL, McCollum LJ (1996) Bromate destruction by UV irradiation and
electric arc discharge. Ozone Sci Eng 18:271–290
Natural Organic Matter Removal by
Heterogeneous Catalytic Wet Peroxide
Oxidation (CWPO)

José Herney Ramı́rez and Luis Alejandro Galeano

Abstract NOM usually reaches drinking water supply sources through metabolic
reactions and soil leaching. It has been, in general, considered that NOM is still one
of the most problematic contaminants present in this kind of influents. Therefore, in
the present chapter, most relevant technologies used for removal of NOM and its
constituents from water have been examined, emphasizing in the past few years. An
overview of the recent research studies dealing the NOM removal by catalytic wet
peroxide oxidation and other closely related heterogeneous Fenton-like AOPs is
presented. As revealed from recent literature reports, heterogeneous Fenton pro-
cesses including CWPO are still emerging, promising catalytic technologies for
NOM removal from water. A wide variety of catalytic solids reported within the
past few years has been examined focusing on their potential in the NOM removal
from water. Main findings offered by several types of catalysts like zeolites,
Fe-functionalized activated carbons, carbon nanotubes, but mainly pillared and
other clay minerals have been critically discussed emphasizing on the NOM
removal by CWPO.

Keywords Al/Fe-pillared clay, Catalytic wet peroxide oxidation, Natural organic

matter, Water treatment

J.H. Ramı́rez (*)

Departamento de Ingenierı́a Quı́mica y Ambiental, Facultad de Ingenierı́a, Universidad
Nacional de Colombia, Bogotá, DC, Colombia
e-mail: [email protected]
L.A. Galeano
Grupo de Investigación en Materiales Funcionales y Catálisis (GIMFC), Departamento de
Quı́mica, Facultad de Ciencias Exactas y Naturales, Universidad de Nari~no, Pasto-Nari~
no,
Colombia
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 69

Water Treatment, Hdb Env Chem (2019) 67: 69–98, DOI 10.1007/698_2017_122,
© Springer International Publishing AG 2017, Published online: 5 December 2017
70 J.H. Ramı́rez and L.A. Galeano

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2 Conventional Techniques Used in NOM Removal from Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.1 Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.2 Coagulation/Flocculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.3 Advanced Oxidation Processes (AOPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.4 Ion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3 NOM Removal from Water by Heterogeneous CWPO and Other Related AOPs . . . . . . . . . 75
3.1 CWPO by Pillared and Other Related Clay Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.2 NOM Removal by CWPO and Other AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.3 Other Solid Catalysts Used for NOM Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

Abbreviations

AC Activated carbon
AERs Anion exchange resins
AMR Atomic metal ratio
AOC Assimilable organic carbon
AOPs Advanced oxidation processes
BAC Biologically activated carbon
BDD Boron-doped diamond
BDOC Biodegradable dissolved organic carbon
CNTs Carbon nanotubes
CWPO Catalytic wet peroxide oxidation
CEC Cationic exchange capacity
CC Chemical coagulation
COD Chemical oxygen demand
4-CP 4-Chlorophenol
DBPs Disinfection by-products
DOC Dissolved organic carbon
EC Electrocoagulation
EO Electro-oxidation
GAC Granular activated carbon
HC Hydrodynamic cavitation
HDC Hydro-dechlorination
HMW High molecular weight
HO● Hydroxyl radical
IMW Intermediate molecular weight
LC-OCD Liquid chromatography-organic carbon detector
LMW Low molecular weight
NA Nano-adsorbents
NOM Natural organic matter
PCMC P-chloro-m-cresol
PILCs Pillared clays
ROS Radical oxygen species
THMs Trihalomethanes
TOC Total organic carbon
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 71

1 Introduction

Waste and surface waters are currently strongly requiring development and appli-
cation of novel, cost-effective treatments. A number of techniques such as chem-
ical, physical, biological, incineration, etc. and their combinations are available, but
each process has its inherent limitations in applicability, effectiveness, and cost.
There are many water systems not suitable for biological treatments, mainly due to
the presence of some highly refractory and toxic pollutants. Their treatments by
conventional chemical processes may have several drawbacks in terms of efficiency
and/or cost.
NOM may cause many problems in wastewater treatment processes, for exam-
ple, undesirable color, taste, and odor, while reacting with common disinfectants to
produce a variety of toxic DBPs [1]. Residual NOM can also promote bacterial
regrowth and pipe corrosion in drinking water distribution systems [2]. NOM also
reduces the overall efficiency of water treatment plants through increased chemical
dosages, interference with the removal of other contaminants and filter fouling [3],
as well as increased levels of complexed heavy metals and adsorbed organic
pollutants [4], among others.
Changes in NOM loading and composition have a significant influence on the
selection, design, and operation of water treatment processes. No single process
alone can be used to treat NOM due to its very high variability.

2 Conventional Techniques Used in NOM Removal from

Water

Diverse processes have been investigated to remove NOM from water such as
adsorption, coagulation/flocculation, advanced oxidation processes, biological and
electrochemical methods, ion exchange, and membrane technology. These pro-
cesses are the most common and economically feasible to remove NOM. In the
following sections, the removal of NOM by some conventional techniques has been
presented and discussed.

2.1 Adsorption

The adsorption process is generally considered as one of the best water treatment
technologies because of its convenience, ease of operation, and simplicity of
design. The mechanism of NOM adsorption is mainly ligand exchange with the
hydroxyl groups of the mineral surface [5]. Different kinds of adsorbents are used
to eliminate NOM, including AC [6]. Li et al. [7] showed that constriction of
internal pores of the carbon caused a reduction in the diffusion rate of the targeted
72 J.H. Ramı́rez and L.A. Galeano

compounds. By comparison of two carbons, the extent of reduction in the

diffusion coefficient caused by adsorption of the same concentration of a pore-
blocking compound, mg/g of AC, was found to be less pronounced for the carbon
with larger volume of mesopores. AC is often used in drinking water treatment
plants to remove or control unpleasant taste and odor, organic compounds, and
NOM. Columns are used in municipal treatments to produce potable water as well
as in disposable cartridges at industrial, commercial, and residential installations.
AC has been also used in the treatment of municipal wastewater either as a
secondary or a tertiary process, with the advantage over other materials of being
able to control odor in the water. The carbon may be either powdered or granular,
the former being added as slurry into the water before chlorination, whereas the
latter used in conventional gravity sand filters alone or together with sand.
GAC is good choice for removing NOM as well as taste and odor compounds.
The removal of NOM by GAC is through reversible and irreversible physical
adsorption caused by nonspecific mechanisms, such as van der Waals forces, dipole
interactions, and hydrophobic interactions [8]. There are two options for locating
GAC units in water treatment plants, i.e., (1) post-filtration adsorption, where the
GAC unit is located after the conventional filtration process, and (2) filtration-
adsorption, in which either all or a fraction of the filter granular media is replaced
by GAC. Compared with filter adsorbents, the post-filtration provides higher
flexibility for both handling GAC and design of specific conditions of adsorption
and thus often allows for lower operational costs.
Many bench-, pilot-, and full-scale studies have shown GAC as a promising
method to effectively remove NOM [9, 10]. However, a major constraint in
operating GAC contactors is the cost of routinely replacing the GAC media due
to the loss of adsorption capacity that occurs once GAC saturates.

2.2 Coagulation/Flocculation

The most common and economically feasible process available to remove NOM is
coagulation and flocculation followed by sedimentation/flotation and filtration.
Most of the NOM can be removed by coagulation, although the hydrophilic,
LMW fractions of NOM are apparently removed less efficiently than the hydro-
phobic, HMW compounds [11]. Coagulation/flocculation in water/wastewater
treatment plants involves the addition of chemicals to alter the physical state of
dissolved and suspended solids and facilitate their removal by sedimentation
[12]. As chemical products, coagulants react with the suspended and colloidal
particles in the water, causing them to bind together and thus allowing for their
removal in the subsequent treatment processes [13]. The aggregation mechanisms
through which particles and colloids are removed include a combination of charge
neutralization, entrapment, adsorption, and complexation with coagulant ions into
insoluble masses [14].
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 73

Coagulation treatment has been employed to decrease turbidity and color and
also to remove pathogens [15]. It is well established through the long and large
literature that the coagulation process efficiency is highly dependent on hydrophilic
and hydrophobic properties (Table 1) of NOM and dissolved organics [16–18].
Coagulation can be induced using chemical salts, such as ferric chloride or alum,
or via electrocoagulation (EC) which uses sacrificial electrodes to provide a pure
source of cations. Unlike chemical coagulation (CC), EC is not a commonly used
water treatment technology. Nevertheless, EC has successfully treated a diverse
variety of water types at the bench-scale, including municipal, textile dye, and
petroleum refinery wastewaters [20–22].

2.3 Advanced Oxidation Processes (AOPs)

AOPs are based on the production of highly reactive, short-lived hydroxyl radicals,
which react with organic contaminants with high reaction rate constants.
AOPs destroy the organic molecules, even the more stable, hard-to-degrade
compounds, including carcinogens and mutagens, by means of the generation of
highly reactive species which oxidize organic matter; thus, AOPs may be of great
interest for public health and turned into a promising study field due to its almost
total degradation potential of soluble organic contaminants in waters and soils,
some of them under reasonably mild temperature and pressure conditions [23–26].
In AOPs, chemical reactions, electron beams, UV light, or ultrasound pulses are
used to obtain high oxidation rates, thanks to the generation of free radicals (mainly
hydroxyl radicals). Indeed, highly reactive HO● are traditionally thought to be the
main active species responsible for the destruction of the contaminants, including
NOM. Their high standard reduction potential of 2.8 V in acidic media enables
these radicals to oxidize almost all organic compounds to carbon dioxide and water,

Table 1 NOM fractions and chemical groups (adapted from [19])

Fraction Chemical groups
Hydrophobic
Strong Humic and fulvic acids, HMW alkyl monocarboxylic and dicarboxylic acids,
acids aromatic acids
Weak Phenols, tannins, IMW alkyl monocarboxylic and dicarboxylic acids
acids
Bases Proteins, aromatic amines, HMW alkyl amines
Neutral Hydrocarbons, aldehydes, HMW methyl ketones and alkyl alcohols, ethers, furans,
pyrrole
Hydrophilic
Acids Hydroxy acids, sugars, sulfonics, LMW alkyl monocarboxylic and dicarboxylic
acids
Bases Amino acids, purines, pyrimidine, LMW alkyl amines
Neutrals Polysaccharides, LMW alky alcohols, aldehydes, and ketones
74 J.H. Ramı́rez and L.A. Galeano

excepting some of the most simple organic compounds, such as acetic, maleic, and
oxalic acids, acetone, or simple chloride derivatives as chloroform [27]; however,
just these species are of interest because they are typically oxidation products of
larger molecules, being continuously generated by chemical, photochemical, or
electrochemical reactions.
Among the more used AOPs, photo-Fenton and photocatalysis have been of
special interest [28]. The photo-Fenton reaction is well known as an efficient and
inexpensive method for wastewater treatment. Photo-Fenton improves the effi-
ciency of dark Fenton or Fenton-like reagents, respectively, by means of the
interaction of radiation (UV or Vis) with Fenton reagents. Light exposure increases
the rate of HO● formation by photoreactions of H2O2 (λ < 360 nm) and/or Fe3+
either producing HO● straightforward or regenerating Fe2+ [29].
Photocatalysis is defined as catalytic activation of a given reaction via a mech-
anism that only proceeds if the system is lighted up. Photocatalytic reactions may
operate via a number of different mechanisms. The main well-known mechanisms
are (1) photolysis of adsorbates, (2) reactions of adsorbed species with photoelec-
trons or holes (photo-electrochemical reaction), and (3) injection of electrons from
an excited adsorbate into a semiconducting mineral [30].
The efficiency of NOM removal using AOPs strongly depends on water char-
acteristics, including the concentration of organic matter. Therefore, characteriza-
tion of the NOM in water should necessarily anticipate the design and optimization
of any AOP treatment. The characteristics of the organics in the treated water must
be also determined to assess their influence on downstream processes.
The reactions of HO● with NOM proceed at least by means of three different
ways: (1) HO● addition on double bonds; (2) H-atom abstraction, which yields
carbon-centered radicals; and (3) the HO● gaining an electron from an organic
substituent. The carbon-centered radicals then react very rapidly with oxygen to
form organic peroxyl radicals. The mutual reactions of peroxyl radicals can lead to
the production of ketones or aldehydes and/or carbon dioxide. The rate of oxidation
depends on radical, oxygen, and pollutant concentrations. Other factors affecting
formation of the radicals are pH, temperature, the presence of ions, the type of
pollutant, and the presence of scavengers such as bicarbonate ions [31].
Finally, HO● can also be produced without using chemicals by means of
cavitation. Generally it is a phenomenon of formation, cyclic growth, and rarefac-
tion with the terminal implosive collapse of vapor bubbles in the liquid phase.
Cavitation, caused by pressure gradients of water due to the influence of geometry,
is called hydrodynamic cavitation (HC). Recent studies show beneficial effective-
ness of HC for degradation of various recalcitrant organic contaminants (pharma-
ceuticals, synthetic and persistent organic chemicals, micropollutants, etc.) from
water and wastewater [32].
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 75

2.4 Ion Exchange

Important properties of AERs include polymer composition, porosity, and charged

functional groups. Performances of AERs for NOM removal are influenced by the
inner characteristics of the resins (strong- or weak-base AER), the water quality
(pH, ionic strength, hardness, etc.), and the nature of organic compounds (molec-
ular weight, charge density, and polarity). The composition of most resins is either
polystyrene or polyacrylic. Polystyrene resins are more hydrophobic than
polyacrylic resins; as a result, polyacrylic resins tend to have more open structure
and higher water content. The porosity of resins is defined as either macroporous or
gel. Macroporous resins are highly porous solids, while gel resins do not contain
any pores [30]. Strong-base resins typically contain either type I (
N+(CH3)3) or
type II (
N+(CH3)2(C2H4OH)) quaternary ammonium functional groups. Due to
their ethanolic content, type II resins are more hydrophilic than type I resins
[33]. Most strong-base anion exchange resins are used in the chloride form.
The advantages and disadvantages of NOM removal by using ion exchange
treatment are presented in Table 2. As is evident this technology is very interesting
since it has proven to be highly efficient, while exhibiting very low formation of
DBP; only one disadvantage can be observed for this technology regarding the
necessity of an additional treatment stage since the NOM removal is not complete.

3 NOM Removal from Water by Heterogeneous CWPO

and Other Related AOPs

AOPs are gaining more and more interest as potential solutions in the field of water
treatment; the use of appropriate catalysts can substantially decrease the energy
consumption of oxidation processes, such as wet air and wet peroxide oxidation of
refractory organic compounds. The main limitation of the conventional Fenton
process is the dissolved homogeneous catalyst that cannot be easily recovered
throughout the process, leading to additional pollution [34]. Besides, another
outstanding issue that has deserved a number of works in the past few years
regarding drawbacks of the homogeneously activated Fenton process has been the
very narrow range of pH values (<~4.0) [35] under which it is operable as efficient
catalytic process itself (Fig. 1); it associates high operating costs for industrial-scale

Table 2 Advantages and disadvantages of NOM using ion exchange treatment

Advantages Disadvantages
Proven technology Additional stage of treatment required
Potential highly efficient
Very low formation of DBPs
Efficient in treating the transphilic fraction of NOM
76 J.H. Ramı́rez and L.A. Galeano

+
100 Fe3+ Fe(OH)2
(c)

% Percentage distribution
Fe(OH)3(s)
80

60

40

FeOH2+ Fe(OH)4
20

0
0 2 4 6 8 10 12 14
pH

Fig. 1 Effect of pH on the catalytic performance of the Fenton process activated under either
homogeneous or heterogeneous conditions: (a) homogeneous system ([Fe] ¼ 5 mg/L) and (b)
heterogeneous catalyst (Al/Fe-PILC FAZA, 5 g/L), amount of DMPO/HO adduct, phenol conver-
sion (after 2 h of reaction), and TOC abatement (after 4 h of reaction) in function of the pH: (open
square) DMPO/HO. Adduct amount (dotted line), phenol conversion ( filled circle), TOC abate-
ment ( filled triangle) (reprinted from [35], with permission of Springer). (c) Speciation diagram of
ferric hydroxyl species as a function of pH for a solution containing 1.0  10
5 M of Fe(III) at
25  C obtained by MINEQL+ software (reprinted from [34], with permission of Elsevier)

applications of other variants of the Fenton process, including photo-Fenton. As it

can be seen, although hydroxyl radical concentration becomes significantly affected
in both Fenton systems over pH ¼ 4.0, the homogeneous one seems much more
susceptible (Fig. 1a, b), according to the speciation undergone by Fe(III) as a
function of pH (Fig. 1c). In this sense, several works have been recently revised
by Clarizia et al. [34], examining and comparing the most relevant papers dealing
with photo-Fenton processes at neutral pH available in the literature. The main
strategy to overcome this practical disadvantage so far (most or the real contami-
nated waters do not match such a range of pH values, including surface waters as
common supply sources to produce drinking water) has been to adopt different
types of chelating agents. Each iron(III)-ligand complex features a particular
mechanism of photolysis, speciation pattern, light absorption properties, quantum
yield, biodegradation, and toxicity that must be considered for choosing proper
chelating agent and operating conditions in the photo-Fenton degradation under
circumneutral pH values.
Therefore, one of the AOPs lately attracting more attention has been the so-called
CWPO; it employs hydrogen peroxide as oxidizing agent in the presence of a solid
Fenton or Fenton-like catalyst. The redox properties of the transition metals
immobilized in solid catalysts (usually either Fe2+/Fe3+ or Cu2+) allow the generation
of hydroxyl radicals in the presence of hydrogen peroxide under very mild conditions
of temperature and pressure [36]. In addition, it enables easy recovery of the catalytic
species, so available for use through a long-term, extended number of catalytic
cycles. Hence, important efforts have been focused on finding heterogeneous cata-
lysts with adequate catalytic activity and convenient stability even at pHs of reaction
exceeding 4.0, taking into account the acidic conditions under which the reaction
takes place more efficiently. Another important advantage linked to the Fenton
process activated in heterogeneous phase is to avoid expensive extra steps to recover
both the excess of dissolved metals and the sludge formed upon application under
near-neutral pH conditions, typical of most water streams [37].
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 77

Several teams have reported different materials as possible carriers of active

sites catalyzing CWPO: alumina-supported Fe [38], Fe-containing zeolites [39, 40],
activated and other functionalized carbonaceous supports [37, 41], and pillared
clays [42, 43] are the most common reported catalysts for the CWPO of NOM and
other organics. The main limitations of the most suggested materials could be
summarized as either low effectiveness under near-neutral pH, low stability against
active metal leaching, and/or high cost. The first approach still thoroughly investi-
gated by several groups has been the use of supported catalysts of the Fenton-active
transition metals on typical hosts like alumina [44, 45] or silica [46, 47]. However,
the most significant drawback of this kind of materials has been definitely poor
chemical stability to leaching of the active metal in the reaction mixture in
comparison to other solid, functional materials. After the pillared and other mod-
ified clay materials, activated carbons and synthetic zeolites have been perhaps the
most studied heterogeneous carriers in the past few years because of their high
effectiveness, and then these are more specifically analyzed hereafter.

3.1 CWPO by Pillared and Other Related Clay Catalysts

The catalytic potential of the clay-modified materials activating the CWPO reaction
has been widely investigated along the past two decades, mainly emphasizing on
Al/Fe-, Al/Cu-, and Al/Fe-Cu-pillared clays [48–53]. The high performance
displayed by Fe, Cu-modified pillared clays in this reaction mainly relies on the
high rates of elimination of several model toxic compounds in terms of both
contaminant’s depletion and both TOC and COD elimination. Besides, this type
of catalysts can be obtained from inexpensive raw materials, increasing the cost-
effective potential scaling-up in order to solve real problems in water treatment.
Several studies have pointed out that smectites once pillared with mixed Al-based
polycations containing iron or copper are materials displaying pretty high perfor-
mance catalyzing the CWPO reaction [51, 52]. Timofeeva et al. [51] reported the
effect of some synthesis variables like hydrolysis ratio of the pillaring solution
(OH/(Al + Fe)), temperature of calcination in the preparation of Al/Fe-PILCs, as
well as the atomic ratio Fe/Cu in Fe, Cu, Al-clays on the catalytic properties of the
resulting materials in the CWPO reaction. Presence of Cu or Fe in isolated sites
within alumina pillars, that is, truly mixed interlayering Al/M-polycations, has been
believed from a time ago [54] to be closely related to the high catalytic response
displayed by this kind of layered materials in the CWPO degradation of several
types of compounds, as more recently strongly supported also by H2-TPR mea-
surements in the case of the Al/Fe-PILCs [52]. In this sense, this and other studies
have evidenced that higher loadings of Fe in Al/Fe-pillaring solutions lead to higher
fractions of the transition metal fixed in the inorganic host, but not necessarily
improving the degradation of organics by a purely catalytic pathway of response in
heterogeneous phase [52, 55]. Although higher fractions of Fe in the interlayering
solutions clearly promote increased amounts of iron incorporated into the PILCs as
78 J.H. Ramı́rez and L.A. Galeano

isolated octahedrally coordinated Fe3+ cations (the most active in the CWPO
reaction), together there is bigger incidence of Fe aggregates, less active but also
less stable against leaching under the strongly oxidizing environment of the cata-
lytic reaction [52, 55, 56]. Thus, leaching of the active metal(s) usually makes more
difficult to interpret the contaminant removals along this type of reaction, since it
implicitly leads to higher contribution of the homogeneously activated Fenton
oxidation to the overall activity [52]. In addition, elimination of the contaminants
should always account for the fraction adsorbed on the catalyst’s surface in order to
rule out a significant contribution, avoiding reporting it as a purely catalytic
degradation. Of course, it must be more carefully assessed in the case of high-
surface solid carriers as, for instance, metal-functionalized activated carbons.
Another important issue of the Fenton solid catalysts useful in the CWPO
reaction is the presence, in most of cases, of an induction period before observing
faster degradation of the contaminants. It is typical of the Fenton-like variant of
reaction and must be mainly ascribed in the case of the iron-functionalized mate-
rials, to the balance (Fe3+/Fe2+) in the accessible, active sites of reaction; as higher
ratio in this couple of oxidation states, as more prolonged must be expected such
induction period. Zhou et al. [57] recently modeled the apparent induction period
followed by a rapid oxidation observed during the catalytic wet peroxide oxidation
of 4-chlorophenol (4-CP) by using Fermi’s kinetic equation (R2 ¼ 0.9938–0.9993).
4-CP oxidation proceeded via 4-chlorocatechol (major) and hydroquinone (minor)
pathways, along the formation of main intermediate (5-chloro-1,2,4-benzenetriol).
Besides CO2, H2O, and Cl
, two main compounds (I and II) formed, the former
identified as 2,4-dioxopentanedioic acid, whereas the latter as ferric-oxalate com-
plex. Finally, it has reported marked structural and active differences between Al/
Fe-PILC and Al/Cu-PILC in which compared to the latter, the former possessed
higher specific surface area and catalytic activity, but its optimal calcination
temperature was lower. The induction period also resulted longer in the case of
the Al/Fe-PILC. In addition, compound II accounted for a considerable proportion
in Al/Fe-PILC system, whereas compound I was almost only component in Al/Cu-
PILC system. Overwhelming advantage of the Al/Fe-PILC on the Al/Cu-PILC
system catalyzing CWPO had been also clearly evidenced earlier dealing on
degradation of the azo-dye methyl orange [52]. On the basis of elemental analyses,
it was found that within the range of 0–10% of atomic metal ratio (AMR), Fe gets
incorporated around 15 times more efficiently in Al/M-PILCs than copper, whereas
the patterns of compensation of the starting CEC showed that increasing values of
AMR(Fe and/or Cu) led to less and less efficient compensation of the aluminosilicate’s
layer charge. AMR is then a key and useful parameter to be considered in prepa-
ration of Al-mixed PILCs with Fe and/or Cu for CWPO, since different as could be
believed by default, higher fractions of these active metals in the mixed
interlayering solutions do not necessarily conduce to more efficient clay catalysts.
However, in other reports published a little bit later [55, 56], adsorption of tartrazine
showed slight rise with increasing content of Fe3+ in Al/Fe-PILCs (AMR(Fe) in the
range of 1.0–20.0%) [55], probably related to the well-known high external surface
featured by iron oxides, inferring that higher loadings of this active metal are
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 79

necessarily forced to form iron oxide aggregates, not very useful for this particular
application. However, apparently this increased incidence of non-pillaring iron
aggregates as a function of AMR(Fe) did not lead to lower stability against leaching
in the CWPO reaction, since pretty low concentration of Fe was reported for all
samples evaluated. According to M€ossbauer analyses, the structure of the incorpo-
rated iron-containing oxides resembled those of naturally occurring minerals
akaganeite (β-FeOOH) or lepidocrocite (γ-FeOOH) [56]. AMR can be calculated
as follows [52]:
ðFe and=or CuÞ
AMRðFe and=or CuÞ ¼  100
ðAl þ ðFe and=or CuÞÞ

In related address, Timofeeva et al. [51] focused in studying the effect of the Fe/Cu
ratio in the Al/Fe-Cu-containing pillaring solution on structural and catalytic
properties, CWPO degradation of phenol, of final catalysts. The increase in copper
loading led to decreased total surface area, micropore volume, and interlayer
distance, whereas the decrease in Fe/Cu ratio favored the formation of oligomeric
iron species. However, according to the authors, the introduction of copper ions also
increased the rate of the catalytic reaction, an effect that was interpreted in terms of
higher rate of radical generation. Moreover, a little bit later in other study [52], no
cooperative effect in the CWPO degradation of methyl orange by the presence of
both active metals in the same Al/M-pillared clay catalyst was found, which was
explained by a possible competition between both active metals for octahedral sites
into the framework of Al13 polycations in this three-metal system.
An important issue that has remained still controversial regarding Al/Fe-PILCs
is whether there is or no formation of truly mixed pillars of both metals. In spite that
several works have suggested the outstanding activity of this kind of materials in
the CWPO reaction as being strongly related to the mixed Al/Fe pillars [52, 54],
some others have ruled it out while proposing that only iron oxides either decorat-
ing the Al2O3 pillars or as external aggregates are stabilized in this type of materials
[58, 59]. In this sense, Bankovic et al. [56] based on DR UV–Vis spectra,
M€ossbauer, and FTIR analyses proposed that in the AlFe1–15 PILCs (AMRFe
values from 1.0 to 15.0%), the Fe3+ ion probably partially substituted Al3+ ions in
Keggin ion, thus forming Al13-xFex oxide pillars, whereas in the case of the AlFe20
PILC, other types of pillars might have been formed including those containing
separate Al or Fe oxide pillars. Besides, it was shown that increasing iron content of
the PILCs resulted in the increasing presence of species with greater clusters of
octahedrally coordinated Fe3+ ions. The structure of the incorporated iron-
containing oxides resembled those of naturally occurring minerals akaganeite
(β-FeOOH) or lepidocrocite (γ-FeOOH) (Fig. 2a). It was in similar address to the
trend already found as a function of the increased content of Fe in final materials,
based in H2-TPR analyses (Fig. 2b) [52]. Finally, same authors reported interesting
behavior of the textural properties in Al/Fe-PILCs as a function of the increasing
content in Fe. Particularly, pillaring with Keggin-like ions led to almost
monomodal distribution of mesopore diameters. The addition of Fe3+ into the
80 J.H. Ramı́rez and L.A. Galeano

0 200 400 600 800 1000

BVAIFeCu5 TM = 440°C
553µmol H2 /g

40

BVAICu5 TM = 445°C
30
657µmol H2 /g
3

H2 consumption (a.u.)
F(R)

20
2
BVAIFe5
TM = 475°C
734µmol H2 /g
10
1

0
BVAIFe2 TM = 455°C
200 300 400 500 600 700 800 585µmol H2 /g

Wavelength [nm]

0 200 400 600 800 1000

T (°C)

Fig. 2 Physicochemical properties of different Al/Fe- and Al/Cu-PILCs as a function of the

AMRFe: (a) DR UV–Vis spectra of (1) Al PILC, (2) AlFe10 PILC (AMRFe ¼ 10%), and
(3) AlFe20 PILC (AMRFe ¼ 20%) (reprinted from [56], with permission of Elsevier). (b)
H2-TPR diagrams of BVAlFe2 (AMRFe ¼ 2.0%), BVAlFe5 (AMRFe ¼ 5.0%), BVAlCu5
(AMRCu ¼ 5.0%), and BVAlFeCu5 (AMRFe + Cu ¼ 5.0%) (reprinted from [52], with permission
of Elsevier)

pillaring solution resulted in changes in the mesopore diameter distribution.

Increasing Fe content led to the broadening of the distribution of mesopore diam-
eters in the sequence Al PILC < AlFe1 PILC < AlFe5 PILC < AlFe10 PILC,
which got inverted for increasing AMRFe values from 10 to 20%. This phenomenon
was proposed to be further investigated.
Later, Khankhasaeva et al. [53] studied the degradation of sulfanilamide in water
by H2O2 in the presence of Fe, Al/M-pillared clays from various cationic forms of
the starting layered aluminosilicate (Fe, Al/M-MM, M ¼ Na+, Ca2+, and Ba2+). The
montmorillonitic materials were exchanged with bulky Fe, Al-polyoxocations
prepared at Al/Fe ¼ 10/1 (AMRFe ~9.0%) and OH/(Al + Fe) ¼ 2.0 and then
calcinated at 500  C and from XRD, and chemical analyses found that the rate of
crystalline swelling was dependent on the nature of the starting interlayer cations in
the clay mineral (Fe, Al
/Na-MM > Fe, Al/Ca-MM > Fe, Al/Ba-MM). In addi-
tion, the catalytic properties of Fe, Al/M-MMs depended on the type of exchange-
able cations, although only slightly the textural properties. These differences were
mainly ascribed to higher iron uptake in the Na-MM cationic form.
Gao et al. [60] recently studied the introduction of nickel in Fe-Al-pillared
montmorillonite and its effect in the CWPO degradation of the azo-dye Orange
II. The effects of active metal molar loading (AMRFe-Ni), Fe/Ni molar ratio, and
calcination temperature on the pillared clays were measured and discussed. It was
proposed the introduction of nickel to the pillaring solution may contribute to better
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 81

active iron stability and catalytic performance. Iron was found in the clays in the
form of FeOOH when nickel was introduced, whose integrity was more easily
maintained when a moderate calcination temperature was used. Solid modified with
4/6 Fe/Ni molar ratio and AMRFe-Ni ¼ 6%, finally heated at 273  C, displayed
better catalytic behavior. Thus, Acid Orange II solution got 72.32% of COD
removal after 3 h of reaction: pH ¼ 3.0, T ¼ 60  C, and H2O2 dosing ¼ 100% of
the theoretical stoichiometric amount. Fe/Ni ratios above 4/6 led to declined
catalytic behavior of pillared clays, which was attributed to formation of large
iron aggregates.
Some other studies have also attempted combination of properties of Al-,
Al/Fe-PILCs with other either transition or precious metals to improve catalytic
properties of this kind of materials in water decontamination. For instance, recently
a two-step treatment of p-chloro-m-cresol (PCMC) in water by catalytic
hydrodechlorination (HDC) followed by CWPO under ambient-like conditions
(25  C, 1 atm) in the presence of catalysts supported on Al-PILCs using Fe and
Pd or Rh as active phases was reported [61]. The bimetallic Pd-Fe catalyst showed
the best performance, allowing complete dechlorination in less than 1 h reaction
time (25  C, 1 atm, pH0 ¼ 6, QH2 ¼ 50 N mL/min, [catalyst]0 ¼ 1 g/L,
[PCMC]0 ¼ 0.7 mmol/L). Meanwhile, CWPO of PCMC with a monometallic Fe
catalyst allowed complete conversion of that pollutant but with only about 33%
reduction of TOC after 4 h. Then, a two-step approach consisting in HDC of PCMC
followed by CWPO has been tested for the first time in two different ways. The first
one used a Pd-Fe bimetallic catalyst in both steps, while in the second approach,
monometallic Pd-Fe catalysts were used for HDC and CWPO, respectively. The
HDC step extended for 30 min was enough to achieve complete dechlorination, the
main reaction product being m-cresol (selectivity >85%). After the HDC step, the
pH of the reaction medium was adjusted to 3.5, and the stoichiometric H2O2 dose
was added to start the CWPO step. It allowed complete conversion of m-cresol in
15 min, with 60% TOC reduction after 4 h of reaction time. However, the stability
of the catalysts against Fe leaching was more rather poor; the Fe leached from the
catalyst in this combined treatment reached 2.5 mg/L in the HDC step and 4.9 mg/L
at the end of the experiment. Although it represents only 6.6% of the initial Fe load
reported, the recorded CWPO activity was undoubtedly influenced by the typical
homogeneous Fenton process. It is a promising combined application of the CWPO
process in order to contribute giving overall response to contamination by haloge-
nated organics, but strong efforts should be made in order to significantly increase
stability of the active metal in the step of the heterogeneous Fenton process.
Thanks to the highly promising potential exhibited by the Al/Fe-PILCs in the
CWPO treatment of a variety of polluted aqueous systems, several efforts have
been taking place along the past decade in order to make possible its preparation in
both higher to lab scales and starting from concentrated precursors. Some studies
have focused on the reduction of the synthesis time, involving the use of either
microwaves [59, 62] or ultrasound [63] in the preparation of the metal interlayering
precursor but increasing consumption of energy as a drawback. Other approaches
have tried to increase concentration of the pillaring precursors, either interlayering
82 J.H. Ramı́rez and L.A. Galeano

polycationic solution or the clay suspension itself [43], where typical concentration
of the oligomerized metal precursor was close to tenfold increased from around
0.06 to 0.63 mol/L. It implied the use of lower hydrolysis ratio (OH/(Al + Fe) ¼ 1.6)
in comparison to typical lab-scale preparations (~2.0–2.4). In addition, the use of
ethanol as suspension medium demonstrated to be advantageous in order to perform
the interlayering step (contact of the interlayering, oligomeric metal solution with
the clay mineral) on concentrated clay suspensions (up to around 50% w/w).
Another important step forward in the same address has been achieved by some
researchers [64, 65] by means of the straightforward addition of the raw clays on the
interlayering Al or Al/Fe solutions. It has allowed to save time and resources (extra
added solvent-free suspension) by working on not previously swollen mineral, but
attaining Al- or Al/Fe-pillared materials with basal spacings around 1.8 nm, sig-
nificant increase in specific surface and pore volume. Moreover, as far as we know
right now, there is no complete solution to this issue, and hence in general, reports
about the application of this type of clay catalysts at industrial level are not still
available. Regarding this issue, as a comparison reference, CWPO treatment in
continuous reactors has started to be studied in the presence of other solid catalysts,
like for instance zeolites. The CWPO degradation of phenol by a Fe-ZSM-5 catalyst
in a fixed bed reactor was recently investigated [66]. The effects of feed flow rate
and catalyst bed height were determined by following conversion of phenol, H2O2,
and TOC concentrations. The Fe-ZSM-5 catalyst achieved the highest activity
(99.2% phenol conversion and 77.7% of TOC conversion) at 80  C, 2 mL/min
feed flow rate and 3.8 cm as catalyst bed height. In spite that the authors claim
remarkable low iron leaching concentration, since it was around 1.0 mg/L, it may
anticipate sustained rapid deactivation of the catalyst under real conditions of
treatment. In addition, such a level of concentration has demonstrated to be not
negligible catalyzing the CWPO reaction based on a close to purely homogeneous
Fenton mechanism. As it was stressed by the authors, further research should be
focused on the deactivated mechanism and regeneration strategies of the catalyst. It
is big evidence promoting the rapid development of scaled-up preparation of Al/Fe-
pillared clays, since the concentrations of iron leached in the CWPO reaction
mixture typically do not exceed 0.3 mg/L. The HPLC patterns of the solution at
different catalyst bed heights demonstrated that low concentration of quinone was
generated and then transformed into low molecular weight organic acids and finally
changed into carbon dioxide and water with the increase of residence time. This
pattern of degradation has been observed in the presence of other efficient CWPO
catalysts.
Finally, some emerging materials attracting interest as CWPO-active clay cata-
lysts along the past 5 years have been some naturally occurring or synthetic clay
minerals, whose either structural or added content of Fe or Cu has been investigated
as active sites of the catalytic reaction [67–69]. First of all, allophane clay materials
with SiO2/Al2O3 ratios between 1.0 and 2.2 were synthesized by a coprecipitation
route and further impregnated with iron or copper species, in targeted loadings
surrounding 2.0–6.0 w/w % [68]. The lower ratio resembled typical Al-rich soil
allophane (AlSi1; BET surface <1.0 m2/g), whereas the higher one looked like
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 83

more as a hydrous feldspathoid with a large interspherule surface, thereby

exhibiting a high surface area (AlSi2; BET surface ~191 m2/g; up to 287 c for 8.5
Fe2O3 wt.%). The iron-based AlSi2 catalysts with taillike structure and high surface
area proved to be far more active in the CWPO elimination of phenol (pH ¼ 3.7,
[phenol]0 ¼ 5  10
4 mol/L, [catalyst] ¼ 0.4 g/L, [H2O2]added ¼ 0.1 mol/L under
constant flow rate of 2.0 mL/h along 4 h for the Fe catalysts and 8 h for the Cu
catalysts). The highest catalytic efficiency (94%/1 h of reaction; total organic
carbon abatement 63%/4 h of reaction) was obtained at 40  C for the calcined
iron oxide-supported AlSi2 allophane sample (300  C/1 h), for which very low
leaching level of iron species was noticed (0.37 mg/L). By contrast, large differ-
ences in terms of catalytic efficiency (conversion rates) and stability were observed
for the copper-based counterparts.
Munoz et al. [67] recently explored the potential application of naturally occur-
ring minerals as inexpensive catalysts in heterogeneous Fenton, namely, catalytic
wet peroxide oxidation (CWPO). Performance of magnetite, hematite, and ilmenite
as CWPO catalysts was tested under different working conditions (25–90  C,
[H2O2] ¼ 250–1,000 mg/L, [catalyst] ¼ 1–4 g/L). In general terms, the use of
naturally occurring Fe minerals is attractive because of pretty low cost of this kind
of minerals. However, CWPO activated by this kind of materials proceed in fairly
longer times of reaction and/or demands for increased temperatures. As expected,
in this study the operating temperature showed to play a key role on the rate of H2O2
decomposition, so that in the presence of magnetite, the H2O2 conversion after 4 h
increased from 8 to 99% by increasing the temperature from 25 to 90  C ([phe-
nol]0 ¼ 100 mg/L). Here it is noteworthy that every Celsius degree of higher
reaction temperature of course also supposes increased cost of operation of the
catalytic system, and then it may rapidly offset the benefit related to the use of a
cheaper catalyst. Conversely, as a clear advantage, leaching is not a big deal in the
case of the treatment of wastewaters given the very low cost featuring this kind of
ferrous minerals. A significant metal leaching may also become not practical in the
use of the catalyst in an extended range of pH values, a crucial difference of the
CWPO process against the conventional Fenton process. Complete phenol conver-
sion and almost 80% TOC reduction were claimed at 75  C with a catalyst loading
of 2 g/L in the presence of theoretical stoichiometric amount of H2O2 required for
complete mineralization of a phenol sample solution (500 mg/L). Among the
minerals compared, magnetite (Fe3O4) was particularly attractive, since it showed
the highest activity and can be easily separated from the liquid phase given its
magnetic properties. Moreover, it must be stressed that such a promising mineral
was also the one leaching a higher Fe concentration along three consecutive runs; of
course it decreased steadily with the cycles of reuse (over 12 mg/L in the first run,
around 4 mg/L after the third run), but it allows to infer quite significant contribu-
tion of homogeneous Fenton reaction.
In summary, Fe-containing naturally occurring minerals could be devised as
interesting CWPO catalysts in the field of wastewater treatment, mainly on those
with significant carbon loadings in order for the exothermal enthalpies of oxidation
to contribute decreasing the costs of heating of the catalytic system over around
84 J.H. Ramı́rez and L.A. Galeano

70  C. Such a kind of materials, together with other types of synthetic-based

supported catalysts, mainly Fe and/or Cu oxides as active sites, has demonstrated
as a general drawback the low stability against metal leaching in the oxidizing
reaction mixture. Outstanding, worth mentioning exception has been the case of
modified allophane clay synthetic materials functionalized by impregnation with
Fe, which recently showed proper activity and chemical stability (Feleached
<0.4 mg/L) in phenol oxidation under still middle temperature of reaction
(40  C). Al/M-mixed pillared clays in general have exhibited lower contents of
the active metals (Cu and/or mainly Fe) incorporated in final materials. They
usually display high performance in contaminant depletion even at room temper-
atures, with output concentrations of active metals typically below 0.3 mg/L, thanks
to the specific location of them in very active sites at the interlayer space of the
starting aluminosilicates. Moreover, in order to ensure such a set of desirable
properties in the CWPO application, cumbersome steps and parameters of prepa-
ration must be carefully followed, which definitely have delayed the scaled-up
preparation of this kind of materials and, in turn, their more widely spread use in the
treatment of a variety of contaminated waters at industrial scale. Therefore, further
work in the short term in these still exciting materials should focus in the develop-
ment of Al/Fe-PILC preparation from concentrated precursors (significantly inten-
sified process), exhibiting physicochemical properties comparable with products
obtained in conventional preparations from diluted precursors as well as under
reproducible conditions at higher to lab scales (let’s say bench followed by pilot
scale).

3.2 NOM Removal by CWPO and Other AOPs

AOPs have been intensively studied about the treatment of wide variety of con-
taminated waters but predominantly wastewaters. NOM removal by such a set of
powerful technologies has attracted interest from more rather short time ago,
strongly focused in the improvement of drinking water treatment systems. In this
context, effect of the NOM removal to decrease the potential of formation of
disinfection by-products, more particularly THMs, has been studied. The presence
of NOM causes many problems in drinking water treatment processes, including
(1) negative effect on water quality by color, taste, and odor problems, (2) increased
coagulant and disinfectant dose requirements (which in turn results in increased
sludge and potential harmful disinfection by-product formation), (3) promoted
biological growth in distribution system, and (4) increased levels of complexed
heavy metals and adsorbed organic pollutants [4, 70]. Among the assessed AOPs
have been O3/H2O2, O3/UV, UV/H2O2, TiO2/UV, H2O2/catalyst, Fenton, and
photo-Fenton processes as well as ultrasound so far, as reviewed in 2010 by
Matilainen et al. [4]. Thus, in this section we focus in reviewing the heterogeneous
Fenton-like applications reported on the past few years together with the most
strongly related others.
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 85

First of all, within this recent period, several efforts have been made in order to
more confidently and in depth characterize NOM. This is because NOM is a very
complex matrix, with widely distributed compositions, chemical functionalities,
polar properties, and molecular weight distributions. In addition, there is a high
variability of their properties as a function of the source (surface water, groundwa-
ter, place, etc.) and even season of the year. For instance, dissolved organic matter
(~6.0–15.0 mg/L as dissolved organic carbon) present in two secondary effluents
was recently characterized and monitored through UV/H2O2 and ozonation treat-
ments by using LC-OCD technique [71]. Biopolymers, humic substances, building
blocks, low molar mass neutrals, and low molar mass acids were the fractions
resolved. Monitoring of the organic matter fractions with LC-OCD demonstrated
that the reduction of effluent’s aromaticity (decreasing in specific UV absorbance –
SUVA) was not strictly correlated with the complete depletion of humic substances
in the effluents for both advanced treatments. However, the UV/H2O2 process led to
an effluent with lower biopolymer content together with important increase in low
molecular mass fractions, although significant amounts of humic acids still
remained after extended oxidation treatments. In spite that both AOPs efficiently
removed different fractions of the dissolved organic matter, the final composition of
the treated effluents was significantly different between the two processes.
During the treatment of natural sources of water by AOPs to remove
micropollutants, NOM gets broken down into smaller species, potentially affecting
biostability by increasing AOC and BDOC. Bazri et al. [72] found that by means of
the UV/H2O2 treatment, both AOC and BDOC increased by about three to four
times over the course of treatment, indicating the reduction of biological stability.
Although a wide range of organic molecular weights were found responsible for
AOC increase, low molecular weight organics seemed to contribute more, which
could be a serious drawback in order to apply in general AOPs in drinking water
facilities. Accordingly, it can be easily anticipated that higher fraction of the TOC
represented in low molecular weight organic compounds in this kind of effluents
may lead to either higher incidence of microbiological growth in distribution pipes
or higher demand of residual chlorine in the effluents of typical disinfection units.
Another very important issue in this field is the pH and alkalinity at which a given
AOP can operate efficiently. Typical range of pH values for surface waters is close
to neutral, sometimes slightly basic. This condition, together with variable alkalin-
ity, may significantly compete with NOM scavenging HO●. A little bit later, Black
et al. [73] compared UV/H2O2 and ozonation of surface water focused on the
performance exhibited by a biofiltration unit (acclimatized biological activated
carbon) before and after the AOP treatment, finding significantly different results
regarding biodegradability of the final oxidized products. Straight oxidation on
source water investigated in this case did not preferentially react with the biode-
gradable or nonbiodegradable NOM. In addition, the type or dose of oxidation
applied did not affect the observed rate of biodegradation. Although the oxidation
prior to biofiltration increased the overall removal of organic matter, it did not
affect the rate of NOM biodegradation. Moreover, most outstanding conclusions
reached in this study regarding NOM and NOM intermediaries recording could be
86 J.H. Ramı́rez and L.A. Galeano

summarized as follows: (1) Ozonation preferentially reacted with higher molecular

weight chromophoric NOM. However, the reduction in high molecular weight
NOM did not appear to increase the biodegradability of the raw water. (2) Advanced
oxidation processes reacted with all molecular weight chromophoric NOM frac-
tions equally. (3) Neither ozonation nor AOP treatment with UV/H2O2 preferen-
tially reacted with either the biodegradable or the nonbiodegradable fractions of
organic matter. (4) Regardless of the oxidation condition applied, the rate of
biodegradation did not change. Therefore, and also according to the same authors,
such a set of final statements are very source-depending and contradicted results
reported by others, who suggested that AOP oxidation increases biodegradability
of NOM.
One of the main aspects speeding up research in NOM removal by advanced
oxidation technologies has been certainly to decrease occurrence of DBPs, espe-
cially THMs. THM generation can be limited by reducing the levels of NOM prior
to the chlorination step. It was recently reported that a solar photo-Fenton system
(total intensity of Suntest solar simulator, 600 W/m2; UV intensity 20–30 W/m2;
experiments performed at room temperature around 25  C, increased up to 30  C
during irradiation) degraded either humic acid solutions (as NOM model com-
pounds) or NOM contained in a river water, dramatically reducing THM formation
during the subsequent chlorination step under close to neutral pH of reaction
[74]. Whereas in non-pretreated river water, 100–160 μg/L of THMs was formed
upon chlorination, values of 20–60 μg/L were reported for water previously treated
through 4 h by neutral photo-Fenton under solar simulator in the presence of 1.0 mg
Fe/L as initial concentration. Undoubtedly, such a very low concentration of
dissolved iron could be one outstanding advantage of this solar photo-Fenton
system, since apparently it would not be too much susceptible against metal
precipitation in the strongly chelating environment provided by dissolved NOM.
It is noteworthy the peroxide concentration used in this study was around four times
the stoichiometric dosage required for full oxidation (calculated on the basis of
2.12 mg H2O2/L consumed per 1.0 mg COD/L as theoretical mass ratio reported by
Deng et al. for NOM dissolved in leachates of landfills when treated by the Fenton
process [75]; together, it must be assumed a ratio 3.33 mg COD/mg TOC
corresponding to own experimental results [76] obtained from a synthetic standard
resembling NOM composition in most surface and underground waters1). Although
highly source dependent, the use of a standard theoretical mass ratio COD/TOC for
NOM could be very useful in the purpose of unbiased comparison between results

1
Distribution of synthetic fractions in the NOM standard model solution (mass %):
1. Polyacrylic acid (PAA) (transphilic fraction; average MW, 130,000 Da), 20
2. Polystyrene sulfonate (PSS1) (hydrophobic fraction; average MW, 200,000 Da), 12.5
3. Polystyrene sulfonate (PSS2) (hydrophobic fraction; average MW, 1,000,000 Da), 12.5
4. Polygalacturonic acid (PGUA) (hydrophilic fraction; MW, 25,000–50,000 Da), 30
5. Humic acid (HA) (hydrophobic fraction; average MW, 1,000,000 Da), 25
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 87

of NOM degradation reported by several Fenton and AOP treatments, in the

presence of widely variable concentrations of H2O2.
From very different focus, some studies have stressed the role played by
dissolved NOM hindering targeted reactions and removal efficiency exhibited
by photocatalytic AOPs. Brame et al. [77] recently claimed the development of
an analytical model to account for various inhibition mechanisms in catalytic
AOPs, including competitive adsorption of inhibitors, scavenging of produced
ROS at the catalyst’s surface and in solution, and the inner filtering of the
excitation illumination, which combine to decrease ROS-mediated degradation,
in the case of the photocatalytic processes. Competitive adsorption by NOM and
ROS scavenging were found to be the most influential inhibitory mechanisms and
should be carefully taken into account in forthcoming studies mainly in hetero-
geneously activated photocatalytic AOPs. Among this kind of technologies, it was
very recently reported the removal of the NOM present in raw drinking water
(around 30 mg TOC/L) by coupling an optimized conventional coagulation-
flocculation process with heterogeneous photocatalysis (either TiO2-P25
suspended catalyst or TiO2-P25/β-SiC foam-supported material). It was claimed
that 80% of mineralization of humic substances was achieved after 220 min of
irradiation on the clarified water (7.8 mg TOC/L), effluent of the coagulation-
flocculation unit. According to the authors, the fraction remaining after the
photocatalytic tests was only the hydrophilic fraction of humic acids. The stability
tests of the supported catalyst with clarified water collected in treatment plant
showed a progressive deactivation due to adsorption of different ions coexisting
with humic substances, resulting in the decrease in catalyst efficiency.
Another interesting family of techniques recently reviewed as promising for
NOM removal from surface waters has been that of the electrochemical methods
like EC and EO [11]. Whereas in EC systems significant increase of NOM removal
rates can be achieved when combined with membrane filtration hybrid systems, in
EO technology electrolysis efficiency is strongly linked to electrode composition.
Efficiency could be increased by changing the reactor design, using commercial
electrodes and exploring the semiconducting properties of oxide mixtures. In this
purpose, particularly Boron-doped diamond (BDD) anodes have proved to be
effective in humic acid removal from aqueous solutions and potentially their total
mineralization.
Kasprzyk et al. [38] studied the NOM removal from water using catalytic
ozonation in the presence of Al2O3. The main purpose of the paper was to show
the potential of alumina for longer-term usage. Alumina found application in water
treatment technology mainly as an ion exchanger for the removal of inorganic
anions such as As, Se, and F. The usage of alumina as a support for active species,
mainly metal or metal oxides in the process of catalytic ozonation of several organic
compounds was also studied.
As so far showed, the assessment of the Fenton systems activated by either
homogeneous or heterogeneous catalysts has been more rather scarcely studied in
NOM removal. The Al/Fe-PILC-catalyzed CWPO removal of NOM from a raw
surface water employed as supply source in a drinking water treatment plant
88 J.H. Ramı́rez and L.A. Galeano

(pH around 7.5) was investigated in semi-batch lab-scale experiments [37]. It has
achieved full color removal in less than 45 min of reaction and 96% of COD
removal in 4 h of reaction for the best clay catalyst (5.0 g/L) under room temper-
ature (18  2  C) and atmospheric pressure (72 kPa). The clay catalyst displayed
high chemical stability against iron leaching even under a very high humic/catalyst
ratio, around 28 times more concentrated than surface water studied, and longtime
reaction (24 h). This kind of clay catalysts is very promising for this application at
real scale given their pretty low cost, since more than 90% in weight is constituted
by natural, widely available layered clay minerals. However, only one additional
study has been published in the past few years regarding the interaction between
humic substances and clay minerals [78]. The aim of the research was to investigate
the influence of montmorillonite as a representative clay mineral on the TiO2
photocatalytic removal of humic acids as model compound of NOM. The effect
of Mt was found to be proceeding through a dose-independent trend mainly
resulting in the humic structural changes rather than an efficient degree of miner-
alization. The molecular size distribution profiles displayed the formation of lower
molecular size fractions through oxidative degradation of higher molecular size
fractions. In comparison to the regular decreasing scheme attained for the specific
UV–Vis parameters of HA, the presence of Mt significantly altered the spectro-
scopic properties of the molecular size subfractions of HA. Therefore, in the field of
the Al/Fe-pillared clay-catalyzed CWPO degradation of NOM, an interesting
chapter in the short term should account for the degree of adsorption as well as to
realize if there is any molecular size and/or polar selectivity displayed by this type
of functional materials to adsorb typical fractions of NOM.

3.3 Other Solid Catalysts Used for NOM Removal

3.3.1 Zeolites

Zeolite-based materials are extremely versatile, and their main applications include
ion exchange resins, catalytic applications in the petroleum industry, separation
process, and as an adsorbent for water, carbon dioxide, and hydrogen sulfide.
Zeolites are the compounds of aluminosilicates and can be artificially synthesized
by reacting sodium aluminate with sodium silicate. The ratio of silica to the alumina
determines the type (X or Y) of the synthetic zeolite. The Y type of synthetic zeolite
is the most commonly applied type in preparation of heterogeneous catalysts
[79]. One way of producing heterogeneous catalyst from synthetic zeolite is by
impregnation of ferric ions followed by calcinations [80]. Another process is by the
ion exchange, for example, where the sodium in zeolite containing high sodium
content is replaced with ferric ions [79].
The synthetic zeolites have been used as heterogeneous catalytic materials for
CWPO treatment of wastewater, where high effectiveness was reported. For
instance, Arimi M. [39] studied the treatment of recalcitrants in industrial effluent
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 89

using a modified natural zeolite as heterogeneous Fenton catalyst. In this case the
effects of pH and temperature on heterogeneous Fenton were studied using the
modified catalysts. The catalysts showed the highest affectivity which achieved
removal of 90% of color and 60% of total organic carbon at 150 g/L pellet catalyst
dosage, 2,000 mg/L H2O2, and 25  C. The catalyst was also applied to pretreat the
raw molasses distillery wastewater and increased its biodegradability by 4%.
Probably even more remarkable was that heterogeneous Fenton with the same
catalyst improved biodegradability (BOD5/COD) of the anaerobic effluent from
0.07 to 0.55, making more feasible the reuse of the treated stream at least as dilution
fresh water for the input raw wastewater before conventional microbiological
treatment. The color of the resultant anaerobic effluent was also reduced. The
kinetics of total TOC removal was found to depend on operation temperature [39].

3.3.2 Fe-Functionalized Activated Carbon

Definitely one type of functional materials more investigated along the past decade
as active solids of the CWPO reaction has been that of the carbon-based ones.
Several motivations have prompted the scientific community toward the application
of hybrid magnetic carbon nanocomposites as catalytic materials for this still
emerging technology. The most relevant literature on this topic has been recently
reviewed by Ribeiro et al. [37], with a special focus on the synergies that can arise
from the combination of highly active and magnetically separable iron species with
the easily tuned properties of carbon-based materials. These are mainly ascribed to
increased adsorptive interactions, together with good structural stability and low
leaching levels of the metal species, as well as to increased regeneration and
dispersion of the active sites, which are promoted by the presence of the carbon-
based materials in the composites. According to the authors, the presence of stable
metal impurities, basic active sites, and sulfur-containing functionalities, as well as
high specific surface area, adequate porous texture, adsorptive interactions, and
structural defects, was shown to increase the CWPO activity of carbon materials,
while the presence of acidic oxygen-containing functionalities had the opposite
effect.
Some efforts in the purpose of giving added value to waste raw materials in
preparation of this kind of carbonaceous catalyst must be remarked. Sewage sludge
was in recent times used as precursor to prepare catalysts for CWPO by both simple
drying and pyrolysis [81]. Iron-functionalized biosolids (Fe/ABS) were obtained
from the dried biosolids, upon contact with aqueous solution of FeCl3 at several
concentrations followed by thermal treatment at 750  C for 30 min. The materials
displayed narrow developed microporosity, with total iron contents up to 9.3%
w/w. The catalysts showed a relatively high activity in the CWPO oxidation (80  C,
pH ¼ 3.0) of three target pollutants (phenol, bromophenol blue, and dimethoate),
allowing a high mineralization (65% TOC reduction for phenol and dimethoate). A
fairly good stability was observed in long-term continuous experiments where the
Fe leaching remained below 11% of the initial loading after 170 h on stream. More
90 J.H. Ramı́rez and L.A. Galeano

recently, highly stable iron on activated carbon catalysts was prepared by chemical
activation of dry sewage sludge with iron chloride at different mass ratios [82]. The
iron content of the resulting catalysts varied between 5.2 and 7.3%, and there was
developed porosity (BET specific surfaces above 800 m2/g). The catalysts were
tested batchwise in the CWPO of antipyrine (50  C), a recognized emergent
pollutant. Working with 500 mg/L of the best catalyst prepared, complete conver-
sion of antipyrine (20 mg/L) and almost 70% of TOC reduction were achieved in
1 h with the stoichiometric theoretical amount of H2O2. In spite that very soundly
results have been claimed in this area so far, metal stability remains being one of the
main drawbacks. In addition, the best results were reported under high tempera-
tures, pH or reaction very low and close to the Fenton’s optimal value (3.0), and
conditions easily reproduced at lab scale but still far for application on a real-scale
process where environmental conditions of reaction are mandatory (RT; natural pH,
being in general a circumneutral one).

3.3.3 Biologically Activated Carbon

The BAC treatment is one of the most promising, environmentally friendly, and
economically feasible processes. The BAC can overcome several limitations of AC
treatment and other conventional water treatment processes. The BAC uses the
highly porous AC as a medium to immobilize microorganisms and remove organic
matters present in water.
It is possible to substantially reduce the GAC replacement costs by implementing
a biofiltration process, where microbial activity on activated carbon possibly extends
GAC adsorption capacity via in situ regeneration of adsorption sites on the external
surface or in inner pores through the biodegradation of previously adsorbed organic
matter [83]. The BAC process combines both biosorption/sorption and biodegrada-
tion functions, providing many benefits for the water treatment. In this work [84],
DOC content in the influent and effluent ranged between 1.1–5.5 and 0.5–2.5 mg/L,
respectively, showing a good DOC removal (see Fig. 3).

3.3.4 Carbon Nanotubes

NA possesses a series of unique physical and chemical properties. A very important

one is that most of the atoms that have high chemical activity and adsorption
capacity are on the surface of the nanomaterials. CNTs have been at the center of
nanoscience and nanotechnology research for a variety of applications such as
adsorbents. The adsorption capacity and strength strongly depend on the type of
NOM and the type of CNT. Factors affecting adsorption have been reported to
include (1) size and chemical characteristics of NOM and (2) pore structure and
surface chemistry of CNT. Due to the polydisperse nature of NOM, various
fractions of NOM tend to have a different degree of adsorptive interactions with
the adsorbent. This preferential adsorption is reflected by the occurrence of dose-
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 91

6 100
5 80 Influent
DOC (mg/L)

% Removal
4
60
3 Effluent
40
2
Removal
1 20

0 0
0 60 120 180 240 300 360

t (d)

Fig. 3 Evolution of DOC concentration (mg/L) in the influent and effluent of the column and
removal percentage over the whole experiment. Vertical lines indicate dates of backwashing
events (reprinted from Gibert et al. [84], with permission of Elsevier)

a b c

Inner (internal) cavity

Inter-wall spaces

External surface

Fig. 4 Schematic structures of fullerene (a), single-walled carbon nanotubes (b), and multiwalled
carbon nanotubes (c), showing inner cavity, inter-wall spaces, and external surface. Fullerene
(C60) has only external surface (reprinted from Yang et al. [87], with permission of Elsevier)

dependent isotherm relationship. For example, the strongly adsorbable fraction of

NOM exhibits a more favorable adsorption at lower CNT dose.
Finally, NOM adsorption is affected by water quality parameters such as ionic
strength and pH which influence the charge and configuration of NOM. Specifi-
cally, the adsorption of negatively charged NOM to the activated carbon surface
generally increases as ionic strength increases and pH decreases [85].
NOM generally carries a negative charge in the natural environment, due to the
carboxylic and phenolic moieties distributed throughout the entire molecule
[86]. These physical and chemical characteristics of NOM are likely to be closely
related to the mechanism of NOM interaction with CNT. Compared to NOM
adsorption onto CNT, the mechanism of NOM adsorption onto activated carbon
is relatively well-known. A few characteristics of NOM interaction with activated
92 J.H. Ramı́rez and L.A. Galeano

carbon are noteworthy and might be helpful for interpretation of CNT-NOM

interaction.
Differences between activated carbon and CNT also need to be recognized for
the proper interpretation of CNT-NOM adsorption phenomena. The activated
carbon consists of micropores with different sizes which provide sites for NOM
adsorption. CNT in contrast provides adsorption sites only along the surface of a
cylindrical structure; see Fig. 4 [87].

4 Conclusions

Removal of NOM and other synthetic surrogates by several AOPs, focused in the
Fenton-like, heterogeneous CWPO, has been critically reviewed. Main advances
achieved along the past few years by these still emerging technologies have mainly
focused on increasing the removal efficiency, not only in terms of color and TOC
but also in the aromatic content, under the lower possible temperature. Moreover,
several efforts are still to be made in order to unify the information about the
amount of H2O2 as oxidizing agent employed per unit of concentration of NOM,
preferably in terms of stoichiometric loading against some widely accepted refer-
ence; a standard model synthetic solution is proposed for. In addition, recording of
molecular weight distribution is also strongly advised in order to get better corre-
lation between mineralization and changes in polar and size of NOM intermediaries
and by-products.
Several types of solid materials have been studied in order to more efficiently
catalyze the heterogeneous activation of the oxidizing agent (higher removal of
organics through as low as possible either H2O2 consumption or temperature of
reaction, under real-water pH values, typically circumneutral): being prepared from
low-cost, widely available clay minerals, Al/Cu- but mainly Al/Fe-pillared clays
have shown to gather in a great extent such a challenging set of features, but their
preparation process must be first seriously intensified before getting proper appli-
cations in real-scale water treatment. Some naturally occurring minerals have lately
shown good rates of reaction but under still high temperatures (e.g., >50  C).
Regarding this type of materials, Fe-functionalized allophane showed interesting
activity in phenol degradation at 40  C with outstanding stability of the active metal
against leaching in comparison to many other supported catalysts reported so far in
the literature for this reaction.
Some zeolites and carbon-based materials are extremely versatile and have been
used as heterogeneous catalytic materials for CWPO treatment of wastewater. In
particular, functional materials, biologically activated carbon, and carbon nanotubes
were used as active solids of the CWPO reaction with a special focus on NOM
removal showing higher efficiencies of reaction.
Finally, in the future several integrated technologies will be used to remove
NOM from supply water, including nanofiltration membranes, coagulation with
subsequent floc separation, and CWPO followed by biofiltration and sorption
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 93

processes (chemisorption and physical adsorption). The evolution of water-related

normativity and progressively more restrictive standards for drinking water, how-
ever, will seek the research of advanced, more efficient, and cost-effective water
treatment processes.

Acknowledgment Financial support from CWPO Project for enhanced drinking water in Nari~
no
(BPIN 2014000100020), CT&I Fund of SGR, Colombia, is kindly acknowledged.

References

1. Sadiq R, Rodriguez MJ (2004) Disinfection by-products (DBPs) in drinking water and

predictive models for their occurrence: a review. Sci Total Environ 321(1–3):21–46. https://
doi.org/10.1016/j.scitotenv.2003.05.001
2. Meylan S, Hammes F, Traber J, Salhi E, von Gunten U, Pronk W (2007) Permeability of low
molecular weight organics through nanofiltration membranes. Water Res 41(17):3968–3976.
https://doi.org/10.1016/j.watres.2007.05.031
3. de Ridder DJ, Verliefde AR, Heijman SG, Verberk JQ, Rietveld LC, van der Aa LT, Amy GL,
van Dijk JC (2011) Influence of natural organic matter on equilibrium adsorption of neutral
and charged pharmaceuticals onto activated carbon. Water Sci Technol 63(3):416–423. https://
doi.org/10.2166/wst.2011.237
4. Matilainen A, Sillanpaa M (2010) Removal of natural organic matter from drinking water by
advanced oxidation processes. Chemosphere 80(4):351–365. https://doi.org/10.1016/j.
chemosphere.2010.04.067
5. Werner S (1992) Chemistry of the solid-water interface. Wiley, New York
6. Bhatnagar A, Sillanpaa M (2017) Removal of natural organic matter (NOM) and its constit-
uents from water by adsorption – a review. Chemosphere 166:497–510. https://doi.org/10.
1016/j.chemosphere.2016.09.098
7. Li Q, Snoeyink VL, Mari~aas BJ, Campos C (2003) Elucidating competitive adsorption
mechanisms of atrazine and NOM using model compounds. Water Res 37(4):773–784.
https://doi.org/10.1016/S0043-1354(02)00390-1
8. Gauden PA, Szmechtig-Gauden E, Rychlicki G, Duber S, Garbacz JK, Buczkowski R (2006)
Changes of the porous structure of activated carbons applied in a filter bed pilot operation. J
Colloid Interface Sci 295(2):327–347. https://doi.org/10.1016/j.jcis.2005.08.039
9. Kim J, Kang B (2008) DBPs removal in GAC filter-adsorber. Water Res 42(1–2):145–152.
https://doi.org/10.1016/j.watres.2007.07.040
10. Sorlini S, Biasibetti M, Collivignarelli MC, Crotti BM (2015) Reducing the chlorine dioxide
demand in final disinfection of drinking water treatment plants using activated carbon. Environ
Technol 36(9-12):1499–1509. https://doi.org/10.1080/09593330.2014.994043
11. Särkkä H, Vepsäläinen M, Sillanpää M (2015) Natural organic matter (NOM) removal by
electrochemical methods – a review. J Electroanal Chem 755:100–108. https://doi.org/10.
1016/j.jelechem.2015.07.029
12. Kimura M, Matsui Y, Kondo K, Ishikawa TB, Matsushita T, Shirasaki N (2013) Minimizing
residual aluminum concentration in treated water by tailoring properties of polyaluminum
coagulants. Water Res 47(6):2075–2084. https://doi.org/10.1016/j.watres.2013.01.037
13. Jiang J-Q, Wang H-Y (2009) Comparative coagulant demand of polyferric chloride and ferric
chloride for the removal of humic acid. Sep Sci Technol 44(2):386–397. https://doi.org/10.
1080/01496390802590020
14. Cheng Y-L, Wong R-J, Lin JC-T, Huang C, Lee D-J, Mujumdar AS (2010) Water coagulation
using electrostatic patch coagulation (EPC) mechanism. Drying Technol 28(7):850–857.
https://doi.org/10.1080/07373937.2010.490492
94 J.H. Ramı́rez and L.A. Galeano

15. Hai FI, Yamamoto K, Fukushi K (2007) Hybrid treatment systems for dye wastewater. Crit
Rev Environ Sci Technol 37(4):315–377. https://doi.org/10.1080/10643380601174723
16. Edzwald JK (1993) Coagulation in drinking water treatment: particles, organics and coagu-
lants. Water Sci Technol 27(11):21–35
17. Jiang JQ, Graham NJD (1996) Enhanced coagulation using Al/Fe(III) coagulants: effect of
coagulant chemistry on the removal of colour-causing NOM. Environ Technol 17(9):937–950.
https://doi.org/10.1080/09593330.1996.9618422
18. Ghernaout D, Ghernaout B, Kellil A (2012) Natural organic matter removal and enhanced
coagulation as a link between coagulation and electrocoagulation. Desalin Water Treat 2
(1-3):203–222. https://doi.org/10.5004/dwt.2009.116
19. Ghernaout D (2014) The hydrophilic/hydrophobic ratio vs. dissolved organics removal by
coagulation – a review. J King Saud Univ Sci 26(3):169–180. https://doi.org/10.1016/j.jksus.
2013.09.005
20. Bukhari AA (2008) Investigation of the electro-coagulation treatment process for the removal
of total suspended solids and turbidity from municipal wastewater. Bioresour Technol 99
(5):914–921. https://doi.org/10.1016/j.biortech.2007.03.015
21. Zodi S, Merzouk B, Potier O, Lapicque F, Leclerc J-P (2013) Direct red 81 dye removal by a
continuous flow electrocoagulation/flotation reactor. Sep Purif Technol 108:215–222. https://
doi.org/10.1016/j.seppur.2013.01.052
22. El-Naas MH, Al-Zuhair S, Al-Lobaney A, Makhlouf S (2009) Assessment of
electrocoagulation for the treatment of petroleum refinery wastewater. J Environ Manage 91
(1):180–185. https://doi.org/10.1016/j.jenvman.2009.08.003
23. Glaze WH, Kang J-W, Chapin DH (1987) The chemistry of water treatment processes
involving ozone, hydrogen peroxide and ultraviolet radiation. Ozone Sci Eng 9(4):335–352.
https://doi.org/10.1080/01919518708552148
24. Andreozzi R, Caprio V, Insola A, Marotta R (1999) Advanced oxidation processes (AOP) for
water purification and recovery. Catal Today 53(1):51–59
25. Benı́tez FJ, Beltrán-Heredia J, Acero JL, Pinilla ML (1997) Ozonation kinetics of phenolic
acids present in wastewaters from olive oil mills. Ind Eng Chem Res 36(3):638–644
26. Casero I, Sicilia D, Rubio S, Pérez-Bendito D (1997) Chemical degradation of aromatic
amines by Fenton’s reagent. Water Res 31(8):1985–1995. https://doi.org/10.1016/S0043-
1354(96)00344-2
27. Bigda RJ (1995) Consider Fenton’s chemistry for wastewater treatment. Chem Eng Prog
62–66
28. Safarzadeh-Amiri A, Bolton JR, Cater SR (1996) The use of iron in advanced oxidation
processes. J Adv Oxid Technol 1(1). https://doi.org/10.1515/jaots-1996-0105
29. Pignatello JJ, Liu D, Huston P (1999) Evidence for an additional oxidant in the photoassisted
Fenton reaction. Environ Sci Technol 33(11):1832–1839. https://doi.org/10.1021/es980969b
30. Schoonen MAA, Xu Y, Strongin DR (1998) An introduction to geocatalysis. J Geochem
Explor 62(1–3):201–215
31. Sillanpää M (2014) Natural organic matter in water: characterization and treatment methods.
doi: https://doi.org/10.1016/C2013-0-19213-6
32. Cehovin M, Medic A, Scheideler J, Mielcke J, Ried A, Kompare B, Zgajnar Gotvajn A (2017)
Hydrodynamic cavitation in combination with the ozone, hydrogen peroxide and the
UV-based advanced oxidation processes for the removal of natural organic matter from
drinking water. Ultrason Sonochem 37:394–404. https://doi.org/10.1016/j.ultsonch.2017.01.
036
33. Gregory J, Dhond RV (1972) Anion exchange equilibria involving phosphate, sulphate and
chloride. Water Res 6(6):695–702. https://doi.org/10.1016/0043-1354(72)90184-4
34. Clarizia L, Russo D, Di Somma I, Marotta R, Andreozzi R (2017) Homogeneous photo-Fenton
processes at near neutral pH: a review. Appl Catal Environ 209:358–371. https://doi.org/10.
1016/j.apcatb.2017.03.011
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 95

35. Tatibouët J-M, Guélou E, Fournier J (2005) Catalytic oxidation of phenol by hydrogen
peroxide over a pillared clay containing iron. Active species and pH effect. Top Catal 33
(1–4):225–232. https://doi.org/10.1007/s11244-005-2531-3
36. Debellefontaine H, Chakchouk M, Foussard JN, Tissot D, Striolo P (1996) Treatment of
organic aqueous wastes: wet air oxidation and wet peroxide oxidation. Environ Pollut 92
(2):155–164. https://doi.org/10.1016/0269-7491(95)00100-X
37. Ribeiro RS, Silva AMT, Figueiredo JL, Faria JL, Gomes HT (2016) Catalytic wet peroxide
oxidation: a route towards the application of hybrid magnetic carbon nanocomposites for the
degradation of organic pollutants. A review. Appl Catal Environ 187:428–460. https://doi.org/
10.1016/j.apcatb.2016.01.033
38. Kasprzyk-Hordern B, Raczyk-Stanisławiak U, Świetlik J, Nawrocki J (2006) Catalytic ozon-
ation of natural organic matter on alumina. Appl Catal Environ 62(3–4):345–358. https://doi.
org/10.1016/j.apcatb.2005.09.002
39. Arimi MM (2017) Modified natural zeolite as heterogeneous Fenton catalyst in treatment of
recalcitrants in industrial effluent. Prog Nat Sci Mater Int 27(2):275–282. https://doi.org/10.
1016/j.pnsc.2017.02.001
40. de Ridder DJ, Verberk JQJC, Heijman SGJ, Amy GL, van Dijk JC (2012) Zeolites for
nitrosamine and pharmaceutical removal from demineralised and surface water: Mechanisms
and efficacy. Sep Purif Technol 89:71–77. https://doi.org/10.1016/j.seppur.2012.01.025
41. Chen C, Apul OG, Karanfil T (2017) Removal of bromide from surface waters using silver
impregnated activated carbon. Water Res 113:223–230. https://doi.org/10.1016/j.watres.2017.
01.019
42. Galeano L-A, Vicente MÁ, Gil A (2014) Catalytic degradation of organic pollutants in
aqueous streams by mixed Al/M-pillared clays (M ¼ Fe, Cu, Mn). Catal Rev 56
(3):239–287. https://doi.org/10.1080/01614940.2014.904182
43. Galeano LA, Bravo PF, Luna CD, Vicente MÁ, Gil A (2012) Removal of natural organic
matter for drinking water production by Al/Fe-PILC-catalyzed wet peroxide oxidation: effect
of the catalyst preparation from concentrated precursors. Appl Catal Environ
111–112:527–535. https://doi.org/10.1016/j.apcatb.2011.11.004
44. Munoz M, de Pedro ZM, Menendez N, Casas JA, Rodriguez JJ (2013) A ferromagnetic
γ-alumina-supported iron catalyst for CWPO. Application to chlorophenols. Appl Catal
Environ 136–137:218–224. https://doi.org/10.1016/j.apcatb.2013.02.002
45. Garcia-Costa AL, Zazo JA, Rodriguez JJ, Casas JA (2017) Microwave-assisted catalytic wet
peroxide oxidation. Comparison of Fe catalysts supported on activated carbon and γ-alumina.
Appl Catal Environ 218:637–642. https://doi.org/10.1016/j.apcatb.2017.06.058
46. Xiang L, Royer S, Zhang H, Tatibouet JM, Barrault J, Valange S (2009) Properties of iron-
based mesoporous silica for the CWPO of phenol: a comparison between impregnation and
co-condensation routes. J Hazard Mater 172(2–3):1175–1184. https://doi.org/10.1016/j.
jhazmat.2009.07.121
47. Zhong X, Barbier J, Duprez D, Zhang H, Royer S (2012) Modulating the copper oxide
morphology and accessibility by using micro
/mesoporous SBA-15 structures as host sup-
port: effect on the activity for the CWPO of phenol reaction. Appl Catal Environ
121–122:123–134. https://doi.org/10.1016/j.apcatb.2012.04.002
48. Barrault J, Bouchoule C, Echachoui K, Frini-Srasra N, Trabelsi M, Bergaya F (1998) Catalytic
wet peroxide oxidation (CWPO) of phenol over mixed (Al-Cu)-pillared clays. Appl Catal
Environ 15(3–4):269–274. https://doi.org/10.1016/S0926-3373(97)00054-4
49. Barrault J, Tatibouët JM, Papayannakos N (2000) Catalytic wet peroxide oxidation of phenol
over pillared clays containing iron or copper species. C R Acad Sci Ser IIc Chem 3
(10):777–783
50. Carriazo J, Guelou E, Barrault J, Tatibouet JM, Molina R, Moreno S (2005) Catalytic wet
peroxide oxidation of phenol by pillared clays containing Al-Ce-Fe. Water Res 39
(16):3891–3899. https://doi.org/10.1016/j.watres.2005.06.034
96 J.H. Ramı́rez and L.A. Galeano

51. Timofeeva MN, Khankhasaeva ST, Talsi EP, Panchenko VN, Golovin AV, Dashinamzhilova
ET, Tsybulya SV (2009) The effect of Fe/Cu ratio in the synthesis of mixed Fe, Cu, Al-clays
used as catalysts in phenol peroxide oxidation. Appl Catal Environ 90(3–4):618–627. https://
doi.org/10.1016/j.apcatb.2009.04.024
52. Galeano LA, Gil A, Vicente MA (2010) Effect of the atomic active metal ratio in Al/Fe-,
Al/Cu- and Al/(Fe–Cu)-intercalating solutions on the physicochemical properties and catalytic
activity of pillared clays in the CWPO of methyl orange. Appl Catal Environ 100
(1–2):271–281. https://doi.org/10.1016/j.apcatb.2010.08.003
53. Khankhasaeva S, Dambueva DV, Dashinamzhilova E, Gil A, Vicente MA, Timofeeva MN
(2015) Fenton degradation of sulfanilamide in the presence of Al, Fe-pillared clay: catalytic
behavior and identification of the intermediates. J Hazard Mater 293:21–29. https://doi.org/10.
1016/j.jhazmat.2015.03.038
54. Guélou E, Barrault J, Fournier J, Tatibouët JM (2003) Active iron species in the catalytic wet
peroxide oxidation of phenol over pillared clays containing iron. Appl Catal Environ 44
(1):1–8. https://doi.org/10.1016/S0926-3373(03)00003-1
55. Banković P, Milutinović-Nikolić A, Mojović Z, Jović-Jovičić N, Žunić M, Dondur V,
Jovanović D (2012) Al, Fe-pillared clays in catalytic decolorization of aqueous tartrazine
solutions. Appl Clay Sci 58:73–78. https://doi.org/10.1016/j.clay.2012.01.015
56. Banković P, Milutinović-Nikolić A, Mojović Z, Jović-Jovičić N, Perović M, Spasojević V,
Jovanović D (2013) Synthesis and characterization of bentonites rich in beidellite with
incorporated Al or Al–Fe oxide pillars. Microporous Mesoporous Mater 165:247–256.
https://doi.org/10.1016/j.micromeso.2012.08.029
57. Zhou S, Zhang C, Hu X, Wang Y, Xu R, Xia C, Zhang H, Song Z (2014) Catalytic wet
peroxide oxidation of 4-chlorophenol over Al-Fe-, Al-Cu-, and Al-Fe-Cu-pillared clays:
sensitivity, kinetics and mechanism. Appl Clay Sci 95:275–283. https://doi.org/10.1016/j.
clay.2014.04.024
58. Carriazo J, Guélou E, Barrault J, Tatibouët JM, Molina R, Moreno S (2005) Synthesis of
pillared clays containing Al, Al-Fe or Al-Ce-Fe from a bentonite: characterization and
catalytic activity. Catal Today 107–108:126–132. https://doi.org/10.1016/j.cattod.2005.07.157
59. Sanabria NR, Centeno MA, Molina R, Moreno S (2009) Pillared clays with Al–Fe and Al–Ce–
Fe in concentrated medium: synthesis and catalytic activity. Appl Catal A Gen 356
(2):243–249. https://doi.org/10.1016/j.apcata.2009.01.013
60. Gao H, Zhao B-X, Luo J-C, Wu D, Ye W, Wang Q, Zhang X-L (2014) Fe–Ni–Al pillared
montmorillonite as a heterogeneous catalyst for the catalytic wet peroxide oxidation degrada-
tion of orange acid II: preparation condition and properties study. Microporous Mesoporous
Mater 196:208–215. https://doi.org/10.1016/j.micromeso.2014.05.014
61. Pizarro AH, Molina CB, Munoz M, de Pedro ZM, Menendez N, Rodriguez JJ (2017)
Combining HDC and CWPO for the removal of p-chloro-m-cresol from water under
ambient-like conditions. Appl Catal Environ 216:20–29. https://doi.org/10.1016/j.apcatb.
2017.05.052
62. Fetter G, Hernández V, Rodrı́guez V, Valenzuela MA, Lara VH, Bosch P (2003) Effect of
microwave irradiation time on the synthesis of zirconia-pillared clays. Mater Lett 57
(5–6):1220–1223
63. Sanabria NR, Ávila P, Yates M, Rasmussen SB, Molina R, Moreno S (2010) Mechanical and
textural properties of extruded materials manufactured with AlFe and AlCeFe pillared ben-
tonites. Appl Clay Sci 47(3-4):283–289. https://doi.org/10.1016/j.clay.2009.11.029
64. Kooli F (2013) Pillared montmorillontes from unusual antiperspirant aqueous solutions:
characterization and catalytic tests. Microporous Mesoporous Mater 167:228–236. https://
doi.org/10.1016/j.micromeso.2012.09.012
65. Salerno P, Mendioroz S (2002) Preparation of Al-pillared montmorillonite from concentrated
dispersions. Appl Clay Sci 22(3):115–123. https://doi.org/10.1016/S0169-1317(02)00133-3
Natural Organic Matter Removal by Heterogeneous Catalytic Wet Peroxide. . . 97

66. Yan Y, Jiang S, Zhang H (2014) Efficient catalytic wet peroxide oxidation of phenol over
Fe-ZSM-5 catalyst in a fixed bed reactor. Sep Purif Technol 133:365–374. https://doi.org/10.
1016/j.seppur.2014.07.014
67. Munoz M, Domı́nguez P, de Pedro ZM, Casas JA, Rodriguez JJ (2017) Naturally-occurring
iron minerals as inexpensive catalysts for CWPO. Appl Catal Environ 203:166–173. https://
doi.org/10.1016/j.apcatb.2016.10.015
68. Garrido-Ramirez EG, Sivaiah MV, Barrault J, Valange S, Theng BKG, Ureta-Za~ nartu MS,
Mora ML (2012) Catalytic wet peroxide oxidation of phenol over iron or copper oxide-
supported allophane clay materials: influence of catalyst SiO2/Al2O3 ratio. Microporous
Mesoporous Mater 162:189–198. https://doi.org/10.1016/j.micromeso.2012.06.038
69. Garrido-Ramı́rez EG, Theng BKG, Mora ML (2010) Clays and oxide minerals as catalysts and
nanocatalysts in Fenton-like reactions – a review. Appl Clay Sci 47(3–4):182–192. https://doi.
org/10.1016/j.clay.2009.11.044
70. Ayekoe CYP, Robert D, Lanciné DG (2017) Combination of coagulation-flocculation and
heterogeneous photocatalysis for improving the removal of humic substances in real treated
water from Agbô River (Ivory-Coast). Catal Today:281:2–28113. https://doi.org/10.1016/j.
cattod.2016.09.024
71. González O, Justo A, Bacardit J, Ferrero E, Malfeito JJ, Sans C (2013) Characterization and
fate of effluent organic matter treated with UV/H2O2 and ozonation. Chem Eng J
226:402–408. https://doi.org/10.1016/j.cej.2013.04.066
72. Bazri MM, Barbeau B, Mohseni M (2012) Impact of UV/H(2)O(2) advanced oxidation
treatment on molecular weight distribution of NOM and biostability of water. Water Res 46
(16):5297–5304. https://doi.org/10.1016/j.watres.2012.07.017
73. Black KE, Berube PR (2014) Rate and extent NOM removal during oxidation and biofiltration.
Water Res 52:40–50. https://doi.org/10.1016/j.watres.2013.12.017
74. Moncayo-Lasso A, Rincon A-G, Pulgarin C, Benitez N (2012) Significant decrease of THMs
generated during chlorination of river water by previous photo-Fenton treatment at near neutral
pH. J Photochem Photobiol A Chem 229(1):46–52. https://doi.org/10.1016/j.jphotochem.
2011.12.001
75. Deng Y, Englehardt JD (2006) Treatment of landfill leachate by the Fenton process. Water Res
40(20):3683–3694. https://doi.org/10.1016/j.watres.2006.08.009
76. Garcı́a AM, Torres R, Galeano LA (2018) RSM optimization of the Al/Fe-pillared clay activated
CWPO degradation of natural organic matter (NOM). Environ Sci Pollut Res. In preparation
77. Brame J, Long M, Li Q, Alvarez P (2015) Inhibitory effect of natural organic matter or other
background constituents on photocatalytic advanced oxidation processes: mechanistic model
development and validation. Water Res 84:362–371. https://doi.org/10.1016/j.watres.2015.07.
044
78. Sen Kavurmaci S, Bekbolet M (2013) Photocatalytic degradation of humic acid in the presence
of montmorillonite. Appl Clay Sci 75–76:60–66. https://doi.org/10.1016/j.clay.2013.03.006
79. Rache ML, Garcı́a AR, Zea HR, Silva AMT, Madeira LM, Ramı́rez JH (2014) Azo-dye orange
II degradation by the heterogeneous Fenton-like process using a zeolite Y-Fe catalyst –
kinetics with a model based on the Fermi’s equation. Appl Catal Environ 146:192–200.
https://doi.org/10.1016/j.apcatb.2013.04.028
80. Noorjahan M, Durga Kumari V, Subrahmanyam M, Panda L (2005) Immobilized Fe(III)-HY:
an efficient and stable photo-Fenton catalyst. Appl Catal Environ 57(4):291–298. https://doi.
org/10.1016/j.apcatb.2004.11.006
81. Mohedano AF, Monsalvo VM, Bedia J, Lopez J, Rodriguez JJ (2014) Highly stable iron
catalysts from sewage sludge for CWPO. J Environ Chem Eng 2(4):2359–2364. https://doi.
org/10.1016/j.jece.2014.01.021
82. Bedia J, Monsalvo VM, Rodriguez JJ, Mohedano AF (2017) Iron catalysts by chemical
activation of sewage sludge with FeCl3 for CWPO. Chem Eng J 318:224–230. https://doi.
org/10.1016/j.cej.2016.06.096
98 J.H. Ramı́rez and L.A. Galeano

83. Kim WH, Nishijima W, Baes AU, Okada M (1997) Micropollutant removal with saturated
biological activated carbon (BAC) in ozonation-BAC process. Water Sci Technol 36
(12):283–298. https://doi.org/10.1016/S0273-1223(97)00722-1
84. Gibert O, Lefevre B, Fernandez M, Bernat X, Paraira M, Calderer M, Martinez-Llado X (2013)
Characterising biofilm development on granular activated carbon used for drinking water
production. Water Res 47(3):1101–1110. https://doi.org/10.1016/j.watres.2012.11.026
85. Hyung H, Kim JH (2008) Natural organic matter (NOM) adsorption to multi-walled carbon
nanotubes: effect of NOM characteristics and water quality parameters. Environ Sci Technol
42(12):4416–4421. https://doi.org/10.1021/es702916h
86. Summers RSRP (1988) Activated carbon adsorption of humic substances. 2. Size exclusion
and electrostatic interactions. J Colloid Interface Sci 122:382–397
87. Yang K, Xing B (2007) Desorption of polycyclic aromatic hydrocarbons from carbon
nanomaterials in water. Environ Pollut 145(2):529–537. https://doi.org/10.1016/j.envpol.
2006.04.020
Separation and Characterization of NOM
Intermediates Along AOP Oxidation

Ana-Marı́a Garcı́a, Ricardo A. Torres-Palma, Luis Alejandro Galeano,

Miguel Ángel Vicente, and Antonio Gil

Abstract Removal of natural organic matter (NOM) in drinking water treatment

systems has been a matter of thorough study in recent years. NOM affects organ-
oleptic properties of water and causes membrane fouling; it may act as energy
source for microorganisms in distribution systems and leads to the formation of
undesired disinfection by-products through its interaction with chlorine. Currently
the role played by advanced oxidation processes in the removal of NOM has gained

A.-M. Garcı́a
Grupo de Investigación en Materiales Funcionales y Catálisis (GIMFC), Departamento de
Quı́mica, Facultad de Ciencias Exactas y Naturales, Universidad de Nari~no, Pasto, Colombia
Grupo de Investigación en Remediación Ambiental y Biocatálisis (GIRAB), Instituto de
Quı́mica, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia – UdeA,
Medellı́n, Colombia
e-mail: [email protected]; [email protected]
R.A. Torres-Palma (*)
Grupo de Investigación en Remediación Ambiental y Biocatálisis (GIRAB), Instituto de
Quı́mica, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia – UdeA,
Medellı́n, Colombia
e-mail: [email protected]
L.A. Galeano
Grupo de Investigación en Materiales Funcionales y Catálisis (GIMFC), Departamento de
Quı́mica, Facultad de Ciencias Exactas y Naturales, Universidad de Nari~no, Pasto, Colombia
e-mail: [email protected]
M.Á. Vicente
GIR-QUESCAT, Departamento de Quı́mica Inorgánica, Universidad de Salamanca,
Salamanca, Spain
e-mail: [email protected]
A. Gil
Departamento de Quı́mica Aplicada, Edificio de los Acebos, Universidad Pública de Navarra,
Pamplona, Spain
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 99

Water Treatment, Hdb Env Chem (2019) 67: 99–132, DOI 10.1007/698_2017_128,
© Springer International Publishing AG 2017, Published online: 9 December 2017
100 A.-M. Garcı́a et al.

great interest; understanding the composition and behaviour of NOM throughout

such a kind of processes may allow to get significant insight in order to improve
efficiency. In this chapter the main techniques useful for characterization are
described, and their use to investigate the changes undergone by NOM throughout
several AOPs has been reviewed.

Keywords AOP, NOM characterization, NOM intermediates, NOM oxidation,

NOM separation

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
2 Separation of NOM and NOM Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.1 Fractionation by Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.2 Reversed-Phase Chromatography (RP-LC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.3 Size-Exclusion Chromatography (LC-SEC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
3 Characterization of NOM Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.1 Ultraviolet Spectroscopy (UV-Vis) and SUVA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.2 Total Organic Carbon (TOC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.3 Fourier Transform Infrared (FT-IR) Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
3.4 Fluorescence Excitation/Emission Matrix (FEEM) Spectroscopy . . . . . . . . . . . . . . . . . . 110
3.5 Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass
Spectrometry (ESI-FT-ICR-MS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4 Oxidation of NOM Through AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.1 Ozone-Based Applications: O3/H2O2 and O3/UV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.2 UV Light-Based Applications: UV/H2O2 and UV/Cl2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.3 Fenton, Photo-Fenton and Fenton-Like Catalysed Processes . . . . . . . . . . . . . . . . . . . . . . . 122
4.4 Heterogeneous Photocatalysis: TiO2/UV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.5 Ultrasound-Based Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129

Abbreviations

AMW Apparent molecular weight distribution

AOPs Advanced oxidation processes
BA Benzoic acid
CAS Conventional activated sludge
C-DBPs Carbonaceous disinfection by-products
CDOM Coloured dissolved organic matter
COD Chemical oxygen demand
DOC Dissolved organic carbon (mg C/L)
DOM Dissolved organic matter
DPBs Disinfection by-products
ESI-FT-ICR- Electrospray ionization Fourier transform ion cyclotron resonance mass
MS spectrometry
FA Fulvic acids
FEEM Fluorescence excitation/emission matrix
Separation and Characterization of NOM Intermediates Along AOP Oxidation 101

FFA Furfuryl alcohol

FT-IR Fourier transform infrared spectroscopy
GC-MS Gas chromatography-mass spectrometry
HA Humic acids
HAAs Haloacetic acids
HMW High molecular weight
HPI Hydrophilic fraction
HPI-A Hydrophilic acids
HPI-B Hydrophilic bases
HPI-N Hydrophilic neutrals
HPO Hydrophobic fraction
HPO-A Hydrophobic acids
HPO-B Hydrophobic bases
HPO-N Hydrophobic neutrals
HS Humic substances
LC-OCD Liquid chromatography-organic carbon detection
LC-SEC Size-exclusion liquid chromatography
LC-UVD Liquid chromatography-ultraviolet detection
LMW Low molecular weight
MBR Membrane biological reactor
Mt Montmorillonite
MTBE Methyl tert-butyl ether
MW Molecular weight
N-DBPs Nitrogenous disinfection by-products
NMR Nuclear magnetic resonance spectroscopy
NOM Natural organic matter
NPOC Non-purgeable organic carbon
OCD Organic carbon detector
PCU Platinum-cobalt units
PFBHA Pentafluorobenzyl hydroxylamine hydrochloride
PS Persulphate
PSS Polystyrene sulphonate
RCSs Reactive chlorine species
RID Refractive index detector
ROS Reactive oxygen species
RP Reversed-phase liquid chromatography
RT Room temperature
SEC Size-exclusion chromatography
SHA Slightly hydrophobic acid fraction
SUVA Specific UV absorbance (L/mg m)
THMs Trihalomethanes
TOC Total organic carbon (mg C/L)
TPI Transphilic fraction
US Ultrasound
UV Ultraviolet
UV254 UV absorbance at 254 nm (m
1)
UVD Ultraviolet detector
UV-Vis Ultraviolet visible
VHA Very hydrophobic acid fraction
102 A.-M. Garcı́a et al.

1 Introduction

Natural organic matter (NOM) is a complex mixture of particulate components,

about 10% of the carbon present in water [1], and soluble fractions varying
significantly from one source to another [2]. The origin of NOM in both fresh and
salt waters comes from natural processes in the environment, including the run-off
leading to larger export of organic material from the terrestrial system, soil organic
matter decomposition (allochthonous) and algal metabolic reactions (autochtho-
nous) [3, 4]. As a consequence, NOM is a heterogeneous mixture of substances with
wide ranges of molecular sizes, reactivity and chemical functionalities [5, 6]
oscillating from large aliphatic chains (mainly hydroxylated, carbonyl and carbox-
ylic acids) to highly coloured aromatics [7]. NOM can be divided into humic and
non-humic substances: the humic substances, humic and fulvic acids, represent
residual degradation products, and the non-humic ones include lignins and deriv-
atives, tannins, carbohydrates, peptides and proteins, amino acids, aromatic acids
and phenols, carboxylic acids and miscellaneous compounds [8].
When NOM is filtered through 0.45 μm porous membranes, dissolved organic
matter (DOM) is obtained [7], which is commonly represented by the amount of
dissolved organic carbon (DOC) in solution. The humic substances being hydro-
phobic compounds are the major constituents of NOM, in general reaching approx-
imately 50% of DOC, represented mainly in humic acids usually including a large
number of aromatic carbons, phenolic structures and conjugated double bonds
[9]. The hydrophilic fraction is about 25–40% of DOC composed by non-humic
substances [3] that include a high proportion of aliphatic carbons and nitrogen
compounds, such as carbohydrates, proteins, sugars and amino acids (Fig. 1)
[11]. Finally, the transphilic fraction represents approximately 25% of the DOC.
This distribution, however, may vary far and wide from one water source to
another.
NOM has been lately found to increase in many surface waters, and particularly
it has been evidenced for its coloured fraction [7]. As a result, nowadays NOM can
seriously affect the organoleptic properties of water (colour, taste and odour) [12],

Fig. 1 Average distribution

of NOM fractions present in
surface waters based on
dissolved organic carbon.
Reproduced with
permission of the Korean
Society of Environmental
Engineers [10]
Separation and Characterization of NOM Intermediates Along AOP Oxidation 103

increase the required doses of coagulant and disinfectant agents in drinking water
plants, promote bacterial growth in distribution systems and increase levels of
heavy metals and adsorbed organic pollutants [13, 14]. In addition, NOM blocks
porosity and strives for sites during adsorption processes [15], imposing either
continuous regeneration of filters based on activated carbon or cleaning of mem-
brane surfaces [7]. Furthermore, during the chlorine disinfection process, it may
react with natural organic matter to form carcinogenic disinfection by-products
(DPBs) [16]. Two prevalent groups of DPBs are regulated in Canada and the United
States: trihalomethanes (THMs) and haloacetic acids (HAAs). The US Environ-
mental Protection Agency (US EPA) has defined maximum acceptable levels of
THMs as 80 and 60 μg/L for the five most common HAAs (HAA5) [17]. Therefore,
it is very important to control and limit NOM content in water supplies for drinking
water production in order to decrease the potential formation of DBPs.
Vulnerability of drinking water distribution systems is very important because
of the more recent strict regulations in public health [18]. Oxidation strategies that
could be used for NOM removal in the drinking water industry include ozonization
combined with either filtration [19], biological process [20] or slow sand filtration
[21] and more precisely advanced oxidation processes (AOPs) [22]. AOPs have
gained great interest due to its high oxidation power over almost any organic
compound. Currently several studies are being conducted to show the potential role
that AOPs can play in the transformation of NOM from natural sources of water.
AOPs are mainly based on the formation and use of hydroxyl (HO•) radicals, which
because of its high oxidation potential [23] are capable to remove a wide range of
substances of difficult degradation; since this type of radicals are highly reactive and
then non-selective, they may react very quickly improving several parameters of the
output stream [4]. Several applications of these processes have been studied involving
combinations of oxidizing agents, radiation and catalysts in order to remove NOM
and organic pollutants [9]. Examples of such processes have included UV-based
(UV/H2O2) and ozone-based (O3/H2O2, O3/UV, O3/H2O2/UV and O3/H2O2/TiO2)
applications, heterogeneous photocatalysis (TiO2/UV), ultrasound, electrochemical-
based processes (anodic oxidation with BDD electrodes, electro-Fenton and photo-
electro-Fenton), homogeneous Fenton, heterogeneous Fenton and the Fenton-like
processes like the so-called catalytic wet peroxide oxidation (CWPO) [14].
Given the very high oxidizing power of HO• radicals, it is expected that use of
AOPs leads to deep mineralization of the organic matter, i.e. final reaction products
corresponding to CO2, water and inorganic ions – Eq. (1).

mineralization
NOM þ H2 O2 ! CO2 þ H2 O þ inorganic ions ð1Þ

However, depending on the complexity of the targeted organic molecule and the
efficiency of the oxidation process, various by-products can be obtained which in
general are expected to be of lower toxicity than the starting molecule. Typically,
AOPs in drinking water treatment would be useful to degrade taste and odour-
causing chemical compounds, as well as to destroy any residual toxicity in water
resulting from these types of contaminants [22]. In many model molecules, it has
104 A.-M. Garcı́a et al.

been determined as an oxidative route through typical attack pathways, where HO•
reacts mainly by abstracting H atoms or adding it to unsaturated bonds [24]. Due to
the widely distributed chemical functionalities and molecular sizes present in
NOM, the tracking of NOM and its by-products [4] through the degradation has
become a challenging issue. Furthermore, other reactive
oxygen species (ROS)
such
as the peroxyl (ROO•) radical, hydroperoxyl HO2• radical, superoxide anion
O
1
2 and singlet oxygen ( O2) can also participate together with the NOM itself in
the degradation process. Thus, understanding the molecular and structural proper-
ties of the targeted NOM and its by-products is extremely important in order to
elucidate the degradation as well as to understand the behaviour of several NOM
fractions throughout the process.
Various analytical techniques have been employed to characterize DOM compo-
sition including (1) ultraviolet spectroscopy (UV-Vis), (2) Fourier transform infra-
red (FT-IR) spectroscopy, (3) nuclear magnetic resonance (NMR) spectroscopy,
(4) fluorescence excitation/emission matrix (FEEM) spectroscopy, (5) mass spec-
trometric methods such as liquid/gas chromatography-mass spectrometry (LC-MS
or GC-MS), (6) ultrahigh-pressure liquid chromatography (UPLC) coupled to quad-
rupole time-of-flight mass spectrometer (QTOF-MS) and (7) electrospray ionization
(ESI) coupled to ultrahigh-resolution Fourier transform ion cyclotron resonance
mass spectrometry (FT-ICR-MS) [25]. The fractionation of NOM into broad chem-
ical classes is the first step to examine its structure. Fractionation by resins is the
method most frequently used for isolation/fractionation of NOM based on its polar
moieties (e.g. hydrophobic, hydrophilic and transphilic). This method currently uses
non-ionic macroporous copolymers, such as XAD resin analogues, followed by ion
exchange resins [26]. Therefore, the first part of this chapter revises the main
methods of separation and characterization of natural organic matter. The first
recommended step is fractionation, mostly based in two methods: (1) resin fraction-
ation and (2) reverse-phase high-performance liquid chromatography. Although
these have been also used as characterization methods, in this chapter they are
separated into several sections for more useful approach. Size-exclusion liquid
chromatography (LC-SEC) has been also employed to separate NOM based on its
molecular weight. In the second part, the main characterization methods of NOM are
briefly described: UV-Vis, SUVA, TOC, FT-IR, FEEM and ECI-FT-ICR-MS. Finally,
the NOM intermediates found in several AOPs are compared, including UV light-
based (UV/H2O2 and UV/Cl2), ozone-based (O3/H2O2 and O3/UV), differences in
reaction pathways of homogeneous and heterogeneous processes, photocatalytic
(TiO2/UV) and ultrasound-based applications.

2 Separation of NOM and NOM Intermediates

Complex mixtures of NOM in water supplies commonly affect operation of drink-

ing water treatment plants [15]. Thus, elucidation of the chemical properties of the
NOM present in a particular water source may greatly help choosing the more
Separation and Characterization of NOM Intermediates Along AOP Oxidation 105

suitable treatment technology. For this purpose, the first step is to separate NOM in
several fractions. The most frequently used methods to separate NOM are fraction-
ation by resins through column-liquid chromatography or reversed-phase liquid
chromatography (RP-LC). Afterwards, each fraction can be further characterized
by size-exclusion liquid chromatography (LC-SEC) in order to obtain molecular
weight distribution. These three methods for separation of NOM will be discussed
in forthcoming sections.

2.1 Fractionation by Resins

Fractionation by adsorption in resins is an effective way of elucidating the chemical

properties of DOM according to its hydrophobic, hydrophilic and transphilic nature.
Often in this process, non-ionic macroporous resins (DAX-8 acrylic esters and XAD-4
styrene divinylbenzene) are used, which can split DOM into three classes: (1) hydro-
phobic fraction (HPO), mainly constituted of humic substances (HS) including humic
acids (HA) and fulvic acids (FA), (2) transphilic fraction (TPI) including hydrophilic
acids (HPI-A) and (3) hydrophilic fraction (HPI), involving hydrophilic bases (HPI-B)
and neutrals (HPI-N). Subsequently, by employing cation-exchange resins and anion-
exchange resins, six classes of DOM could be further obtained as follows: hydropho-
bic acids (HPO-A), humic and fulvic acids ranging from 450 to 1,000 Da; hydrophobic
bases (HPO-B), proteins and amino acids ranging from 250 to 850 Da; hydrophobic
neutrals (HPO-N), hydrocarbons ranging from 100 to 70,000 Da; hydrophilic acids,
fatty acids ranging from 250 to 850 Da; hydrophilic bases (HPI-B), proteins and amino
acids ranging from 100 to 1,000 Da; and hydrophilic neutrals (HPI-N), polysaccha-
rides ranging from 120 to 900 Da [4, 27].
As an adaptation of the methods proposed by Leenheer et al. [11] and Fabris
et al. [28], the fractionation method starts conditioning the chromatographic col-
umns, glass tubes with varied diameters from 5 to 50 mm and heights from 5.0 cm
to 1.0 m, which involves the following steps:
1. Cleaning with ultrapure type I water (MilliQ or similar purified water), which is
passed through the resin packed into the column in order to remove any
remaining methanol (the resins are preserved in methanol when not in use).
2. Cleaning with 0.1 M NaOH, which is used for conditioning resins.
3. Repetition of steps (1) and (2).
4. Keeping of the resins in 0.1 M NaOH for approximately 12 h.
5. Monitoring by UV-Vis and total organic carbon (TOC), which are used to detect
interferences. If impurities are still present, water and methanol (ffi100 mL) can
be added to each column to complete cleaning. Then, the conditioning process
(NaOH/water wash) is repeated until the TOC of the effluent from each column
becomes pretty close to zero and the absorbance (λ254) < 0.0001 m
1. In some
cases a control of the conductivity (<10 μS/cm) is also recommended [4].
106 A.-M. Garcı́a et al.

6. Conditioning with H3PO4 0.1 N and finally ultrapure water again to obtain a
similar pH to surface water samples.
7. Set the pH of the sample to around 2.0 [29].
Once the columns are conditioned, 100 mL of the water containing the NOM is
added first through a DAX-8 column using a flow of around 3 mL/min. From the
total eluted volume, samples are taken and recorded by means of TOC measure-
ments. The remaining volume is fed in the column of the XAD-4 resin and the TOC
of the eluted solution also measured. In order to enrich the fraction retained in
the XAD-4 resin, the eluted sample could be recirculated; it also serves as
preconditioning of the resin, which improves the adsorption of the fraction of
interest in the column (Fig. 2). Finally, the hydrophobic fraction of the NOM
water retained in the DAX-8 resin and the transphilic fraction retained in the
XAD-4 resin are eluted using 0.01 mol/L NaOH in each case. These solutions
can also be stored for further TOC analysis.
When analysing a real water source, some limitations can be presented to apply
the fractionation method to samples containing a low concentration of organic
matter. When the NOM concentration is very low, let’s say below 5.0 mg
TOC/L, rotary evaporation could be advised not exceeding 50 C and if necessary
followed by drying in vacuum oven.
Although this technique is recognized for its easy implementation, it has been
also recognized as a time-consuming one [15]. In addition, other limitations have
been reported and should be taken into account such as either the need of a relative
large volume of sample (~100–300 mL), chemical alterations that may occur in the
sample due to the use of extreme pH levels along resin’s conditioning, contamina-
tion of the sample by resin’s bleeding or irreversible binding of some DOM
components on the resins, among others [7].

Fig. 2 Columns packed

with DAX-8 and XAD-4
resins for NOM
fractionation
Separation and Characterization of NOM Intermediates Along AOP Oxidation 107

2.2 Reversed-Phase Chromatography (RP-LC)

Methods by reversed-phase liquid chromatography (RP-LC) have been established

as fast techniques to distinguish between hydrophilic and hydrophobic fractions of
NOM, taking advantage of their differences in polarity [15]. RP-LC has been used
to compare the hydrophilic and hydrophobic contents of the NOM fractions from
different water sources. It employs a polar mobile phase, commonly mixtures
methanol-water, and a non-polar stationary phase, typically C18 column (octadecyl
carbon chain C18-bonded silica); thus, NOM molecules get eluted later from the
column as their polarity decreases [30].

2.3 Size-Exclusion Chromatography (LC-SEC)

Size-exclusion chromatography (LC-SEC) has been widely used to determine the

molecular weight distribution of humic substances [15]. It should be noted that in
SEC, the components of a sample are separated according to the hydrodynamic size
of the molecules. Since the peak distribution is established according to the
molecular size of the analyte, in the ideal case when the molecules are larger than
the pore diameters, they more easily pass through the column (first peaks). Smaller
molecules entering the pores of the stationary phase must diffuse in and out of them
until they are able to leave the column (final peaks) [28].
LC-SEC is often used to obtain the apparent molecular weight distribution
(AMW) of several compounds. The relationship between AMW and the resulting
elution time obtained by LC-SEC must be determined using compounds of known
molecular weight [31]. Therefore, the previous preparation of a calibration curve on
the basis of commercial standards with known molecular weight is necessary.
The calibration curve can be raised from a range of polystyrene sulphonate
(PSS) macromolecule standards (1, 5, 13 and 20 kDa) used in concentrations of
0.1–1.0 g/L; the PSS standards and NOM compounds can be traced at 254 nm. It is
important to preadjust the ionic strength and pH of the standard solutions for the
properties in solution to be very similar to those in the mobile phase. It must be done
to suppress charge effects in order to ensure that separation takes place mainly by
differences in the molecular size and not because of charge interactions [3, 31]. The
mobile phase is usually phosphate buffer of pH 7.0 prepared in ultrapure water,
together with sodium chloride to obtain an ionic strength equivalent to 0.1 mol/L
NaCl. One of the drawbacks of LC-SEC with UV detection is the low response
obtained for NOM structures with low molecular UV absorptivities such as pro-
teins, sugars, amino acids and aliphatic acids. In this sense, LC-SEC has been
improved in recent years by coupling to dissolved organic carbon/nitrogen [3] or
refractive index detectors (RID).
108 A.-M. Garcı́a et al.

3 Characterization of NOM Intermediates

The properties and amount of NOM can significantly affect the efficiency of the
degradation process. It is also important to be able to understand and predict the
reactivity of NOM and its fractions at different treatment steps [6]. Ultraviolet
spectroscopy (UV-Vis) and total organic carbon (TOC) are the most common
parameters employed to follow the overall composition of NOM surrogates. In
addition to adsorption in resins, size-exclusion chromatography (LC-SEC) and
reversed-phase chromatography (RP-LC) are used for both separation and charac-
terization of NOM. Techniques such as nuclear magnetic resonance (NMR) spec-
troscopy, Fourier transform infrared (FT-IR) spectroscopy and fluorescence
excitation/emission matrix (FEEM) spectroscopy can also be used to characterize
these types of substances. FT-IR allows to elucidate the main chemical functional-
ities in the molecule, whereas the fluorescence spectroscopy is a relatively low-cost
and easily handled analysis [32]. FEEM spectroscopy provides a unique perspective
of the NOM profile, usually not available from other modes of detection [17].
Lately, new more sophisticated methods have been developed whereby NOM
structures can be determined more precisely, among which pyrolysis coupled
to gas chromatography-mass spectrometry (Py-GC-MS), multidimensional NMR
techniques and electrospray ionization Fourier transform ion cyclotron resonance
mass spectrometry (ESI-FT-ICR-MS) are worth mentioning [6]. The latter allows
identification of thousands of mass peaks from single given isolated sample, usually
in the range of 200–1,000 Da [7]. Then, hereafter the main characteristics of
selected techniques (UV-Vis, TOC, FT-IR, FEEM and ESI-FT-ICR-MS) most
frequently employed for the characterization of NOM intermediates are displayed.

3.1 Ultraviolet Spectroscopy (UV-Vis) and SUVA

The amount of natural organic matter in water has been determined by means of
several parameters including UV-Vis and specific ultraviolet absorbance (SUVA).
SUVA has recently become a useful surrogate’s parameter for NOM characteriza-
tion as a function of molecular weight, aromatic content and hydrophobic/hydro-
philic nature [32]. Absorption at 254 nm by π electrons has been proposed as a key
parameter to follow degradation of the aromatic content in arenes, phenols, benzoic
acids, aniline derivatives, polyenes and polycyclic aromatic hydrocarbons with one,
two or more aromatic rings [33]. SUVA corresponds to the ratio of absorbance in a
water sample at determined wavelength within the ultraviolet range (usually at
254 nm), normalized to concentration of dissolved organic carbon (DOC) (UV254/
DOC) [6]. In general, a high value of SUVA indicates the presence of high
proportion of aromatic compounds and π-conjugated functionalities in the sample.
SUVA can be also interpreted qualitatively describing hydrophobic and hydrophilic
contents of organics in water. Although no clear limit values have been defined,
Separation and Characterization of NOM Intermediates Along AOP Oxidation 109

SUVA > 4 indicates mainly hydrophobic and especially aromatic compounds,

whereas SUVA < 3 can be used to indicate predominantly hydrophilic character
[12]. In the same way, the quinoid structures and keto-enol-systems are well-known
to absorb mainly in the visible range [32]. In addition to SUVA, colour and TOC
measurements are also useful. Rodrı́guez and Nú~nez [31] reported a SUVA ratio of
0.029 for natural fulvic acids, 0.040 for natural humic acids and 0.050 for com-
mercial humic acids, whereas 5.87, 23.33 and 35.53 were experimental values for
the same set of samples in terms of the ratio (colour – Pt-Co units)/TOC in mg C/L),
respectively.
Some other ratios of absorbance have been reported for the spectral differenti-
ation of humic substances and expressed as energies [34]. The E254/E456 (A254nm/
A456nm) gives an indication about the intensity of the UV-absorbing functional
groups compared to the coloured ones, whose values are in the range 4–11 as a
consequence of higher content of organic matter due to the presence of tannin-like
or humic-like substances derived from plants and soil organic matter. Meanwhile,
the E465/E665 is commonly used to indicate the degree of condensation of the
aromatic carbon network and is characteristic for different NOM fractions: it is
usually <5.0 for HAs and in the range 6.0–8.5 for fulvic acids.

3.2 Total Organic Carbon (TOC)

The content of organic carbon is widely used as a parameter to represent NOM

concentration in water [35]. In drinking water systems, where the TOC concentra-
tion is too low, the work with high-sensitivity TOC apparatus is recommended. It
may involve a special platinum wool catalyst, whose higher surface imposes larger
injection volumes.
TOC is a measurement of non-purgeable carbon in organic compounds present
in a water sample, of course including all NOM species. Dissolved organic carbon
(DOC) can be measured when the sample is passed through a 0.45 μm filter. This
parameter is very useful to complement other characterization methods, for exam-
ple, in the recording along resin fractionation [4].
When examining content of natural organic matter in drinking water, it is
expectable that the content of inorganic carbons such as carbonates and hydrogen
carbonates could be much higher than the organic fraction. Usually the organic
fraction is only around 1.0% of the total carbon. Therefore, a TOC determination
via the difference method (TOC ¼ TC
IC) will not be appropriate in this case due
to large statistical errors that could get propagated. The non-purgeable organic
carbon (NPOC) parameter is then more advised in this case. The drinking water
sample is first acidified to a pH value of 2.0 to transform the carbonates and
hydrogen carbonates into carbon dioxide; CO2 is then removed by sparging
with pure air as the carrier gas. What remains in the solution can be oxidized to
CO2, detected via NDIR and corresponds to non-volatile organic carbonaceous
compounds.
110 A.-M. Garcı́a et al.

3.3 Fourier Transform Infrared (FT-IR) Spectroscopy

The FT-IR allows to realize the chemical functionalities present in the NOM mole-
cules, but it has been more rather scarcely reported. Main characteristics documented
[31] for humic substances are O-H stretching (alcohols, phenols and carboxylic
groups, ʋ: 3,400 cm
1), C-H stretching (CH3 and CH2, ʋ: 2,850–2,960 cm
1), O-H
stretching (hydrogen-bonded carboxylic groups, ʋ: 2,620 cm
1), C ¼ O stretching
(carboxylic groups, ʋ: 1,720 cm
1), C ¼ C stretching (alkenes and aromatic rings, ʋ:
1,630 cm
1), N-H bending (N-H structures, ʋ: 1,540 cm
1), C-H bending (CH3
and CH2, ʋ: 1,455 cm
1), O-H bending (carboxylic groups, ʋ: 1,410 cm
1), C-H
bending (CH3, ʋ: 1,375 cm
1), C-O stretching (alcohols, aliphatic ethers, ʋ: 1,095
and 1,030 cm
1) and C-H bending (tri- and tetra-substituted aromatic rings, ʋ:
805 cm
1).

3.4 Fluorescence Excitation/Emission Matrix (FEEM)

Spectroscopy

Fluorescence spectroscopy has become a very useful tool for the analysis of NOM
in water. Fluorometers are capable of generating high-dimensional fluorescence
excitation/emission matrices efficiently and without extensive sample preparation.
In natural or treated waters, humic-like substances typically represent the majority
of fluorophores in both lake and river waters [17]. Fluorophores can be categorized
according to their tendency to fluoresce in five distinct regions of the FEEM (see
Table 1), through the fluorescent regional integration (FRI) procedure; it is used to
integrate fluorescence intensity within each region to make easier interpretation of
FEEM and also to quantify region-specific changes in fluorescence.

Table 1 Excitation and emission wavelength ranges for fluorescent regions I–V
Excitation wavelength Emission wavelength
Region Characteristics (nm) (nm)
I Aromatic protein I 200–250 200–330a
II Aromatic protein II 200–250 330–380
III Associated with fulvic 200–250 380–550
acids
IV Soluble microbial products 250–340 200–380a
V Associated with humic 250–400 380–550
acids
Taken from [17]
a
Lower limit was extended from 280 to 200 nm to match the detector range
Separation and Characterization of NOM Intermediates Along AOP Oxidation 111

3.5 Electrospray Ionization Fourier Transform Ion

Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-
MS)

Electrospray ionization (ESI) is called a “soft” ionization technique that ionizes

polar compounds from aqueous solutions prior to injection into a mass spectrom-
eter. ESI has a large mass range, ionizing compounds 10 < m/z < 3,000 as quasi-
molecular ions, (M + nH)n+ or (M
nH)n
eliminating the need of deep fragmen-
tation. ESI has been coupled with Fourier transform ion cyclotron resonance mass
spectrometry (FT-ICR-MS), an ultrahigh-resolution mass spectrometer that allows
to obtain the highest resolution and mass accuracy in the characterization. Thus,
individual molecules within a variety of natural organic mixtures can be detected,
its elemental composition determined, and changes at molecular level examined
[36]. Due to a high accuracy (<1 ppm), this technique allows differentiation
between NOM components having small differences in molecular mass and unam-
biguous assignment of molecular formulas up to approximately 600 Da. However,
structural information cannot be obtained, due to high number of possible isomers,
but it can be coupled with other components in order to obtain optical and structural
information of NOM [7].

4 Oxidation of NOM Through AOPs

The implementation of advanced oxidation processes and the determination of their

actual effectiveness on natural waters are often difficult, considering that they largely
depend on the particular water-contaminated matrix. It is well-known that AOP
treatment of organic compounds at relatively high concentrations (>50 ppm) in
complex matrices may be much energy and oxidant consuming [22]. High concen-
trations of NOM may lead to formation of recalcitrant oxidation by-products that
negatively further impact the quality of water, interfere with the elimination of the
targeted compounds and reduce the effectiveness of the selected AOP [23]. In recent
times a significant part of the research has been focused in realizing the role played
by AOPs in the catalytic degradation of NOM. Throughout the oxidation process, a
series of intermediates can be formed (Eq. 2) [37]:

RH þ HO • ! Intermediates ! CO2 þ H2 O ð2Þ

Action of the AOPs can be divided in two stages: (1) formation of hydroxyl
radicals and (2) reaction of such oxidizing species with organic pollutants in water.
However, throughout AOPs in situ formation of other reactive oxygen species
(ROS) [38] may also occur:
hydroperoxyl radical (HO2•), singlet oxygen (1O2)
and superoxide radical ( O2•
. The kinetic constant reported for the reaction of
NOM with hydroxyl radicals has ranged from 1.9  104 to 1.3  105 (mg/L)
1.s
1,
112 A.-M. Garcı́a et al.

which according to the authors is comparable with those observed for other organic
contaminants [23]. Moreover, NOM itself must be considered as an important
scavenger of HO• radicals, e.g. high concentrations of NOM may result in signif-
icant reduction of MTBE destruction potential. The reaction of HO• radicals in
aqueous systems has been discussed in detail in several reports [39, 40]. It can be
summarized in three types of well-known pathways:
1. Addition to aromatic rings and double bonds between C-C, C-N and S-O
(in sulphoxides), but not to C-O, double bonds; this addition is typically very
fast, close to diffusion-controlled [24].

HO • þ R
H ! H2 O þ R • ð3Þ
HO • þ C ¼ C ! HO
C
C • ð4Þ

2. H-abstraction reactions from C-H, N-H or O-H bonds (related to the R-H bond-
dissociation energy), reactions leading to formation of carbon-centred radicals,
which in the presence of O2 (Eqs.

5 and 6) are
converted into the corresponding
peroxyl radicals (HO2• or O2•
and R
O • [24]:

R • þ O2 !! Rð
Hþ Þ þ HO2• ð5Þ

R þ O2 !! R
OO • !! R
O •
•
ð6Þ

3. Electron transfer reactions [41]

The organic intermediates formed in the first stage of the oxidation may further
react with HO• and oxygen. Ideally, the overall process eventually leads to full
mineralization towards CO2, H2O and, if the contaminant contains heteroatoms
such as N and O, inorganic acids [24]. ROS usually do not achieve complete
mineralization in the oxidation of natural organic matter. Instead, a series of
intermediates such as aldehydes, keto acids and carboxylic acids, among others,
are formed, which affect the potential formation of disinfection by-products [12],
since they may act as precursors of haloacetaldehydes, haloketones and
haloacetonitriles [42].
The fundamental aspects of AOPs and the most important findings reported in
the degradation of NOM along the past few years are discussed in the next sections.
The general conditions of operation for several AOPs are summarized in Table 2.

4.1 Ozone-Based Applications: O3/H2O2 and O3/UV

Ozonation is a common technology applied in treatment of drinking water either for

enhancing the subsequent conventional processes or for improving the quality and
disinfection of the treated product [32]. In a conventional ozonation process, ozone
reacts with NOM by an electrophilic addition to double bonds in a very selective
Table 2 General conditions of operation reported for several AOPs
Oxidizing
AOPs Reaction conditions agent Catalytic species General mechanism
Ozone-based applications: T ¼ variable, P ¼ atmo- O3 Some combinations with hv
O3 þ H2 O ! O2 þ H2 O2
O3/H2O2 and O3/UV spheric, irradiation: photocatalyst have been reported H2O2 + hv ! 2HO•
optional, UV synergistic H2 O2 Ð HO
þ
2 þH
H2 O2 þ HO • ! HO2• þ H2 O
O3 þ H2 O2 ! HO2• þ HO •
UV light-based applications: T ¼ variable, P ¼ atmo- H2O2, UV light hv •
H2 O2 =HO
2 ! 2HO ðλ < 300 nmÞ
UV/H2O2 and UV/Cl2 spheric, irradiation: UV, H2O, O2 H2 O2 þ HO • ! HO2• þ H2 O
solar • •

HO
2 þ HO ! HO2 þ HO
2HO• ! H2O2 + O2
HO2• þ HO • ! H2 O þ O2
Fenton and photo-Fenton T ¼ RT
0 C, P ¼ atmo- H2O2 Mainly Fe2+, Cu2+ in homogeneous Fe2+ + H2O2 ! HO• + Fe3+ + OH

spheric, irradiation: phase FeIII(OH)2+ + hv ! HO• + Fe2+
optional, UV
Fenton-like catalysed pro- T ¼ RT
70 C, H2O2 Mainly Fe3+ in heterogeneous phase Fe3þ þ H2 O2 ! HO2• þ Fe2þ þ Hþ
cesses: catalytic wet peroxide P ¼ atmospheric, irradia-
oxidation (CWPO) tion: not mandatory
Heterogeneous photocatalysis: T ¼ variable, P ¼ atmo- H2O2, Mainly TiO2, heterogeneous phase hv
TiO2 ! e
þ hþ
(TiO2/UV) spheric, irradiation: UV, H2O, O2 h+ + HO
! HO•
solar h+ + H2O ! H+ + HO•
e
þ O2 ! O2•

O2•
þ Hþ ! HO2•
Separation and Characterization of NOM Intermediates Along AOP Oxidation

O2•
þ HO2• ! O2 þ H2 O2 þ HO •
2O2•
þ 2H2 O ! 2HO
þ O2 þ H2 O2
H2 O2 þ O2•
! O2 þ HO
þ HO •
H2O2 + e
! HO
+ HO•
e
+ h+ ! heat/light
(continued)
113
Table 2 (continued)
114

Oxidizing
AOPs Reaction conditions agent Catalytic species General mechanism




Ultrasound-based applications T ¼ variable, H2O, O2 High-frequency sound waves
(US, US/H2O2) P ¼ atmospheric (>16 kHz). Several combinations H2 O ! H • þ HO •




suitable with other AOPs
O2 ! 2O
O + H2O ! 2HO•
H• + O2 ! O + HO•
H • þ O2 ! HO2•
Adapted from [37] and supplemented with [23, 43]
a
RT room temperature
A.-M. Garcı́a et al.
Separation and Characterization of NOM Intermediates Along AOP Oxidation 115

way. Simultaneous use of H2O2 or UV radiation has been found as a useful strategy
to enhance degradation rates and to promote production of hydroxyl radicals,
translating the conventional ozonation into an AOP [14, 43]. Lamsal et al. [44]
compared the performance displayed by three advanced oxidation processes includ-
ing O3/UV, H2O2/O3 and H2O2/UV in the NOM removal. They found that combi-
nation of O3 or UV with H2O2 resulted in higher TOC and UV254 depletion in
comparison to every individual process. Upon treatment with ozone alone, NOM
oxidation occurred with the removal of conjugated double bonds, due to the
high electrophilic character of ozone but rather minimal mineralization. O3/UV
displayed the most efficient removal (TOC, 31%; UV254, 88%) followed by H2O2/
UV and H2O2/O3. Among the three assessed processes, H2O2/UV was found to be
the most effective treatment for the reduction of THM and HAA formation poten-
tial. However, Stylianou et al. [32] recently found that although O3/H2O2 increased
the NOM mineralization degree, 9–17% and 8–15%, for Aliakmonas and Axios
Rivers – northern Greece, respectively, it showed negligible impact in reduction of
the UV254. The application of single ozonation resulted in high reduction of humic-
like peak fluorescence intensities (50–85%), whereas the co-addition of H2O2 did
not present the expected reduced fluorescence intensity. It was argued that hydroxyl
radicals might also get scavenged by dissolved organic carbon (DOC), carbonates
and other inorganic compounds, normally found in natural waters; thus, the rela-
tively high scavenging rate calculated based on DOC and alkalinity values for water
of Aliakmonas River was 7.2  104 s
1. The emission comparative spectrum of raw
and treated water is displayed in Fig. 3 (left); the ozonation of Aliakmonas River
caused the formation of one new discrete peak with maximum absorbance at
315–335 nm (tryptophan-like), also observed in the emission spectra of O3/H2O2-
treated samples although with much lower intensity. It suggested that oxidation of
humic-like components was the first step of the O3–AOP treatment, while the
produced protein-like intermediates were subsequently oxidized towards both
nonfluorescent and probably also smaller molecular weight moieties.

Fig. 3 (Left) Emission spectra of Aliakmonas River at λ = 290 nm (humic-like substances close to
325–340 nm) and (right) OCD and UVD chromatograms of Aliakmonas River before and after
bubble-less treatment with applied dosage of 1.0 mg O3/mg DOC. Both reproduced with permis-
sion from Springer Publishing Company [32]
116 A.-M. Garcı́a et al.

Size-exclusion chromatography has been usually coupled to ultraviolet detector

(LC-UVD) but recently also to organic carbon detector (LC-OCD). The latter is
probably the most sensitive and reliable technique for the detailed characterization
of NOM. For instance, a comparison between LC-OCD and fluorescence spectros-
copy can be seen at Fig. 3; in the fluorescence measurements, the removal of humic-
like components was almost completed with O3 or O3/H2O2 treatment, whereas the
LC-OCD removal related with humic substances did not exceed 20% in any case
(UVD and OCD).
Finally, the application of O3 or simultaneous O3–AOP decreased building
blocks and low molecular weight neutral concentrations, indicating that hydroxyl
radicals can further react with the intermediates towards CO2 formation or other
smaller (not detectable) by-products. This agreed with Lamsal et al. [44], who
found by LC-SEC that during degradation of NOM, the reduction of larger molec-
ular weight NOM (first peaks) was usually higher than that corresponding to lower
molecular weight NOM (last peaks), probably as a result of the higher rate constants
of reaction between HO• and the fraction of larger MW NOM. It probably obeys to
more extended intrinsic conjugated aromaticity, offering larger number of target
reaction sites as also confirmed by Tubić et al. [45]. Then, NOM was partially
oxidized, and higher molecular weights were transformed into smaller and more
biodegradable compounds such as aldehydes and carboxylic acids [44].
Recently Zhong et al. [46], exploring the pathways of degradation of aromatic
carboxylic acids in ozone solutions as the main by-products in the degradation of
NOM by AOPs, found that the reaction mechanism in the ozonation of benzoic acid
(BA) would involve three steps: (1) BA hydroxylation, (2) hydroxylated products of
BA getting oxidized to generate ring-opened compounds together with unsaturated
carbonyl compounds and (3) short-chain aldehydes (formaldehyde, glyoxal, methyl
glyoxal) and carboxylic acids (formic and acetic acids) finally transformed into
CO2 and H2O, instead due to the stability of carboxylic acids in O3 solution, would
be accumulated in the solution.

4.2 UV Light-Based Applications: UV/H2O2 and UV/Cl2

The presence of UV light is essential in several advanced oxidation process as it can

participate both directly and indirectly in the degradation of NOM. AOPs based on
UV include UV/H2O2, UV/O3, UV/chlorine, UV/persulphate (UV/PS) and hetero-
geneous and homogeneous photocatalysis, all of them very interesting methods
producing reactive species [42]. UV radiation can degrade NOM, splitting large
molecules into organic acids of lower molecular weight; changes of NOM resulting
from the application of UV light may also subsequently affect the formation of
disinfection by-products (DBPs) when a sequential disinfecting step with chlorine
is used [16]. It happens since the generated intermediates through the oxidation of
the humic and fulvic acids may react with chlorine, leading to DBPs [47].
Separation and Characterization of NOM Intermediates Along AOP Oxidation 117

Upon irradiation, the amount of HO• produced in the UV/H2O2 process strongly
depends on the H2O2 concentration, and in turn, H2O2 dosage depends on intrinsic
characteristics and concentration of the organic targets; there is an optimum dosage
necessary to achieve the best oxidizing performance. The H2O2 can react with HO•,
behaving itself as a HO•-inhibiting agent under certain conditions, but it also absorbs
UV energy. Indeed, Wang et al. [48] in a previous study found that the HO•-
scavenging effect became significant when the H2O2 concentration was higher than
0.1% (32.6 mM), with optimal conditions between 0.01 and 0.05% (3.25–16.3 mM)
of H2O2. The UV-absorbing compounds in the humic acids were degraded almost
completely under a 450 W high-pressure mercury vapour lamp used as light source
(25 C), UV254 decreased from 0.433 to 0.006 cm
1, and 90% of mineralization was
achieved. The FT-IR spectra after the UV/H2O2 treatment displayed that most of the –
OH stretching corresponding to –COOH and –COH (3,400–3,200 cm
1) got removed
from original structure. González et al. [49] treated DOM present in two secondary
effluents from either a conventional activated sludge (CAS) or a membrane biological
reactor (MBR) by means of UV/H2O2. The monitoring of the organic matter fraction
by LC-OCD demonstrated that the reduction of the aromaticity in the effluent
(decreasing SUVA) was not strictly correlated with the complete depletion of
humic substances in the effluents (Fig. 4a) unlike Wang et al. [48] who found a
clear decrease in the UV absorption together with almost full mineralization. During
the first 30 min of oxidation, certain reduction of biopolymers and an important
increase of low molecular weight (LMW) compounds (building blocks, neutrals and
LMW acids) were achieved [49].
Xie et al. [42] employed the sulphate radical anion (SO4•
, 2.5–3.1 V) which
features high redox potential but being more selective than HO• to react very fast
with organic pollutants. The impact of UV/PS and UV/H2O2 pretreatments on the
formation of both C-DBPs (carbonaceous disinfection by-products) and N-DBPs
(nitrogenous disinfection by-products) was assessed. UV/H2O2 with an initial
dosage of 30 μM in H2O2 led to significant increased formation of both C-DBPs
and N-DBPs in comparison with UV/PS. In this treatment some C-DBPs such as
chloroform and haloacetic acids only increased marginally, while N-DBPs such as
haloacetonitriles and trichloronitromethane decreased slightly under low dosages of
PS (10 μM). Recently several reports have described UV/Cl2 as an alternative to
traditional AOPs taking into account that this process is expected to provide
substantial cost savings over conventional AOPs [47]. Aqueous chlorine solutions
include two species, hypochlorous acid (HOCl) and hypochlorite ion (ClO
),
related in Eq. (7):

HOCl $ Hþ þ ClO
pKa ¼ 7:58 at 20 C ð7Þ

The photolysis of both species with different photophysical properties (HOCl

absorbs UV at 227 nm and ClO
at 292 nm) leads to production of hydroxyl
radicals in several reaction pathways (Eqs. 8–10):
118 A.-M. Garcı́a et al.

Fig. 4 (a) Evolution of DOM fractions as a function of the consumed H2O2 and (b) relative
contribution of every fraction to total DOM for the MBR effluent after UV/H2O2 treatment.
Reproduced with permission of Elsevier from [49]

HOCl þ hv ! HO • þ Cl • ð8Þ
ClO
þ hv ! O •
þ Cl • ð9Þ
O •
þ H2 O ! HO • þ OH
ð10Þ

Then, the UV/chlorine system can generate both non-selective HO• and reactive
chlorine species (RCSs) such as Cl • , Cl2•
and ClO • [50].
Pisarenko et al. [47] before investigated the use of UV/chlorine in oxidation of
NOM in surface water and the impact of the treatment on formation of disinfection
by-products and the structure of NOM. The results showed the destruction
Separation and Characterization of NOM Intermediates Along AOP Oxidation 119

of chromophoric components of the NOM at doses ranging 2–10 mg/L Cl2.

Wang et al. [50] indeed confirmed these results finding that the UV/Cl2 system
degraded ~80% of chromophores and 76.4–80.8% of fluorophores, including elec-
tron donor groups like double bonds, aromatic and phenolic functionalities getting
preferentially degraded by the UV/chlorine process. Finally, the DOC removal was
15.1–18.6%, since the oxidation degraded high MW fractions into low MWs
without appreciable decrease in the carbon loading by mineralization. According
to Fang et al. [51], HO• reacts with NOM under a second-order rate constant of
2.5  104 (mg/L)
1 s
1, while Cl• reacts with NOM at 1.3  104 (mg/L)
1 s
1;
therefore, the degradation through the HO• pathway would be about 1.4 times faster
than that through the Cl• pathway. However, although there is a synergistic mech-
anism involved with the addition of chlorine [24], NOM treatment by the
UV/chlorine system is similar to that of HO•-based AOPs, particularly as a function
of the molecular weight; namely, high MW fractions are decomposed at a higher
rate (~4.5 times) than medium MW fractions, generating low fractions. Finally,
these results supported the conclusion that the chlorine-based AOP was also
effective reducing the aromatic content in the NOM.

4.2.1 NOM as a Photosensitizing Agent

During direct photolysis electrons may migrate from basal to excited states of
NOM, from where they can be transferred to oxygen either to form 1O2 or to
provoke homolytic breaks in NOM producing organic radicals that further react
with oxygen. In this case, the dissolved organic matter (DOM) can be considered a
photosensitizing agent [52] that by different pathways may generate ROS and
provoke its self-degradation [53]. Thus, the chromophoric natural organic matter
is one of the main sources promoting formation of ROS species through its
interaction with light in a cascade of photochemical reactions, in the earlier stages
of AOP reactions (see Fig. 5).
Birben et al. [55] recently reported that even photosensitization via light absorp-
tion leading to the formation of reactive oxygen species could also initiate self-
degradation of HAs in a photocatalytic process. The hydroxyl radical is the most
reactive and less selective of the ROS, and the formation of singlet oxygen can
occur through the transfer of energy from excited triplet states of coloured dissolved
organic matter (CDOM) to O2:
3
C DOM∗ þ 3 O 2 ! CDOM þ 1 O 2 ð11Þ

In the case of superoxide, although CDOM is the main source, the precise
reactions forming this species remain unclear [54].
The triplet excited states of natural organic matter (3NOM∗) were found by
Li et al. [56] to play a dominant role in the photodegradation (1,700 W Xenon lamp
filtered light for λ > 290 nm) of acetaminophen by photolysis (see Fig. 6). Similarly,
Porras et al. [53] established, based in kinetic and analytical studies, an accelerating
effect on the rate of ciprofloxacin decomposition caused by humic substances.
120 A.-M. Garcı́a et al.

Fig. 5 Photophysical and photochemical reactions of CDOM species: (a) primary, (b) secondary
and (c) secondary in fresh water. Reproduced with permission of Springer from [54]

Fig. 6 Schematic representation of initial step in the indirect photodegradation of acetaminophen

in NOM-enriched solutions. Reproduced with permission of Elsevier from [56]
Separation and Characterization of NOM Intermediates Along AOP Oxidation 121

In general, NOM reaches triplet excited states after irradiation, and dissolved
oxygen acts as a quencher for these triplet excited states through an energy
transfer process to generate singlet oxygen (1O2) and superoxide anion O2•
. It
was found that under increasing concentration of oxygen, the steady-state con-
centration of 3NOM* would be expected to drop and the decay rate of the targeted
process decreases too. However, the results showed that the degradation remained
stable even in excess of oxygen in the case of acetaminophen, suggesting that the
contribution of 1O2 gradually stands out and offsets the decreased 3NOM*. Porras
et al. [53] employed furfuryl alcohol (FFA) scavenger, highly selective to 1O2, and
demonstrated that singlet oxygen also participates in the reaction.
Due to the strong complexability of iron with the humic substances, the leaching
and stability of the iron species were investigated by Birben et al. [55] through
photocatalytic experiments (Fe-doped Ti catalyst) in the presence or absence of
humic acids in deionized water. This procedure was employed as a strategy to
demonstrate the efficiency of the metal-ion doping. Thus, the catalyst was prepared
to improve trapping of the photoexcited electrons of the conduction band towards
the catalyst’s surface while minimizing charge carrier recombination. Fe3+ was the
chosen ion due to its similar ionic radius (0.69 Å) to that of Ti4+ (0.75 Å) as well as
energy level pairs Fe2+/Fe3+–Ti3+/Ti4+ favouring the separation of the photo-
generated electron-hole pairs. It was found that in the presence of the Fe-doped
TiO2 (Evonik P-25), the concentration of the Fe species dissolved in the medium
was 0.013 mg/L, whereas in the presence of catalyst and humic acids (HAs 50 mg/L,
average molecular weight < 100 kDa), the concentration of iron species increased
almost fivefold in the medium reaching a value of 0.070 mg/L. After 60 min of
irradiation (λ ¼ 300–800 nm; light intensity 250 W/m2), a significant concentration of
Fe leached (0.116 mg/L) was found in the presence of HAs. It was attributed to strong
chelating effect of the humic sub-fractions, resulting in the release of iron into the
aqueous medium. The reactions that can be triggered by the formation of the Fe(III)–
HA complex under solar irradiation are shown in Eqs. (12)–(20) [55]:

HA þ hv ! HA∗ ð12Þ
HA þ O2 ! Products þ O2•
=HO2• ð13Þ
O2•
=HO2• ! H2 O2 ð14Þ
FeðIIIÞ þ HA ! FeðIIIÞ
HA ð15Þ
FeðIIIÞ þ hv ! HA • þ þ FeðIIÞ ð16Þ
þ
FeðIIIÞ þ hþ ! FeðIVÞ
HA ! HA∗ þ FeðIIIÞ ð17Þ
FeðIIÞ þ O2 ! FeðIIIÞ þ O2•
=HO2• ð18Þ
FeðIIÞ þ H2 O2 ! FeðIIIÞ þ • O H þ OH
ð19Þ
HA þ OH ! Photocatalytic degradation products ð20Þ

Finally, low achieved efficiencies of the photocatalytic removal in terms of

UV-Vis absorbance (254, 280, 365 and 456 nm) and DOC mineralization rate
(0.044 mg/L min in the presence of HAs-doped catalyst; 0.188 mg/L min in the
presence of the free catalyst) were attributed to reactions of complexation between
Fe3+ and HA molecular fractions on the catalyst’s surface.
122 A.-M. Garcı́a et al.

4.3 Fenton, Photo-Fenton and Fenton-Like Catalysed

Processes

The Fenton reaction is a non-expensive and environmental-friendly oxidation

method, widely studied for wastewater treatment. The mechanism of the process
has been extensively studied, and it is here summarized in Table 2. The hydroxyl
radicals as usual attack the organic matter present in water, but some parallel
reactions occur, and then the hydroxyl radicals also produce other radicals with
less oxidizing power, the so-called scavenging effect of HO• [18]. Many interfer-
ences in the water source may occur, e.g. other dissolved organic compounds
present, alkalinity, etc., which may compete with NOM by radicals. For instance,
both carbonate and bicarbonate anions scavenge hydroxyl radicals to form carbon-
ate radicals; nitrates and nitrites absorb UV light around 230 and 300 nm, respec-
tively, and then concentrations exceeding 1.0 mg/L may strongly limit the
effectiveness of UV-based technologies; phosphates, sulphates, chloride, bromide
and fluoride ions also may act as scavengers at concentration over 100 mg/L for
phosphates and sulphates [23, 24].
Fenton and photo-Fenton processes have been established as alternative to
coagulation in treatment of drinking water, usually when the water sources contain
natural organic matter at levels of up to 15 mg/L [57]. A drawback in the applica-
tion of conventional homogeneous Fenton in drinking water facilities is the influence
of pH, given that optimum pH for this application is 2.54 when Fe3+ and FeOH2+
species are in the same abundance. As pH increases, the precipitation of amorphous
ferric oxyhydroxides occurs (Eq. 21), which do not redissolve readily and are
considerably less Fenton-active in comparison to the free metal ions (Eqs. 18 and
19). The presence of coordinating ligands may affect the pH dependence consider-
ably; lowering pH not only keeps Fe(III) soluble but also reduces parasite decom-
position of H2O2 [24]:

Fe3þ Ð FeOH2þ Ð FeðOHÞþ 4þ

2 Ð Fe2 ðOHÞ2 Ð other polynuclear species
Ð Fe2 O3  nH2 OðsÞ ð21Þ

Molnar et al. [58] treated a groundwater rich in natural organic matter

(10.6  0.37 mg C/L) employing the Fenton process; they evaluated the influence
of pH at 5.5 and 6.0, iron concentrations between 0.10 and 0.50 mM Fe(II) and
molar ratios Fe(II):H2O2 of 1:5–1:20. High NOM removal was found at pH 5.5
(55% DOC removal) with a dose of 0.25 mM Fe(II) and under molar ratio 1:5. It
was also confirmed that the Fenton process was much more effective in removing
NOM than conventional coagulation with similar dose of FeCl3. The distribution of
NOM fractions upon treatment (HPI-N ¼ 75%, HPI-A ¼ 4%, FA ¼ 21%) changed
in comparison to the raw water (FA ¼ 68%, HA ¼ 14%). The fraction of humic
acids was completely removed, whereas the fraction of fulvic acids decreased and
the contribution of the hydrophilic fraction in the final effluent was 79%
(HPI-N + HPI-A).
Separation and Characterization of NOM Intermediates Along AOP Oxidation 123

When the Fenton degradation is carried out in the dark, low molecular weight
organic acids such as glyoxylic, maleic, oxalic, acetic and formic are accumulated
because of their high stability in the reaction medium. Under light, however, these
acids can be mineralized via Fe photocatalysed reactions [24]. The photo-Fenton
process has been employed to enhance efficiency in the generation of hydroxyl
radicals and also in disinfection units employing UV light sources [59]. A 55% of
NOM mineralization was achieved by Moncayo-Lasso et al. [60] by the photo-
Fenton process on a river surface water (5.3 mg C/L) at natural pH (~6.5)
employing 0.010 mM (0.6 mg/L) of Fe3+ (almost 24-fold less than that employed
by Molnar et al. [58]) and 10 mg/L of H2O2. In this case, the experiments were
carried out by using a solar compound parabolic collector. In 2012, Moncayo-Lasso
et al. [33] dramatically reduced THM formation potential, thanks to photo-
degradation of the MON fraction more related to formation of THMs; the experi-
ments were carried by chlorination of river surface water with 7.1 mg C/L at pH
near 7.0, initial [H2O2] ¼ 60 mg/L and initial [Fe3+] ¼ 1.0 mg/L. The mineraliza-
tion reached 55% at 3 h of treatment (25–30 C). Low molecular weight products
were obtained at the end of the process; according to the authors, higher mineral-
ization rates were not achieved since the addition of HO• on the aromatic rings
generates radicals resembling hydroxy-cyclohexadienyl (HCHD•), whose subse-
quent oxidation leads to breaking of the aromatic rings towards less oxidizable,
open-chain products.
Galeano et al. [13] studied the removal of humic acids using an Al/Fe-pillared
clay catalyst, where it was established that the fraction of Fe inserted in true “mixed
pillars” within the clay layers was responsible for initiating the Fenton-like, cata-
lytic cycle. The results showed that once the first 15 min of the process passed
(equilibrium period, without addition of hydrogen peroxide), it established a kind of
induction period, explained by the competition between H2O2 and NOM molecules
for active iron. It happened in the early stages of peroxide addition, taking into
account that natural organic matter has an important impact complexing metal ions,
and then an interaction mainly between the aromatic moieties of the HAs and the
metal inserted in the mineral took place in advance. Afterwards, once the peroxide
molecules achieved minimal interaction with the metal, the concentration of NOM
started to get decreased by the attack of the formed oxidizing radicals. The results
showed almost full depletion of the starting chemical oxygen demand (96.3% COD
removal in 4 h of reaction) and complete colour removal (in less than 1 h of
reaction) under the following conditions: [colour455]0 ¼ 42 PCU, catalyst load-
ing ¼ 5.0 g/L, [H2O2]added ¼ 0.047 mol/L, H2O2 addition flow rate ¼ 6.0 cm3/h,
final stoichiometric ratio [H2O2]/[COD]0 ¼ 1.0, pH of reaction ¼ 3.7, room
temperature (291  2.0 K) and pressure (72 kPa). The highly performing
[Fe]active/[H2O2] ratio employed was 0.119; this ratio is very useful in order to
realize the best set of operating parameters in Fenton and Fenton-like processes,
since it may guarantee the most efficient use of the hydrogen peroxide by the
catalyst, improving cost operation of the technology (see Fig. 7a).
As a result of the above study, two general statements can be raised: Natural
organic matter could be not only complexed by iron but also adsorbed on the
124 A.-M. Garcı́a et al.

Fig. 7 Schematic representation of (a) relationship between three main factors governing CWPO
degradation of NOM and (b) possible initial pathways of radical attack on NOM substrates in the
heterogeneous Fenton-like CWPO system as activated by Al/Fe-PILCs: (1) attack of radicals on
NOM adsorbed on the catalyst’s surface and (2) radical attack on NOM dissolved in the reaction
medium

catalyst’s surface [61] so that the radicals can attack it, while it is inside the pores or
on the surface of the solid (see Fig. 7b). A second pathway of attack can be
established by an adsorption-desorption equilibrium where the dissolved NOM is
in the fluid phase and gets attacked by the oxidizing radicals diffused from the
catalyst surface.

4.4 Heterogeneous Photocatalysis: TiO2/UV

The TiO2 photocatalytic treatment has been considered to be effective in the

destruction of NOM. TiO2-catalysed system is attractive due to its potential to
degrade organic macromolecules [62]. The photocatalysis offers a potentially cost-
effective avenue for contaminant removal through extensive material reuse, use of
solar illumination energy and reutilization of existing UV disinfection facilities to
achieve more efficient treatment in drinking water treatment plants [63]. The TiO2
photocatalytic mechanism initiates with the absorption of UV light with energy
greater than +3.2 eV (TiO2 band gap, energy corresponding to wavelengths below
370 nm). It results in generation of conduction band electrons (e
) and valence
band hole (h+) pairs involved in the production of HO•, O2• and HO2• . H2O2 can also
be formed in situ, what improves the production of HO• and slows down the
recombination of the charges [43].
Brame et al. [63] proposed a model to explain various inhibition ways in
catalytic AOPs, including role played by NOM as scavenger itself during the
removal of a target pollutant. The model is schematized at Fig. 8 and assumes
that the organic solute is adsorbed on the photocatalyst surface and the degradation
may occur both on catalyst surface and in the bulk solution.
Sen Kavurmaci and Bekbolet [64] investigated the influence of a montmorillon-
ite (Mt) on the TiO2 photocatalytic removal of HAs as the model compounds of
Separation and Characterization of NOM Intermediates Along AOP Oxidation 125

Fig. 8 Mass transport

pathways during
photocatalytic degradation.
Reproduced with
permission of Elsevier
from [63]

natural organic matter. The study about the interaction of Mt with organics
dissolved in water is very important in order to better figure out the NOM degra-
dation in the presence of the Al-/Fe-clay catalysts analysed above. Experiments
were done in the absence or presence of TiO2 under dark or light conditions and
presence or absence of Mt. The adsorptive removal of colour436 was higher than the
removal of UV254 or UV365, which was interpreted in terms of the coloured
moieties in the HAs being the main responsible of the interactions with the TiO2
surface. In fact, the oxidative removal displayed the following order: col-
our436 > UV365 > UV254 > DOC. Similar results had been before reported for
the interaction of HAs with the Al/Fe-PILC catalysed CWPO treatment [13], but
the very fast colour removal was there explained instead by higher susceptibility of
the chromophores present in HAs against the oxidizing species.
The presence of Mt slightly altered the photocatalytic reactivity of HA, predom-
inantly the colour moieties, probably because of the increased turbidity in the
colloidal medium. In addition, the presence of Mt and absence of TiO2 did not
change the removal efficiency of DOC under irradiation. The mechanism in
absence of Mt is summarized in Eq. (22):


TiO2 þ hvðλ < 388
nmÞ ! TiO2 hþ

VB þ eCB !    ! ROS
HO • =HO2• =O
2 !    ! HO þ HAads ! A þ H2 O !
• •
ð22Þ
via radical reactions !    ! HAox !   
Lower molecular weight degradation products !! CO2 þ H2 O

Short-chain aldehydes and ketones have been identified as key degradation

products in this type of photocatalytic degradation of NOM by Liu et al.
[62]. The addition of hydrogen peroxide did not change the reaction pathway
126 A.-M. Garcı́a et al.

producing similar degradation products. The GC-MS analyses of aldehydes and

ketones in raw and treated waters were carried out by derivatization of the carbonyl
compounds with O-2,3,4,5,6-(pentafluorobenzyl)hydroxylamine hydrochloride
(PFBHA), and the oxime derivatives were subsequently recovered by extraction
with hexane. The photocatalytic NOM oxidation (365 nm; 0.1 g catalyst/L; pH
7.0–7.6) reached around 80% of mineralization and 100% of UV254 removal after
4 h of reaction. The higher elimination of aromaticity in comparison with the DOC
implied that loss of aromaticity and conjugation is easier to achieve than mineral-
ization of the NOM. According to LC-SEC results, TiO2-photocatalytic treatment
preferentially degraded the high molecular weight fractions together with a con-
siderable decrease in the fraction of hydrophobic acids, in pretty similar fashion
above-mentioned for other AOPs. This fraction has shown to be more prone against
degradation, unlike the hydrophilic charged and neutral fractions, which tend to
increase throughout anyone of the processes, preventing the complete mineraliza-
tion to be achieved. These fractions consist mostly of aldehydes, ketones, alcohols
and small carbohydrates. The analyses of a raw water, Myponga Reservoir, Ade-
laide, Australia, revealed five carbonyl compounds being present: formaldehyde,
acetaldehyde, acetone, n-propanal and n-butanal. In general, after 15 min of
irradiation, formaldehyde and acetone notably increased, while acetaldehyde,
propanal and butanal got easily degraded.

4.5 Ultrasound-Based Applications

Some applications have employed ultrasound waves to produce an oxidative

environment due to cavitation bubbles generated during the rarefaction phase of
sound waves. The cavitation bubble violently collapses during the compression
cycle, and localized hot spots are formed, which may reach temperatures and
pressures in excess of 5,000 K and 1,000 atm, respectively. The high temperatures
result in the splitting and decomposition of chemical compounds present inside the
bubbles, including water, which leads to formation of HO• radicals and hydrogen
peroxide [65].
The monitored parameters in an experimental ultrasound study are mainly
sonication time, irradiation power, NOM concentration, temperature, pH, conduc-
tivity, redox potential and turbidity [35]. An acid pretreatment can be used to
eliminate carbonates and bicarbonates in the sample and to enhance the TOC
removal efficiency [66]. NOM removal is strongly influenced in this type of
technologies by the power, initial NOM concentration and sonication time [67].
Sonochemical destruction of contaminants is particularly effective on volatile
substrates; alternative decomposition mechanisms have been postulated to account
for the destruction of semi-volatile and non-volatile solutes [66, 68, 69]. The easy
application of the technology as well as no production of toxic by-products like
THMs formed through chlorination make the system very attractive for NOM
removal [35]. However, NOM may significantly influence the effectiveness of
Separation and Characterization of NOM Intermediates Along AOP Oxidation 127

ultrasound, since it often interferes with the treatment process by binding organic
and inorganic contaminants and scavenging reactive species [65], as explained
before. Olson et al. [66] evaluated, more than two decades ago, the potential of
an advanced oxidation process involving ozone and ultrasound for catalytic degra-
dation of humic acids; they suggested that any volatile organic compound could
potentially be oxidized directly by pyrolysis inside the cavitation bubbles. How-
ever, NOM does not have a volatile nature. In spite of that, volatile intermediates,
which undergone pyrolysis, were produced through reaction between hydroxyl
radicals with dissolved fulvic acids. The same authors showed that ultrasound
combined with ozone showed better results in comparison with ozone alone (40%
removal TOC) or low-frequency ultrasound (55 W, 20 kHz; no degradation). In
fact, after 60 min the combination of both methods reached 90% of TOC removal
under ultrasonic power of 27 W and 3.2 mg/min of ozone [66]. Interestingly, the pH
increased during the process due to volatilization of small molecular weight
carboxylic acids and carbon dioxide, a feature clearly different in comparison of
most of the rest of AOPs. The same trend in pH evolution was later observed by
Chen et al. [65]. Such changes could be not so evident in all cases due to relatively
high pH-buffering capacity displayed by humic acids [35]. Interestingly, they also
reported that the use of high-frequency ultrasound (354 kHz, energy density of
450 W/L) acting alone was able to remove NOM. The TOC removals reported over
two samples treated by ultrasound, (1) a commercial Aldrich humic acid and
(2) DOM extracted from Pahokee peat (purchased from the International Humic
Substances Society Sonochemical reactions of dissolved organic matter, IHSS),
were 33.3% and 19.1%, respectively. At 354 kHz under intensity of 120 W/L, no
significant depletion was observed of none of the targeted substrates.
As a result of ultrasonication, the NOM structure changes on the contents of
chromophores,
COOH,
OH-substituted benzene rings, intramolecular electron
donor-acceptor complexes and complex unsaturated chromophores; it also changes
in dissociation or protonation of carboxyl and phenolic groups in humic acids, as
observed by Naddeo et al. [35].
Al-Juboori et al. [70] evidenced that pulse treatment at high power and long
treatment time achieved the highest reduction in very hydrophobic acid fraction
(VHA). For charged hydrophilic acids and neutral hydrophilic acids, the highest
increment was attained under continuous treatment for a long time together with
low and high powers, respectively. Ultrasound in combination with hydrogen
peroxide (US/H2O2) has displayed better results in the efficiency removal of HA
(91.5%) than US alone (69.3%) or H2O2 alone (20%) [67].

5 Conclusions

The selection of one particular AOP for degradation of NOM strongly depends on
the physicochemical properties of the target water. For instance, the conventional
Fenton reaction catalysed in homogeneous regime requires operating pH values
128 A.-M. Garcı́a et al.

below 4.0, whereas waters containing strongly UV-absorbing substrates may be

difficult to be treated by UV/H2O2 and other UV-based technologies. Several NOM
fractions used to have high aromatic content, whose UV adsorption may increase
energy consumption. Moreover, the application of AOPs for NOM removal remains
in general quite interesting since the reactions of HO• radicals on this type of
substrates have shown similar rate constants in comparison to other more studied
organic pollutants. Like in other contaminated systems, the presence of carbonates,
bicarbonates, sulphates, chlorides, bromides and fluorides may act as scavengers of
the oxidizing radicals decreasing overall performance of the process. In addition,
NOM may also get involved in metal complexing that could affect the Fenton
processes. However, especially the heterogeneous Fenton variants remain being the
most interesting ones to be further investigated, since they could operate efficiently
even under circum-neutral pH values, typical of most supply sources feeding
drinking water plants. Furthermore, it has been recently evidenced that coloured
NOM triplet excited states can also promote side pathways increasing formation of
ROS in photoactivated processes that could be useful in photocatalytic degradation
of NOM. Finally, attention must be paid to the selective efficiency displayed by the
AOPs as a function of the polar character. There is probably enough evidence
demonstrating that the hydrophilic fraction is the most refractory in NOM, whereas
the hydrophobic one is rapidly degraded and even mineralized to CO2. Thus, it is
recommendable to find a process that allows for the more efficient elimination of
the hydrophilic fraction at the lowest possible cost of reagents and energy.
Since the natural organic matter is a complex mixture mainly of organic con-
tents, its molecular tracing through AOP treatments is still challenging from the
analytical point of view. It explains in part the more rather delayed assessment of
intermediates and by-products occurring in the NOM degradation by AOPs that is
evidenced in literature in comparison with other widely studied contaminants as, for
instance, phenols and azo-dyes. However, a set of analytical tools is now available,
making possible to efficiently differentiate both the polar character (resin fraction-
ation; RP-LC) and the molecular size distribution (LC-SEC); besides, some spec-
troscopic measurements are very useful in order to infer several features of
dissolved NOM like the aromatic character, the predominant polar nature and
even the degree of condensation of the carbonaceous networks. Within these
analytical issues, the role still to be played by special variants of fluorescence
spectroscopy (FEEM) and mass spectrometry (ESI-FT-ICR-MS) is very interesting.
It is noteworthy that TOC equipments remain being probably the most useful
technique in the field of the overall characterization of NOM, its intermediates
and by-products.

Acknowledgements Financial support from CWPO Project for Enhanced Drinking Water in
Nari~
no (BPIN 2014000100020), CT&I Fund of SGR, Colombia, is kindly acknowledged. MAV
and AG thank the support from the Spanish Ministry of Economy and Competitiveness (MINECO)
and the European Regional Development Fund (FEDER) (projects MAT2013-47811-C2-R and
MAT2016-78863-C2-R). AMG also gratefully thanks PhD scholarship granted by Nari~ no Depart-
ment (BPIN 2013000100092) and Managed by CEIBA Foundation, Colombia.
Separation and Characterization of NOM Intermediates Along AOP Oxidation 129

References

1. Camargo Valero M, Cruz Torres LE (1999) Sustancias húmicas en aguas para abastecimiento.
Ing Invest 44:63–72
2. Chiou CT, Malcolm RL, Brinton TI, Kile DE (1986) Water solubility enhancement of some
organic pollutants and pesticides by dissolved humic and fulvic acids. Environ Sci Technol 20
(5):502–508
3. Leenheer JA, Croué J–P (2003) Aquatic organic matter: understanding the unknown structures
is key to better treatment of drinking water. Environ Sci Technol 37(1):18A–26A
4. CBCL Limited, Newfoundland and Labrador, Department of Environment and Conservation,
Water Management Division (2011) Study on characteristics and removal of natural organic
matter in drinking water systems in newfoundland and labrador – final report. Department of
Environment and Conservation, Water Management Division, St. John’s
5. Frimmel FH, Abbt-Braun G, Heumann KG, Hock B, Lüdemann H-D, Spiteller M (2002)
Refractory organic substances in the environment. Wiley–VCH Verlag GmbH, Weinheim
6. Matilainen A, Gjessing ET, Lahtinen T, Hed L, Bhatnagar A, Sillanpaa M (2011) An overview
of the methods used in the characterisation of natural organic matter (NOM) in relation to
drinking water treatment. Chemosphere 83(11):1431–1442
7. Lavonen E (2015) Tracking changes in dissolved natural organic matter composition. PhD
thesis, Swedish University of Agricultural Sciences, Uppsala
8. Navalón S (2010) Parámetros de calidad del agua relacionados con la presencia de materia
orgánica y microorganismos. PhD thesis, Universidad Politécnica de Valencia, Valencia
9. Matilainen A, Vepsalainen M, Sillanpaa M (2010) Natural organic matter removal by coag-
ulation during drinking water treatment: a review. Adv Colloid Interf Sci 159(2):189–197
10. Cui X, Choo K-H (2014) Natural organic matter removal and fouling control in low–pressure
membrane filtration for water treatment. Environ Eng Res 19(1):1–8
11. Leenheer JA (1981) Comprehensive approach to preparative isolation and fractionation of
dissolved organic carbon from natural waters and wastewaters. Environ Sci Technol 15
(5):578–587
12. Cehovin M, Medic A, Scheideler J, Mielcke J, Ried A, Kompare B, Zgajnar Gotvajn A (2017)
Hydrodynamic cavitation in combination with the ozone, hydrogen peroxide and the UV–
based advanced oxidation processes for the removal of natural organic matter from drinking
water. Ultrason Sonochem 37:394–404
13. Galeano LA, Bravo PF, Luna CD, Vicente MÁ, Gil A (2012) Removal of natural organic
matter for drinking water production by Al/Fe–PILC–catalyzed wet peroxide oxidation: effect
of the catalyst preparation from concentrated precursors. Appl Catal B 111–112:527–535
14. Matilainen A, Sillanpaa M (2010) Removal of natural organic matter from drinking water by
advanced oxidation processes. Chemosphere 80(4):351–365
15. Xing L, Murshed MF, Lo T, Fabris R, Chow CWK, van Leeuwen J, Drikas M, Wang D (2012)
Characterization of organic matter in alum treated drinking water using high performance
liquid chromatography and resin fractionation. Chem Eng J 192:186–191
16. Wang H, Zhu Y, Hu C (2017) Impacts of bacteria and corrosion on removal of natural organic
matter and disinfection byproducts in different drinking water distribution systems. Int
Biodeterior Biodegrad 117:52–59
17. Trueman BF, MacIsaac SA, Stoddart AK, Gagnon GA (2016) Prediction of disinfection by–
product formation in drinking water via fluorescence spectroscopy. Environ Sci Water Res
Technol 2(2):383–389
18. Giannino M (2014) Drinking water and water management: new research. Nova Science
Publishers, New York
19. Fan X, Tao Y, Wang L, Zhang X, Lei Y, Wang Z, Noguchi H (2014) Performance of an
integrated process combining ozonation with ceramic membrane ultra–filtration for advanced
treatment of drinking water. Desalination 335(1):47–54
130 A.-M. Garcı́a et al.

20. Abdul Hamid KI, Sanciolo P, Gray S, Duke M, Muthukumaran S (2017) Impact of ozonation
and biological activated carbon filtration on ceramic membrane fouling. Water Res
126:308–318. https://doi.org/10.1016/j.watres.2017.09.012
21. Papageorgiou A, Voutsa D, Papadakis N (2014) Occurrence and fate of ozonation by–products
at a full–scale drinking water treatment plant. Sci Total Environ 481:392–400
22. Linden KG, Mohseni M (2014) Advanced oxidation processes: applications in drinking water
treatment. In: Ahuja S (ed) Comprehensive water quality and purification. Elsevier,
Amsterdam
23. Kommineni S, Zoeckler J, Stocking A, Liang S, Flores A, Kavanaugh M, Rodriguez R,
Browne T, Roberts R, Brown A, Stocking A (2008) 3.0 advanced oxidation processes.
National Water Research Institute, Fountain Valley
24. Pignatello JJ, Oliveros E, MacKay A (2006) Advanced oxidation processes for organic
contaminant destruction based on the Fenton reaction and related chemistry. Crit Rev Env
Sci Technol 36(1):1–84
25. Li Y, Fang Z, He C, Zhang Y, Xu C, Chung KH, Shi Q (2015) Molecular characterization and
transformation of dissolved organic matter in refinery wastewater from water treatment
processes: characterization by fourier transform ion cyclotron resonance mass spectrometry.
Energy Fuel 29(11):6956–6963
26. Świetlik JS, Sikorska E (2005) Characterization of natural organic matter fractions by high
pressure size–exclusion chromatography, specific UV absorbance and total luminescence
spectroscopy. Pol J Environ Stud 15(1):145–153
27. Hu HY, Du Y, Wu QY, Zhao X, Tang X, Chen Z (2016) Differences in dissolved organic
matter between reclaimed water source and drinking water source. Sci Total Environ
551–552:133–142
28. Fabris R, Chow C, Tran T, Gray S, Drikas M (2008) Development of combined treatment
processes for the removal of recalcitrant organic matter. CMSE Internal Technical Report
2008–316, CSIRO, Canberra
29. Pavlik JW, Perdue EM (2015) Number–average molecular weights of natural organic matter,
hydrophobic acids, and transphilic acids from the suwannee river, georgia, as determined using
vapor pressure osmometry. Environ Eng Sci 32(1):23–30
30. Pan Y, Li H, Zhang X, Li A (2016) Characterization of natural organic matter in drinking
water: sample preparation and analytical approaches. Trends Environ Anal Chem 12:23–30
31. Rodrı́guez FJ, Nú~nez LA (2011) Characterization of aquatic humic substances. Water Environ
J 25(2):163–170
32. Stylianou SK, Katsoyiannis IA, Ernst M, Zouboulis AI (2017) Impact of O3 or O3/H2O2
treatment via a membrane contacting system on the composition and characteristics of the
natural organic matter of surface waters. Environ Sci Pollut Res Int. https://doi.org/10.1007/
s11356–017–9554–8
33. Moncayo-Lasso A, Rincon A-G, Pulgarin C, Benitez N (2012) Significant decrease of THMs
generated during chlorination of river water by previous photo–Fenton treatment at near
neutral pH. J Photochem Photobiol A 229(1):46–52
34. Uyguner CS, Bekbolet M (2005) Implementation of spectroscopic parameters for practical
monitoring of natural organic matter. Desalination 176(1–3):47–55
35. Naddeo V, Belgiorno V, Napoli RMA (2007) Behaviour of natural organic matter during
ultrasonic irradiation. Desalination 210(1–3):175–182
36. Kujawinski EB, Del Vecchio R, Blough NV, Klein GC, Marshall AG (2004) Probing
molecular–level transformations of dissolved organic matter: insights on photochemical deg-
radation and protozoan modification of DOM from electrospray ionization Fourier transform
ion cyclotron resonance mass spectrometry. Mar Chem 92(1–4):23–37
37. Galeano LA, Vicente MA, Gil A (2014) Catalytic degradation of organic pollutants in aqueous
streams by mixed Al/M–pillared clays (M ¼ Fe, Cu, Mn). Catal Rev 56(3):239–287
Separation and Characterization of NOM Intermediates Along AOP Oxidation 131

38. Tsydenova O, Batoev V, Batoeva A (2015) Solar–enhanced advanced oxidation processes for
water treatment: simultaneous removal of pathogens and chemical pollutants. Int J Environ
Res Public Health 12(8):9542–9561
39. Von Sonntag CS, Schuchmann HP (1991) The elucidation of peroxyl radical reactions in
aqueous solution with the help of radiation–chemical methods. Angew Chem Int Ed Engl 30
(10):1229–1253
40. Von Sonntag C, Schuchmann HP (1997) Peroxyl radicals in aqueous solutions. Peroxyl
radicals. Wiley, New York
41. Von Sonntag C (2008) Advanced oxidation processes: mechanistic aspects. Water Sci Technol
58(5):1015–1021
42. Xie P, Ma J, Liu W, Zou J, Yue S (2015) Impact of UV/persulfate pretreatment on the
formation of disinfection byproducts during subsequent chlorination of natural organic matter.
Chem Eng J 269:203–211
43. Rubio-Clemente A, Torres-Palma RA, Pe~nuela GA (2014) Removal of polycyclic aromatic
hydrocarbons in aqueous environment by chemical treatments: a review. Sci Total Environ
478:201–225
44. Lamsal R, Walsh ME, Gagnon GA (2011) Comparison of advanced oxidation processes for the
removal of natural organic matter. Water Res 45(10):3263–3269
45. Tubić A, Agbaba J, Dalmacija B, Perović SU, Klašnja M, Rončević S, Ivančev-Tumbas I
(2011) Removal of natural organic matter from groundwater using advanced oxidation pro-
cesses at a pilot scale drinking water treatment plant in the central banat region (Serbia). Ozone
Sci Eng 33(4):267–278
46. Zhong X, Cui C, Yu S (2017) Exploring the pathways of aromatic carboxylic acids in ozone
solutions. RSC Adv 7(55):34339–34347
47. Pisarenko AN, Stanford BD, Snyder SA, Rivera SB, Boal AK (2013) Investigation of the use
of chlorine based advanced oxidation in surface water: oxidation of natural organic matter and
formation of disinfection byproducts. J Adv Oxid Technol 16(1):137–150
48. Wang GS, Liao CH, Chen HW, Yang HC (2006) Characteristics of natural organic matter
degradation in water by UV/H2O2 treatment. Environ Technol 27(3):277–287
49. González O, Justo A, Bacardit J, Ferrero E, Malfeito JJ, Sans C (2013) Characterization and
fate of effluent organic matter treated with UV/H2O2 and ozonation. Chem Eng J 226:402–408
50. Wang WL, Zhang X, Wu QY, Du Y, Hu HY (2017) Degradation of natural organic matter by
UV/chlorine oxidation: molecular decomposition, formation of oxidation byproducts and
cytotoxicity. Water Res 124:251–258
51. Fang JY, Fu Y, Shang C (2014) The roles of reactive species in micropollutant degradation in
the UV/free chlorine system. Environ Sci Technol 48(3):1859–1868
52. Giannakis S, Gamarra Vives FA, Grandjean D, Magnet A, De Alencastro LF, Pulgarin C
(2015) Effect of advanced oxidation processes on the micropollutants and the effluent organic
matter contained in municipal wastewater previously treated by three different secondary
methods. Water Res 84:295–306
53. Porras J, Bedoya C, Silva-Agredo J, Santamaria A, Fernandez JJ, Torres-Palma RA (2016)
Role of humic substances in the degradation pathways and residual antibacterial activity
during the photodecomposition of the antibiotic ciprofloxacin in water. Water Res 94:1–9
54. Blough NV, Zepp RG (1995) Active oxygen in chemistry. In: Foote CS, Valentine JS,
Greenberg A, Liebman JF (eds) Structure energetics and reactivity in chemistry series1st
edn. Chapman & Hall, London, pp 280–333
55. Birben NC, Uyguner-Demirel CS, Kavurmaci SS, Gürkan YY, Turkten N, Cinar Z, Bekbolet
M (2017) Application of Fe–doped TiO2 specimens for the solar photocatalytic degradation of
humic acid. Catal Today 281:78–84
56. Li Y, Pan Y, Lian L, Yan S, Song W, Yang X (2017) Photosensitized degradation of
acetaminophen in natural organic matter solutions: the role of triplet states and oxygen.
Water Res 109:266–273
132 A.-M. Garcı́a et al.

57. Murray CA, Parsons SA (2004) Removal of NOM from drinking water: Fenton’s and photo–
Fenton’s processes. Chemosphere 54(7):1017–1023
58. Molnar J, Agbaba J, Watson M, Tubić A, Kragulj M, Maletić S, Dalmacija B (2015)
Groundwater treatment using the Fenton process: changes in natural organic matter charac-
teristics and arsenic removal. Int J Environ Res 9(2):467–474
59. Giannakis S, Polo Lopez MI, Spuhler D, Sanchez Perez JA, Fernandez Ibanez P, Pulgarin C
(2016) Solar disinfection is an augmentable, in situ–generated photo–Fenton reaction part 2: a
review of the applications for drinking water and wastewater disinfection. Appl Catal B
198:431–446
60. Moncayo-Lasso A, Sanabria J, Pulgarin C, Benitez N (2009) Simultaneous E. coli inactivation
and NOM degradation in river water via photo–Fenton process at natural pH in solar CPC
reactor. A new way for enhancing solar disinfection of natural water. Chemosphere 77
(2):296–300
61. Greathouse J, Johnson K, Greenwell H (2014) Interaction of natural organic matter with
layered minerals: recent developments in computational methods at the nanoscale. Minerals
4(2):519–540
62. Liu S, May L, Fabris R, Chow C, Drikas M, Amal R (2008) TiO2 photocatalysis of natural
organic matter in surface water: impact on trihalomethane and haloacetic acid formation
potential. Environ Sci Technol 42:6218–6223
63. Brame J, Long M, Li Q, Alvarez P (2015) Inhibitory effect of natural organic matter or other
background constituents on photocatalytic advanced oxidation processes: mechanistic model
development and validation. Water Res 84:362–371
64. Sen Kavurmaci S, Bekbolet M (2013) Photocatalytic degradation of humic acid in the presence
of montmorillonite. Appl Clay Sci 75–76:60–66
65. Chen D, Ziqi H, Weavers LK, Chin Y-P, Walker HW, Hatcher PG (2004) Sonochemical
reactions of dissolved organic matter. Res Chem Intermed 30(7–8):735–753
66. Olson TM, Barbier PF (1994) Oxidation kinetics of natural organic matter by sonolysis and
ozone. Water Res 28(6):1383–1391
67. Pourzamani H, Majd AMS, Attar HM, Bina B (2015) Natural organic matter degradation using
combined process of ultrasonic and hydrogen peroxide treatment. Anu Inst Geocienc 38
(1):63–72
68. Serna-Galvis EA, Silva-Agredo J, Giraldo-Aguirre AL, Flórez-Acosta OA, Torres-Palma RA
(2016) High frequency ultrasound as a selective advanced oxidation process to remove
penicillinic antibiotics and eliminate its antimicrobial activity from water. Ultrason Sonochem
31:276–283
69. Guzman-Duque FL, Pétrier C, Pulgarin C, Pe~nuela G, Herrera-Calderón E, Torres-Palma RA
(2016) Synergistic coupling between electrochemical and ultrasound treatments for organic
pollutant degradation as a function of the electrode material (IrO2 and BDD) and the ultrasonic
frequency (20 and 800 kHz). Int J Electrochem Sci 11(9):7380–7394
70. Al-Juboori RA, Yusaf T, Aravinthan V, Bowtell L (2016) Investigating natural organic carbon
removal and structural alteration induced by pulsed ultrasound. Sci Total Environ
541:1019–1030
Photo(Catalytic) Oxidation Processes
for the Removal of Natural Organic Matter
and Contaminants of Emerging Concern
from Water

€
Monica Brienza, Can Burak Ozkal, and Gianluca Li Puma

Abstract Natural organic matter (NOM) is a heterogeneous complex of organic

materials and is ubiquitous in natural aquatic systems. The amount of NOM in the
environment is continuously increasing because of global warming and/or changes
in precipitation patterns and has negative impact on drinking water as it produces an
undesirable colour and as a vector for the introduction of contaminants. For these
reasons, several technologies have been proposed to address the impact of NOM in
aqueous systems. Among these, advanced oxidation processes (AOPs) refer to
oxidation processes that result in the formation of highly reactive radical species.
This chapter presents an overview of recent research studies dealing with photon-
activated AOPs for the removal of NOM and emerging contaminants in water.

Keywords Advanced oxidation processes, Degradation, Energy efficiency, NOM,

Water pollutants

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
2 Advanced Oxidation Processes (AOPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
3 Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3.1 Heterogeneous Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3.2 Homogenous Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
4 Photocatalysis Treatment for Contaminant Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
4.1 Photocatalytic NOM Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
4.2 Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142

M. Brienza (*), C.B. Özkal, and G. Li Puma

Faculty of Engineering, Namik Kemal University, Tekirdağ, Turkey
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 133
Water Treatment, Hdb Env Chem (2019) 67: 133–154, DOI 10.1007/698_2017_189,
© Springer International Publishing AG 2018, Published online: 14 April 2018
134 M. Brienza et al.

4.3 Pharmaceuticals and Personal Care Products (PPCPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143

5 Efficiency of AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.1 AOP Efficiency Based on Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.2 AOPs Efficiency Based on Energy Consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150

Abbreviations

AOPs Advanced oxidation processes

COD Chemical oxygen demand
DBPs Disinfection by-products
DOC Dissolved organic carbon
DOM Dissolved organic matter
ECs Emerging contaminants
EDCs Endocrine-disrupting compounds
EEO Electrical energy per order
FA Fulvic acid
Fe2+/H2O2 Fenton
GAC Granular activated carbon
H2O2 Hydrogen peroxide
HA Humic acid
IC Inorganic carbon
NOM Normal organic matter
O3/H2O2 Peroxone
O3/UV Ozonation
PPCPs Pharmaceuticals and personal care products
ROS Radical oxygen species
TCE Trichloroethylene
THMFP Trihalomethanes formation potential
TOC Total organic carbon
US Ultrasound
UV254 Ultraviolet absorbance at 254 nm
UWW Urban wastewater
VCOCs Volatile chlorinated organic carbons
VUV Vacuum UV

1 Introduction

The treatment, reuse and disposal of polluted water originating from many different
sources, including agriculture, industrial processes and rapid urban development,
require the strengthening of advanced treatment systems that prevents the intro-
duction of contaminants to surface and groundwaters. The development of such
systems is best addressed, from a technical and economical standpoint, through the
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 135

development of treatment systems that are capable of handling relatively small

volumes of effluents containing toxic, persistent organics (xenobiotics, etc.), rather
than systems that focus on the decontamination of large volumes of water [1].
A large body of research and development in recent years has demonstrated that
advanced oxidation processes (AOPs) can effectively degrade a large variety of
micropollutants and microcontaminants via the production of hydroxyl and other
radical oxygen species (ROS). These species unselectively and through multistep
oxidative pathways may lead to the removal of water contaminants and to the
reduction of its toxicity [2].
AOPs include a range of advanced oxidative processes such as ozone (O3),
Fenton (Fe2+/H2O2), electrolysis (electrodes with current), sonolysis (ultrasounds),
photolysis, photocatalysis (light with catalyst), photo-Fenton (Fenton reaction with
light).
The selection of the most effective AOP is highly dependent on the character-
istics of the wastewater such as the environmental matrix, the organic load, pH,
dissolved oxygen, dissolved organic matter, temperature and the target pollutants.
Wastewaters can be defined as complex environmental matrices often containing
dissolved organic matter (DOM), carbonate/bicarbonate, anions and many other
species, which collectively act as hydroxyl radical scavengers limiting the effi-
ciency of AOPs [3].
Natural organic matter (NOM) results from the decomposition of organic matter,
primarily from vegetation and plants. Its chemical composition contains a large
range of molecular size and is ubiquitous to all surface, ground and soil waters
[4]. It is an important component that interacts with metal ions and minerals in water
and soil forming complexes of widely differing chemical and biological nature. One
common approach for the characterization of NOM includes the fractionation of the
mixture into its hydrophobic and hydrophilic fractions. The hydrophobic fraction
includes humic substances such as fulvic acids (FA) and humic acid (HA) that
account for 50% of the total organic carbon (TOC) in water [5]. The hydrophilic
fraction contains high amount of aliphatic carbons and nitrogenous compounds, such
as carbohydrates, sugars and amino acids [4]. The amount, character and properties
of NOM vary considerably according to the origins of the water. In the last decade,
the amount of NOM in the environment has been continuously increasing, as a result
of global warming and/or changes in precipitation patterns [6]. In consequence, a
negative impact on drinking water has occurred, such as undesirable colour, taste and
odour. NOM also favours bacterial regrowth in water distribution systems which
represent a significant problem [7]. NOM is also a precursor for the formation of
disinfection by-products (DBPs) in water, such as trihalomethanes (THMFP) which
have been linked to an increase of the incidence of cancer in humans, low birth
weight and bird defects [8]. For these reasons, several treatment processes for the
removal of NOM have been considered and installed in water treatment plants, such
as ozonation [9], adsorption [10], coagulation [11], electrochemical treatment [12]
and AOPs.
This chapter reviews AOPs activated by photons used for the treatment of water
in the presence of NOM and contaminants of emerging concern. The fundamental
aspects of each AOPs and the efficiency of the radicals as oxidative species for the
136 M. Brienza et al.

destruction of common pesticides, pharmaceuticals and emerging contaminants

will be presented. The impact of the water matrix components that have a deter-
mining role on the AOPs oxidative mechanism will be discussed in detail.

2 Advanced Oxidation Processes (AOPs)

AOPs are based on the generation of very powerful, non-selective radical oxidative
species (ROS) such as hydroxyl (•OH), peroxyl (•OHH), superoxide (•O2
) radicals
and singlet oxygen (•O) that rapidly attack and oxidize a wide spectrum of organic
matter in water, unselectively [13]. Glaze and colleagues [13] were the first to
investigate the effectiveness of AOPs on the treatment of chlorinated organics in
contaminated groundwater. AOPs include heterogeneous and homogenous
photocatalysis, Fenton and Fenton-like processes, ozonation, ultrasound, micro-
wave and γ-irradiation and electrochemical and wet oxidation processes.
Among chemical-driven AOPs, Fenton and Fenton-like processes involving the
use of Fe2+ or other metal species in combination with H2O2 are in general pH
dependent and function within a narrow operating range, usually at acidic pH (<4.0).
These processes have found numerous applications for organic degradation such as
the removal of pharmaceuticals, pesticides and endocrine-disrupting chemicals.
Fenton processes present several advantages including the operation in the absence
of light and a very fast initial rate of reaction. However, the accumulation of iron
sludge at the end of treatment requires post-treatment and the cost of pH adjustment
on large volumes of water are major drawback. Fenton processes have been coupled
with a range of conventional water treatment processes such as coagulation, biolog-
ical oxidation and membrane filtration to achieve a higher degree of contaminant
degradation and mineralization [14, 15].
Peroxone, a mixture of O3 and H2O2, is mostly applied for the removal of toxic
contaminants (hydrocarbons, pesticides) and micropollutants, frequently as a pretreatment
step before adsorption in granular activated carbon (GAC) beds. Peroxone is able to
reduce the concentration of micropollutants in the influent stream to the beds and prolongs
its lifetime. The energy requirement and the necessity of on-site production of O3 are the
main limitations, although peroxone is known to provide an outstanding bactericidal
performance [16].
Sonochemical oxidation processes involve the use of ultrasound waves propa-
gating through the aqueous medium. They produce intense vibrations to the water
molecules that cause the production of hydroxyl radicals. In general, the production
of •OH radicals is localized near the sound emission source, decreasing exponen-
tially with distance, and this presents a significant limitation for the treatment of
large volumes of water. Thereby, it is more often applied in combination with other
oxidants such as H2O2 and dioxygen or combined with UV radiation and other
AOPs (including Fenton reagent and Fenton-type reactions). Sonochemical pro-
cesses have found a variety of applications including the degradation of pesticides,
aromatic compounds, endocrine disrupters and pharmaceuticals and disinfection
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 137

by-products [17–20]. Despite its technical potential for decontamination purposes,

most studies have been executed at laboratory scale, and industrial applications are
limited [21].
Electrochemical oxidation using direct electrochemistry (anodic oxidation) and
indirect electrochemistry (electro-Fenton) and their combination with sonochemical,
physicochemical and photochemical treatment methods have fulfilled many appli-
cations in water detoxification/decontamination including industrial, agricultural
and pharmaceutical treatment [21, 22]. Low-energy requirements, using small
amounts of chemical reagents and the capability of producing efficient mineraliza-
tion, make electrochemical oxidation a promising process for full-scale industrial
implementation in comparison to other AOPs. A detailed evaluation and a compar-
ison with other AOPs have been presented in a recent review paper [1].
Alongside chemical-driven AOPs, photon-driven AOPs have the advantage of
providing a simple, relatively inexpensive, clean and efficient treatment of contam-
inated water in terms of degradation, mineralization and total detoxification. Cou-
pling UV irradiation with various oxidants such as O3 and H2O2 and photocatalysis
such as Fe3+ and semiconductor nanomaterials (e.g. TiO2) results in efficient
oxidative processes. Among various photon-driven AOPs, the photolysis of H2O2,
(H2O2/UV) and O3 (O3/UV), the photo-Fenton process (H2O2/Fe2+/UV) and het-
erogeneous photocatalysis (TiO2/UV) have attracted the utmost attention in the last
decades [1, 23]. The main mechanisms by which photon-driven AOPs degrade and
mineralize water contaminants also exhibiting a bactericidal effect include ROS
attack and the direct photochemical action of UV irradiation [24]. Among all of the
oxidative treatment, photocatalytic processes have received significant attention for
the treatment of water.

3 Photocatalysis

The word photocatalysis contains a prefix and a word, “photo” and “catalysis”.
Generally speaking, photocatalysis involves the activation of a photocatalytic
material or substance by light photons, which in turn increases the rate of a
chemical reaction without being consuming. The photocatalyst can be species
dissolved in the liquid phase (homogeneous photocatalysis) or can be solids
suspended in the liquid or immobilized on surfaces (heterogeneous photocatalysis).

3.1 Heterogeneous Photocatalysis

Heterogeneous photocatalysis makes use of semiconductor solid materials (e.g. ZnO,

TiO2, ZrO2, CdS, ZnS) which catalyse the production of ROS and the removal of
organic and inorganic contaminants when photoactivated by light photons. Among
many semiconductors, titanium dioxide (TiO2) has received significant attention in
138 M. Brienza et al.

fundamental research and in practical applications, due to its favourable characteristics,

such as abundance and low cost, chemically inert and stable properties, low toxicity and
relatively high photoactivity compared to other semiconductor materials [25].
The energy gap between the valence and the conduction bands of TiO2 (anatase)
is 3.2 eV, which implies that the absorption of photons of wavelength of less than
384 nm may photoactivate electrons (e
) from the valence band towards the
conduction band, leaving holes (h+) in the valence band (Reaction 1) [26]. The
electrons and the holes can in turn drive reduction and oxidation reactions, respec-
tively. For example, in the presence of an oxygenated water solution, (e
) can
reduce adsorbed O2 to form the superoxide radical (•O2
) (Reaction 3), and the (h+)
can oxidize an electron acceptor such as water to form the hydroxyl radical (•OH)
(Reaction 3).

TiO2 þ hv ! e
þ
cb þ hvb ð1Þ

•

O2 þ ecb ! O2 ð2Þ
H2 Oads þ hþ vb ! OHads þ H
• þ
ð3Þ
O2•
þ Hþ ! HO2• ð4Þ
HO2 þ HO2• ! H2 O2 þ O2
•
ð5Þ
H 2 O 2 þ e
cb ! HO þ HO
•

ð6Þ
þ •þ
D þ hvb ! D ð7Þ
A þ e
cb ! A
•

ð8Þ
e
þ
cb þ hvb ! TiO2 þ heat ð9Þ

Reactions 5 and 6 in the sequence above show the formation of hydrogen peroxide,
which is known to split into two hydroxyl radicals through aqueous photolysis or to accept
an electron (Reaction 6). Reactions 7 and 8 show how the hole (h+vb) can react directly
with an adsorbed organic electron donor (D) and how a conduction band hole (e
cb) can
reduce an adsorbed electron acceptor. The competing recombination of the two charge
carriers release heat (Reaction 9).

3.2 Homogenous Photocatalysis

3.2.1 Photo-Fenton Treatment

The Fenton process was discovered by Fenton in 1894 [27] during the oxidation of
maleic acid. The Fenton reaction involved the reaction between dissolved Fe2+ and
hydrogen peroxide (H2O2) which results in the formation of hydroxyl and peroxyl
radicals (Reactions 10 and 11).

Fe2þ þ H2 O2 ! Fe3þ þ • OH þ OH
ð10Þ

Fe3þ þ H2 O2 ! Fe2þ þ • OOH þ Hþ ð11Þ
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 139

The efficiency of the above reactions is improved by irradiation with near UV

and visible light [28], which drives the photoreduction of Fe3+ to Fe2+, regenerating
the catalyst and simultaneously producing further •OH (Reaction 12).

Fe3þ þ H2 O þ hv ! Fe2þ þ Hþ þ • OH ð12Þ

In addition, Fe3+ hydroxyl complexes under acidic condition (e.g. Fe(OH)2+)

undergo photoreduction as reported in Reaction 13 [28].

FeðOHÞ2þ þ hv ! Fe2þ þ • OH ð13Þ

The Fenton reaction carried out in the presence of irradiation is known as photo-
Fenton. This reaction, of course, is wavelength dependent, and the quantum yields
of •OH and Fe2+ ion formation decrease as the wavelength increases. The quantum
yield of •OH formation is 0.14 at 313 nm and 0.017 at 360 nm [29]. The basic
photo-Fenton process has found many applications for the degradation and miner-
alization of pesticides, dyes, chlorophenols and chlorinated compounds [28, 30].

3.2.2 Photocatalytic Ozonation (O3/UV)

Ozone is a powerful oxidant with an oxidation potential of 2.07 eV that increases to

2.8 eV in the presence of irradiation. The AOP with ozone and UV irradiation is
initiated by the photolysis of ozone. The photodecomposition of ozone leads to two
hydroxyl radicals, which do not act if they recombine producing hydrogen
peroxide [31].
O3 þ H2 O þ hv ! H2 O2 þ O2 ð14Þ

In this system, there are three components that are able to produce hydroxyl radicals:
UV radiation, ozone and hydrogen peroxide. Therefore, the reaction mechanisms
involving O3/H2O2, as well the combination UV/H2O2, are of great importance. O3/
UV has attracted great attention for the elimination of volatile chlorinated organic
carbons (VCOCs) such as CHCl3, CCl4, trichloroethylene (TCE), tetrachloroethylene
and 1,1,2-trichloroethane [32]. Besides effluents containing pesticides, endocrine dis-
rupters, pharmaceutical compounds, antibiotics, surfactants, dyes and nitrobenzene
have been set as targets in different O3/UV applications.

3.2.3 Photolysis of Hydrogen Peroxide (UV/H2O2)

In this process, H2O2 is split into two hydroxyl radicals by adsorption of UVC light.
The most accepted mechanism for the H2O2 photolysis is the rupture of the O–O
bond by activation of ultraviolet light.
140 M. Brienza et al.

H2 O2 þ hv ! 2 • OH ð15Þ

This reaction is pH dependent and becomes more efficient under alkaline


conditions, probably because at 253.7 nm the anion peroxide HO2
has a high
molar adsorption coefficient (240 vs 18.6 M
1 cm
1) [13]. The hydroxyl radical
formed can further attack hydrogen peroxide leading to the reactions sequence
(Reactions 16, 17, and 18):

H2 O2 þ • OH ! HO2 þ H2 O ð16Þ

• OH þ HO
2 ! HO2 þ OH


ð17Þ


H2 O2 þ HO2 ! • OH þ O2 þ H2 O þ • OH ð18Þ

One of the pioneering studies in the field of UV/H2O2 was the study by Eckenfelder
et al., which set the target on groundwater decontamination [33]. The H2O2/UV process
has been found to be efficient for the elimination of cyanides and other organic
pollutants, such as benzene, trichloroethylene and tetrachloroethylene [34].

3.2.4 Peroxone Process (O3/H2O2)

The peroxone process was studied by Staehelin and Hoigné [35]. The decomposi-
tion of O3 into •OH radicals is accelerated by the presence of hydrogen peroxide
according to Reaction 19 [36].
H2 O2 þ 2O3 ! 2 • OH þ 3 O2 ð19Þ

The main advantage of peroxone treatment is the short reaction time; in fact, due
the quick reaction, time is not necessary to use high doses of ozone to obtain faster
reactions with pollutants. Von Gunten [37, 38] reported a good review including
ozone-AOPs as drinking water treatment.

3.2.5 Vacuum Ultraviolet (VUV)

The application of ultraviolet irradiation in water treatment can be distinguished as

UV-A (380–315 nm), UV-B (315–280 nm), UV-C (280–200 nm), V-UV (200–100 nm)
and extreme UV (100-1) [39]. Photolysis of water at 185 nm is a highly efficient process
for the generation of hydroxyl radicals. At this wavelength, the homolysis and photo-
chemical ionization of water lead to the formation of •OH with quantum yields of 0.33
and 0.045, respectively [40].
hv ð185 nmÞ
H2 O ƒƒƒƒƒ!  OH þ Hþ Φ ¼ 0:33 ð20Þ
hv ð185 nmÞ  þ
H2 O ƒƒƒƒƒ! OH þ H Φ ¼ 0:045 ð21Þ
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 141

The problem connected with the VUV treatment is the formation of by-products,
especially nitrite, which occurs from the photolysis of nitrate in the water.
Among the photochemical reactions described above, the photo-Fenton process
and heterogeneous photocatalysis have been reported to provide superior oxidation
conditions compared to H2O2 and O3 photolysis processes, although the latter have
been commercialized. Solar-driven photo-Fenton and heterogeneous photocatalysis
have drawn significant interest due to the potential use of solar radiation (solar
photocatalytic processes) and have been investigated in numerous studies, from
bench to pilot and to industrial scale.

4 Photocatalysis Treatment for Contaminant Removal

In the last decade, various AOPs have been evaluated for their efficacy and econom-
ical feasibility for the removal of water and wastewater contaminants. The literature
data presented in this chapter focuses primarily on the photocatalytic treatment and
its effectiveness in degrading emerging contaminants such as pesticides, pharma-
ceuticals and endocrine-disrupting compounds (EDCs) and for the control of taste
and odour.

4.1 Photocatalytic NOM Removal

The characterization of NOM in the contaminated water is essential prior to the

design and optimization of an AOP treatment, to determine the potential of the
water for the formation of DBPs and other toxic by-products. Further characteri-
zation of the water effluent is also required after AOPs treatment, to determine the
possible formation of DBPs and toxic degradation products, which may determine
the suitability of an AOP treatment for the reduction of NOM. The reactions of •OH
radicals with NOM proceed through three different ways: (1) by the addition of
•OH radicals to double bonds; (2) by H-atom abstraction, which yields carbon-
centred radicals; and (3) by a reaction mechanism in which the OH radical accept
electron from an organic substituent [2].
The degradation of NOM is much more rapid compared to total DOC minerali-
zation; thereby, the reduction in the absorbance at 254 (UV254) nm may indicate the
degradation of organics, while the reduction in DOC may take much longer time. A
rapid reduction in UV254 could indicate the presence of NOM with high molecular
mass, such as aromatic rings and their breakdown into lower molecular mass
by-products presenting negligible UV absorbance. These by-products may be less
prone to oxidation by •OH radical and may act as a barrier against total mineraliza-
tion. As the degradation of NOM fractions continue upon •OH radical attack, the
by-products formed may display several hydrophilic/hydrophobic properties com-
pared to its parent compound. In consequence, fractionation studies represent good
142 M. Brienza et al.

manuals for unravelling the possible reactions and prevailing mechanisms occurring
during the photocatalytic oxidation of NOM species [41, 42].
The shift of the molecular weight distribution towards lower values during
oxidation has been reported in numerous literature findings but most frequently
with the UV/H2O2 process [42–45]. Further studies are now focusing on the identi-
fication of DBPs and other by-products during the photocatalytic oxidation of NOM
[4]. Current investigations in the field of AOPs have already extended their vision by
setting simultaneous objectives on the removal of DBPs, NOM, mineralization and
toxicity in the water. This multidisciplinary approach is essential for determining the
most effective AOP capable of producing a safe effluent.
Traditional treatment processes, such as filtration, physical or chemical disin-
fection processes, biological processes alone or combined with other processes,
have shown several limitations in terms of removing complex organic matter, the
bacterial content and/or other recalcitrant contaminants in the aqueous matrix
[46]. The determination of the desired treatment goals are essential factors for the
proper AOP choice and design. These goals could include biodegradability
enhancement, the total mineralization of organic compounds or the desired level
of water detoxification. Any of these scenarios necessitate the optimization of the
process conditions considering the type, fractional distribution and amount of
organic matter present in the water. The alkalinity and pH of the water also play
a major role on the photocatalytic oxidation of NOM. NOM is less efficiently
adsorbed onto the surface of photocatalysts at elevated pH with a decisive decline
between pH 5–10 [47]. Concurrently at alkaline pH, carbonate or bicarbonate
species act as efficient ROS scavengers that actively decrease the rates of degrada-
tion of the target pollutants, as shown for the degradation of pharmaceuticals in
alkaline secondary treated urban wastewater (UWW) effluents [47].
Biologically treated urban wastewater contains trace and bulk organics such as
humic acids and other low molecular organic acids with a wide range of molecular
size distribution, which would act as a strict barrier against the oxidative conditions
of a photocatalytic process. In most of the scenarios, these defined factors act as
unavoidable radical scavengers, which favour surface charge recombination in
TiO2 photocatalysis.
In order to make a proper comparison of the efficiency of AOPs and most
adequate choice of a pretreatment, it is necessary to consider simultaneously the
degradation/mineralization performance of the process and the energetic require-
ments of the treatment processes.

4.2 Pesticides

The European Water Framework Directive 2000/60/EC [48] established that 33 pri-
ority substances present high toxicity, high environmental persistence, endocrine-
disrupting capabilities and bioaccumulation potential. Among these hazardous
chemicals, there are also pesticides, such as atrazine, alachlor, isoproturon,
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 143

pentachlorophenol and chlorfenvinphos. These recalcitrant compounds and their

metabolites (e.g. glyphosate AMPA) have been detected in groundwater and drink-
ing wells of various EU countries, for example, Italy [49], Hungary [50], Spain [51]
and the UK [52]. Table 1 summarizes the representative AOP treatment of common
pesticides.

4.3 Pharmaceuticals and Personal Care Products (PPCPs)

Pharmaceuticals and personal care products (PPCPs) are a wide group of emerging
environmental contaminants. Increasing number of studies have confirmed the presence
of various PPCPs in several environmental matrices such as groundwater [65], surface
water and within the water distribution system (e.g. at the tap) [66]. Nowadays, it is
known that some antibiotics may cause long-term and irreversible change to the
microorganism genome even at trace concentrations. Some PPCPs have also been
demonstrated to disrupt the human endocrine system, and hence, their presence in
aquatic systems has been a source of concern [67]. In addition to their potential negative
effect on human and wildlife, pharmaceuticals and personal care products are often
resistant to biological degradation processes [68]. The class and range of molecules
studied are vast. Table 2 reports selected representative AOP studies for the degradation
of three commonly investigated pharmaceuticals detected in water.

5 Efficiency of AOPs

This section evaluates the efficiency of AOPs on the basis of effluent toxicity and the
energy consumption. Comparison is not trivial due to the different processes involved in
the production of radicals. Furthermore, for the case of AOPs and oxidative treatment,
water matrix constituents which may become target for non-selective oxidants (most
pronounced the •OH) has to be paid the utmost attention.

5.1 AOP Efficiency Based on Toxicity

Several bioassays have been used to measure the response of organisms exposed to
target compounds and complex water matrices such as surface water, groundwater,
wastewater or seawater. Standard bioassays are best developed through the use of a
battery of organisms such as plants and algae, invertebrates, microorganisms and
fishes. The most common toxicity tests used to evaluate the effectiveness of AOP
treatment are Daphnia magna [69], Vibrio fischeri [70], lettuce seeds [71] and
zebrafish [72]. Wastewater from several sources (industrial, hospital or domestic)
necessitates choice of proper methodology for toxicity evaluation.
Table 1 Representative AOP treatment of common pesticides
144

Pesticides AOPs Experimental conditions Efficiency Reference

Atrazine Coupled solar photo-Fenton and het- Gesaprim solution with [atrazine] ¼ 35 mg/l (19 mg/l of TOC); TOC removal (%): 46 (1 h) and 30 (4 h) after solar photo-Fenton [53]
[ATZ] erogeneous TiO2 photocatalysis [H2O2]0/COD0 ¼ 3 and 10 ppm Fe2+ at pH 2.8; and TiO2 photocatalysis, respectively
processes [TiO2] ¼ 200 mg/l, UV ¼ solar irradiation; volume COD removal (%): 90 (2 h) of photo-Fenton reaction
treated ¼ 60 l
Atrazine: 68% (6 h) of photoreaction, the treated effluent was
nontoxic
UV/H2O2 Natural, drinking water and wastewater mixed with organic ATZ ¼ 80% degradation was achieved at 990 mJ/cm2 [54]
micropollutants; [ATZ] ¼ 2.6(0.2) mg/l; pH ¼ 7.4 (0.5);
[H2O2] ¼ 10 mg/l
O3/UV Distilled-deionized water solution with non-ionic surfactant, Improve the efficiency of the treatment by adding the surfactant. [55]
Brij35; treated volume, 203 ml; [ATZ] ¼ 0.01 mM; total light The enhancement (%) was 42 and 52 at pH 2.5 and
intensity ¼ 300  10
6 E/l/S (35 W) 7, respectively
VUV photolysis; UV/photocatalysis Xe lamp (150 W) at 172 nm; T ¼ 25  C; [ATZ] ¼ 1  10
4 M VUV produce OH• and H•; in absence of oxygen, H• are more [56]
prone to participate in the mineralization reaction; total miner-
alization of ATZ
Alachlor Photo-Fenton Alachlor ¼ 10 mg/l; volume ¼ 20 ml; T ¼ 25  1  C; UV Degradation (%) of alachlor ¼ 60 (60 min) without ligand [57]
[ALC] radiation ¼ <300 nm; ligand (citrate, EDTA and pyrophos- Degradation (%) of alachlor ¼ 100 in 15 min and in 30 min
phate) ¼ 1  10
4 M; [H2O2] ¼ 4  10
3 M; [Fe(II)] ¼ 1  10 with citrate and EDTA, respectively

4
M
Total TOC abetment under photo-Fenton with citrate
Ozonation processes; UV photolysis; Distilled (6 mg/l IC) and surface water from Genova River Ozonation processes depend on pH and water quality [58]
UV/H2O2 (2 mg/l IC); gas flow rate ¼ 20 l/h; [ALC] ¼ 3.7  10
5 M; Ozonation rate of alachlor is improved when ozone is com-
[O3] ¼ 1.8  10
4 M; pH ¼ 7  0.2; [H2O2] ¼ 10
3 M; bined with hydrogen peroxide or UV radiation
Io ¼ 1.6  10
6 E/L s
TiO2 photocatalysis UV light ¼ 400 W metal-halide lamp with major peak of Efficiency depend on the thickness of a TiO2 film [59]
spectrum; [TiO2] ¼0.1 g/l; [ALC] ¼ 5 mg/l Removal rate of alachlor with Fe3+ and UV (without TiO2) was
0.28 mg/l/h in 10 h
Removal rate of alachlor with Fe3+ and UV (with TiO2) was
0.32 mg/l/h in 10 h
TOC decrease (%) under TiO2/UV from 100 to 81, 51, 44 in
4, 8 and 10 h, respectively
TOC decrease (%) under Fe3+/UV (without TiO2) from 100 to
70 in 10 h
FeCl3 photocatalysis, TiO2 UV lamp ¼ Xenon arc lamp; volume ¼ 25 ml; [ALC] ¼ 30–60- The most effective method was to use 15 mg/l of FeCl3 that in [60]
photocatalysis and photolysis μg/l; [TiO2] ¼ 150 mg/l; [FeCl3] ¼ 15 mg/l; [H2O2] ¼ 0.05% 15 min was able to destroy alachlor
(v/v) FeCl3 is cheaper and offers shorter reaction half-live for ALC
M. Brienza et al.
Isoproturon TiO2 photocatalysis Volume ¼ 250 ml double-distilled water; 94.8% degradation and 78.45% mineralization in 80 min [61]
[Isoproturon] ¼ 0.5 mM; UV irradiation ¼ 125 W medium Degussa P25 was more efficient as compared to other
pressure mercury lamp; λ ¼ 238 nm; [TiO2] ¼ 1 g/l (P25; photocatalysts
Hombikat UV100; PC500 and TTP)
The degradation rate is not influenced from pH but improves
adding at 3 g/l of catalyst
Addition of electron acceptors (hydrogen peroxide, potassium
bromate, potassium persulphate) gives beneficial effect on the
degradation of isoproturon
UV/H2O2; UV/TiO2; UV/H2O2/Fe(II); V ¼ 0.5 l; UV intensity ¼ 5  10
6 E/s; [Isoproturon] ¼ 5  10 The best performance was obtained by photo-Fenton: [62]

5
UV/H2O2/TiO2 mol/l; [H2O2] ¼ 5  10
4 mol/l; [Fe(II)] ¼ 5  10
5 mol/l; Isoproturon was completely removed in 15 min, while TOC is
[TiO2] ¼ 1 g/l reduced of 89% after 60 min of irradiation
Glyphosate UVC/H2O2 Λ ¼ 253.7 nm; [glyph] ¼ 0.30 mM, [H2O2] ¼ 2.20 mM; TOC conversion after 5 h was 29% [63]
[glyph] pH ¼ 3.5, 7 and 10 63.5% glyph conversion was obtained under irradiation of two
lamps of 40 W
Best condition for degradation was at the highest value of pH
(pH 7 and pH 10)
Ozonation, photolysis and heteroge- [Glyph] ¼ 42.275 mg/l; [O3] ¼ 14 mg/l; pH ¼ 7 and 10; Ozonation at pH 6.5 ¼ 20% TOC reduction while at pH [64]
neous photocatalysis [TiO2] ¼ 0.1 g/l; V ¼ 200 ml; λ > 290 nm 10 97.5% TOC removal
TiO2 photocatalysis at pH 6.5 ¼ 92% and 99.9% TOC and
glyph removal, respectively
pH 10 the degradation rate showed to be highest in both
processes
The half-lives obtained for glyphosate degradation were 1.8
and 6.2 min for O3/pH 10 and TiO2/UV, respectively
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . .
145
146 M. Brienza et al.

Table 2 Representative AOP treatment for widely used pharmaceutical compounds

PCPPs AOPs Experimental conditions Reference
Carbamazepine UV/H2O2 Surface river water; [74, 75]
(CBZ) [CBZ] ¼ 240–710 μg/l;
UV ¼ 254 nm;
[H2O2] ¼ 10 mg/l
UV/H2O2 Water; solar
photodegradation; vol-
ume ¼ 500 ml,
[CBZ] ¼ 0.5 mmol,
[H2O2] ¼ 100 mM
TiO2 P25 photocatalysis; Surface lake water; irradia- [76]
TiO2 Hombikat UV tion ¼ simulation solar light;
100 photocatalysis [catalyst] ¼ various;
[CBZ] ¼ various
UV-AOP *(UV/PS, UV lamp ¼ 75 W (253.7 nm); [77]
UV/H2O2, UV/PMS) [CBZ] ¼ 21.16 μM,
[oxidant] ¼ 0.5–5 mM,
pH ¼ 3–11
UVC and VUV Pure water, Lamp1 ¼ 254 nm; [78]
Lamp2 ¼ 254 and 185 nm
Diclofenac (DCF) Sunlight Surface lake water; [79]
[DCF] ¼ 1 μg/l, vol-
ume ¼ 30 ml, irradiation ¼ full
sunlight for 2and 4 h
TiO2/solar light solar photo- Freshwater; solar irradiation; [80]
Fenton [DCF] ¼ 50 mg/l; vol-
ume ¼ 35 l (22 l irradiated);
[H2O2] ¼ 200–400 mg/l;
[TiO2] ¼ 0.2 g/l; [Fe
(II)] ¼ various
Ozonation, photolysis, pho- Water and wastewater; vol- [81]
tolytic ozonation, ume ¼ 250 ml;
photocatalysis and [DCF] ¼ 0.1 mM;
photocatalytic ozonation [O3] ¼ 50 g/nm3; UV ¼ mer-
cury vapour lamp;
[TiO2] ¼ 0.5 g/l
Sulfamethoxazole TiO2/UV-A UVA: 324  λ  400 nm; [82]
[SMX] [SMX] ¼ 100 μM;
[TiO2] ¼ 0.1 g/l; pH ¼ vari-
ous; [NOM] ¼ 0–20 mg/l;
[NaHCO3] ¼ 0–100 mM
Hydrolysis, photolysis, Distillate and seawater; [83]
solar photo-Fenton [SMZ] ¼ 50 mg/l; intensity
¼250 W/m2; [Fe(II)] ¼ 2.6,
5.2 and 10.4 mg/l;
[H2O2] ¼ 30 to 210 mg/l; vol-
ume ¼ 39 l; pH ¼ 2.5–2.8
O3; O3/H2O2; UV/H2O2 Milli-Q and surface lake [84]
waters; T ¼ 5–25 C; pH vari-
ous; [SMX] ¼ 1 μM; LP-UV;
[O3] ¼ 20–200 μM
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 147

Brienza and co-workers [73] reported that for a specific domestic wastewater effluent,
among the four standard bioassays (Vibrio fischeri, Daphnia magna, Pseudokirchneriella
subcapitata and Brachionus calyciflorus), the most sensitive to the variation of contam-
inant concentrations was Pseudokirchneriella subcapitata. The oxidative processes eval-
uated through specific estrogenic assays [endocrine-disrupting substances were measured
with cell lines expressing oestrogen receptor alpha (ERα) based on human cell] were able
to remove emerging contaminants and the detected oestrogenic activity.
Heringa and co-workers [85] demonstrated through a UV/H2O2 treatment pro-
cess that water matrices’ effects must be considered and that hydroxyl radicals were
not solely responsible for the increase in toxicity.
The EU Water Framework Directive requires the achievement of a “good chem-
ical and biological status” of all water bodies by 2015 [48]. In order to obtain water
bodies that meet both standards/characteristics, assessment of tertiary treatment
efficiency should be supplemented by proper toxicity evaluation. In Table 3, the
effect of selected AOPs on final toxicity of water solution is summarized.

5.2 AOPs Efficiency Based on Energy Consumption

There is increasing attention on developing cost and energy-efficient AOPs espe-

cially in the municipal water sector for the treatment of the so-called emerging
contaminants (ECs) [90]. In addition to AOPs, other technologies that can be applied
for the removal of ECs include ozonation, activated carbon or membrane technolo-
gies (reverse osmosis) which have relatively high capital and operating costs.
The major operating cost in AOPs is electrical energy consumption. The most
common way to compare AOPs based on their electrical energy efficiency is to use
the parameter of electrical energy per order (EEO). The EEO is the electric energy in
kilowatt hours (kWh) required to reduce the concentration of a target contaminant
by one order of magnitude (90% removal) in 1 m3 of contaminated water [91]. EEO
can be calculated using the following equations:
1; 000Pt
EEO ¼   Batch operation ð22Þ
Vlog CCfi
P
EEO ¼   Continuous operation ð23Þ
Flog CCfi

where P is the electrical power input in the processes [kW], V is the volume [l] of
water treated, ci and cf correspond to the initial and final the concentration after one
order of magnitude reduction (mol l
1) and F is the flow rate [m3/h] in continuous
flow system [91].
EEO can be also used to estimate if the treatment is economically acceptable for
commercial applications as suggested by Arslan-Altan [92]; in fact, in the last
148 M. Brienza et al.

Table 3 Toxic evaluation of AOP treatment

Toxicity
Emerging contaminants AOP test Comment Reference
Cyanide TiO2/UV- V. fischeri • EC50 values was signifi- [86]
Phenol A Fern cantly different for V. fischeri
spore commercial kit, V. fischeri
bioassay lab culture and Polystichum
setiferum fern spore
• In all test, the toxicity
decrease in correspondence
of cyanide or phenol
degradation
Mepanipyrim O3/Hg- V. fischeri • Toxic unit (TU) increase [87]
UV from 2.22 to 16.66 at 120 min
• At 120 min, formation of
main photoproducts was
observed
• TU decrease rapidly from
120 to 180 min
Five pesticides (ala- Photo- V. fischeri • Decrease in the beginning [88]
chlor, atrazine, Fenton of the treatment
chlorfenvinphos, diuron, • Followed stable toxic
isoproturon) level during the rest of the
photo-Fenton treatment
4- Solar D. magna • Increasing of acute and [89]
Methylaminoantipyrine irradiation chronic toxicity from
4- 27–55% to 60–85%, respec-
Formylaminoantipyrine tively
4- • Target compounds were
Acetylaminoantipyrine totally removed; the toxicity
on D. magna was made up by
formation of intermediate
product

decades, several researches have used EEO to evaluate their investigation of AOPs
for contaminant degradation.
Mehrjouei and co-workers [93] determined the EEO for economic comparative
studies of three heterogeneous advanced oxidation treatments for removing oxalic
acid and dichloroacetic acid. The treatments involved in this study were catalytic
ozonation (TiO2/O3), photocatalytic oxidation (TiO2/UVA) and photocatalytic
ozonation (TiO2/O3/UVA). The catalytic ozonation has been the most energy effi-
cient with EEO values of 0.017 and 0.050 kWh/mM per order for oxalic acid and
dichloroacetic acid, respectively. The equivalent values for the TiO2/UVA/O3 and
the TiO2/UVA/O2 processes were 0.017 and 0.063 kWh/mM for oxalic acid degra-
dation and 0.050 and 0.35 kWh/mM for dichloroacetic acid degradation [93].
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 149

In another study, a comparison of AOPs was made among ozone and Fenton
processes combined with UV and H2O2 for the treatment of water [94]. The param-
eters considered were COD and colour removal rates and electrical energy per order.
This interesting work reported that the most efficient treatment able to remove 100%
colour and COD with less energy consumption of 0.01 kWh/m3 order1 was O3/UV/
Fe2+/H2O2. Hence, this process can be suitable for the treatment of industrial or
highly organic effluents.
The treatment costs with AOPs and their combination with ultrasound (US) are
relatively higher for hydrophilic pollutants such as reactive azo dyes and phenol
than that of hydrophobic contaminants such as trichloroethylene [95]. It has been
also pointed out that high costs of ultrasonic waste treatment reported in the
literature so far is the expected result of very high densities used in treatability
studies with single ultrasonic irradiation. To get to the energy efficiency standpoint,
the mechanism of degradation plays the key role in this kind of situation.
In the case of phenol degradation, among UV (254 nm), US (300 kHz) and O3
(2 mg/l) and TiO2 photocatalysis and their combination, US was found to be the least
energy-efficient process alternative. Energy efficiency can be improved by proper
combination of AOPs; significant reduction in process duration can be established by
the use of ultrasonic irradiation combined with AOP technologies [95].
For the case of azo-dye degradation, US-coupled H2O2 process was found to be ten
times more energy efficient compared to US/UV alternative, while UV/O3 was found to
be ten times more energy efficient compared to US/UV and US/O3 alternatives.
Adequate use of H2O2 with ultrasound and/or UV cavitation may promote oxidative
capacity of a well-known reaction. From the reduced total process time and energy
requirement standpoint, sono-photocatalysis was defined as an adequate option for
oxidative degradation of pollutants that have less complex organic structure [95].

6 Conclusions

Advanced oxidation processes are effective treatments for the purification of water
and reuse. Heterogeneous and homogenous processes are able to destroy emerging
contaminants including pesticides, pharmaceuticals and personal care products,
hormones, etc. On one hand, the complex mechanisms that are involved during
oxidative processes affects the range of their applications, and the major research is
focused to determine by-products and to understand the potential toxicity. In
addition, the requirement of energy for the pre- and/or post-treatment of water is
the main limit of AOP applications. On the other hand, the concern about water
scarcity and its contamination brings a growing demand for AOPs. So, there is a
need to focus more research to the development of these technologies and their
application in treating water.
150 M. Brienza et al.

References

1. Oturan MA, Aaron J (2014) Advanced oxidation processes in water/wastewater treatment:

principles and applications. A review. Crit Rev Environ Sci 44:2577–2641
2. Kleiser G, Frimmel FH (2000) Removal of precursors for disinfection by-products (DBPs) –
differences between ozone-and OH-radical-induced oxidation. Sci Total Environ 256:1–9
3. Robert D, Malato S (2002) Solar photocatalysis: a clean process for water detoxification. Sci
Total Environ 291:85–97
4. Matilainen A, Sillanpää M (2010) Removal of natural organic matter from drinking water by
advanced oxidation processes. Chemosphere 80:351–365
5. Thurman EM (1985) Classification of dissolved organic carbon. In: Organic geochemistry of
natural waters. Martinus Nijhoff/Dr. W. Junk Publishers, The Hague
6. Eikebrokk B, Vogt RD, Liltved H (2004) NOM increase in northern European source waters:
discussion of possible causes and impacts on coagulation/contact filtration processes. Water
Sci Tech-W Sup 4:47–54
7. Volk C, Bell K, Ibrahim E, Verges D, Amy G, LeChevallier M (2000) Impact of enhanced and
optimized coagulation on removal of organic matter and its biodegradable fraction in drinking
water. Water Res 34:3247–3257
8. Richardson SD, Plewa MJ, Wagner ED, Schoeny R, DeMarini DM (2007) Occurrence,
genotoxicity, and carcinogenicity of regulated and emerging disinfection by-products in drink-
ing water: a review and roadmap for research. Mutat Res 636:178–242
9. Siddiqui MS, Amy GL, Murphy BD (1997) Ozone enhanced removal of natural organic matter
from drinking water sources. Water Res 31:3098–3106
10. Newcombe G, Drikas M (1997) Adsorption of NOM onto activated carbon: electrostatic and
non-electrostatic effects. Carbon 35:1239–1250
11. Matilainen A, Vepsäläinen M, Sillanpää M (2010) Natural organic matter removal by coag-
ulation during drinking water treatment: a review. Adv Colloid Interf Sci 159:189–197
12. Särkkä H, Vepsäläinen M, Sillanpää M (2015) Natural organic matter (NOM) removal by
electrochemical methods – a review. J Electroanal Chem 755:100–108
13. Glaze WH, Kang JW, Chapin DH (1987) The chemistry of water treatment processes involv-
ing ozone, hydrogen peroxide and ultraviolet radiation. Ozone Sci Eng 9:335–352
14. Lucas MS, Dias AA, Sampaio A, Amaral C, Peres JA (2007) Degradation of a textile reactive Azo
dye by a combined chemical–biological process: Fenton’s reagent-yeast. Water Res 41:1103–1109
15. Mantzavinos D, Psillakis E (2004) Enhancement of biodegradability of industrial wastewaters
by chemical oxidation pre-treatment. J Chem Technol Biot 79:431–454
16. Tarr MA (2003) Chemical degradation methods for wastes and pollutants: environmental and
industrial applications. CRC Press, New York
17. Hua I, Hoffmann MR (1997) Optimization of ultrasonic irradiation as an advanced oxidation
technology. Environ Sci Technol 31:2237–2243
18. Liang J, Komarov S, Hayashi N, Kasai E (2007) Improvement in sonochemical degradation of
4-chlorophenol by combined use of Fenton-like reagents. Ultrason Sonochem 14:201–207
19. Ma Y-S, Sung C-F (2010) Investigation of carbofuran decomposition by a combination of
ultrasound and Fenton process. J Environ Eng Manag 20:213–219
20. Namkung K-C, Burgess AE, Bremner DH, Staines H (2008) Advanced Fenton processing of
aqueous phenol solutions: a continuous system study including sonication effects. Ultrason
Sonochem 15:171–176
21. Ma Y-S (2012) Short review: current trends and future challenges in the application of sono-
Fenton oxidation for wastewater treatment. Sustain Environ Res 22:271–278
22. Martı́nez-Huitle CA, Brillas E (2009) Decontamination of wastewaters containing synthetic
organic dyes by electrochemical methods: a general review. Appl Catal B-Environ 87:105–145
23. Zaviska F, Drogui P, Mercier G, Blais J-F (2009) Procédés d’oxydation avancée dans le
traitement des eaux et des effluents industriels: application a la dégradation des polluants
réfractaires. Rev Sci Eau 22:535–564
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 151

24. Gumy D, Rincon AG, Hajdu R, Pulgarin C (2006) Solar photocatalysis for detoxification and
disinfection of water: different types of suspended and fixed TiO2 catalysts study. Sol Energy
80:1376–1381
25. Daghrir R, Drogui P, Robert D (2013) Modified TiO2 for environmental photocatalytic appli-
cations: a review. Ind Eng Chem Res 52:3581–3599
26. Fujishima A, Zhang X, Tryk DA (2008) TiO2 photocatalysis and related surface phenomena.
Surf Sci Rep 63:515–582
27. Fenton HJH (1894) LXXIII. Oxidation of tartaric acid in presence of iron. J Chem Soc Trans
65:899–910
28. Pignatello JJ, Oliveros E, MacKay A (2006) Advanced oxidation processes for organic con-
taminant destruction based on the Fenton reaction and related chemistry. Crit Rev Environ Sci
Technol 36:1–84
29. Faust BC, Hoigné J (1990) Photolysis of Fe (III)-hydroxy complexes as sources of OH radicals
in clouds, fog and rain. Atmos Environ 24:79–89
30. Kaichouh G, Oturan N, Oturan MA, El Kacemi K, El Hourch A (2004) Degradation of the
herbicide imazapyr by Fenton reactions. Environ Chem Lett 2:31–33
31. Peyton GR, Glaze WH (1988) Destruction of pollutants in water with ozone in combination
with ultraviolet radiation. 3. Photolysis of aqueous ozone. Environ Sci Technol 22:761–767
32. Bhowmick M, Semmens MJ (1994) Ultraviolet photooxidation for the destruction of VOCs in
air. Water Res 28:2407–2415
33. Eckenfelder WW, Bowers AR, Roth JA (1993) Chemical oxidation: technology for the nineties,
vol 2. CRC Press, New York
34. Doré M (1989) Chimie des Oxydants et Traitement des Eux. Tec & Doc
35. Staehelin J, Hoigné J (1982) Decomposition of ozone in water in the presence of organic solutes
acting as promoters and inhibitors of radical reactions. Environ Sci Technol 19:1206–1213
36. Glaze WH, Kang JW (1989) Advanced oxidation processes – description of a kinetic model for
the oxidation of hazardous materials in aqueous-media with ozone and hydrogen-peroxide in a
semibatch reactor. Ind Eng Chem Res 28(11):1573–1580
37. von Gunten U (2003) Ozonation of drinking water: part I. Oxidation kinetics and product formation.
Water Res 37:1443–1467
38. von Gunten U (2003) Ozonation of drinking water: part II. Disinfection and by product formation in
presence of bromide, iodide or chlorine. Water Res 37:1469–1487
39. Oppenlander T (2007) Photochemical purification of water and air: advanced oxidation processes
(AOPs) – principles, reaction mechanisms, reactor concepts. Wiley, Weinheim
40. Gonzalez MG, Oliveros E, W€orner M, Braun AM (2004) Vacuum-ultraviolet photolysis of
aqueous reaction systems. J Photoch Photobio C 5:225–246
41. Buchanan W, Roddick F, Porter N (2006) Formation of hazardous by-products resulting from the
irradiation of natural organic matter: comparison between UV and VUV irradiation. Chemosphere
63:1130–1141
42. Sanly Lim M, Chiang K, Amal R, Fabris R, Cho C, Drikas M (2007) A study on the removal of
humic acid using advanced oxidation processes. Sep Sci Technol 42:1391–1404
43. Espinoza LAT, Frimmel FH (2008) Formation of brominated products in irradiated titanium
dioxide suspensions containing bromide and dissolved organic carbon. Water Res 42:1778–1784
44. Goslan EH, Gurses F, Banks J, Parsons SA (2006) An investigation into reservoir NOM
reduction by UV photolysis and advanced oxidation processes. Chemosphere 65:1113–1119
45. Katsumata H, Sada M, Kaneco S, Suzuki T, Ohta K, Yobiko Y (2008) Humic acid degradation
in aqueous solution by the photo-Fenton process. Chem Eng J 137:225–230
46. Birben NC, Uyguner-Demirel CS, Bekbolet M (2016) Photocatalytic removal of microbio-
logical consortium and organic matter in greywater. Catalysts 6(6):91
47. Valencia S, Marı́n J, Velásquez J, Restrepo G, Frimmel FH (2012) Study of pH effects on the
evolution of properties of brown-water natural organic matter as revealed by size-exclusion
chromatography during photocatalytic degradation. Water Res 46:1198–1206
152 M. Brienza et al.

48. Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000
establishing a framework for community action in the field of water policy. Off J Eur Commun
22.12.2000, L327/1-L327/69
49. Meffe R, de Bustamante I (2014) Emerging organic contaminants in surface water and ground-
water: a first overview of the situation in Italy. Sci Total Environ 481:280–295
50. Székács A, M€ ortl M, Darvas B (2015) Monitoring pesticide residues in surface and ground
water in Hungary: surveys in 1990-2015. J Chem. Article ID717948
51. Jurado A, Vazquez-Su~né E, Carrera J, López de Alda M, Pujades E, Barceló D (2012)
Emerging organic contaminants in groundwater in Spain: a review of sources, recent occur-
rence and fate in a European context. Sci Total Environ 440:82–94
52. Stuart M, Lapworth D, Crane E, Hart A (2012) Review of risk from potential emerging contam-
inants in UK groundwater. Sci Total Environ 416:1–21
53. Pineda Arellano CA, González AJ, Martı́nez SS, Salgado-Tránsito I, Franco CP (2013)
Enhanced mineralization of atrazine by means of photodegradation processes using solar energy
at pilot plant scale. J Photoch Photobio A 272:21–27
54. Rozas O, Vidal C, Baeza C, Jardim WF, Rossner A, Mansilla HD (2016) Organic micropollutants
(OMPs) in natural waters: oxidation by UV/H2O2 treatment and toxicity assessment. Water Res
98:109–118
55. Chu W, Chan KH, Graham NJD (2006) Enhancement of ozone oxidation and its associated
processes in the presence of surfactant: degradation of atrazine. Chemosphere 64:931–936
56. Gonzalez MC, Braun AM, Prevot AB, Pelizzetti E (1994) Vacuum-ultraviolet (VUV) photol-
ysis of water: mineralization of atrazine. Chemosphere 28:2121–2127
57. Katsumata H, Kaneco S, Suzuki T, Ohta K, Yobiko Y (2006) Photo-Fenton degradation of
alachlor in the presence of citrate solution. J Photoch Photobio A 180:38–45
58. Beltrán FJ, González M, Rivas FJ, Acedo B (2000) Determination of kinetic parameters of
ozone during oxidations of alachlor in water. Water Environ Res 72:689–697
59. Ryu CS, Kim M-S, Kim B-W (2003) Photodegradation of alachlor with the TiO2 film immobilised
on the glass tube in aqueous solution. Chemosphere 53:765–771
60. Pe~nuela GA, Barceló D (1996) Comparative degradation kinetics of alachlor in water by
photocatalysis with FeCl3, TiO2 and photolysis, studied by solid-phase disk extraction followed
by gas chromatographic techniques. J Chromatogr A 754:187–195
61. Haque MM, Muneer M (2003) Heterogeneous photocatalysed degradation of a herbicide derivative,
isoproturon in aqueous suspension of titanium dioxide. J Environ Manag 69:169–176
62. Bobu MM, Siminiceanu I, Lundanes E (2005) Photodegradation of Isoproturon in water by
several advanced oxidation processes. Chem Bull “Politehnica” Univ 50(64):45–48
63. Manassero A, Passalia C, Negro AC, Cassano AE, Zalazar CS (2010) Glyphosate degradation
in water employing the H2O2/UVC process. Water Res 44:3875–3882
64. Assalin MR, De Moraes SG, Queiroz SCN, Ferracini VL, Duran N (2009) Studies on degrada-
tion of glyphosate by several oxidative chemical processes: ozonation, photolysis and hetero-
geneous photocatalysis. J Environ Sci Health B 45:89–94
65. Sui Q, Cao X, Lu S, Zhao W, Qiu Z, Yu G (2015) Occurrence, sources and fate of pharma-
ceuticals and personal care products in the groundwater: a review. Emerg Contam 1:14–24
66. Benotti MJ, Trenholm RA, Vanderford BJ, Holady JC, Stanford BD, Snyder SA (2009) Pharmaceu-
ticals and endocrine disrupting compounds in U.S. drinking water. Environ Sci Technol 43:597–603
67. Bredhult C, Bäcklin B-M, Olovsson M (2007) Effects of some endocrine disruptors on the prolifer-
ation and viability of human endometrial endothelial cells in vitro. Reprod Toxicol 23:550–559
68. Verlicchi P, Al Aukidy M, Zambello E (2012) Occurrence of pharmaceutical compounds in
urban wastewater: removal, mass load and environmental risk after a secondary treatment: a
review. Sci Total Environ 429:123–155
69. ISO 6341:2012 (2012) Water quality. Determination of the inhibition of the mobility of
Daphnia Magna straus (Cladocera, Crustacea) – acute toxicity test. International Organiza-
tion for Standardization
Photo(Catalytic) Oxidation Processes for the Removal of Natural Organic. . . 153

70. ISO 1134-3:2007 (2007) Water quality. Determination of the inhibitory effect of water samples
on the light emission of Vibrio fischeri (luminescent bacteria test) – part 3: method using freeze-
dried bacteria. International Organization for Standardization
71. Greene JC, Bartels CL, Warren-Hicks WJ, Parkhurst BR, Linder GL, Peterson SA, Miller WE
(1988) EPA 600/3-88/029. Protocol for short term toxicity screening of hazardous waste sites.
US Environmental Protection Agency
72. ISO 7346-1:1996 (1996) Water quality. Determination of the acute lethal toxicity of sub-
stances to a freshwater fish [Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)] –
part 1: static method. International Organization for Standardization
73. Brienza M, Mahdi Ahmed M, Escande A, Plantard G, Scrano L, Chiron S, Bufo SA, Goetz V (2016)
Use of solar advanced oxidation processes for wastewater treatment: follow-up on degradation
products, acute toxicity, genotoxicity and estrogenicity. Chemosphere 148:473–480
74. Pereira VJ, Weinberg HS, Linden KG, Singer PC (2007) UV degradation kinetics and
modeling of pharmaceutical compounds in laboratory grade and surface water via direct and
indirect photolysis at 254 nm. Environ Sci Technol 41:1682–1688
75. Vogna D, Marotta R, Andreozzi R, Napolitano A, D’Ischia M (2004) Kinetic and chemical assess-
ment of the UV/H2O2 treatment of antiepileptic drug carbamazepine. Chemosphere 54:497–505
76. Doll TE, Frimmel FH (2005) Photocatalytic degradation of carbamazepine, clofibric acid and
iomeprol with P25 and Hombikat UV100 in the presence of natural organic matter (NOM) and
other organic water constituents. Water Res 39:403–411
77. Kim I, Yamashita N, Tanaka H (2009) Performance of UV and UV/H2O2 processes for the
removal of pharmaceuticals detected in secondary effluent of a sewage treatment plant in
Japan. J Hazard Mater 166:1134–1140
78. Kim I, Tanaka H (2009) Photodegradation characteristics of PPCPs in water with UV treatment.
Environ Int 35:793–802
79. Buser HR, Poiger T, Müller MD (1998) Occurrence and fate of the pharmaceutical drug diclofenac
in surface waters: rapid photodegradation in a lake. Environ Sci Technol 32:3449–3456
80. Pérez-Estrada LA, Maldonado MI, Gernjak W, Agüera A, Fernández-Alba AR, Ballesteros
MM, Malato S (2005) Decomposition of diclofenac by solar driven photocatalysis at pilot
plant scale. Catal Today 101:219–226
81. Moreira NFF, Orge CA, Ribeiro AR, Faria JL, Nunes OC, Pereira MFR, Silva AMT (2015)
Fast mineralization and detoxification of amoxicillin and diclofenac by photocatalytic ozon-
ation and application to an urban wastewater. Water Res 87:87–96
82. Hu L, Flanders PM, Miller PL, Strathmann TJ (2007) Oxidation of sulfamethoxazole and
related antimicrobial agents by TiO2 photocatalysis. Water Res 41:2612–2626
83. Trovó AG, Nogueira RFP, Agüera A, Fernandez-Alba AR, Sirtori C, Malato S (2009)
Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological
evaluation. Water Res 43:3922–3931
84. Huber MM, Canonica S, Park GY, Von Gunten U (2003) Oxidation of pharmaceuticals during
ozonation and advanced oxidation processes. Environ Sci Technol 37:1016–1024
85. Heringa MB, Harmsen DJH, Beerendonck EF, Resus AA, Krul CAM, Metz DH, Ijpelaar GF (2011)
Formation and removal of genotoxic activity during UV/H2O2-GAC treatment of drinking water.
Water Res 45:366–374
86. Marugán J, Bru D, Pablos C, Catalá M (2012) Comparative evaluation of acute toxicity by
Vibrio fischeri and fern spore based bioassays in the follow-up of toxic chemicals degradation
by photocatalysis. J Hazard Mater 213–214:117–122
87. Lelario F, Brienza M, Bufo SA, Scrano L (2016) Effectiveness of different advanced oxidation
processes (AOPs) on the abatement of the model compound mepanipyrim in water. J Photoch
Photobio A 321:187–201
88. Lapertot M, Ebrahimi S, Dazio S, Rubinelli A, Pulgarin C (2007) Photo-Fenton and biological
integrated process for degradation of a mixture of pesticides. J Photoch Photobio A 186:34–40
154 M. Brienza et al.

89. Gómez MJ, Sirtori C, Mezcua M, Fernández-Alba AR, Agüera A (2008) Photodegradation
study of three dipyrone metabolites in various water systems: identification and toxicity of
their photodegradation products. Water Res 42:2698–2706
90. Sichel C, Garcia C, Andre K (2011) Feasibility studies: UV/chlorine advanced oxidation
treatment for the removal of emerging contaminants. Water Res 45:6371–6380
91. Bolton JR, Bircher KG, Tumas W, Tolman C (2001) Figures-of-merit for the technical
development and application of advanced oxidation technologies for both electric-and solar-
driven systems. Pure Appl Chem 73:627–637
92. Arslan-Altan L (2004) Advanced oxidation of textile industry dyes. In: Parsons S (ed) Advanced
oxidation processes for water and wastewater treatment. IWA Publishing, London, pp 302–328
93. Mehrjouei M, Mülle S, M€oller D (2014) Energy consumption of three different advanced
oxidation methods for water treatment: a cost-effectiveness study. J Clean Prod 65:178–183
94. Asaithambi P, Saravanathamizhan R, Matheswaran M (2015) Comparison of treatment and
energy efficiency of advanced oxidation processes for the distillery wastewater. Int J Environ
Sci Technol 12:2213–2220
95. Mahamuni NN, Adewuyi YG (2010) Ultrasonics sonochemistry advanced oxidation processes
(AOPs) involving ultrasound for waste water treatment: a review with emphasis on cost
estimation. Ultrason Sonochem 17:990–1003
Homogeneous Fenton and Photo-Fenton
Disinfection of Surface and Groundwater

Marı́a Inmaculada Polo-López, Samira Nahim-Granados,

~ez
and Pilar Fernández-Ibán

Abstract Polluted surface water and groundwater represent a significant human

health risk as it is a vehicle for a number of diseases derived from the exposition to
untreated drinking water. Historically, chlorination became a great advance on
reducing the impact of many pathogens associated with polluted drinking water
in developed countries, with the consequent benefits to societies growing and
welfare. Nevertheless, other treatments have been investigated during the last
decades with the aim of increasing their capability for treating water and overcom-
ing the limitations of chlorination and other conventional technologies including
UVC radiation and ozone. Fenton and photo-Fenton process have been demon-
strated to be a good option as alternative water disinfection process during the last
years. The aim of this chapter is to briefly describe the fundamentals of this process
with special focus on particular aspects related to pathogens inactivation in water.
Moreover, the most recent scientific contributions on the application of Fenton and
photo-Fenton for water disinfection are discussed.

Keywords Compound parabolic collector, Fenton, Photo-Fenton, Solar treatment,

Water disinfection

Contents
1 Background of Fenton and Photo-Fenton Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
2 Fundamental Aspects and Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
2.1 Effect of Water pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

M.I. Polo-López (*) and S. Nahim-Granados

Plataforma Solar de Almerı́a – CIEMAT, Almerı́a, Spain
e-mail: [email protected]; [email protected]
P. Fernández-Ibá~
nez
Nanotechnology and Integrated BioEngineering Centre, School of Engineering, University of
Ulster, Newtownabbey, Northern Ireland
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 155
Water Treatment, Hdb Env Chem (2019) 67: 155–178, DOI 10.1007/698_2017_129,
© Springer International Publishing AG 2018, Published online: 25 February 2018
156 M.I. Polo-López et al.

2.2 Effect of Inorganic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158

2.3 Effect of Natural Organic Matter (NOM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
3 Microbial Contamination of Groundwater and Surface Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4 Inactivation Mechanisms of Fenton and Photo-Fenton Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5 Fenton Process: Examples of Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
6 Solar Driven Photo-Fenton Process: Examples of Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174

Abbreviations

AOP Advanced oxidation process

ARB Antibiotic-resistant bacteria
ARG Antibiotic-resistant gene
CPC Compound parabolic collector
DOM Dissolved organic matter
MWWE Municipal wastewater effluent
NOM Natural organic matter
PS Persulfate
ROS Reactive oxygen species
SE Secondary effluents

1 Background of Fenton and Photo-Fenton Reaction

Currently, photo-Fenton process constitutes one of the most powerful water treat-
ments belonging to the so-called advanced oxidation processes (AOPs). It takes the
advantage of using solar light as source of photons and generates a high rate of
hydroxyl radicals (HO•). Historically, the first report on Fenton reactions was done
by Henry J. Fenton, where iron(II) salt activation by H2O2 could oxidize tartaric
acid [1]. Later, in 1934, the hydroxyl radical, the second most powerful oxidant
(E
¼ 2.73 V) after fluoride, was proposed as the main responsible for the oxidative
capacity of the Fenton reaction [2]. During the 1950s, a number of reactions that
today still describe the classical thermal Fenton reactions were reported [3–5]. The
main reactions involving the decomposition of H2O2 in dark and pure acid solutions
are:


Fe2þ þ H2 O2 ! Fe3þ þ OH þ HO • K  70 M1 s1 ð1Þ


Fe3þ þ H2 O2 ! Fe2þ þ HO2• þ Hþ K ¼ 1  2  102 M1 s1 ð2Þ


HO • þ H2 O2 ! HO2• þ H2 O K ¼ 1:7  2:5  107 M1 s1 ð3Þ


HO • þ Fe2þ ! Fe3þ þ OH K ¼ 3:2  108 M1 s1 ð4Þ
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 157

Fe3þ þ HO2• ! Fe2þ þ O2 þ Hþ K ¼ 1:2  106 M1 s1 pH 3 ð5Þ


Fe2þ þ HO2• þ Hþ ! Fe3þ þ H2 O2 K ¼ 1:3  106 M1 s1 pH 3 ð6Þ
HO2• þ HO2• ! H2 O2 ð7Þ

Reaction 2 is extremely slow as compared with Reaction 1, which limits the

whole process of HO• generation. Later, in the 1990s, the strong acceleration of this
reaction in the presence of radiation started to be investigated as novel process for
water treatment [6]. This photo-assisted Fenton reaction, so-called photo-Fenton,
leads to much faster HO• generation rates and therefore a higher degree of oxidation
than the Fenton (dark) reaction. Briefly, the efficiency of the process increases when
the system is irradiated at wavelengths below 580 nm due to the light absorption of
the Fe3+ aquo complexes generated by Reaction 2 to be reduced to Fe2+ complexes
(Reaction 8), generating an extra HO• and enabling the iron cycle to restart [7].

Fe3þ ðLÞn þ hν ! Fe2þ ðLÞn1 þ Lox

•
ð8Þ

Since the first application of the Fenton reaction as oxidative process to degrade
toxic organic compounds in water in the middle of the 1960s [8], the interest of
researchers on the fundamental knowledge and practical application of Fenton and
photo-Fenton process to treat polluted water has increased tremendously. Never-
theless, the application of this process to disinfect water, i.e., to inactivate water-
borne pathogens, was initiated in the last decade. The first demonstration of the
capacity of photo-Fenton to disinfect water was reported by Rincón and Pulgarı́n in
2006. These authors demonstrated that the use of low reagent concentrations
(0.3 mg L1 Fe and 10 mg L1 H2O2) enhanced markedly the inactivation kinetics
of E. coli cells in water [9]. Since then, other pathogens, chemical and biological
parameters related to the iron chemistry, and the efficiency of the treatment in
several types of surface waters have been investigated.

2 Fundamental Aspects and Parameters

2.1 Effect of Water pH

It is very well known that pH affects strongly the speciation and therefore the
solubility of iron in water, establishing the optimum for Fenton or photo-Fenton
reaction a pH  3. The three fractions of iron(II) species found in water as a
function of the water pH are Fe(H2O)62+ or Fe2+, which appears as predominant at
acid conditions; Fe(H2O)4(OH)2 or Fe(OH)2 at alkaline conditions; and Fe
(H2O)5(OH)+ or FeOH+ coexisting at pH lower than 5 [7].
However, the speciation of iron(III) differs from the iron(II), and in strongly
acidic solution, the main specie is the hexaaqua ion, Fe(H2O)63+ [7]. When pH
increases, the hydrolysis of Fe(H2O)63+ occurs depending on several water param-
eters including the ionic strength and the total iron concentration. Consequently,
158 M.I. Polo-López et al.

this ion precipitates as amorphous ferric oxyhydroxides [10], which are consider-
ably less active. Therefore, the reaction of ferrous ion and H2O2 will lead to the
precipitation of iron when Fe(III) oxyhydroxides are formed (Reaction 1) when pH
is higher than 3.
Recently, the research trend is to investigate the naturally occurring or artifi-
cially prepared iron oxides (like magnetite, goethite, hematite, etc.) formed after the
oxidation of ferric oxyhydroxides at near-neutral pH; quelates of iron such as
citrate, EDDS, etc. are also under investigation. These Fe complexes are investi-
gated from the point of view of their capability for promoting efficient Fenton or
photo-Fenton reactions for water and wastewater treatment at near-neutral pH.

2.2 Effect of Inorganic Compounds

Iron chemistry and Fenton reactivity are negatively affected by the presence of
several inorganic chemical compounds in water. They mainly produce precipitation
of iron, scavenging of radicals, and/or less reactive Fe complex formation. One of
the most negative effects is produced by the presence of carbonates (CO32) and
bicarbonates (HCO3). These anions may react with HO•, scavenging it and ending
in a reduction of their availability to oxidize the target pollutants [7, 11, 12]. The
reactions involved include:

HO • þ HCO •
3 ! CO3 þ H2 O ð9Þ
•
HO þ CO3 ! CO3 þ H2 O
• 2
ð10Þ

Therefore, for the treatment of any kind of water by Fenton or photo-Fenton, the
oxidation of pollutants in presence of CO32 will be in direct competition with the
oxidation by HO•, and if CO3• formation rate exceeds the hydroxyl radical
formation, the balance of the process will be negative from the point of view of
capacity to treat contaminated waters [12]. On the other hand, CO3• is also a
radical with a wide range of reactivity with organic molecules, but with slower
reactions than those of HO•, while the main known scavengers of both (CO3• and
HO•) are the dissolved natural organic matter and, if present, H2O2. In addition
and regarding water disinfection, it has been also described by some authors that
HCO3 may protect microorganisms from sunlight as it is photo absorptive and
therefore acts as a screen of light [13, 14].
On the other hand, phosphate ions have been shown to have an important
detrimental role during Fenton reactions because they react with iron and
coprecipitate as stable complex at neutral and acidic conditions as well as they
scavenge hydroxyl radicals [7, 15]. Other anions present in natural waters, includ-
ing sulfates, nitrates, and chlorides, may also react with iron, H2O2, or other ROS,
limiting the capability of Fenton or photo-Fenton to oxidize organic chemical and
biological pollutants due to the reduction of the HO• generated [11, 14–16].
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 159

Table 1 Main oxidative reactions occurring during photo-Fenton in the presence of NOM
Reference
Pathway Reactions (equation)
Classical photo-Fenton Fe2+ + H2O2 ! Fe3+ + OH + HO• (1)
reactions (main reactions) Fe3þ ðLÞn þ hv ! Fe2þ ðLÞn1 þ Lox
• (8)
1 3 ∗
Direct oxidation of DOM DOM + hv DOM DOM (11)
by sunlight and 3DOM∗ 3
DOM∗ + O2 ! DOM + 1O2 (12)
energy transfer
Complexation of iron with Fe3þ  ðDOMÞn þ hvFe2þ  ðDOMÞðn1Þ þ DOMþ
ox
(13)
DOM
•
DOM reaction with O2 DOM þ O2 þ hv ! DOMþ
ox þ O2 (14)

2.3 Effect of Natural Organic Matter (NOM)

In contrast to inorganic compounds, the presence of NOM in water has been

reported to have both a positive and negative effect during Fenton or photo-Fenton
reaction. The natural organic compounds present in any water source include humic
and non-humic substances. In general, humic composition is the fraction including
aromatic and aliphatic compounds, carboxylic, phenolic-OH, amino and quinone
groups, etc. However, the humic composition that may differ significantly from one
to another water sources due to their composition is the result of many random
environmental transformations (microbiological, chemical, and photochemical
reactions) of biological rests [14, 15, 17]. Therefore, and due to the high variability
of NOM in water sources, the presence of humic substances may be a limiting
factor [18] or not [19–21] for the Fenton processes. Briefly, the most significant
oxidative reactions of NOM during photo-Fenton are summarized in Table 1.
On the other hand, NOM may react with free radicals, including HO• (Reaction
15). This reaction was reported as a second-order rate kinetics with a kinetic
constant value of 2  104 s1 (mgC/L)1 [22].

DOM þ HO • ! DOMþ
ox þ OH

ð15Þ

In summary, the oxidative capability of photo-Fenton in the presence of NOM

will depend on several reasons including the iron complexation generated in the
specific water source, the iron (Fe2+/Fe3+) transformation, and the types of oxida-
tive radicals generated during the process [23].

3 Microbial Contamination of Groundwater and Surface

Water

Traditionally, groundwater has been considered a microbe-free water source, espe-

cially in deep and confined aquifers. Nevertheless, the presence of indicator bacte-
ria or human pathogens has been widely detected in the last years in many
160 M.I. Polo-López et al.

groundwater sources. Their pollution has been attributed to a nearby connection

with contaminated surface waters and environment, including a leaking from a
waste lagoon, septic tanks, sewer line, old or improperly designed landfill, etc.
Obviously, surface water shows higher microbial contamination load than ground-
water, like rivers, lagoon, dams, and bacterial “hot spots” like municipal wastewa-
ter treatment plants.
From a realistic point of view, it is impossible to monitor every possible
pathogen present in a contaminated surface water source due to each type of
pathogen requires a specific test, which is time-consuming and would be prohibitive
in terms of cost. Therefore, microbial indicators of water quality have been
established as model of pathogens for water guidelines and regulations, and there-
fore they have been also studied for research purposes. They include E. coli (the
most widely investigated bacterium in water) as an indicator of fecal contamination
or some specific phages (MS2) as indicator of the presence of viral contamination.
However, the wide spectrum of naturally occurring microorganisms in surface
waters is not well represented by these strains, as many other groups of pathogenic
species may be present, including bacteria, viruses, fungi, protozoa, and parasites.
Moreover, E. coli shows the lowest resistance to be inactivated by any disinfection
treatment [24], including photo-Fenton as it is clearly observed in Fig. 1.
Today the advanced analytical methods in molecular biology include genetic
tools as quantitative PCR (Polymerase Chain Reaction) and metagenomics analysis
are transforming this area of research. However, culture-based methodologies
are still being the most used technique for monitoring and quantification of

Low Medium High resistance

Treatment time: 0< t1 < 2,5h < t2 < 4h < t3
4
Log-reduction

0
E. faecalis E. coli FRNA SOMCPH Fusarium SRC
Bacteria (t1 ) Virus-phages (t2 ) Spores (t3 )

Fig. 1 Resistance of several microbial groups of bacteria, viruses, and spores of fungi and bacteria
using solar photo-Fenton (natural pH, 10–20 mg L1 of Fe2+ and H2O2) in secondary effluents
(Reprinted from [15], with permission from Elsevier)
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 161

Table 2 Summary of priority pathogen list reported by the WHO (Publication date: 27 February
2017) (http://www.who.int/medicines/publications/global-priority-list-antibiotic-resistant-bacteria/en/)
Microorganism Antibiotic resistance Priority
Acinetobacter baumannii Carbapenem Criticala
Pseudomonas aeruginosa Carbapenem Criticala
Enterobacteriaceaeb Carbapenem and third-generation cephalosporin Criticala
Enterococcus faecium Vancomycin High
Staphylococcus aureus Methicillin, vancomycin intermediate and resistant High
Helicobacter pylori Clarithromycin High
Campylobacter Fluoroquinolone High
Salmonella spp. Fluoroquinolone High
Neisseria gonorrhoeae Third-generation cephalosporin, fluoroquinolone High
Streptococcus pneumoniae Penicillin-non-susceptible Medium
Haemophilus influenzae Ampicillin Medium
Shigella spp. Fluoroquinolone Medium
a
Mycobacteria (including Mycobacterium tuberculosis) was not included as it is already a globally
established priority for innovative new treatments
b
Klebsiella pneumonia, Escherichia coli, Enterobacter spp., Serratia spp., Proteus spp.,
Providencia spp., and Morganella spp.

microbiological contamination of water sources [25]. The use of qPCR for micro-
bial monitoring in wastewater and groundwater sources has made possible to detect
the presence of the so-called antibiotic-resistant bacteria (ARB), which currently is
becoming one of the most important concerns for public health. In relation to water
issues, ARB are an environmental water health issue associated with municipal
wastewater treatment plants and hospital wastewater [26]. Their spread in the
aquatic environment favors also the spread of genetic resistance material that can
be introduced in food chains resulting in a reduction of the antibiotics’ efficacy
against animal and human diseases. To date, methicillin-resistant Staphylococcus
aureus and vancomycin-resistant Enterococcus spp. are the most investigated ARB
[27]. Very recently (Feb. 2017), the World Health Organization (WHO) reported a
list of “priority pathogens list for R&D of new antibiotics” highlighting the
importance of this type of pathogens on research and the implementation of new
water treatments (Table 2).

4 Inactivation Mechanisms of Fenton and Photo-Fenton

Process

The inactivation of any microbial agent means the loss of their growth capability,
and the objective of any water disinfection process is to effectively inactivate
waterborne pathogens. To obtain a successful inactivation, the chemical or physical
agent applied must generate injuries in key biological structures (mainly proteins,
lipids or DNA) that leads to functionality losses ending in the cells’ inactivation or
death. In Fenton and photo-Fenton process, as it has been explained before, the
162 M.I. Polo-López et al.

generation of reactive oxygen species (ROS), and mainly hydroxyl radicals, is

considered the main responsible inactivation agents. ROS may react with proteins
and lipids at cell membrane site altering their functionality directly as well as
initiating the lipid peroxidation chains inside the cells increasing cell permeability
and leading to final inactivation [28, 29]. On the other hand, ROS may also react
with internal cells’ components, including DNA. In this case, the attack occurs at
the DNA bases or sugars leading to strand breakage and base release, generating
mutations and other genetic alterations [30].
The proposed mechanisms to explain the inactivation of microorganisms by
ROS and HO• generation during Fenton and photo-Fenton process are shown in
Fig. 2. It is accepted that generated HO• (via Reactions 1–8) attacks mainly the
external cell membrane leading its degradation and resulting in microorganism
death. This degradation will depend on the reaction rate of HO• generation, and
considering the short living of this radical, the attacks will occur only locally, at cell
membrane level, and therefore, diffusion to inside cells cannot be considered.
However, other reactions may take place at internal cell level which may also be
considered as source of oxidative damage, especially in the case of photo-Fenton
driven at near-neutral pH, where the reaction rate of external HO• generation is
reduced compared with those occurring at acid solutions [14]. Briefly, the main
reactions that may occur inside cells are summarized as follows:
1. Near UVA light may inactivate enzymes, including catalase (CAT) or super
oxygen dismutase (SOD). Their inactivation will lead to increased intracellular

Fig. 2 Summary of the main reactions pathways involved during bacterial inactivation by photo-
Fenton
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 163

concentrations of H2O2 and O2•, as they are responsible for the elimination of
these metabolic generated ROS [31]. Moreover, other protein like ferritin may
be also damaged, which will determine an increase release of Fe2+ [31].
2. Some intracellular photosensitizers may absorb photons in the UVA and visible
spectrum and attack biomolecules or react with O2 generating ROS such as HO•,
H2O2, 1O2, and O2•. Another source of intracellular ROS increment can be
generated by the oxidation of flavoproteins (FADH2). As a consequence, intra-
cellular iron-sulfur clusters [4Fe-4S] may be oxidized leading other proteins,
release of Fe2+ and generation of H2O2.
3. Fenton and photo-Fenton intracellular reactions by diffusion of added H2O2 and
Fe2+. The diffusion may occur as H2O2 is relatively stable and uncharged (unlike
HO• and O2•) and Fe2+ may freely diffuse favored by osmotic forces into the
cells.
4. Fe3+ (with a higher charge density than Fe2+) can be adsorbed on specific
membrane-binding proteins, leading the deposition of iron on the external cell
membrane and the formation of Fe3+-bacteria exciplexes. Therefore, this means
a possible way of direct oxidation over the cell membrane (proteins and lipids)
by HO• generation, and the subsequent regeneration of Fe2+.
5. Iron oxides including magnetite, goethite, lepidocrocite, or feroxyhyte can be
generated after precipitation of iron at near-neutral pH as oxyhydroxides and
further oxidation [32]. Iron oxides can be adsorbed onto bacterial surfaces, and if
H2O2 and light are present, they can act as semiconductors and/or heterogeneous
catalysts.

5 Fenton Process: Examples of Application

The application of “classical” Fenton process for water disinfection has not been
widely extended or intended for real applications due to several practical reasons:
1. The limitations of HO• generation by the low kinetic rate of Reaction 2;
meanwhile, the opposite trend occurs in the case of classical photo-Fenton, as
the irradiation of the system strongly increase the oxidative capacity of the
process. This is clearly observed in many works in the literature where the
efficiency of Fenton and photo-Fenton applications for water treatment is com-
pared, for example, the inactivation of F. solani spores using solar photo-Fenton
(Fig. 3).
2. The higher amount of iron is needed to obtain good disinfection rates, consid-
ering that reagents are one of the most important costs for real or industrial
application. In line with this, the development of modified Fenton reagents to
increase the oxidative capacity of the system will be also a disadvantage as
advanced and costly techniques are required to obtain doped or modified iron
oxides. Nevertheless, several recent contributions on this area have been
reported in literature. A recent study on modified Fenton system including
164 M.I. Polo-López et al.

a) 30

3
10

Temperature (ºC)
25
F. solani (CFU/mL)

Temperature

pH
2
10

5
4
1
10 3
pH
2
DL = 2 CFU/mL
1
0
10 0
10:00 11:00 12:00 13:00 14:00 15:00
Local Time (HH:mm)

b) Solar exposure
0 1h 2h 3h 4h 5h
40
3
10

35
F. solani (CFU/mL)

Temperature (ºC)

2
10
Temperature
30

1
10
25

DL

0
10 20
0 5 10 15 20 25
QUV (kJ/L)

Fig. 3 F. solani microconidia concentrations in simulated municipal wastewater effluents

(SMWWE) for 5 h dark Fenton (at pH 3) (a) and solar photo-Fenton (at pH 3 (filled triangle),
pH 4 (filled square), pH 5 (filled diamond), and pH 8 (filled circle) as function of solar cumulative
irradiance (QUV)) (b) with 5 mg L1 Fe2+ and 10 mg L1 H2O2. Temperature and pH are shown
with dashed lines (Reprinted from [33], with permission from Elsevier)
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 165

ascorbic acid and prooxidants for the inactivation of Cryptosporidium-contam-

inated drinking water samples has been published. In this work, the higher
efficiency on Cryptosporidium viability decrease (0% after 5 min of exposure
time) was obtained with 80 mg L1 of iron(II), 30 mg L1 of ascorbic acid,
30 mmol of H2O2, and 25 mg L1 of prooxidants [34]. Castro-Rios et al.
investigated the capability of heterogeneous Fenton, using pillared clay prepared
by ultrasound and microwave in a semi-batch reactor for the inactivation of total
coliforms and E. coli in natural water from Pasto River [35]. Relative good
inactivation efficiencies were obtained in this work, between 42 and 75% in
180–240 min of treatment and where best operational conditions found were
pH 3.7, 0.5 g L1 of catalyst load, and 0.12–0.18 mg L1 of H2O2 concentration
[35]. The inactivation of Ascaris lumbricoides eggs through a Fenton reaction
has been also investigated recently. In this study, maximum degradation (91.2%)
was achieved with 500 mg L1 dose of H2O2 and a 3:1 (H2O2/Fe2+) molar ratio
at pH 6 [36]. The inactivation of Ascaris eggs with FeOx/C nanocatalyst and
H2O2 and further modification procedure using iron oxide nanocatalyst
supported on activated carbon has been also investigated [37, 38]. In all these
works, in spite of the efficiency obtained, the amount of iron or modified iron
needed was very high which, from the economic point of view, is a clear
disadvantage.

6 Solar Driven Photo-Fenton Process: Examples

of Application

One of the driving forces on the progress of solar photo-Fenton process for water
disinfection has been their application using the solar Compound Parabolic Collec-
tor (CPC) reactors (Fig. 4) [39]. This static system consists on a cylindrical photo-

Fig. 4 View of several solar CPC pilot plants located at Plataforma Solar de Almeria, The Solar
Research Centre in Spain
166 M.I. Polo-López et al.

reactor placed on the linear focus of a parabolic reflective surface. This configura-
tion enhanced the collection of photons due to the reflector (mirror) geometry that
reflects indirect light onto the photo-reactor (receiver tube). Briefly, the main
advantages of this technology are collecting both direct and diffuse solar radiation,
the use of non-imaging concentration optics with diffuse focus, complete and
homogeneous distribution of photons at the absorber wall, and constant concentra-
tion factor (CF: 1) for all values of sun zenith angle within the acceptance angle
limit of 90
[39]. The CPC mirror made of anodized aluminum has the advantage of
a high reflectivity in the UVA range (87–90%) and 90% for the visible and infrared
fraction of the solar spectrum, with high resistance to the environmental conditions.
Typically, this reactor is operated by water recirculation; therefore centrifugal
pumps are used to permit a flow rate enough to guarantee a turbulent regime that
favors the homogenization of the sample.
The application of solar photo-Fenton for wastewater and surface water disin-
fection using CPC has been deeply investigated during the last years. A summary of
those works reporting experimental results of this technology to date are shown in
Table 3.
Since the first study reported by Moncayo-Lasso et al. [40] that demonstrated the
efficiency of solar photo-Fenton for surface water disinfection, a number of con-
tributions have investigated other aspects related to this process. A great part of the
research carried out by Pulgarin’s group has been focused on the use of this process
at very low levels of iron, H2O2, and near-neutral pH with the aim of disinfecting
drinking water. The treatment for drinking purposes requires obviously very mild
reaction conditions. In line with this, there are a number of articles investigating the
lethal effectiveness of low amounts of H2O2 under sunlight for inactivating a
variety of pathogens for drinking also at pilot scale [45, 47, 53]. The effectiveness
of this process is also attributed to photo-Fenton mechanisms at intracellular level
[57, 58]. On the other hand, disinfection of wastewater involves a number of
chemical and biological complex reactions which determine the use of photo-
Fenton under strongest conditions, i.e., higher concentrations of Fe and H2O2, to
guarantee the quality of the treated water for disposal or reuse [52].
Recently, significant research has been done to show the most important findings
related to the effect of fundamental parameters as described below:
1. Type of pathogen: different microbial or waterborne pathogens have been
evaluated, ranging from the very well-known Escherichia coli to the high-
resistant spores of Clostridium sp. and human viruses [59]. In 2013, Agull-
ó-Barceló et al. [43] reported an experimental work investigating, among other
solar processes, the efficiency of solar photo-Fenton for secondary effluents
disinfection focusing on the inactivation of several groups of naturally occurring
pathogens. Figure 5 shows the influence of the type of microorganism on the
inactivation efficiency at acidic (optimal for photo-Fenton) and neutral
pH. These results clearly show that monitoring a single pathogen may not be
sufficient to assure a low microbial risk of the water. Moreover, the influence of
the pH on the processes was investigated, demonstrating the benefits of acidic
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 167

Table 3 Chronology experimental contributions on surface and wastewater disinfection by solar

photo-Fenton at acid and near-neutral pH in CPC reactors
Water
volume [Fe2+]:[H2O2]a
Water source Microbial target (L) (mg L1) Reference
River E. coli 20 0.6:10 [40]
SE Total coliforms 80 5.58-Fe2(SO4) [41]
3+
+ 71.5-
EDDS:50
SE Antibiotic resistant (ofloxacin and tri- 250 5:75 [42]
methoprim) Enterococci sp.
SE E. coli, Spores of sulfite reducing 10 10:20 [43]
clostridia, somatic coliphages,
F-specific RNA bacteriophages
Synthetic SE E. faecalis 7 20:50 [44]
Well Total coliforms, E. coli, Salmonella 25 0.01-natural [45]
spp. Fe:10; 0.23-Fe
oxides: 10
Real and E. coli and E. faecalis 20 10:50 [46]
synthetic SE
Well Total coliforms, E. coli, Salmonella 25 0.01-natural [47]
spp. Fe:10
SE Wild enteric E. coli and total coliform 7 20:50 [48]
SE Antibiotic resistant (clarithromycin 60 5.02-Fe3+:160 [49]
and sulfamethoxazole) Enterococci (pH 4)
sp.
SE and syn- Fusarium sp. No inactivation at natu- 60 5:60 [50]
thetic SE ral pH
SE Clostridium sp. 60 10:50 [51]
SE Multidrug resistant E. coli to ampicil- 8.5 5.02:10 [52]
lin, ciprofloxacin, and tetracycline
Alkaline Wild total coliforms, E. coli, Salmo- 25 0.10-total Fe: [53]
surface nella spp. 10
SE Bacillus sp. and Clostridium sp. 60 10:80 (pH 3) [54]
SE Curvularia sp. 60 10:20 (pH 3) [55]
Groundwater E. coli and Klebsiella pneumoniae Natural iron- [56]
0.3:10
Modified from [15] and updated
SE secondary effluents from municipal wastewater treatment plant
a
Reagent concentrations leading faster inactivation kinetics

conditions against neutral pH. This work also confirmed that solar photo-Fenton
at pilot plant scale is capable to strongly reduce the microbial load on secondary
effluents achieving the required levels established in different national and
international guidelines for wastewater reuse [43]. Recently, the presence of
antibiotic-resistant bacteria (ARB) has attracted the interest of research, and the
efficiency of Fenton and photo-Fenton for reduction of both ARB and ARG are
168 M.I. Polo-López et al.

50
a) 5
10
Concentration (CFU or PFU/100mL)
40
4

UVA irradiance (W m )
10

-2

Temperature (ºC)
30
3
10
20

2
10
10

1 DL
10
0
11:00 12:00 13:00 14:00 15:00 16:00
Time (HH:mm)

b) 5
50
10
Concentration (CFU or PFU/100mL)

40
4

UVA irradiance (W m )
10
-2

30
Temperature (ºC)
3
10
20

2
10
10

1 DL
10
0
11:00 12:00 13:00 14:00 15:00 16:00
Time (HH:mm)

Fig. 5 Inactivation of naturally occurring E. coli (filled square); SRC, sulfite reducing clostridia
(filled inverted triangle); SOMCPH, somatic coliphages (filled circle); and FRNA, F-specific
RNA bacteriophages (filled triangle) in secondary effluents by solar photo-Fenton with 10 mg L1
of Fe+2 and 20 mg L1 of H2O2 at pH 3 (a) and natural pH (b). UVA irradiance (dashed line) and
temperature (dashed line) (Reprinted from [43], with permission from Elsevier)

also found in literature [49, 60]. Ferro et al. [52] investigated at pilot scale the
capability of solar photo-Fenton on the inactivation of a multidrug resistant
E. coli to ampicillin, ciprofloxacin, and tetracycline. In this work, performed at
pH 4, best inactivation rate was attained with 0.090/0.294 mM of Fe2+/H2O2. In
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 169

addition, the antibiotic resistance of the survived colonies was analyzed by

Kirby-Bauer disk diffusion method. These results demonstrated that the antibi-
otic resistance did not decrease the ARB quality by this solar process, therefore
other processes with a higher oxidative capacity may be found to combat this
issue in water [52].
2. Type of water matrix and influence of natural organic matter: this is a critical
parameter, where the majority of the studies conducted at pilot scale show a
negative effect or a reduced effect produced by the presence of NOM on the
photo-Fenton efficiency. Ortega-Gómez et al. [61] demonstrated the competitive
role of NOM (using resorcinol as a model of organic matter) in clean water for
the oxidant species (HO•) against bacteria (Enterococcus faecalis) when a photo-
oxidation and photo-disinfection processes are occurring simultaneously. These
authors confirmed this negative effect at high resorcinol concentrations (20, 30,
and 40 mg L1) and for different photo-Fenton reagent concentrations (Fe2+/
H2O2: 2.5/5, 5/10 and 10/20 mg L1). For high concentrations of NOM, the
photo-Fenton might be worked at stronger oxidative conditions.
As previously mentioned, secondary effluents from a wastewater treatment plant
represent a challenging condition, due to it contains not only a high complexity of
ions and organic matter but also the presence of a rich consortium of microorgan-
isms which makes this water harder to purify. Recent contributions have demon-
strated the important influence of complex wastewater on the efficiency of photo-
Fenton for disinfection using real secondary effluents in a solar pilot reactor
[46, 50]. As an example, Fig. 6 shows a comparison between the inactivation of
spores of Curvularia spp. (a phytopathogenic fungi) by solar photo-Fenton at pilot
scale and near-neutral pH in distilled water and in real secondary effluents [55]. The
high difference of both graphs clearly demonstrated that under similar operational
conditions, the significant effect of the water matrix plays an important role on the
efficiency of the process.
In addition, the very well-known effect of hydroxyl radical scavenging by
inorganic compounds such as carbonate/bicarbonate has been also investigated in
secondary effluents. Ortega-Gómez et al. [48] reported the influence of reducing the
amount of bicarbonate from secondary effluents in the inactivation rate of naturally
occurring total coliforms and E. coli by solar photo-Fenton in CPC reactors (Fig. 7).
They concluded that although reducing the concentration of bicarbonate in water
may enhance the inactivation rates of bacteria, when an excess of hydroxyl radical
is not generated, the negative effect of bicarbonate is attenuated.
3. Optimization of operational conditions: process optimization can be done via
reagents concentrations and pH, which is very important and desirable to remain
close to neutral for either drinking of wastewater reuse. Most of contributions on
this demonstrate that the addition of low concentrations of iron and H2O2 lead to
high log removal of water pathogens (4–6 log reduction value, LRV), although
the treatment times to achieve these values are still longer (30 min to few hours)
than conventional disinfection methods, chlorination, UVC, and ozone. When
the process is run without the interference of other pathogens, NOM, or ions, the
170 M.I. Polo-López et al.

a) Fenton
103
Curvularia sp. (CFU mL-1)

102

Solar photo-inactivation
1/2.5 mg L-1 Fe2+/H2O2
2.5/5 mg L-1 Fe2+/H2O2
101
5/10 mg L-1 Fe2+/H2O2
10/20 mg L-1 Fe2+/H2O2

DL= 2 CFU mL-1

100
0 5 10 15 20 25 30 35
-1
QUV (kJ L )

Fenton

b) 103
Curvularia sp. (CFU mL-1)

102

Solar photo-inactivation
101 10/20 mg L-1 Fe2+/H2O2 neutral pH
10/20 mg L-1 Fe2+/H2O2 pH 3
20/40 mg L-1 Fe2+/H2O2 neutral pH
-1
DL= 2 CFU mL

100
0 5 10 15 20 25 30 35
QUV (kJ L-1)

Fig. 6 Inactivation of Curvularia sp. by solar photo-Fenton at pilot scale reactor using several
reagents’ concentration in (a) distilled water at near-neutral pH and (b) real secondary effluents at
acid and near-neutral pH (Reprinted from [55], with permission from Elsevier)

behavior of disinfection at higher reagents concentrations did not show a clear

enhancement, as observed in Fig. 6a, where Curvularia spp. is inactivated in
distilled water [55]. Similar results have been reported for other pathogens
[33, 50, 62].
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 171

Fig. 7 Influence of bicarbonate concentration on the inactivation of total coliform (open

circle) and E. coli (open diamond) in secondary effluent by solar photo-Fenton (20/50 mg L1
of Fe2+/H2O2). H2O2 (open square). Empty symbols, HCO3 ¼ 100  5 mg L1. Full symbols,
HCO3 ¼ 250  12 mg L1 (Reprinted from [48], with permission from Elsevier)

On the contrary, it has been also reported that when the concentration of iron is
high enough (>10 mg L1), the negative effect of iron precipitates due to light
screening makes the disinfection process slower. Rodrı́guez-Chueca et al. [46]
investigated the influence of the presence of precipitated iron in the efficiency of
solar photo-Fenton under natural sunlight for the inactivation of E. coli and
E. faecalis. The precipitated formed at pH 5 with 10 mg L1 of iron added to the
sample negatively affected the inactivation results as compared with the samples
without iron precipitated and only in the presence of the little solved iron (below
0.1 mg L1); this was especially clear in the case of E. faecalis (Fig. 8). In these
experiments, the lower efficiency in the presence of iron precipitates was attributed
to light screening of these suspended particles which induced higher turbidity in the
sample, reducing therefore the overall capability of the oxidative process. Mean-
while, this effect was not so significant in the case of E. coli, probably because
E. coli is a more sensitive bacterium as compared to E. faecalis, and the limited
oxidative action produced by this process in the presence of precipitated iron still
produced enough injuries in this higher sensitive bacteria, leading to complete
inactivation without differences between the presence or not of precipitated iron
(Fig. 8).
The modification of the classical photo-Fenton reactions is also actively
investigated for water disinfection with the aim of increasing the microbial inactiva-
tion rate by performing the process at natural water pH. In this sense, the
172 M.I. Polo-López et al.

Fig. 8 Comparison of
E. coli and E. faecalis 0
inactivation by solar photo-
Fenton with 10/20 mg L1 -1
of Fe2+/H2O2 in the
presence (full symbol) and -2

Log (Nt/N0)
absence (empty symbols) of
precipitated iron (Reprinted -3 E. coli E. faecalis
from [46], with permission
from Elsevier)
-4

-5

-6
0 5 10 15
QUV (kJ/L)

main modifications on water disinfection by solar photo-Fenton are summarized as

follows:
1. Heterogeneous Fenton-like processes catalyzed by iron (hydr)oxide particles.
Nieto-Juarez and Kohn reported the removal by absorption and inactivation of
MS2 coliphage at near-neutral pH, with 200 mg L1 of commercial hematite
(α-Fe2O3), goethite (α-FeOOH), magnetite (Fe3O4), and amorphous iron(iii)
hydroxide (Fe(OH)3). In general, all particles exhibited a similar virus adsorp-
tion capacity and inactivation, although their exposition to sunlight and H2O2
drastically enhanced the inactivation rate [63]. Recently, hematite (α-Fe2O3),
goethite (α-FeOOH), wüstite (FeO), and magnetite (Fe3O4) at concentration of
0.6 mg L1 Fe3+ with and without addition of 10 mg L1 H2O2 under solar
radiation were also investigated for bacterial inactivation at neutral pH. It was
demonstrated that all the semiconductor iron (hydr)oxides showed photoactivity
under sunlight with the exception of magnetite which was the only one that
needs H2O2 as electron acceptor [64].
2. H2O2 versus persulfate (PS). To date, sulfate radical (SO4•) has been increas-
ingly applied as an efficient oxidant for water treatment. A recent contribution
has demonstrated an E. coli O157:H7 inactivation five times faster via persulfate
(S2O82) activation using Fe2+ than HO•. This capacity was attributed to the
highly selective reactivity of SO4• with electron-rich moieties present on the
cell membrane of E. coli [65]. Garkusheva et al. [66] also have reported about
the feasibility of the solar/PS/Fe2+ system for removal of herbicide atrazine
(4 mg L1) and inactivation of E. coli (105 CFU mL1) in several water matrixes
(milliQ, lake, and diluted wastewater) [66]. Another interesting application of
this process was performed for the treatment of ballast water using PS activated
with zerovalent iron (Fe0) as a chemical biocide against two species of
marine phytoplankton, Pseudonitzshia delicatissima (a diatom) and Dunaliella
tertiolecta (green alga) [67].
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 173

3. Iron chelates. The complexation of iron with several chelates to make it soluble
for longer periods has been widely investigated during the last years. Many
examples of the investigation of complexes with polycarboxylate ligands
like ethylenediaminetetraacetic acid (EDTA), citric acid and oxalic acid,
nitrilotriacetic acid, tartaric acid, and humic acids are found in literature
[15]. Recently the use of natural and/or artificial but biodegradable substances
like (S,S)-ethylenediamine-N,N0 -disuccinic acid (EDDS), an structural isomer of
EDTA. Regarding water disinfection, the first approach of the use of EDDS was
performed by Klamert et al. in 2012. These authors reported a slight increased
efficiency on the reduction of total coliforms (>3-log in 120 min) with 0.1 mM
of iron, 0.2 mM of EDDS, and 50 mg L1 of H2O2 in secondary effluents at
neutral pH [41]. Recently, Bianco et al. [68] reported on Fe/EDDS complex
activation by H2O2 and persulfate ions for water disinfection. This work con-
cluded that HO• seems to be more effective on the E. faecalis inactivation than
sulfate radical. Moreover, it is also discussed the dual role that EDDS concen-
tration plays on the final efficiency, as it kept iron in dissolution at neutral pH but
also may act trapping generated radicals. And, the latter effect may overpass the
benefits of using EDDS and affect negatively the efficiency of the process if the
concentration of EDDS is not well selected [68].

7 Concluding Remarks

Fenton and photo-Fenton reactions have widely demonstrated their capability to

treat and disinfect different types of water sources. In the last years, especially solar
photo-Fenton driven by natural sunlight has gained great attention due to its high
efficiency for disinfection of secondary effluents (wastewater).
The chemical composition of secondary effluents plays a very important role on
the efficiency of photo-Fenton for water disinfection. The presence of organic
matter is considered as the main competitor for hydroxyl radicals against bacteria;
nevertheless, other parameters like inorganic compounds and natural occurring
pathogens also play a competition for HO• and, therefore reducing the efficiency
of the process.
As for other disinfection techniques, the biological nature of the waterborne
pathogens is also a key parameter on the photo-Fenton efficiency, with the following
gradient of susceptibilities: non-forming spore bacteria < fungi < viruses < forming
spore bacteria < helminths < protozoa. When using photo-Fenton for disinfection of
secondary wastewater effluents, the presence of different groups of pathogens and the
composition in terms of organic matter make the scenario quite complex, which may
require additional investigation to assure the final microbial quality of the treated
effluent and low health microbial risk when considering reclaimed wastewater.
Up to date, there is no commercial application of this process for water disin-
fection yet; nevertheless, the scaling up of the process from laboratory to pilot plant
scale (dozens of liters) has been widely demonstrated. In line with this, the use of
174 M.I. Polo-López et al.

solar CPC reactors has been demonstrated to be a good technological option for
solar photo-Fenton application as a tertiary treatment for secondary wastewater
effluents disinfection.
The current trend on photo-Fenton research is to increase the process efficiency
at near-neutral pH. Nevertheless, many aspects related to microbial inactivation in
water by iron chelates and iron oxides under solar radiation are unknown, and new
findings are expected to increase the knowledge in this area.

Acknowledgments The authors thank the financial supports given by the Spanish Ministry of
Economy and Competitiveness under the WATER4CROP project (CTQ2014-54563-C3-3) and
the European project WATERSPOUTT H2020-Water-5c-2015 (GA 688928).

References

1. Fenton HJH (1984) Oxidation of tartaric acid in presence of iron. J Chem Soc 65:899–910
2. Haber F, Weiss J (1934) The catalytic decomposition of hydrogen peroxide by iron salts. Proc
R Soc A 134:332–351
3. Barb WG, Baxendale JH, George P, Hargrave KR (1949) Reactions of ferrous and ferric ions
with hydrogen peroxide. Nature 163:692–694
4. Barb WG, Baxendale JH, George P, Hargrave KR (1951) Reactions of ferrous and ferric ions
with hydrogen peroxide. Part I. The ferrous ion reaction. Trans Faraday Soc 47:462–500
5. Barb WG, Baxendale JH, George P, Hargrave KR (1951) Reactions of ferrous and ferric ions
with hydrogen peroxide. Part II. The ferric ion reaction. Trans Faraday Soc 47:591–616
6. Bauer R (1990) Applicability of solar irradiation for photochemical wastewater treatment.
Cancer Lett 49:1225–1233
7. Pignatello JJ, Oliveros E, MacKay A (2006) Advanced oxidation processes for organic
contaminant destruction based on the Fenton reaction and related chemistry. Crit Rev Environ
Sci Technol 36:1–84
8. Brown RF, Jamison SE, Pandit UK, Pinkus J, White GR, Braendlin HP (1964) The reaction of
Fenton’s reagent with phenoxyacetic acid and some halogen-substituted phenoxyacetic acids.
J Org Chem 29(1):146–153
9. Rincón AG, Pulgarı́n C (2006) Comparative evaluation of Fe3+ and TiO2 photoassisted
processes in solar photocatalytic disinfection of water. Appl Catal B 63:222–231
10. Sylva RN (1972) The hydrolysis of iron(III). Rev Pure Appl Chem 22:115–130
11. Pignatello JJ (1992) Dark and photoassisted iron(3+)-catalyzed degradation of chlorophenoxy
herbicides by hydrogen peroxide. Environ Sci Technol 26:944–951
12. Canonica S, Kohn T, Mac M, Real FJ, Wirz J, von Gunten U (2005) Photosensitizer method to
determine rate constants for the reaction of carbonate radical with organic compounds.
Environ Sci Technol 39:9182–9188
13. Fernández-Ibá~
nez P, Sichel C, Polo-López MI, de Cara-Garcı́a M, Tello J (2009)
Photocatalytic disinfection of natural well water contaminated by Fusarium solani using
TiO2 slurry in solar CPC photo-reactors. Catal Today 144:62–68
14. Giannakis S, Polo López MI, Spuhler D, Sánchez Pérez JA, Fernández-Ibá~nez P, Pulgarin C
(2016) Solar disinfection is an augmentable, in situ-generated photo-Fenton reaction – Part 1:
A review of the mechanisms and the fundamental aspects of the process. Appl Catal B
199:199–223
15. Giannakis S, Polo López MI, Spuhler D, Sánchez Pérez JA, Fernández-Ibá~nez P, Pulgarin C
(2016) Solar disinfection is an augmentable, in situ-generated photo-Fenton reaction – Part 2:
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 175

A review of the applications for drinking water and wastewater disinfection. Appl Catal B
198:431–446
16. Kiwi J, Lopez A, Nadtochenko V (2000) Mechanism and kinetics of the OH-radical interven-
tion during Fenton oxidation in the presence of a significant amount of radical scavenger (Cl-).
Environ Sci Technol 34:2162–2168
17. Rose AL, Waite TD (2003) Kinetics of iron complexation by dissolved natural organic matter
in coastal water. Mar Chem 84:85–103
18. Bogan BW, Trbovic V (2003) Effect of sequestration on PAH degradability with Fenton’s
reagent: roles of total organic carbon, humin, and soil porosity. J Hazard Mater 100:285–300
19. Bissey LL, Smith JL, Watts RJ (2006) Soil organic matter-hydrogen peroxide dynamics in the
treatment of contaminated soils and groundwater using catalyzed H2O2 propagations (modified
Fenton’s reagent). Water Res 40:2477–2484
20. Li ZM, Shea PJ, Comfort SD (1998) Nitrotoluene destruction by UV-Catalyzed Fenton
oxidation. Chemosphere 36:1849–1865
21. Tyre BW, Watts RJ, Miller GC (1991) Treatment of four biorefractory contaminants in soils
using catalyzed hydrogen peroxide. J Environ Qual 20:832–838
22. Goldstone JV, Pullin MJ, Bertilsson S, Voelker BM (2002) Reactions of hydroxyl radical with
humic substances: bleaching, mineralization, and production of bioavailable carbon substrates.
Environ Sci Technol 36:364–372
23. Ng TW, Chow AT, Wong PK (2014) Dual roles of dissolved organic matter in photo-irradiated
Fe(III)-contained waters. J Photochem Photobiol A 290:116–124
24. Rutala WA, Weber DJ (2004) Registration of disinfectants based on relative microbicidal
activity. Infect Control Hosp Epidemiol 25:333–341
25. Garrido-Cardenas JA, Polo-López MI, Oller-Alberola I (2017) Advanced microbial analysis
for wastewater quality monitoring: metagenomics trend. Appl Microbiol Biotechnol. https://
doi.org/10.1007/s00253-017-8490-3
26. Rizzo L, Manaia C, Merlin C, Schwartz T, Dagot C, Ploy MC, Michael I, Fatta-Kassinos D
(2013) Urban wastewater treatment plants as hotspots for antibiotic resistant bacteria and
genes spread into the environment: a review. Sci Total Environ 447:345–360
27. Ferro G, Polo-Lopez MI, Fernández-Iba~nez P (2016) Conventional and new processes for
urban wastewater disinfection: effect on emerging and resistant microorganisms. In: Fatta-
Kassinos D, Dionysiou DD, Kümmerer K (eds) Advanced treatment technologies for urban
wastewater reuse. Handbook of Environmental Chemistry, vol 45. Springer, Cham, pp
107–128
28. Cabiscol E, Tamarit J, Ros J (2000) Oxidative stress in bacteria and protein damage by reactive
oxygen species. Int Microbiol 3:3–8
29. Reed RH (2004) The inactivation of microbes by sunlight: solar disinfection as a water
treatment process. Adv Appl Microbiol 54:333–365
30. Halliwell B, Gutteridge JM (1992) Biologically relevant metal ion-dependent hydroxyl radical
generation. FEBS Lett 307:108–112
31. Castro-Alférez M, Polo-López MI, Fernández-Ibá~nez P (2016) Intracellular mechanisms of
solar water disinfection. Sci Rep 6:38145
32. Jolivet JP, Chanéac C, Tronc E (2004) Iron oxide chemistry. From molecular clusters to
extended solid networks. Chem Commun 10:481–487
33. Polo-López MI, Garcı́a-Fernández I, Velegraki T, Katsoni A, Oller I, Mantzavinos D,
Fernández-Ibá~nez P (2012) Mild solar photo-Fenton: an effective tool for the removal of
Fusarium from simulated municipal effluents. Appl Catal B 111–112:545–554
34. Matavos-Aramyan S, Moussavi M, Matavos-Aramyan H, Roozkhosh S (2017)
Cryptosporidium-contaminated water disinfection by a novel Fenton process. Free Radic
Biol Med 106:158–167
35. Castro-Rı́os K, Corpas EJ, Cárdenas V, Taborda G (2017) Inactivation efficiency of total
coliforms and Escherichia coli in doped natural water by heterogeneous Fenton: effect of
process factors. J Mater Environ Sci 8:364–369
176 M.I. Polo-López et al.

36. Escobar-Megchún SI, Nájera-Aguilar HA, González-Hilerio M, Gutiérrez-Jiménez J, Gutiér-

rez-Hernández RF, Rojas-Valencia MN (2014) Application of the Fenton process in the
elimination of Helminth eggs. J Water Health 12:722–726
37. Morales AA, Ramı́rez-Zamora RM, Schouwenaars R, Pfeiffer H (2013) Inactivation of Ascaris
eggs in water using hydrogen peroxide and a Fenton type nanocatalyst (FeOx/C) synthesized
by a novel hybrid production process. J Water Health 11:419–429
38. Morales-Pérez AA, Maravilla P, Solı́s-López M, Schouwenaars R, Durán-Moreno A, Ramı́rez-
Zamora RM (2016) Optimization of the synthesis process of an iron oxide nanocatalyst
supported on activated carbon for the inactivation of Ascaris eggs in water using the hetero-
geneous Fenton-like reaction. Water Sci Technol 73(5):1000–1009
39. Malato S, Fernández-Ibá~nez P, Maldonado MI, Blanco J, Gernjak W (2009) Decontamination
and disinfection of water by solar photocatalysis: recent overview and trends. Catal Today
147:1–59
40. Moncayo-Lasso A, Sanabria J, Pulgarin C, Benitez N (2009) Simultaneous E. coli inactivation
and NOM degradation in river water via photo-Fenton process at natural pH in solar
CPC reactor. A new way for enhancing solar disinfection of natural water. Chemosphere
77:296–300
41. Klamerth N, Malato S, Agüera A, Fernández-Alba A, Mailhot G (2012) Treatment of munic-
ipal wastewater treatment plant effluents with modified photo-Fenton as a tertiary treatment for
the degradation of micro pollutants and disinfection. Environ Sci Technol 46:2885–2892
42. Michael I, Hapeshi E, Michael C, Varela A, Kyriakou S, Manaia C, Fatta-Kassinos D (2012)
Solar photo-Fenton process on the abatement of antibiotics at a pilot scale: degradation
kinetics, ecotoxicity and phytotoxicity assessment and removal of antibiotic resistant entero-
cocci. Water Res 46:5621–5634
43. Agulló-Barceló M, Polo-López MI, Lucena F, Jofre J, Fernández-Ibá~ nez P (2013) Solar
advanced oxidation processes as disinfection tertiary treatments for real wastewater: implica-
tions for water reclamation. Appl Catal B 136:341–350
44. Ortega-Gómez E, Esteban Garcı́a B, Ballesteros Martı́n MM, Fernández-Ibá~ nez P, Sánchez
Pérez JA (2013) Inactivation of Enterococcus faecalis in simulated wastewater treatment plant
effluent by solar photo-Fenton at initial neutral pH. Catal Today 209:195–200
45. Ndounla J, Pulgarin C (2014) Evaluation of the efficiency of the photo Fenton disinfection of
natural drinking water source during the rainy season in the Sahelian region. Sci Total Environ
493:229–238
46. Rodrı́guez-Chueca J, Polo-López MI, Mosteo R, Ormad M, Fernández-Ibá~ nez P (2014)
Disinfection of real and simulated urban wastewater effluents using a mild solar photo-Fenton.
Appl Catal B 150:619–629
47. Ndounla J, Kenfack S, Wéthé J, Pulgarin C (2014) Relevant impact of irradiance (vs. dose) and
evolution of pH and mineral nitrogen compounds during natural water disinfection by photo-
Fenton in a solar CPC reactor. Appl Catal B 148:144–153
48. Ortega-Gómez E, Garcı́a BE, Martı́n MB, Ibá~nez PF, Pérez JS (2014) Inactivation of natural
enteric bacteria in real municipal wastewater by solar photo-Fenton at neutral pH. Water Res
63:316–324
49. Karaolia P, Michael I, Garcı́a-Fernández I, Agüera A, Malato S, Fernández-Ibá~ nez P, Fatta-
Kassinos D (2014) Reduction of clarithromycin and sulfamethoxazole-resistant Enterococcus
by pilot-scale solar-driven Fenton oxidation. Sci Total Environ 468:19–27
50. Polo-López MI, Castro-Alférez M, Oller I, Fernández-Ibá~ nez P (2014) Assessment of solar
photo-Fenton, photocatalysis, and H2O2 for removal of phytopathogen fungi spores in syn-
thetic and real effluents of urban wastewater. Chem Eng J 257:122–130
51. Ruiz-Aguirre A, Polo-López MI, Fernández-Ibá~nez P, Zaragoza G (2015) Assessing the
validity of solar membrane distillation for disinfection of contaminated water. Desalin Water
Treat 55:2792–2799
Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater 177

52. Ferro G, Fiorentino A, Alférez MC, Polo-López MI, Rizzo L, Fernández-Ibá~ nez P (2015)
Urban wastewater disinfection for agricultural reuse: effect of solar driven AOPs in the
inactivation of a multidrug resistant E. coli strain. Appl Catal B 178:65–73
53. Ndounla J, Pulgarin C (2015) Solar light (hv) and H2O2/hv photo-disinfection of natural
alkaline water (pH 8.6) in a compound parabolic collector at different day periods in Sahelian
region. Environ Sci Pollut Res 22:17082–17094
54. Ruiz-Aguirre A, Polo-López MI, Fernández-Ibá~nez P, Zaragoza G (2017) Integration of
membrane distillation with solar photo-Fenton for purification of water contaminated with
Bacillus sp. and Clostridium sp. spores. Sci Total Environ 595:110–118
55. Aguas Y, Hincapie M, Fernández-Ibá~nez P, Polo-López MI (2017) Solar photocatalytic
disinfection of agricultural pathogenic fungi (Curvularia sp.) in real urban wastewater. Sci
Total Environ 607–608:1213–1224
56. Gutiérrez-Zapata HM, Sanabria J, Rengifo-Herrera JA (2017) Addition of hydrogen peroxide
enhances abiotic sunlight-induced processes to simultaneous emerging pollutants and bacteria
abatement in simulated groundwater using CPC solar reactors. Sol Energy 148:110–116
57. Sichel C, Fernández-Iba~nez P, De Cara M, Tello J (2009) Lethal synergy of solar UV-radiation
and H2O2 on wild Fusarium solani spores in distilled and natural well water. Water Res
43:1841–1850
58. Spuhler D, Rengifo-Herrera JA, Pulgarı́n C (2010) The effect of Fe2+, Fe3+, H2O2 and the
photo-Fenton reagent at near neutral pH on the solar disinfection (SODIS) at low temperatures
of water containing Escherichia coli K12. Appl Catal B 96:126–141
59. Ortega-Gómez E, Ballesteros Martı́n MM, Carratala A, Fernández Iba~ nez P, Sánchez Pérez
JA, Pulgarı́n C (2015) Principal parameters affecting virus inactivation by the solar photo-
Fenton process at neutral pH and μM concentrations of H2O2 and Fe2+/3+. Appl Catal B
174–175:395–402
60. Macku’ak T, Nagyov K, Faberov M, Grabic R, Koba O, Gal M, Birosova L (2015) Utilization
of Fenton-like reaction for antibiotics and resistant bacteria elimination in different parts of
WWTP. Environ Toxicol Phar 40:492–497
61. Ortega-Gómez E, Ballesteros Martı́n MM, Esteban Garcı́a B, Sánchez Pérez JA, Fernández
Ibá~
nez P (2014) Solar photo-Fenton for water disinfection: an investigation of the competitive
role of model organic matter for oxidative species. Appl Catal B 148–149:484–489
62. Garcı́a-Fernández I, Polo-López MI, Oller I, Fernández-Ibá~nez P (2012) Bacteria and fungi
inactivation using Fe3+/sunlight, H2O2/sunlight and near neutral photo-Fenton: a comparative
study. Appl Catal B 121–122:20–29
63. Nieto-Juarez JI, Kohn T (2013) Virus removal and inactivation by iron (hydr)oxide-mediated
Fenton-like processes under sunlight and in the dark. Photochem Photobiol Sci 12:1596–1605
64. Ruales-Lonfat C, Barona JF, Sienkiewicz A, Bensimon M, Vélez-Colmenares J, Benı́tez N,
Pulgarı́n C (2015) Iron oxides semiconductors are efficient for solar water disinfection: a
comparison with photo-Fenton processes at neutral pH. Appl Catal B 166–167:497–508
65. Wordof DN, Walker SL, Liu H (2017) Sulfate radical-induced disinfection of pathogenic
Escherichia coli O157:H7 via iron-activated persulfate. Environ Sci Technol Lett 4:154–160
66. Garkusheva N, Matafonova G, Tsenter I, Beck S, Batoev V, Linden K (2017) Simultaneous
atrazine degradation and E. coli inactivation by simulated solar photo-Fenton-like process
using persulfate. J Environ Sci Health A 52:849–855
67. Ahn S, Peterson TD, Righter J, Miles DM, Tratnyek PG (2013) Disinfection of ballast water
with iron activated persulfate. Environ Sci Technol 47:11717–11725
68. Bianco A, Polo-López MI, Fernández Iba~nez P, Brigante M, Mailhot G (2017) Disinfection of
water inoculated with Enterococcus faecalis using solar/Fe(III)EDDS-H2O2 or S2O82 pro-
cess. Water Res 118:249–260
AOPs Methods for the Removal of Taste
and Odor Compounds

M. Antonopoulou and I. Konstantinou

Abstract The production of drinking water with good quality including the chem-
ical, microbiological, and aesthetic characteristics remains one of the main con-
temporary challenges for drinking water industry. As the most predominant and
problematic earthy-musty taste and odor (T&O) compounds are recalcitrant to
conventional water treatment, advanced oxidation processes (AOPs) have been
recently studied and employed in drinking water treatment for taste and odor
control. In the light of recent developments, the present chapter reviews the
effectiveness of various AOPs for T&O compounds removal from aqueous
media. More specifically, an overview of the recent research studies dealing with
AOPs for the removal of geosmin, 2-methylisoborneol, 2,4,6-trichloroanisole,
2-isopropyl-3-methoxypyrazine, and 2-isobutyl-3-methoxypyrazine from water
reservoirs and drinking water, is presented. The fundamentals and experimental
setup involved in relative technologies and the effectiveness of each process are
further discussed. Special attention was also given to the degradation products and
mechanisms that have been proposed for all the compounds in interest. Future
research directions regarding the application of AOPs for T&O control and recom-
mendations for further development are also highlighted.

Keywords AOPs, Drinking water, Odor, Removal, Taste

M. Antonopoulou
Laboratory of Industrial Chemistry, Department of Chemistry, University of Ioannina,
Ioannina 45110, Greece
Department of Environmental and Natural Resources Management, University of Patras,
Seferi 2, Agrinio 30100, Greece
I. Konstantinou (*)
Laboratory of Industrial Chemistry, Department of Chemistry, University of Ioannina,
Ioannina 45110, Greece
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 179
Water Treatment, Hdb Env Chem (2019) 67: 179–210, DOI 10.1007/698_2017_119,
© Springer International Publishing AG 2017, Published online: 10 November 2017
180 M. Antonopoulou and I. Konstantinou

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2 Geosmin (GSM) and 2-Methylisoborneol (2-MIB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3 2,4,6-Trichloroanisole (TCA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
4 2-Isopropyl-3-Methoxypyrazine (IPMP) and 2-Isobutyl-3-Methoxypyrazine (IBMP) . . . 200
5 Coupling AOPs with Other Treatment Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206

1 Introduction

Taste and odor (T&O) are two important aesthetic characteristics of the drinking
water and problems associated with both of them are of growing interest. Various
compounds causing taste and odor problems have been identified up to now in
source water and in distribution systems. The majority of them can be perceived at
very low concentrations in the ng L
1 range and can be assessed directly with
human senses [1–3]. Although T&O compounds usually do not pose a health risk in
commonly detected concentrations, their presence has been associated with its
quality and safety, resulting in general decreased consumer acceptability and
consequently in an increase of bottled-water consumption [4]. Changes in aesthetic
properties of drinking water can also impart major costs to the drinking water
industry, whereas important T&O episodes can affect treatment plant operation and
even cause severe drinking water shortage, as well [3].
Numerous compounds have been identified during T&O events in drinking
water including β-ionone, β-cyclocitral, cis-3-hexen-1-ol, 1-penten-3-one, various
aldehydes [5–7], sulfur-containing compounds such as hydrogen sulfide, mercap-
tans and organic sulfides often emitted from sewage and wastewater treatment
plants [8], benzothiazole and its derivatives [9], chlorophenols, bromophenols
[10], and trihalomethanes [11]. The most reported compounds in literature that
cause unpleasant taste and odor in ng L
1 levels (Table 1) are the geosmin (GSM),
2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-
methoxypyrazine (IPMP), and 2-isobutyl-3-methoxypyrazine (IBMP) [12–
14]. The basic physicochemical properties of T&O of interest are summarized in
Table 2 [15–20].
In view of the global concern about the aesthetic characteristics, a drinking water
taste and odor wheel was developed by Suffet et al. [22] and identifies the main
tastes and odors in water. According to Fig. 1, the eight major odor categories are
earthy-musty, chlorinous, grassy, sulfurous/septic, fragrant/vegetable, fishy/rancid,
medicinal, and chemical [22–24]. Specific descriptors for each odor category are
also given.
Compounds giving rise to taste and odor in water can be derived by both natural
and anthropogenic sources (Fig. 2), and the corresponding episodes may be devel-
oped from either one or the other or a combination of both. They are mainly produced
by numerous benthic and pelagic aquatic microorganisms, such as cyanobacteria and
AOPs Methods for the Removal of Taste and Odor Compounds 181

Table 1 Chemical structure and odor/taste threshold of the selected T&O compounds [1, 21]
Odor threshold Taste threshold
Compound Structure (ng L
1) (ng L
1)
Geosmin 4 7.5
OH

2-Methylisoborneol (2-MIB) 15 2.5

OH

2-Isopropyl-3- 0.2 9.9

methoxypyrazine (IPMP)
O
N

2-Isobutyl-3- 1 0.4
methoxypyrazine (IBMP)

O
N

2,4,6-Trichloroanisole 0.03 25
(TCA) O

Cl Cl

Cl

actinomycetes that emerged in eutrophic surface waters. In addition, odorous com-

pounds can be formed as by-products during oxidation and disinfection of drinking
water as well as in the distribution systems through leaching from the polyethylene
pipes [23].
Conventional technologies such as adsorption with the use of granular activated
carbon (GAC), powered activated carbon (PAC), alum coagulation, and sand
filtration [25, 26] have been used to remove T&O from the water. Although
adsorption is widely applied for the control of taste and odor, extremely high
dosages of the adsorbent are required many times, whereas the presence of natural
 182

Table 2 Basic physicochemical properties of T&O compounds of interest [15–20]

Molecular Molecular Polarizability Henry’s law constant Boiling point

Compound formula weight Solubility mg L
1 log Kow 10
24 cm3 atm m3 mol
1 C
Geosmin C12H22O 182.31 157.0 3.7 21.8 1.2  10
5 165
2-Methylisoborneol (2-MIB) C11H20O 168.28 194.5 3.13 20 8.9  10
5 197
2-Isopropyl-3-methoxypyrazine (IPMP) C8H12N2O 152.19 2438.0 2.41 17.2 3.1  10
6 120–125
2-Isobutyl-3-methoxypyrazine(IBMP) C9H14N2O 166.22 1034.0 2.72 19 4.1  10
6 83–86
2,4,6-Trichloroanisole (TCA) C7H5Cl3O 211.47 10.0 3.91 18.9 1.3  10
4 240
M. Antonopoulou and I. Konstantinou
AOPs Methods for the Removal of Taste and Odor Compounds 183

e
hlorid
Sodiu

ydroc
m ch

ine h
- Quinffeine
lorid

- Ca
e- -

te
lf a
er
Salty

su
- Bitt

te
ro ho m
Su

lf a
er nt nu
ga

su
us l
- f Me umi
- T Ch - O t
r-

n
- A - ing alky ily
ge

- l
-A
e

un
-S
zin

-P
a

st Dr ling
we
pyr

- M Co en g
oxy
et

g n
rin yi
-
eth

et ding t
in* yl 3-mnel* s*

lic
sm r le

Bitter
eo rop bo iso

al
Sa
- G -Isop yliso d an

-
- 2 -Methenate

lty
y
Citri / arth
c ac el l
- E bin - 2 alog wn
Sw - H kno
id - to
Fe ee ota sty
y /P - Mu ork - Un
- So
ee th e F rth
t
ur / a C y
ou os -E y/
acid
ic old Mudd
M N /M -
/ sty
sty -M
u
Sou
r/A Mu y
cidic T E y / Mold
S
rth
Ea
A
T
glue
- Model airplane
Styrene - - Sweet solvent mical - Chlorino
*MTBE - - Sweet organic che Chemical / Chlorinous / us / Blea
chy
m-Xylene - - Cat urine n - Free
-
Unknown - Plastic Hydrocarbo Ozonous - Swimmi - Mon
chlorin
- l) us ng pool ochlor e*
Miscellaneo
cry late (me dic ina
Methyl methaixolane - - Sweet (tutty-fruity) Gr - Ozonou - Dic amine*
thyl-1 ,3-d - Sweet ODOR Str assy s - O hloramine*
*2-Ethyl-4-meethyl-1 ,3-dixolane -- - Shoe polish l/
zone in
Ma ept
aw / solutio
ina
dim Cumene / W Hay
Vegetable / Fruity /

*2-Ethyl-5,5’- - Petroleum - n*
S
rsh ic /

die ne - ent dic lic - G Gra

1,3-Penta an - - Varnish Solv oo / ras ssy
Me eno
ncid

y / Su

Ind - Gasoline tty / dy s y (fre

Unknown - - Paint / Pu h (gr sh
Sw lfur

es - P ee , s
Ra

*Alkyl ben zen -W

- D n, sh wee
am ous

oo
hy/

rie a t)
Flowery

dy -
Fragant

/Pe Hay d g rp) -

py

r
Fis

ina
l - S ncil /Wo ass - cis-3
/

dic we sha ody c -H

-D

- - Me et
tob vings - U is-3- exe
- B nkn Hexe nyl a
ec

ls
e

no l - ac
lga

ay

he o co - U -Cyc own n-1 ceta

rop hen s -
- R resh fish

ing
/A

-ol* te
ck

- B kn n lo
hlo op *
- R anc fish

e -C ow citral*
h

*C rom than
so
- F otten

ke

ve - Se py
- B anc id fis

- Fruity / Orange like

yc
*B ome loc n
aty
- li

ge

itra
-R

- S ubb ggs

d
- A utte id

tat tic
-R

we
- R ancid ium

*lo
- R n e ion

l*
- R qua ry

wa ery

ion
ott - On eky
/S
r

p
e

m
- Cucumber
- Geranium
w -

cid
ep kno ine
Un dien n -

-C
an
Un kno al -

- D nkn thyl
- Sweet
4-H Un lam

re

- U ime wn sulf apta

w -

im ow tris
kn wn
eth O now n -

- D nkno gen erc

-
y

yl cta n -

eth n
eth

U
- H opr own
tan l -
ta

- Is nkn
-
bu na

yl
im

yd o p y
al

-U

dis
Tr

ro
n k

- Trans-2-cis-6-nonadienal*

- Decanal

ulf
- Diphenyl ether

- 4-Nonyl phenol
U
-2,

ide
ulf
lm
ns

*
ide
tra

ide n

*
*m
s,

*
an
*tr

Fig. 1 The drinking water taste and odor wheel (reproduced from (Suffet et al. 1999) [22] with
permission from the copyright holders, IWA Publishing)

organic matter (NOM) usually leads to reduced adsorption capacity and simulta-
neously requires additional steps for the regeneration of the used adsorbent
[13, 27]. Common chemical oxidants such as chlorine, chlorine dioxide, or potas-
sium permanganate have also been applied mainly for the removal of earthy and
musty odor compounds, GSM and 2-MIB [1, 28]. Nonetheless, reduced removal
efficiency was often exhibited due to the resistance of the tertiary alcohols like
GSM and 2-MIB toward oxidation [29]. Rate constants for the reactions of both
aforementioned compounds with different oxidants are summarized in Table 3.
Chlorine dioxide, a selective oxidant which mainly reacts with activated aromatic
systems and deprotonated amines, has shown relatively low rate constants. Similar
low reactivity was exhibited for permanganate, which reacts predominantly with
olefins and phenols.
Other conventional water treatment methods such as thermal oxidation and
biofiltration involve high operating costs and could generate toxic secondary
184 M. Antonopoulou and I. Konstantinou

Fig. 2 Origins and sources of T&O compounds in the aquatic environment

Table 3 Second-order rate constants for the reaction of selected T&O compounds with common
oxidants (M
1 s
1) [5, 30, 31]
Compound O3 HO• ClO2 KMnO4
Geosmin (GSM) 0.1 7.8  109 <1 <0.01
2-Isopropyl-3-methoxypyrazine (IPMP) 50 4.9  109 <10 <1
2-Methylisoborneol(2-MIB) 0.4 5.1  109 <1 <0.01
2,4,6-Trichloroanisole(TCA) 0.06 5.1  109 <10
3 <1

pollutants [8]. As conventional water treatment processes presented significant

weaknesses in order to act as a reliable barrier toward T&O control, the scientific
community puts the focus on the development of more efficient technologies for the
treatment and removal of T&O compounds [1, 32].
Among different alternative treatment options, AOPs have been proven as
emerging technologies with significant importance in environmental remediation
applications. In the last two decades, research activities have centered on AOPs for
the destruction of various categories of organic contaminants and especially
nonbiodegradable compounds [1, 14, 33]. More recently, AOPs have been applied
increasingly for the removal of T&O compounds, and until now numerous studies
have been devoted to the treatment of mainly five compounds, i.e., geosmin (GSM),
2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-
methoxypyrazine (IPMP), and 2-isobutyl-3-methoxypyrazine (IBMP) [1, 14].
AOPs can be broadly defined as aqueous-phase oxidation methods based on the
formation of highly reactive species. Hydroxyl radicals (HO•), with oxidation
potential equal to 2.8 V, are the primary oxidants in AOPs, while other radical
and active oxygen species such as superoxide radical anions (O2•–), hydroperoxyl
radicals (HOO•), singlet oxygen (1O2), and holes (h+) are also involved. A number
AOPs Methods for the Removal of Taste and Odor Compounds 185

of systems can be termed as AOPs, and typical AOP systems can be divided into
chemical, photochemical, and electrochemical processes, as depicted in Fig. 3.
Most of them use a combination of strong oxidizing agents (e.g., H2O2, O3) with
catalysts (e.g., transition metal ions) and irradiation (e.g., ultraviolet, visible) and
have considerable similarities due to the participation of hydroxyl radicals which
enhance the degradation process. In most cases, the complete mineralization of the
target pollutant into CO2, H2O, and mineral acids is achieved [1, 33, 34]. Hydroxyl
radicals are short-lived, simply produced, powerful electrophiles and unselective
oxidants [34] which have shown high rate constants with T&O compounds
(Table 3). Ozone has also been found to be a relatively good oxidant for T&O
compounds removal [5].
Even though the study of T&O compounds removal by AOPs has attracted the
scientific research quite recently, many scientific studies have already been
published as presented in a recent review on the evaluation and comparison of
various AOPs for the treatment of T&O compounds. The efficiency of the applied
process, reaction kinetics, effect of operational parameters and water quality,
identity of intermediate, and the possible transformation pathways have been
presented [1].
This chapter aims to give an overview of the most recent progresses and
achievements of various AOPs for the control of five T&O compounds in aqueous
media together with possible future challenges that should be addressed. Geosmin,
2-methylisoborneol, 2,4,6-trichloroanisole, 2-isopropyl-3-methoxypyrazine, and
2-isobutyl-3-methoxypyrazine are reviewed herein as: (1) they were identified to

Fig. 3 Types and classifications of main advanced oxidation processes

186 M. Antonopoulou and I. Konstantinou

be the major T&O compounds with extremely low taste and odor thresholds,
frequently detected in aquatic systems; (2) adequate data concerning their removal
with the application of AOPs are existing up to now in the literature. An extensive
presentation of the recent literature published in the past 4 years concerning the
removal of the selected T&O compounds using various AOPs is provided to gain
up-to-date information on the degree of degradation, reaction kinetics, identifica-
tion of transformation by-products, and possible degradation pathways. Further-
more, special attention is devoted to present important gaps that still need to be
investigated by the scientific community, giving the most important research
directions. In general, special emphasis is given to provide an updated integrated
picture of the current status and trends prevailing in the specific field.

2 Geosmin (GSM) and 2-Methylisoborneol (2-MIB)

Geosmin (GSM) (trans-1,10-dimethyl-trans-9-decalol) and 2-methylisoborneol

(2-MIB) are semi-volatile alicyclic alcohols and the most frequent and undesirable
earthy-musty T&O compounds detected in drinking water [35, 36]. Both com-
pounds are secondary metabolites produced by various microorganisms such as
cyanobacteria, actinomycetes, protozoa, molds, and fungi, causing major concern
for the drinking water industry [35]. GSM and 2-MIB are highly potent (detectable
to humans at <10 ng L
1) and extremely stable, resisting natural degradation and
conventional treatment processes, as well [3].
Besides their frequent occurrence in water bodies, the concentration of these
T&O compounds in drinking water is not regulated in many countries, as they have
no known toxicological effects in environmental relevant concentrations toward
humans and most aquatic organisms. However, for satisfactory quality of drinking
water, a guideline level of 20 ng L
1 in South Korea and 10 ng L
1 in Japan and
China was established [36].
Several chemical and photochemical AOPs in both homogeneous and heteroge-
neous phase have been studied for the removal of GSM and 2-MIB. Ozonation and
associated oxidation processes (O3/H2O2, UV/O3, UV/O3/H2O2), Fenton (Fe2+/
H2O2) and photo-Fenton process (UVC/Fe2+/H2O2, UVA/Fe2+/H2O2, solar/Fe2+/
H2O2), UV/H2O2 oxidation, heterogeneous photocatalysis using various catalysts,
and irradiation sources as well as ultra-sonication have been applied with promising
results [1]. The feasibility of a number of AOPs was tested at low initial concen-
trations relevant to those found in environmental matrices. The efficiency of the
aforementioned processes was based on the formation of HO• radicals, resulting in
final concentrations lower than the human taste threshold. However, it was worth
mentioning that undesired transformation products (TPs) have been formed in some
cases, pointing out that simultaneous with the parent compound removal, the
overall abatement of T&O is vitally important. The presence of organic matter
[e.g., humic acids (HA) and/or fulvic acids (FA)] or inorganic ions (e.g., carbonate
and bicarbonate) in real waters was acknowledged as a limitation factor because
AOPs Methods for the Removal of Taste and Odor Compounds 187

they can act as scavengers of HO• radicals leading to slower degradation kinetics.
2-MIB was found to be more resistant to the removal by different AOPs than GSM,
due to the greater steric hindrance in its chemical structure [1].
Current research on the removal of GSM and 2-MIB by various AOPs in water
has been compiled in Tables 4 and 5, considering only the works published in the
last 4 years. Detailed experimental conditions, and water matrix, applied for each
treatment process, as well as results expressed as the observed degradation effi-
ciency, are presented.
UV/H2O2 process showed promising results for the removal of GSM and 2-MIB
in both pilot and laboratory scales [37, 38, 45]. The efficiency of this process is
based on the formation of HO• radicals produced via photolysis of H2O2 according
to the reactions 1–5 [48, 49]:

H2 O2 þ hv ! 2HO ∙ k ¼ φH2O2 I α ð1Þ

H2 O2 þ HO ∙ ! HO2∙ þ H2 O k ¼ 2:7  107 M
1 s
1 ð2Þ
HO2∙ þ HO2∙ ! H2 O2 þ O2 k ¼ 8:3  105 M
1 s
1 ð3Þ
H2 O2 þ HO2∙ ! HO ∙ þ O2 þ H2 O k ¼ 3:0 M
1 s
1 ð4Þ
HO ∙ þ HO ∙ ! H2 O2 k ¼ 5:5  109 M
1 s
1 ð5Þ

where M is molarity (mol dm
3), φH2O2 is the quantum yield for photodissociation
of H2O2, Ia (M s
1) is the intensity of absorbed light, and k (M
1 s
1) is the rate
constant.
Optimal conditions during the UV/H2O2 process were assessed using 300 ng L
1
and 275 ng L
1 of GSM and 2-MIB as initial concentrations, respectively, and an
efficiency higher than 96% was achieved [37, 45]. The process is influenced by
many factors (e.g., parent compound concentration, pH, H2O2 concentration, UV
intensity), and the removal by UV/H2O2 was enhanced with an increase in H2O2
concentration and UV intensity. In contrast, removal efficiency decreased with
increasing parent compound concentration [37] and pH values [38]. Besides the
investigation of UV/H2O2 process, UV/chlorine AOP for the destruction of both
compounds was also studied by Wang et al. [38]. This process is based on the
formation of both HO• and chlorine radicals (•Cl) produced from photolysis of
HOCl/OCl
at wavelengths less than 400 nm via Eqs. (6)–(8) [50]:

HOCl þ hv ! HO ∙ þ Cl ∙ ð6Þ
OCl
þ hv ! O ∙
þ Cl ∙ ð7Þ
O ∙
þ H2 O ! HO ∙ þ HO
ð8Þ

The UV/chlorine process exhibited comparable efficiency at pH 7.5 and 8.5 with
the UV/hydrogen peroxide (UV/H2O2) process under parallel conditions but showed
higher efficiency at pH 6.5 [38]. The higher performance of UV/chlorine process was
attributed to the following factors: (a) at lower pH values, HOCl absorbs UV light
about 2.3 times more efficiently than H2O2 producing more HO•; (b) HOCl reacts
more slowly with HO• than H2O2 (rate constant with HO• for HOCl, 8.46  104 M
1
s
1 vs. 2.7  107 M
1 s
1 for H2O2) [38, 50–52]. A possible disadvantage of
188 M. Antonopoulou and I. Konstantinou

Table 4 Summary of AOPs removal performance for GSM

Initial Removal
concentration Matrix scale AOP features efficiency References
514 ng L
1 Raw water (from drinking UV/H2O2 (laboratory scale) 99.03% [37]
water treatment plant) Low-pressure UV lamp (254 nm)
[H2O2]: 1.93 mg L
1
UV intensity: 86 mJcm
2
300 ng L
1 Raw water (from drinking UV/H2O2 (pilot scale) 97.14% [37]
water treatment plant) UV system (low-pressure UV lamps /
254 nm)
[H2O2]: 7.5 mg L
1
UV intensity: 400 mJcm
2
~350 ng L
1 Water (from water purifi- UV/chlorine >90% [38]
cation plant) MP UV reactors
[Chlorine]: 10 mg L
1
UV dose: 2000  150 mJ cm
2
pH: 6.5
~350 ng L
1 Water (from water purifi- UV/H2O2 ~85% [38]
cation plant) MP UV reactors
[H2O2]: 4.8 mg L
1
UV dose: 2000  150 mJ cm
2
pH: 6.5
100 ng L
1 Distilled water UV/H2O2 38.28% [36]
Low-pressure mercury UV-C lamp (254 nm)
UV fluence ¼ 3,348 mJ cm
2
[H2O2]: 20 mg/L
pH: 4.1–5.0
100 ng L
1 Distilled water Fenton < 20% [36]
[Fe(II)], 2 mg L
1; [H2O2], 20 mg L
1
pH: 4.1–5.0
100 ng L
1 Distilled water Photo-Fenton 78.86% [36]
Low-pressure mercury UV-C lamp (254 nm)
UV fluence: 5,022 mJ cm
2
[Fe(II)], 2 mg L
1; [H2O2], 20 mg L
1
pH: 3
50 ng L
1 River water Photo-Fenton Final concen- [36]
Low-pressure mercury UV-C lamp (254 nm) tration
<20 ng/L
UV fluence: 3,348 mJ cm
2
[Fe(II)], 2 mg L
1; [H2O2], 20 mg L
1
pH: 7.2–7.4
40 μg L
1 Milli-Q water UV/persulfate (PDS) 94.5% [32]
6 W low-pressure Hg UV lamp (254 nm/
1.79 mW cm
2)
I0/V: 1.26 μE s
1 L
1
2 mM phosphate buffer
[PDS]0, 10 μM; pH, 7.0
600 s reaction time
40 μg L
1 Reservoir water UV/persulfate (PDS) >95% [32]
6 W low-pressure Hg UV lamp (254 nm/
1.79 mW cm
2)
I0/V: 1.26 μE s
1 L
1
[PDS]0 ¼ 100 μM, 20  C
1,200 s reaction time
40 μg L
1 River water UV/persulfate (PDS) >95% [32]
6 W low-pressure Hg UV lamp (254 nm/
1.79 mW cm
2)
I0/V: 1.26 μE s
1 L
1
[PDS]0 ¼ 100 μM, 20  C
1,200 s reaction time

(continued)
AOPs Methods for the Removal of Taste and Odor Compounds 189

Table 4 (continued)
Initial Removal
concentration Matrix scale AOP features efficiency References
1 mg L
1 Milli-Q water UV-A (315–400 nm)/TiO2 ~100% [39]
F15 W/T8 black light tubes (max. emission (in 30 min)
~365 nm; I, 71.7 mW cm
2)
[TiO2]: 200 mg L
1
1 mg L
1 Milli-Q water UV-A (315–400 nm)/SiW12O404
~100% [39]
F15 W/T8 black light tubes (max. emission (in 120 min)
~365 nm; I, 71.7 mW cm
2)
[SiW12O404
]: 200 mg L
1
100 ng L
1 Milli-Q water UV-A/TiO2–USY zeolite composite coatings 99% [40]
UV-A lamps (Hitachi, FL8BL-B, 8 W (in 120 min)
wavelength, 320–4,000 nm)
TiO2–USY zeolite composite coatings (6 mg
of zeolite +4 mg of TiO2)
100 ng L
1 Milli-Q water UV/TiO2 pellets 96% [41]
Bed reactor-UVB lamps (100 W; spectral
output, 280–330 nm)
Hombikat K01/C TiO2 pellets (22 kg)
18.5 ng L
1 Fish farm water UV/TiO2 pellets 91% [41]
Bed reactor-UVB lamps (100 W; spectral
output, 280–330 nm)
Hombikat K01/C TiO2 pellets (22 kg)
50 ng L
1 Distilled water UV-A/immobilized TiO2 ~80% [42]
GE black light blue bulbs (8 W; spectral
range, 350–400 nm)
Immobilized TiO2 (0.25 mg/cm2)
50 ng L
1 Tainted water (from a UV-A/immobilized TiO2 ~60% [42]
recirculating aquaculture GE black light blue bulbs (8 W; spectral
system) range, 350–400 nm)
Immobilized TiO2 (0.25 mg cm2)
1 μg L
1 Milli-Q water Simulated solar light (SSL)/Pd/WO3 >99% [43]
Simulated solar lamp (in 20 min)
Light intensity:0.6 mWcm
2/0.8 mWcm
2
[Pd/WO3]:150 mg L
1
~10 μg L
1 Surface water Ozonation 45% (reaction [13]
pH: 7.9–8.1 time, 40 min)
T: 23  1  C
O3 dose: 2 mg O3/mg DOC
~10 μg L
1 Surface water Electro-peroxone process 54% (reaction [13]
Electrodes: anode was a Pt plate/cathode time, 5 min)
was a carbon-polytetrafluorethylene (car-
bon-PTFE)
pH: 7.9–8.1
T: 23  1  C
O3 dose: 2 mg O3/mg DOC
Current: 40 mA
4 ng L
1 Ultrapure water Electrochemical oxidation (EO)/persulfate ~100% [44]
Boron-doped diamond (BDD) electrode
Current density: 5.0 mA cm
2
[Na2SO4], 30 mM; pH, 2.0
Reaction time: 15 min (undivided cell)
Table 5 Summary of AOPs removal performance for 2-MIB
190

Initial
concentration Matrix scale AOP features Removal efficiency References
764 ng L
1 Raw water (from drinking water treatment plant) UV/H2O2 (laboratory scale) 99.99% [45]
Low-voltage light lamp (254 nm; 70 W; dose, 86 mJ cm
2)
[H2O2]: 3.93 mg L
1
UV dose: 86 mJ cm
2
275 ng L
1 Raw water (from drinking water treatment plant) UV/H2O2 (pilot scale) 96.58% [45]
UV system (low-voltage light lamp, wavelength of 254 nm, 2000 W)
[H2O2]: 6 mg L
1
UV dose: 350 mJ cm
2
100 ng L
1 Distilled water UV/H2O2 52.10% [36]
Low-pressure mercury UV-C lamp (254 nm)
UV fluence ¼ 3,348 mJ cm
2
[H2O2]: 20 mg/L
pH: 4.1–5.0
100 ng L
1 Distilled water Fenton < 20% [36]
[Fe(II)], 2 mg L
1; [H2O2], 20 mg L
1
pH: 4.1–5.0
100 ng L
1 Distilled water Photo-Fenton 100% [36]
Low-pressure mercury UV-C lamp (254 nm)
UV fluence: 5,022 mJ cm
2
[Fe(II)], 2 mg L
1; [H2O2], 20 mg L
1
pH: 3
50 ng L
1 River water Photo-Fenton Final concentra- [36]
Low-pressure mercury UV-C lamp (254 nm) tion < 20 ng/L
UV fluence: 3,348 mJ cm
2
[Fe(II)], 2 mg L
1; [H2O2], 20 mg L
1
pH: 7.2–7.4
1 mg L
1 Milli-Q water UV-A (315–400 nm)/TiO2 ~100% (in 25 min) [39]
F15 W/T8 black light tubes (max. emission ~365 nm; I, 71.7 mW cm
2)
[TiO2]: 200 mg L
1
M. Antonopoulou and I. Konstantinou
1 mg L
1 Milli-Q water UV-A (315–400 nm)/SiW12O404
~100% (in 100 min) [39]
F15 W/T8 black light tubes (max. emission ~365 nm; I, 71.7 mW cm
2)
[SiW12O404
]: 200 mg L
1
4 ng L
1 Ultrapure water Electrochemical oxidation (EO)/persulfate >95% [44]
Boron-doped diamond (BDD) electrode
Current density: 5.0 mA cm
2
[Na2SO4], 30 mM; pH, 2.0
Reaction time: 15 min (undivided cell)
100 ng L
1 Milli-Q water UV/TiO2 pellets 96% [41]
Bed reactor-UVB lamps (100 W; spectral output, 280–330 nm)
Hombikat K01/C TiO2 pellets (22 kg)
14 ng L
1 Fish farm water UV/TiO2 pellets 84% [41]
Bed reactor-UVB lamps (100 W; spectral output, 280–330 nm)
Hombikat K01/C TiO2 pellets (22 kg)
50 ng L
1 Distilled water UV-A/immobilized TiO2 ~67% [42]
GE black light blue bulbs (8 W; spectral range, 350–400 nm)
Immobilized TiO2 (0.25 mg/cm2)
50 ng L
1 Tainted water (from a recirculating aquaculture UV-A/immobilized TiO2 ~64% [42]
system) GE backlight blue bulbs (8 W; spectral range, 350–400 nm)
Immobilized TiO2 (0.25 mg cm2)
~10 μg L
1 Surface water Ozonation ~40% (reaction time, [13]
pH: 7.9–8.1 40 min)
AOPs Methods for the Removal of Taste and Odor Compounds

T: 23  1  C
O3 dose: 2 mg O3/mg DOC
~10 μg L
1 Surface water Electro-peroxone process 48% (reaction time, 5 min) [13]
Electrodes: anode was a Pt plate/cathode was a carbon-polytetrafluorethylene
(carbon-PTFE)
pH: 7.9–8.1
T: 23  1  C
O3 dose: 2 mg O3/mg DOC
Current: 40 mA
40 μg L
1 Milli-Q water UV/persulfate (PDS) 86.0% [32]
6 W low-pressure Hg UV lamp (254 nm/1.79 mW cm
2)
I0/V: 1.26 μE s
1 L
1
191

2 mM phosphate buffer
[PDS]0, 10 μM; pH, 7.0

(continued)
Table 5 (continued)
192

Initial
concentration Matrix scale AOP features Removal efficiency References
40 μg L
1 Reservoir water UV/persulfate (PDS) ~80% [32]
6 W low-pressure Hg UV lamp (254 nm/1.79 mW cm
2)
I0/V: 1.26 μE s
1 L
1
[PDS]0 ¼ 100 μM, 20  C
1,200 s reaction time
40 μg L
1 River water UV/persulfate (PDS) ~80% [32]
6 W low-pressure Hg UV lamp (254 nm/1.79 mW cm
2)
I0/V: 1.26 μE s
1 L
1
[PDS]0 ¼ 100 μM, 20  C
1,200 s reaction time
1 mg L
1 Distilled water UV/PDMS-coated SiO2/N-TiO2 >80% [46]
UV lamp irradiation (365 nm)
5:5 w/w PDMS-coated SiO2/N-TiO2
1 mg L
1 Distilled water Vis/PDMS-coated SiO2/N-TiO2 ~80% [46]
Blue light-emitting diode (LED) 455 nm
5:5 w/w PDMS-coated SiO2/N-TiO2
400 ng L
1 Water (from water purification plant) UV/chlorine ~90% [38]
MP UV reactors
[chlorine]: 10 mg L
1
UV dose: 2000  150 mJ cm
2
pH: 6.5
400 ng L
1 Water (from water purification plant) UV/H2O2 ~80% [38]
MP UV reactors
[H2O2]: 4.8 mg L
1
UV dose: 2000  150 mJ cm
2
pH: 6.5
23.2 μg L
1 Milli-Q water Ozonation 29.1% [47]
[O3] 0.5 mg L
1
pH: 6.7
23.2 μg L
1 Milli-Q water Catalytic ozonation by γ-AlOOH 27.5% [47]
M. Antonopoulou and I. Konstantinou

[catalyst]: 200 mg L
1

[O3]: 0.5 mg L
1
pH: 6.7
AOPs Methods for the Removal of Taste and Odor Compounds 193

UV/chlorine AOP which needs attention is related with the potential formation of
chlorination by-products (DBPs), especially with the usage of high chlorine dose.
However, this limitation can be overcome by the careful management of chlorate
formation using low doses of free chlorine, promoting further research and potential
applications of the UV/chlorine process for the T&O control [38].
Photo-Fenton process, a combination of UV–vis irradiation with the so-called
Fenton’s reagent, consisting of a mixture of H2O2 and Fe2+, has also been used for
T&O control. Photo-Fenton process was found to enhance the degradation of GSM
and 2-MIB compared to Fenton and UV/H2O2 processes, by generating more HO•
radicals according to the following reactions (9–11) [36]:

Fe2þ þ H2 O2 ! Fe3þ þ OH
þ HO ∙ ð9Þ

Fe3þ þ H2 O2 þ hv ! Fe2þ þ HO ∙ þ Hþ ð10Þ
H2 O2 þ hv ! 2HO ∙ ð11Þ

The comparative study shows that the degradation followed the decreasing
order: photo-Fenton > UV/H2O2 > UV > Fenton. The degradation was enhanced
by decreasing the pH, concentration of organic matter, and initial concentration of
the parent compound. However, the presence of organic matter (NOM, HA, and
FA) had only a slight influence on the degradation of T&O compounds, due to
sufficient UV fluence during the photo-Fenton process. The rates were found to be
dependent upon organic matter molecular size. The degradation efficiencies in the
presence of NOM increased with decreasing molecular size and followed the order:
NOM < HA < FA [36].
In real river water supplying a drinking water treatment plant (DWTP), a slightly
reduced degradation efficiency of both compounds was observed. Nevertheless,
with the application of photo-Fenton process, the guideline level in South Korea of
both GSM and 2-MIB was reached using initial concentrations under 30–50 ng L
1.
The toxicity of the treated solutions was evaluated using D. magna, and the results
revealed the formation of nontoxic intermediates. During the photo-Fenton process,
dehydration and open-ring pathways were the main common degradation pathways.
For GSM, six aliphatic compounds were identified, i.e., nonanoic acid, isobutyl
isobutyrate, butyl butyrate, methyl isobutyrate, methyl methacrylate, and methyl
propionate [36]. 2-Methylenebornane, 2-methyl-2-bornene, camphor, 2-ethyl-1-
hexanol, nonanal, and isooctyl alcohol were identified during the treatment of
2-MIB by photo-Fenton process showing that 2-MIB degradation proceeds through
C–C dissociation and subsequent skeleton rearrangement as well [36].
In recent years, UV/persulfate process has proved to be an effective method for
organic compounds degradation, including GSM and 2-MIB [32]. This process is
based on the formation of sulfate radical (SO4•
), a strong one-electron oxidant
with high-standard redox potential [E ¼ 2.60 V vs. normal hydrogen electrode
(NHE)] [12, 53, 54], according to the following Eq. 12:
194 M. Antonopoulou and I. Konstantinou

∙

8 þ hv ! 2SO4
S2 O2
ε ¼ 21:1 M
1 cm
1 , φ ¼ 0:7 mol Einstein
1 ð12Þ

HO• is simultaneously formed from the reaction of water and hydroxyl ions with
SO4•
[32, 55–57]:

SO4∙
þ S2 O2
∙

8 $ S2 O8 þ SO4
2

k ¼ 5:5  105 M
1 s
1 ð13Þ
HO ∙ þ S2 O2
∙

8 $ S2 O8 þ HO


k ¼ 1:4  107 M
1 s
1 ð14Þ
SO4 þ H2 O ! HSO4 þ HO k ¼ 8:3 M
1 s
1
∙

∙
ð15Þ
SO4∙
þ HO
! SO2
∙
4 þ HO k ¼ 6:5  10
7
M
1 s
1 ð16Þ

Second-order rate constants for 2-MIB and GSM reacting with SO4•
were
calculated to be 4.2  0.6  108 M
1 s
1 and 7.6  0.6  108 M
1 s
1,
respectively, at a pH of 7.0 [32]:

SO4∙
þ GSM ! Oxidation products k ¼ 7:6  0:6  108 M
1 s
1 ð17Þ
HO ∙ þ GSM ! Oxidation products k ¼ 5:7  0:2  109 M
1 s
1 ð18Þ
∙

1
1
SO4 þ 2
MIB ! Oxidation products k ¼ 4:2  0:6  10 M s ð19Þ
8

∙
1
1
HO þ 2
MIB ! Oxidation products k ¼ 4:3  0:6  10 M s
9
ð20Þ

At neutral pH, HO• contribution was found to be more significant than SO4•
for
2-MIB and GSM in ultrapure water. Critical operating parameter dictating process
performance was found to be the dosage of persulfate. Although pH did not affect
the degradation directly, faster degradations of both compounds were observed in
acidic media using phosphate buffer. This trend was connected with the different
scavenging effects of hydrogen phosphate and dihydrogen phosphate species in the
aqueous media. The degradation rate was appreciably reduced in the presence of
bicarbonate and natural organic matter (NOM) acting as HO• and SO4•
radical
scavengers and directly affecting process efficiency.
The process was also effective in removing 2-MIB and GSM in real waters,
showing, however, slower degradation kinetics [32].
Heterogeneous photocatalysis, a process combining semiconducting materials
with various activating irradiation sources, can be characterized as the most studied
photochemical AOPs for the removal of GSM and 2-MIB. From a mechanistic
point of view, the reactions that take place, generating various species that can
oxidize water or organic compounds, are described below [35]:

TiO2 þ hv ! e
CB þ hVB
þ
ð21Þ
hVB þ H2 O ! HO þ Hþ
þ ∙
ð22Þ
O2 þ e

CB ! O2
∙

ð23Þ
O2 þ H ! HO2∙
∙
þ
ð24Þ
HO2 þ HO2∙ ! H2 O2 þ O2
∙
ð25Þ
H 2 O 2 þ e
∙
CB ! HO þ OH


ð26Þ
AOPs Methods for the Removal of Taste and Odor Compounds 195

The most employed catalyst as clearly seen in Tables 4 and 5 is TiO2 in different
forms (powder, pellets, films) [39, 41, 42]. Except this semiconductor, Pd
nanoparticle-modified WO3 (Pd/WO3) catalysts [43] and polyoxometalates [39]
have also been used for the photocatalytic degradation of 2-MIB and GSM. The
available studies showed that the degradation rates of both compounds are highly
influenced by the catalyst concentration. Other parameters that affect performance
are the light wavelength and intensity, the solution pH, the initial concentration of
the parent compound, dissolved oxygen (DO), and the water matrix (i.e., the
presence of humic substances, bicarbonates). Photocatalytic reactions usually
obey to Langmuir–Hinshelwood kinetic model which is reduced mainly to pseudo
first-order kinetics for μg L
1 to ng L
1 concentration ranges [39, 41, 42]. The
photocatalytic degradation and mineralization of GSM and 2-MIB in water were
studied and compared using SiW12O404
(POM) and TiO2. Both photocatalysts
were found to be effective in degradation of target compounds. However, the
degradation of both compounds was slightly slower in the presence of POM.
Degradation pathway is proposed for target compounds during their photocatalytic
treatment. Quite similar intermediates have been identified, using either POM or
TiO2 with HO• radical attack to be mainly responsible for the mechanism [39].
In the case of GSM, the majority of the primary identified intermediates were
cyclic ketones, whereas linear saturated and unsaturated products were produced as
a consequence of ring opening. During 2-MIB photocatalytic degradation, alcohol-,
ketone-, and diketone- derivatives of 2-MIB, oxygenated cyclic compounds, and
open-chain aliphatic compounds were identified [39].
As the use of catalyst in slurry form requires an additional treatment step to
remove them from the treated aqueous media, Hombikat K01/C titanium dioxide
pellets, immobilized TiO2, films consisting of N-TiO2/PDMS-coated SiO2, and stable
TiO2–USY zeolite composite coatings have also been used [40–42, 46]. All the
materials showed significant potential for the removal of extremely low GSM and
2-MIB concentrations in ultrapure and real water.
Heterogeneous photocatalysis is likely to benefit from the use of renewable
energy sources, thus the use of novel semiconductor materials with photo response
to visible light is also necessary. Xue et al. [43] studied the photocatalytic removal
of GSM in the presence of Pd/WO3, and high removal percentages were achieved.
This catalyst also exhibited a superior reuse performance. 8a-Hydroxy-4a-methyl-
octahydro-naphthalen-2-one, 8,8a-dimethyl-decahydro-naphthalen-1-ol, and
2-ethyl-cyclohexanone were identified as intermediate products [43].
In addition, E-peroxone process is an emerging technology which has been recently
used for the treatment of GSM and 2-MIB and combines conventional ozonation with
an electrolysis process according to the following reactions 27 and 28 [13]:

H2 O2 þ O3 ! HO ∙ þ O2∙
þ Hþ þ O2 ð27Þ
O2 þ 2Hþ þ 2e
! H2 O2 ð28Þ

E-peroxone process typically involves the electrochemical conversion of O2 in

the reactor (sparkled with O2/O3 gas mixture) to H2O2. The process presented great
196 M. Antonopoulou and I. Konstantinou

potential for the treatment of 2-MIB and GSM with significantly lower bromate
formation compared to conventional ozonation, for a given specific ozone dose
[13]. The efficiency of the process was attributed to the higher HO• production than
in conventional ozonation, thus enhancing the removal of the parent compounds
during water treatment. One more advantage of the applied technology was the in
situ formation of H2O2 that could eliminate the problems associated with the use
and storage of concentrated H2O2 [13].
However, it should be pointed out that the E-peroxone process may lead to a
reduced disinfection efficiency during water treatment, due to enhanced O3 decom-
position in the presence of H2O2 [58]. Moreover, a posttreatment step is required for
the removal of residual H2O2 [13].
Electrochemical oxidation, which uses boron-doped diamond (BDD) electrodes
in the presence of a suitable electrolyte, is a relatively new process in water
treatment and, therefore, less studied than other AOPs, for the control of T&O in
water [44].
Two mechanisms can be considered for electrochemical degradation of the
organic contaminants, (a) oxidation by the adsorbed HO• formed at the anode
surface, and (b) indirect oxidation in the liquid bulk by the oxidants that are formed
electrochemically in the presence of inorganic ions such as chloride, sulfate, or
phosphate [44, 59].
The relatively high removal efficiency of 2-MIB and GSM at BDD electrodes in
sulfate solution can be attributed to the formation of persulfate according the
reactions 29–31 [44]:

BDD þ H2 O ! BDDðHO ∙ Þ þ Hþ þ e
ð29Þ

2HSO


4
2e ! S2 O8 þ 2H
2
þ
ð30Þ


2SO4
2e ! 2S2 O8
2
2

ð31Þ

Other reactive species (e.g., superoxide and singlet oxygen) can also be gener-
ated in the EO, participating in the degradation process [44]:

2HO ∙ þ S2 O2

8 ðBDDÞ ! 2SO4 þ O2 þ 2H
2
1 þ
ð32Þ
4HO þ S2 O8 ðBDDÞ ! 2SO4 þ 2O2 þ 4Hþ
∙ 2
2
∙

ð33Þ

High-current density and low-solution pH were found to be favorable for 2-MIB

and GSM degradation. In contrast, NOM acting as a scavenger of the generated
reactive species could reduce the removal efficiency. 2-MIB and GSM electro-
chemical degradation proceeded mainly through dehydration, b-scission ring open-
ing, and oxidation reactions [44].
Ultrasonic irradiation, an attractive AOP, has been considered as alternative for
2-MIB and GSM removal [28]. Although the formation of reactive species (e.g., H•
and HO•) takes place through water sonolysis, according to the reactions 34–43
[60], the degradation of both compounds was found to proceed via pyrolysis, upon
cavitational collapse:
AOPs Methods for the Removal of Taste and Odor Compounds 197

H2 O þ ! H ∙ þ HO ∙ ð34Þ






O2 þ ! O∙ þ O∙ ð35Þ
O þ H2 O ! 2HO ∙
∙
ð36Þ
O ∙ þ HO ∙ ! HO2∙ ð37Þ
H ∙ þ O2 ! HO2∙ ð38Þ
2HO ∙ ! H2 O2 ð39Þ
2HO ∙ ! H2 O þ O ∙ ð40Þ
H ∙ þ HO ∙ ! H2 O ð41Þ
2HO2∙ ! H2 O2 þ O2 ð42Þ
2H ∙ ! H2 ð43Þ

A summary of transformation pathways of GSM and 2-MIB degradation apply-

ing various AOPs is presented in Figs. 4 and 5, respectively.

3 2,4,6-Trichloroanisole (TCA)

2,4,6-Trichloroanisole (TCA) is a typical T&O compound, which can cause

unpleasant taste and odor even at ng L
1 levels in drinking water [12]. Three
main routes can be considered for its occurrence in aquatic systems:
(a) biomethylation of the parent halophenols by actinomycetes [65] and fungi
[66] during the biological treatment process of wastewater or in water distribution
systems, (b) biotransformation of the parent phenolic compound by biofilm in
waterworks [67, 68], and (c) the leaching from the polyethylene pipes in the
distribution system [69]. In contrast to other T&O compounds, TCA has been
reported to cause cancer and potential genetic damages in human cells [12]. Several
methods have been investigated to remove TCA in different phases [70–72]. Based
on literature data, TCA is extremely resistant to removal by the conventional
treatment processes including coagulation and sand filtration [71]. Although, up
to now limited publications have been devoted to the removal of TCA from water
by advanced oxidation processes, the results are promising.
Ozonation and catalytic ozonation processes showed significant efficacy to
destroying TCA. Catalytic ozonation by various solid catalysts exhibited significant
removal efficiency for TCA in drinking water compared with the sole ozonation
[71, 72]. It was proposed that HO• radicals produced during decomposition of ozone
contributed significantly to TCA degradation compared with molecular ozone
[5, 71, 72]. A possible reaction mechanism for catalytic ozonation of TCA has
been proposed by Qi and co-workers [71] and includes (1) chemisorption of ozone
on the catalyst surface leading to the formation of active species (HO•) that could
oxidize TCA, (2) chemisorption of TCA molecules on the catalyst surface and their
further oxidation by gaseous or aqueous ozone, and (3) reaction between both
chemisorbed species of ozone and TCA. The factors which may affect TCA
removal are mainly the catalyst and ozone dosage. Ozonation-based processes
198 M. Antonopoulou and I. Konstantinou

O
O O

OH
O O
UV/TiO2
UV/TiO2;UV/POM
UV/TiO2
OH

UV/TiO2;UV/POM;SSL/Pd/WO3
-H2O UV/TiO2;UV/POM
O OH CH3
π bond rgm OH
HO addition HO O
UV/TiO2;UV/POM UV/TiO2;UV/POM
OH
UV/TiO2;UV/POM UV/TiO2;UV/POM;SSL/Pd/WO3 CH3
GSM UV/TiO2;UV/POM
-H2O -
bo H2 O
2O

-CH3 rgm nd
-H

-H2 sci
ssi
on
2O
-H

US US O UV/TiO2;UV/POM

-H2 UV/TiO2;UV/POM
US

US US
O O
O O
O O O

O
O
UV/POM UV/POM UV/POM UV/POM
O UV/TiO2 UV/TiO2;UV/POM
UV/TiO2 SSL/Pd/WO3
O
O
O O

O
UV/TiO2;UV/POM OH
UV/TiO2 UV/TiO2;UV/POM UV/TiO2 UV/TiO2 UV/TiO2
O
O
O O
OH
UV/TiO2 Photo-Fenton O
O O Photo-Fenton O
O Photo-Fenton

O O O
Photo-Fenton Photo-Fenton Photo-Fenton

Fig. 4 Proposed transformation pathways of GSM under various AOPs (based on the studies
[1, 28, 36, 39, 43, 61, 62])

may be also affected by the presence of natural organic matter and the pH of the
aqueous media [71, 72].
UV/persulfate process was also an effective method for the removal of TCA
[12].The second-order rate constant of TCA reaction with sulfate radical (SO4•-)
was determined to be 3.72  0.1  109 M
1 s
1 [12].

SO4∙
þ TCA ! Oxidation products k ¼ 3:72  0:1  109 M
1 s
1 ½12 ð44Þ
HO ∙ þ TCA ! Oxidation products k ¼ 5:1  109 M
1 s
1 ½5 ð45Þ

As expected, increasing dosage of persulfate increased the observed pseudo first-

order rate constant for TCA degradation. The effects of water matrix [i.e., NOM,
pH, carbonate/bicarbonate (HCO3
/CO32
), and chloride ions (Cl
)] were also
AOPs Methods for the Removal of Taste and Odor Compounds 199

O O
-H2O β-scission -H elimination
OH

UV/TiO2;UV/POM 2-MIB UV/TiO2;UV/POM HO addition O

-H UV/TiO2;UV/POM;
US; Photo-Fenton -H2O US;Photo-Fenton;

Re
2O O3;O3/H2O2

ar
O3;O3/H2O2

ra
ng
em
en
t
O
HO

O O
US; Photo-Fenton US OH OH
UV/POM O3;O3/H2O2 O3;O3/H2O2

O
O O O
O
O

UV/POM
UV/TiO2;UV/POM UV/TiO2;UV/POM UV/TiO2;UV/POM UV/TiO2;UV/POM
O
O O
O
O O HO OH

O
O3/H2O2 O3;O3/H2O2
O3;O3/H2O2
O O

US
US
O3;O3/H2O2

O
OH
OH Photo-Fenton
Photo-Fenton Photo-Fenton
O
HO
HO OH
OH OH
OH
OH O O O
O3;O3/H2O2 O
UV/TiO2;UV/POM O3;O3/H2O2 O3;O3/H2O2
HO O
OH HO

O O O O OH
UV/TiO2;UV/POM O3;O3/H2O2 O O3/H2O2 O3;O3/H2O2
O
O O O O
O HO
HO C OH
OH
OH OH
OH C OH
O
O3/H2O2 O O3;O3/H2O2
O3;O3/H2O2 O3;O3/H2O2 O O3/H2O2

Fig. 5 Proposed transformation pathways of 2-MIB under various AOPs (based on the studies
[1, 28, 36, 39, 43, 63, 64])
200 M. Antonopoulou and I. Konstantinou

evaluated. Degradation rate of TCA decreased with pH increase from 4.0 to 9.0,
which could be explained by the lower radical scavenging effect of dihydrogen
phosphate than hydrogen phosphate in acidic condition (pH < 6). An inhibitory
effect of NOM on TCA degradation was observed that could be attributed to the
ability of NOM to act: (a) as an inner filter hindering the photolysis of persulfate
and (b) as scavenger of the generated radicals [12]. The presence of CO32
/HCO3

significantly decreased the efficiency, whereas a slight decrease of TCA degrada-
tion rate constant was observed in the presence of 10 mM Cl
.
The degradation mechanism of TCA was also investigated, and four oxidation
products [i.e., 2,4,6-trichlorophenol (TCP), 2,6-dichloro-1,4-benzoquinone, and
two aromatic ring-opening products] were detected (Fig. 6). According to the
literature data, TCA degradation is initiated by an electron abstraction of the
aromatic ring by SO4•- radicals and the consequent formation of a cation radical
(Fig. 6). Sequential reaction of the cation radical with H2O and O2 produces an
organic peroxy radical, with subsequent elimination of methanol and superoxide
radical-generating TCP. Further hydroxylation and Cl
release from TCP formed
the corresponding hydroquinone which is converted to 2,6-dichloro-1,4-benzoqui-
none by two-electron oxidation (Fig. 6). Subsequent oxidation of the identified
aromatic intermediates leads to ring cleavage and formation of aliphatic
products [12].

4 2-Isopropyl-3-Methoxypyrazine (IPMP) and 2-Isobutyl-

3-Methoxypyrazine (IBMP)

2-Isopropyl-3-methoxypyrazine (IPMP) and 2-isobutyl-3-methoxypyrazine

(IBMP) are two main taste and odor compounds found in aquatic systems and
drinking water. They cause a rotten vegetable odor and have been frequently
detected in water reservoir systems worldwide in concentrations ranging from
10 to 65 ng L
1 [14, 20, 73, 74]. Up to now ozonation, catalytic ozonation, and
heterogeneous photocatalysis have been studied for the removal of IPMP [14, 75,
76]. In general ozonation was found to be efficient for the degradation of IPMP in
aqueous solution with initial concentration in ng L
1 level [14]. The removal
efficiency of IPMP increased in alkaline pH and decreased with the increase of
initial concentrations of the parent compound. In comparative studies between
ozonation and catalytic ozonation, the latter was reported to be more efficient
[76]. However, in both processes the significant participation of HO• radicals was
proved [14, 76]. During ozonation, the TPs of IPMP were identified by GC/MS
techniques and included 2-isopropyl-3-methylpyrazine, 2-hydroxy-3-
methylbutyric acid methyl ester, 3-methyl-2-oxobutanoic acid methyl ester,
4-methyl-2-oxovaleric acid, 2-methylpropanoic acid, 3-methyl-2-oxobutanoic
acid, and 3-methylbutanoic acid [14]. Qi et al. [76] found that the major interme-
diate by-products of IPMP in catalytic ozonation by γ-AlOOH were aliphatic
AOPs Methods for the Removal of Taste and Odor Compounds 201

O
H2O

Cl Cl
O O

Cl Cl Cl Cl +H 2
O

+SO4 -H
-SO4 2- Cl

ipso O
Cl Cl hydroxylation HO

Cl Cl

OH OH
O Cl
HO +O 2
Cl Cl Cl Cl
Cl Cl
+SO4
-SO4 2- -CH3OH
O O
-O2

Cl Cl
Cl
+H2O -H+/Cl-

O
OH

Cl Cl
Cl Cl
+SO4 Ring cleavage
+SO4
-H+ products
-H+

O
OH

Fig. 6 Proposed transformation pathways and main TPs of 2,4,6-TCA using UV/persulfate
(reproduced from Luo et al. [12] with permission of the copyright holders, Elsevier)

amines, i.e., methylamine, ethylamine, dimethylamine, n-propylamine,

n-methylethylamine, and diethylamine.
The photocatalytic degradation of IPMP has been also investigated using TiO2
Degussa P25 as catalyst in ultrapure water [75]. Under the studied conditions
(C ¼ 10 mg L
1, CTiO2 ¼ 100 mg L
1, and I ¼ 600 W m
2), 95% of IPMP was
removed within 20 min of irradiation. The major transformation products of TiO2
photocatalysis of IPMP have been characterized by accurate mass measurements,
and the transformation was found to proceed through hydroxylation, oxidation, and
demethylation pathways. HO• radicals were found to be the most significant reactive
species during the photocatalytic process. The contribution of O2•
and h+ was also
confirmed. Based on the identified TPs during the applied AOPs (ozonation, catalytic
202 M. Antonopoulou and I. Konstantinou

ozonation, and heterogeneous photocatalysis) for the degradation of IPMP, the

transformation pathways are presented in Fig. 7.
Finally, the oxidation of IBMP in aquatic samples by ozone has been recently
reported [14]. At pH 6.8 the removal efficiency of IBMP (100 ng L
1) reached over
90% within 15 min of ozonation. Five intermediates have been identified by
GC-MS, i.e., 2-isobutyl-3-methylpyrazine, 1-(3-methoxy-2-pyrazinyl)-2-methyl-
1-propanol, 4-methyl-2-oxovaleric acid, 1-(3-methoxy-2-pyrazinyl)-2-methyl-1-
propanone, 5-methylcaproic acid, and 4-methyl-2-oxovaleric acid, and the possible
degradation pathway of IBMP by ozonation is depicted in Fig. 8.

5 Coupling AOPs with Other Treatment Processes

Despite that AOPs are effective processes for the removal of numerous organic
pollutants, their major limitation is related with their cost compared with other
conventional treatments [77]. The coupling of AOPs with conventional processes
has gained a lot of attention over the past several years for the treatment of water
and wastewater. In particular, a combination of both processes is expected to lead to
the highest efficiency and simultaneously reduce the overall treatment costs
[78]. These hybrid methods are also becoming popular for T&O control, as they
can generate complementary oxidation conditions and overcome the limitations of
the individual conventional methods.
UV/H2O2 in pilot scale has been employed in combination with GAC adsorption
for the removal of GSM and 2-MIB during the bloom season (September to
November) [79]. The authors pointed out the benefits of the integration of processes
for the removal of emerging cyanobacterial metabolites, as well as the need for
further investigation of the process performance under extreme environmental
conditions [79].
Conventional water treatment processes integrated with ozonation for the T&O
control have also been recently studied at a drinking water treatment plant (DWTP).
GSM and 2-MIB were not removed effectively during the drinking water treatment
process and even seem to be increasing in the drinking water due to cell lyses and
re-circulation of filter backwash water. However, optimization of the process can
lead to the effective oxidation of T&O compounds [80].
Other configurations, like biologically active carbon (BAC) filters, have also
been combined with ozonation achieving high removal efficiency for GSM and
2-MIB. Simultaneously, bromate formation was controlled by lowering the pH less
than 7 [81]. A water treatment plant adopting O3-BAC process was evaluated by
Guo et al. [2], for the removal of multiple odorants causing different types of odor.
The combined process has exhibited high efficiency in the simultaneous removal of
GSM and 2-MIB, causing musty odor, and bis(2-chloroisopropyl) ether and the
thioethers, diethyl disulfide and dimethyl disulfide, causing septic odor. However,
for complete removal of the septic odorants, further treatment by sand filtration and
chlorination was required. It is worth pointing out that careful management of
AOPs Methods for the Removal of Taste and Odor Compounds 203

N OH
N O CH3
CH3 N O CH3
N HC
CH3
SSL/TiO2 CH3 N C CH2 O OH
SSL/TiO2 O CH2 OH N HC
OH
SSL/TiO2 CH2
C OH

N O CH3 N O CH3
B N O CH3
CH3 CH2
N HC CH3 N HC
N O
CH3 C SSL/TiO2
IPMP CH3 OH
SSL/TiO2 O CH3
A
D OH

N CH3
N O CH2 N O CH3 N O CH3
CH3 OH
N HC CH3 CH3 CH3
N HC N C N HC
CH3 HO CH3 H2C
O3 CH3 SSL/TiO2 OH
SSL/TiO2
SSL/TiO2

N O CH3
O N O CH3 N O CH3
N C CH3 CH3
N C N HC
SSL/TiO2 CH3 H2 O
HC
SSL/TiO2 SSL/TiO2

O O
N H N H O O
H
H
H H HO O O O3 OH
N N N O3
O O UV/TiO2 * OH
UV/TiO2 * UV/TiO2 *
O H3C CH3
CH3H2C CH3CH2NH2
OH CH2CH3 CH3NH2 N
N Ο3/γ−AlOOH H
O3 H Ο3/γ−AlOOH Ο3/γ−AlOOH
O Ο3/γ−AlOOH

H3C CH2CH3 CH3CH2CH2NH2 O HCOOH, HCHO CH3COOH

N UV/TiO2 * UV/TiO2 *
H Ο3/γ−AlOOH
O
Ο3/γ−AlOOH
O
O3
O O
NH2 OH
H OH
OH
UV/TiO2 *
O O O O3
3 O O3

Fig. 7 Proposed transformation pathways and main TPs of IPMP under various AOPs (based on
the studies [14, 75, 76])

sedimentation process should be considered in order to avoid the release of odorants

in this treatment stage [2].
204 M. Antonopoulou and I. Konstantinou

N O

N
IBMP

N
N O N O

N
N N
OH O

O
O
O
O
OH
OH

O
O

Fig. 8 Proposed transformation pathways and main TPs of IBMP using ozonation (based on the
study [14])

Investigations in pilot scale for the removal of 2-MIB with a low- or medium-
pressure ultraviolet-based advanced oxidation process (AOP) were performed in a
water treatment plant (WTP) located in South Korea using flocculation/coagulation
followed by sedimentation, sand filtration, and final chlorination as the final step.
The comparison of the different experimental setup showed that low-pressure UV
AOP can provide higher removal rates with lower electrical energy demand com-
pared to medium-pressure systems [82].
An integrated process including coagulation, ozonation, ceramic membrane
ultrafiltration, and activated carbon filtration was investigated for the removal of
different pollutants including 2-MIB and GSM from micro-polluted source water.
The removal efficiencies were enhanced in the combined system reaching the
values of 96% for GSM and 88% for 2-MIB [83].
From a practical point of view, the integration of processes may be technically
and economically feasible. The possibility to minimize the dose of the oxidant
agent usually contributes significantly in the lower cost of the chemical process and
followed also by a lower cost of conventional process that can reduce the overall
cost while improving the overall removal.
AOPs Methods for the Removal of Taste and Odor Compounds 205

6 Conclusions

The number of studies dedicated to T&O control with the application of AOPs
follows an increasing trend during the recent years. Investigations on advanced
oxidation methods for degradation of T&O compounds are mainly referred to
ultrapure, river, and reservoir water in lab and pilot scale. With the application of
various AOPs, high removal percentages were achieved for the T&O compounds of
interest in ultrapure and real water samples. Percentages from ~60 to 100% of GSM
and 2-MIB and 95% of IPMP were removed by heterogeneous photocatalysis using
different catalysts and experimental conditions. UV/persulfate process led to the
removal higher than about 95%, 80%, and 90% for GSM, 2-MIB, and 2,4,6-TCA,
respectively. The removal of 2-MIB was approximately in the range of
~52–99.99% for UV/H2O2 and up to 100% for photo-Fenton in acidic pH. In case
of GSM, ~38.28–99%, >90%, and 79% degradation were achieved with the
application of UV/H2O2, UV/chlorine, and photo-Fenton (pH ¼ 3), respectively.
Large variations in compounds degradation from 27.5 to 90% were observed by
O3-based processes (ozonation, catalytic ozonation, and electro-peroxone process),
depending on the studied compound and the applied experimental conditions.
The water quality parameters like pH, NOM, and inorganic species played a
significant role in the whole processes. The presence of inorganic and organic water
constituents often inhibited the degradation of target pollutants through radical
scavenging mechanisms. The majority of the studies are focused mainly on the
investigation of the operational parameters and kinetics, while the identification of
the TPs formed during the processes is less frequently studied. Elucidation of
chemical structures of by-products to evaluate the degradation pathways is an
important demand. Data regarding the T&O potency of the TPs are limited up to
now, as well. T&O assessment of TPs is of great importance and should be included
in the various studies. Structure characterization of by-products and their simulta-
neous assessment of their possible taste and odor properties are closely related
topics of interest that need to be addressed and will give useful insights for the
applicability of a process on a practical level under real conditions. Additionally,
the existing studies are generally performed for individual compounds at concen-
trations close to those found in the environment and limited studies addressing the
degradation of mixtures of compounds.
The main conclusion arrived from the overall assessment of the literature is that
despite the current extensive research in T&O removal, significant knowledge gaps
remain. Overall, while there are promising results in removing T&O compounds
using AOPs under laboratory conditions and pilot scale, more intensive research is
needed before these methods can be considered as economically feasible and
practically sustainable alternatives in water treatment facilities. In order to promote
the feasibility of AOPs in the future, several aspects have to be more extensively
addressed. Thus, more work needs to be done (1) on the elucidation of the structure
of the products generated during the treatment, (2) on the study of the formation of
potential T&O intermediate products, (3) on the performance of complete
206 M. Antonopoulou and I. Konstantinou

economic studies for the estimation of the overall costs, (4) on the application of
integrated or hybrid systems for enhanced removal, and (5) on the assessment of the
processes for the degradation of mixtures of compounds. Moreover, a lot more is
needed from engineering design and modeling, related to their industrial develop-
ment and process scaling-up.

References

1. Antonopoulou M, Evgenidou E, Lambropoulou D, Konstantinou I (2014) A review on

advanced oxidation processes for the removal of taste and odor compounds from aqueous
media. Water Res 53:215–234
2. Guo Q, Yang K, Yu J, Wang C, Wen X, Zhang L, Yang M, Xia P, Zhang D (2016)
Simultaneous removal of multiple odorants from source water suffering from septic and
musty odors: verification in a full-scale water treatment plant with ozonation. Water Res
100:1–6
3. Watson SB, Monis P, Baker P, Giglio S (2016) Biochemistry and genetics of taste- and odor-
producing cyanobacteria. Harmful Algae 54:112–127
4. Watson SB (2013) Ecotoxicity of taste and odour compounds. Chapter 33 In: Férard JF, Blaise
C (eds) Encyclopedia of aquatic ecotoxicology, Springer, pp 337–352
5. Peter A, von Gunten U (2007) Oxidation kinetics of selected taste and odor compounds during
ozonation of drinking water. Environ Sci Technol 41:626–631
6. Cotsaris E, Bruchet A, Mallevialle J, Bursill DB (1995) The identification of odorous metab-
olites produced from algal monocultures. Water Sci Technol 31:251–258
7. Jo CH, Dietrich AM (2009) Removal and transformation of odorous aldehydes by UV/H2O2. J
Water Supply Res Technol 58(8):580–586
8. Sun Α, Xiong Ζ, Xu Υ (2008) Removal of malodorous organic sulfides with molecular oxygen
and visible light over metal phthalocyanine. J Hazard Mater 152:191–195
9. Andreozzi R, Caprio V, Marotta R (2001) Oxidation of benzothiazole,
2-mercaptobenzothiazole and 2-hydroxybenzothiazole in aqueous solution by means of
H2O2/UV or photoassisted Fenton systems. J Chem Technol Biotechnol 76(2):196–202
10. Acero JL, von Gunten U, Piriou P (2005) Kinetics and mechanisms of formation of
bromophenols during drinking water chlorination: assessment of taste and odor development.
Water Res 39:2979–2993
11. Bichsel Y, von Gunten U (2000) Formation of iodo-trihalomethanes during disinfection and
oxidation of iodide-containing waters. Environ Sci Technol 34(13):2784–2791
12. Luo C, Jiang J, Ma J, Pang S, Liu Y, Song Y, Guan C, Li J, Jin Y, Wu D (2016) Oxidation of
the odorous compound 2,4,6-trichloroanisole by UV activated persulfate: kinetics, products,
and pathways. Water Res 96:12–21
13. Yao W, Qu Q, von Gunten U, Chen C, Yu G, Wang Y (2017) Comparison of methylisoborneol
and geosmin abatement in surface water by conventional ozonation and an electro-peroxone
process. Water Res 108:373–382
14. Wang C, Li C, Li H, Lee H, Yang Z (2017) The removal efficiency and degradation pathway of
IPMP and IBMP in aqueous solution during ozonization. Sep Purif Technol 179:297–303
15. Pirbazari M, Borow HS, Craig S, Ravindran V, McGuire MJ (1992) Physical chemical
characterization of five earthy-musty-smelling compounds. Water Sci Technol 25(2):81–88
16. An N, Xie H, Gao N, Deng Y, Chu W, Jiang J (2012) Adsorption of two taste and odor
compounds IPMP and IBMP by granular activated carbon in water. Clean Soil Air Water 40
(12):1349–1356
17. Ding Z, Peng S, Xi W, Zheng H, Chen X, Yin L (2014) Analysis of five earthy-musty odorants
in environmental water by HS-SPME/GC-MS. Int J Anal Chem 2014:11 p. Article ID 697260
AOPs Methods for the Removal of Taste and Odor Compounds 207

18. Li X, Lin P, Wang J, Liu Y, Li Y, Zhang X, Chen C (2016) Treatment technologies and
mechanisms for three odorants at trace level: IPMP, IBMP, and TCA. Environ Technol 37
(3):308–315
19. Meylan W, Howard PH (1991) Bond contribution method for estimating Henry’s law con-
stants. Environ Toxicol Chem 10:1283–1293
20. Deng X, Liang G, Chen J, Qi M, Xie P (2011) Simultaneous determination of eight common
odors in natural water body using automatic purge and trap coupled to gas chromatography
with mass spectrometry. J Chromatogr A 1218:3791–3798
21. Young WF, Horth H, Crane R, Ogden T, Arnott M (1996) Taste and odour threshold
concentrations of potential potable water contaminants. Water Res 30:331–340
22. Suffet IH, Khiari D, Bruchet AE (1999) A drinking water taste and odor wheel for the
millennium: beyond geosmin and methylisoborneol. Water Sci Technol 40(6):1–13
23. Khiari D, Barrett S, Chinn R, Bruchet A, Piriou P, Matia L, Ventura F, Suffet IH, Gittelman T,
Leutweiler P (2002) Distribution generated taste-and-odor phenomena: AWWA Research
Foundation and American Water Works Association, Denver, CO, USA
24. Suffet IH, Rosenfeld P (2007) The anatomy of odour wheels for odours of drinking water,
wastewater, compost and the urban environment. Water Sci Technol 55(5):335–344
25. Jung S, Baek K, Yu M (2004) Treatment of taste and odor materials by oxidation adsorption.
Water Sci Technol 49(9):289–295
26. Cook D, Newcombe G, Sztajnbok P (2001) The application of powdered activated carbon for
MIB and geosmin removal: predicting PAC doses in four raw waters. Water Res
35:1325–1333
27. Chestnutt TE, Bach MT, Mazyck TW (2007) Improvement of thermal reactivated carbon for
the removal of 2-methylisoborneol. Water Res 41(1):79–86
28. Song W, O’Shea KE (2007) Ultrasonically induced degradation of 2-methylisoborneol and
geosmin. Water Res 41(12):2672–2678
29. Rosenfeldt EJ, Melcher B, Linden KG (2005) UV and UV/H2O2 treatment of
methylisoborneol (MIB) and geosmin in water. J Water Supply Res Technol 54(7):423–434
30. Hoigne J, Bader H (1994) Kinetics of reactions of chlorine dioxide (Oclo) in water. 1. Rate
constants for inorganic and organic-compounds. Water Res 28(1):45–55
31. Waldemer RH, Tratnyek PG (2006) Kinetics of contaminant degradation by permanganate.
Environ Sci Technol 40(3):1055–1061
32. Xie P, Ma J, Liu W, Zou J, Yue S, Li X, Wiesner MR, Fang J (2015) Removal of 2- MIB and
geosmin using UV/persulfate: contributions of hydroxyl and sulphate radicals. Water Res
69:223–232
33. Ribeiro A, Nunes OC, Pereira MFR, Silva AMT (2015) An overview on the advanced
oxidation processes applied for the treatment of water pollutants defined in the recently
launched Directive 2013/39/EU. Environ Int 75:33–51
34. Boczkaj G, Fernandes A (2017) Wastewater treatment by means of advanced oxidation
processes at basic pH conditions: a review. Chem Eng J 320:608–633
35. Liato V, Aı̈der M (2016) Geosmin as a source of the earthy-musty smell in fruits, vegetables
and water: origins, impact on foods and water, and review of the removing techniques.
Chemosphere 181:9–18
36. Park JA, Nam HL, Choi JW, Ha J, Lee SH (2017) Oxidation of geosmin and
2-methylisoborneol by the photo-Fenton process: kinetics, degradation intermediates, and
the removal of microcystin-LR and trihalomethane from Nak-Dong River water, South
Korea. Chem Eng J 313:345–354
37. Tan F, Chen H, Wu D, Wang N, Gao Z, Wang L (2016) Optimization of geosmin removal from
drinking water using UV/H2O2. J Resid Sci Tech 13(1):23–30
38. Wang D, Bolton JR, Andrews SA, Hofmann R (2015) UV/chlorine control of drinking water
taste and odour at pilot and full-scale. Chemosphere 136:239–244
208 M. Antonopoulou and I. Konstantinou

39. Fotiou T, Triantis TM, Kaloudis T, Papaconstantinou E, Hiskia A (2014) Photocatalytic

degradation of water taste and odour compounds in the presence of polyoxometalates and
TiO2: intermediates and degradation pathways. J Photochem Photobiol A Chem 286:1–9
40. Wee LH, Janssens N, Vercammen J, Tamaraschi L, Thomassen LCJ, Martens JA (2015) Stable
TiO2 USY zeolite composite coatings for efficient adsorptive and photocatalytic elimination of
geosmin from water. J Mater Chem A 3:2258–2264
41. Pestana CJ, Robertson PKJ, Edwards C, Wilhelm W, Mckenzie C, Lawton LA (2014) A
continuous flow packed bed photocatalytic reactor for the destruction of 2-methylisoborneol
and geosmin utilizing pelletised TiO2. Chem Eng J 235:293–298
42. Pettit S, Rodriguez-Gonzalez L, Michaels J, Alcantar N, Ergas S, Kuhn J (2014) Parameters
influencing the photocatalytic degradation of geosmin and 2- methylisoborneol utilizing
immobilized TiO2. Catal Lett 144:1460–1465
43. Xue Q, Liu Y, Zhou Q, Utsumi M, Zhang Z, Sugiura N (2016) Photocatalytic degradation of
geosmin by Pd nanoparticle modified WO3 catalyst under simulated solar light. Chem Eng J
283:614–621
44. Bu L, Zhou S, Shi Z, Deng L, Gao N (2017) Removal of 2-MIB and geosmin by
electrogenerated persulfate: performance, mechanism and pathways. Chemosphere
168:1309–1316
45. Tan F, Chen H, Wu D, Lu N, Wang L, Gao Z (2016) Optimization of removal of
2-methylisoborneol from drinking water using UV/H2O2. J Adv Oxid Technol 19(1):98–104
46. Lee JH, Park EJ, Kim DH, Jeong MG, Kim YD (2016) Superhydrophobic surfaces with
photocatalytic activity under UV and visible light irradiation. Catal Today 260:32–38
47. Xu Β, Qi F (2016) Reaction mechanism of 2-methylisoborneol and 2,4,6-trichloroanisole in
catalytic ozonation by γ-AlOOH: role of adsorption. Clean Soil Air Water 44(9):1099–1105
48. Buxton GV, Greenstock CL (1988) Critical review of rate constants of reactions of hydrated
electrons, hydrogen atoms and hydroxyl radicals (OH/O
) in aqueous solution. J Phys Chem
Ref Data Monogr 17:513–886
49. Popov E, Mametkuliyev M, Santoro D, Liberti L, Eloranta J (2010) Kinetics of UV-H2O2
advanced oxidation in the presence of alcohols: the role of carbon centered radicals. Environ
Sci Technol 44:7827–7832
50. Wang D, Bolton JR, Hofmann R (2012) Medium pressure UV combined with chlorine
advanced oxidation for trichloroethylene destruction in a model water. Water Res 46
(15):4677–4686
51. Goldstein S, Aschengrau D, Diamant Y, Rabani J (2007) Photolysis of aqueous H2O2: quantum
yield and applications for polychromatic UV actinometry in photoreactors. Environ Sci
Technol 41(21):7486–7490
52. Watts MJ, Linden KG (2007) Chlorine photolysis and subsequent OH radical production
during UV treatment of chlorinated water. Water Res 41(13):2871–2878
53. Avetta P, Pensato A, Minella M, Malandrino M, Maurino V, Minero C, Hanna K, Vione D
(2015) Activation of persulfate by irradiated magnetite: implications for the degradation of
phenol under heterogeneous photo-Fenton like conditions. Environ Sci Technol 49
(2):1043–1050
54. Lau TK, Chu W, Graham NJD (2007) The aqueous degradation of butylated hydroxyanisole
by UV/S2O82
: study of reaction mechanisms via dimerization and mineralization. Environ
Sci Technol 41(2):613–619
55. Yu XY, Bao ZC, Barker JR (2004) Free radical reactions involving Cl., Cl2.-, and SO4-. in the
248 nm photolysis of aqueous solutions containing S2O82
and Cl
. J Phys Chem A 18
(2):295–308
56. Buxton GV, Salmon GA, Wood N (1990) A pulse radiolysis study of the chemistry of
oxysulphur radicals in aqueous solution. In: Physico-chemical behaviour of atmospheric
pollutants, Springer, The Netherlands, pp 245–250
57. Neta P, Huie RE, Ross AB (1988) Rate constants for reactions of inorganic radicals in aqueous
solution. J Phys Chem Ref Data Monogr 17(3):1027–1284
AOPs Methods for the Removal of Taste and Odor Compounds 209

58. Von Gunten U (2003) Ozonation of drinking water: part II. Disinfection and by-product
formation in presence of bromide, iodide or chlorine. Water Res 37(7):1469–1487
59. Darsinou B, Frontistis Z, Antonopoulou M, Konstantinou I, Mantzavinos D (2015) Sono-
activated persulfate oxidation of bisphenol A: kinetics, pathways and the controversial role of
temperature. Chem Eng J 280:623–633
60. Sharma VK, Triantis TM, Antoniou MG, He X, Pelaez M, Han C, Song W, O’Shea KE, de la
Cruz AA, Kaloudis T, Hiskia A, Dionysiou DD (2012) Destruction of microcystins by
conventional and advanced oxidation processes: a review. Sep Purif Technol 91:3–17
61. Bamuza-Pemu EE, Chirwa EMN (2011) Photocatalytic degradation of geosmin: intermediates
and degradation pathway analysis. Chem Eng Trans 24:91–96
62. Bamuza-Pemu EE, Chirwa EM (2012) Photocatalytic degradation of geosmin: reaction path-
way analysis. Water SA 38(5):689–696
63. Qi F, Xu B, Chen Z, Ma J, Sun D, Zhang L (2009) Efficiency and products investigations on
the ozonation of 2-methylisoborneol in drinking water. Water Environ Res 81(12):2411–2419
64. Li X, Huang Y, Wang D (2010) Efficiency and mechanism of degradation of
2-methylisoborneol (2-MIB) by O3/H2O2 in water. 4th international conference on bioinfor-
matics and biomedical engineering (iCBBE), Chengdu, China, pp 1–4
65. Zaitlin B, Watson SB (2006) Actinomycetes in relation to taste and odour in drinking water:
myths, tenets and truths. Water Res 40(9):1741–1753
66. Urase T, Sasaki Y (2013) Occurrence of earthy and musty odor compounds (geosmin,
2-methylisoborneol and 2,4,6-trichloroanisole) in biologically treated wastewater. Water Sci
Technol 68(9):1969–1975
67. Benanou D, Acobas F, de Roubin MR, Sandra FDP (2003) Analysis of off-flavors in the
aquatic environment by stir bar sorptive extraction-thermal desorption capillary GC/MS/
olfactometry. Anal Bioanal Chem 376(1):69–77
68. Copete ML, Zalacain A, Lorenzo C, Carot JM, Esteve MD, Climent M, Salinas MR (2009)
Haloanisole and halophenol contamination in Spanish aged red wines. Food Addit Contam A
26(1):32–38
69. Maillet L, Lenes D, Benanou D, Le Cloirec P, Correc O (2009) The impact of private networks
on off-flavour episodes in tap water. J Water Supply Res Technol 58(8):571–579
70. Vlachos P, Stathatos E, Lyberatos G, Lianos P (2008) Gas-phase photocatalytic degradation of
2,4,6-trichloroanisole in the presence of a nanocrystalline titania film. Applications to the
treatment of cork stoppers. Catal Comm 9(10):1987–1990
71. Qi F, Xu B, Zhao L, Chen Z, Zhang L, Sun D, Ma J (2012) Comparison of the efficiency and
mechanism of catalytic ozonation of 2,4,6-trichloroanisole by iron and manganese modified
bauxite. Appl Catal Environ 121–122:171–181
72. Qi F, Xu B, Chen Z, Ma J, Sun D, Zhang L, Wu F (2009) Ozonation catalyzed by the raw
bauxite for the degradation of 2,4,6-trichloroanisole in drinking water. J Hazard Mater
168:246–252
73. Ma Z, Xie P, Chen J, Niu Y, Tao M, Qi M, Zhang W, Deng X (2013) Microcystis blooms
influencing volatile organic compounds concentrations in lake Taihu. Fresen Environ Bull
22:95–102
74. Peter A, Koster O, Schildknecht A, von Gunten U (2009) Occurrence of dissolved and particle-
bound taste and odor compounds in Swiss lake waters. Water Res 43:2191–2200
75. Antonopoulou M, Konstantinou I (2015) TiO2 photocatalysis of 2-isopropyl-3-
methoxypyrazine taste and odor compound in aqueous phase: kinetics, degradation pathways
and toxicity evaluation. Catal Today 240:22–29
76. Qi F, Xu B, Chen Z, Feng L, Zhang L, Sun D (2013) Catalytic ozonation of 2-isopropyl-3-
methoxypyrazine in water by gamma-AlOOH and gamma-Al2O3: comparison of removal
efficiency and mechanism. Chem Eng J 219:527–536
77. Sarria V, Kenfack S, Guillod O, Pulgarin C (2003) An innovative coupled solar biological
system at field pilot scale for the treatment of biorecalcitrant pollutants. J Photochem Photobiol
A Chem 139(1):89–99
210 M. Antonopoulou and I. Konstantinou

78. Klavarioti M, Mantzavinos D, Kassinos D (2009) Removal of residual pharmaceuticals from

aqueous systems by advanced oxidation processes. Environ Int 35:402–417
79. Zamyadi A, Sawade E, Ho L, Newcombe G, Hofmann R (2015) Impact of UV–H2O2 advanced
oxidation and aging processes on GAC capacity for the removal of cyanobacterial taste and
odor compounds. Environ Health Insights 9(S3):1–10
80. Swanepoel A, Du Preez HH, Cloete N (2017) The occurrence and removal of algae (including
cyanobacteria) and their related organic compounds from source water in Vaalkop Dam with
conventional and advanced drinking water treatment processes. Water SA 43(1):67–80
81. Edwards-Brandt J, Shorney-Darby H, Neemann J, Hesby J, Conrad T (2007) Use of ozone for
disinfection and taste and odor control at proposed membrane facility. Ozone Sci Eng
29:281–286
82. Scheideler J, Lee KH, Raichle P, Choi T, Dong HS (2015) UV-advanced oxidation process for
taste and odor removal – comparing low pressure and medium pressure UV for a full-scale
installation in Korea. Water Pract Technol 10(1):66–72
83. Fan X, Tao Y, Wang L, Zhang X, Lei Y, Wang Z, Noguchi H (2014) Performance of an
integrated process combining ozonation with ceramic membrane ultra-filtration for advanced
treatment of drinking water. Desalination 335:47–54
Wastewater Treatment by Heterogeneous
Fenton-Like Processes in Continuous
Reactors

Bruno M. Esteves, Carmen S.D. Rodrigues, and Luis M. Madeira

Abstract The treatment of several industrial effluents, such as textile, pharmaceu-

tical, and phenol-containing wastewaters, often face limitations toward conven-
tional treatment processes. Solutions for such problematic include the use of several
advanced oxidation processes (AOPs) and particularly the Fenton one. However,
most of the research has been focused in the homogeneous process, while recent
trends point for the use of heterogeneous systems, with the catalyst immobilized in
a solid support. In addition, process optimization and catalyst screening are com-
monly carried out in batch reactors, which often are not the best solution for
continuous industrial units. In this chapter, a review is made regarding the appli-
cation of heterogeneous Fenton-like advanced oxidation processes in continuous
systems (fixed-bed, fluidized-bed, and continuous stirred-tank reactors). The appli-
cation of this catalytic process for pollutant/wastewater treatment is summarized,
giving emphasis to the effect of the key operational parameters (e.g., pH, feed dose
of H2O2, catalyst load, and feed flow rate) affecting the oxidative performance of
such systems. Moreover, the main physicochemical properties of heterogeneous
catalysts (e.g., source of support and particle size) and preparation methods (e.g.,
type of precursor and metal ion) affecting the catalytic efficiency of Fenton’s
oxidation, and the stability of the catalyst itself, are also discussed. Finally, some
operational issues of concern regarding solid catalysts operating in continuous-flow
reactors are addressed.

Keywords Catalyst, Continuous reactor, Fenton, Heterogeneous, Wastewater

treatment

B.M. Esteves, C.S.D. Rodrigues, and L.M. Madeira (*)

LEPABE – Laboratório de Engenharia de Processos, Ambiente, Biotecnologia e Energia,
Departamento de Engenharia Quı́mica, Faculdade de Engenharia da Universidade do Porto,
R. Dr. Roberto Frias, 4200-465 Porto, Portugal
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 211
Water Treatment, Hdb Env Chem (2019) 67: 211–256, DOI 10.1007/698_2017_81,
© Springer International Publishing AG 2017, Published online: 27 September 2017
212 B.M. Esteves et al.

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
2 Chemical Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
2.1 Batch Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
2.2 Continuous Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3 Heterogeneous Fenton/Fenton-Like Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
3.1 Fenton’s Oxidation: Mechanism and Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
3.2 Operational Parameters of Influence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
3.3 Influence of Catalyst’s Physicochemical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
3.4 Operational Issues Regarding Heterogeneous Catalysts: Stability . . . . . . . . . . . . . . . . . . 244
3.5 Performance of Continuous vs Batch Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249

Abbreviations

AB Alcian Blue-tetrakis dye

AC Activated carbon
AOPs Advanced oxidation processes
AY36 Acid yellow 36 dye
BB3 Basic blue 3 dye
BOD5 Biochemical oxygen demand (5 days)
CNF Carbon nanofibers
CNT Carbon nanotubes
COD Chemical oxygen demand
CSB Chicago Sky Blue dye
CSTR Continuous stirred-tank reactor
CWHPO Catalytic wet hydrogen peroxide oxidation
CWPO Catalytic wet peroxide oxidation
EDCs Endocrine disrupting compounds
FBR Fluidized-bed reactor
LHSV Liquid hourly space velocity
NM Natural magnetite
NP Natural pyrite
OII Orange II dye
PAN Polyacrylonitrile
PBR Packed-bed reactor
POPs Persistent organic pollutants
PPCPs Pharmaceutical and personal care products
RB19 Reactive blue 19
SBET Specific surface area
SW Sewage
TDS Total dissolved solids
TOC Total organic carbon
UFBR Upflow fixed-bed reactor
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 213

UV Ultraviolet
WHPCO Wet hydrogen peroxide catalytic oxidation
WW Wastewater

1 Introduction

The increasing worldwide demand for clean water requires the development of
cost-effective techniques for wastewater reclamation. The unceasing research and
development of new products, technologies, and manufacturing processes lead to
the exponential growth of many water-intensive industries, with new and poten-
tially hazardous compounds being continuously introduced into the environment
through different industrial wastewater streams.
Management of such effluents is a subject of major importance and has been
under great scrutiny by the scientific community over the last decades [1–3]. Waste-
water coming from major polluting industries, such as the chemical (e.g., fertilizer,
petrochemical), pharmaceutical, dye and textile, pulp and paper, food, and many
others, often contain persistent organic pollutants (POPs) that are biorefractory in
nature and resistant to conventional wastewater treatments. Moreover, several
organic compounds are potentially hazardous to public health and the environment,
since they exhibit toxicity toward microorganisms and plants [4, 5], as well as
carcinogenic [6, 7], mutagenic, and endocrine disruptor effects on the metabolic
activity [8, 9].
With the fast industrial development, environmental regulation and health
quality standards imposed by different governments also become more stringent.
Consequently, for many industries, the selection and practice of any given treat-
ment process relies on the characteristics of the wastewater produced, as to its
pollutant’s nature and quantity, and the level of reduction required for safe dis-
charge, at the lowest operation and maintenance cost available.
Wastewater treatment technologies such as biological degradation [10, 11],
precipitation [12, 13], membrane separation [14–16], coagulation/flocculation
[17–19], adsorption [20–22], direct oxidation [23–25], as well as different combi-
nations of the cited processes [26] have been extensively studied for the treatment
of different pollutants and widely applied at industrial scale.
However, apart from biological and chemical processes, most technologies do
not involve chemical transformations, hence only transfer the pollutant from one
phase to another, causing secondary loading to the environment [27]. On the other
hand, biological processes are often inefficient given the toxicity and low biode-
gradability of many molecules found in industrial wastewaters [28–30]. Direct
chemical oxidation is widely used to degrade biorefractory substances, and high
degradation efficiencies are possible with such techniques; nevertheless, the use of
strong oxidants at slightly demanding operating conditions (namely, temperatures)
and equipment necessary often make the process economically unviable [23].
214 B.M. Esteves et al.

In this context, the development of economically attractive and efficient waste-

water treatment technologies has been an interesting topic of discussion. Among all
treatment practices available, the advanced oxidation processes (AOPs) may con-
stitute a useful technology for the mineralization of aromatics, pesticides, solvents,
and volatile organics, just to give a few examples, into stable compounds – H2O,
CO2, and inorganic salts. Even if complete mineralization is not possible/viable, the
partial oxidation of nonbiodegradable organics often originates biodegradable
intermediates, allowing the application of subsequent treatment steps (e.g., biolog-
ical processes) [2].
AOPs have in common the fact that they form and take advantage of the great
oxidative capacity of the hydroxyl radical (HO•) which, immediately after the
fluorine, is the known species with greater oxidation potential (Table 1) [31, 32].
Also, hydroxyl radicals are nonselective and highly reactive species that attack
most organic and many inorganic solutes, with high rate constants, typically in the
range of 10
6–10
9 L mol
1 s
1 [33–35].
The versatility of the AOPs is also enhanced by the fact that there are numerous
ways for HO• production, such as chemical, photochemical, and electrochemical,
allowing the selection of the method that best fulfills specific treatment require-
ments. AOPs are commonly classified in respect to the reactive phase as homoge-
neous, if the catalyst is dissolved in solution (thus forming a single phase), or
heterogeneous, if the metal ions are impregnated in the matrix of a solid phase (e.g.,
activated carbon, clay, zeolite, carbon nanotube). Table 2 shows some conventional
and nonconventional AOPs based on the type of process and source used for
hydroxyl radical generation.
Heterogeneous Fenton/Fenton-like processes, often called wet hydrogen perox-
ide catalytic oxidation (WHPCO) or catalytic wet peroxide oxidation (CWPO),
were extensively studied over the last three decades and will be the subject of this
chapter. Particular emphasis will be given to their application in continuous systems
for the treatment of model compounds and industrial wastewaters.

Table 1 Oxidation potential of common oxidants in acidic medium oxidation potential of the
highly reactive hydroxyl radical formed from the reaction between hydrogen peroxide and ferrous
iron – Fenton’s reagent
Oxidant Oxidation potential (V)
Fluorine (F2) 3.03
Hydroxyl radical (HO•) 2.80
Atomic oxygen (O) 2.42
Ozone (O3) 2.07
Hydrogen peroxide (H2O2) 1.78
Hydroperoxyl radical (HO2•) 1.70
Potassium permanganate (KMnO4) 1.68
Hypochlorous acid (HClO) 1.49
Chlorine (Cl2) 1.36
Oxygen (O2) 1.23
Bromine (Br2) 1.09
Adapted from Bigda [31]
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 215

Table 2 Examples of common advanced oxidation processes (AOPs)

Advanced oxidation processes
Homogeneous Heterogeneous
Using energy Without energy Using energy Without energy
O3 + UV O3 TiO2 + O2 + UV O3 + solid catalyst
H2O2 + UV O3 + H2O2 TiO2 + H2O2 + UV H2O2 + Fe2+/Fe3+/mn+
solid
O3 + H2O2 + UV H2O2 + Fe2+ H2O2 + solid cata- H2O2 + Fe0/Fe (nano-
(Fenton) lyst + UV (photo-Fenton) zerovalent iron)
H2O2 + Fe2+ + UV H2O2 + Fe3+/mn+
(photo-Fenton) (Fenton like)
Electro-Fenton
Photo-electro-
Fenton
Adapted from Poyatos et al. [36]

2 Chemical Reactors

2.1 Batch Reactor

Discontinuous reactors, also called batch reactors, are commonly used for liquid
phase reactions, with the possibility of using solid catalysts in suspension (so-called
slurry reactors). For both cases, agitation is required to homogenize the solution and
equalize the temperature inside the reactor, to keep it at the desired level by efficient
heat exchange through a recirculation jacket (or coil), which is connected to a
cooling/heating system (see Fig. 1). In batch operation, the reactants and solution to
be treated are fed to the reactor at the beginning of the process. Therefore, the
operation proceeds at constant volume, and it is commonly admitted that there are
no spatial variations of composition and temperature within the vessel; composi-
tion, however, varies over time [37].
Typically, batch reactors are used in the processing industry and medical
products manufacturing, in laboratory applications (e.g., whenever a process is
still in test phase), or in the study of reaction kinetics (essential stage for modeling
and upscale). Batch reactors are also vastly used in wastewater treatment studies by
AOPs, namely, by the Fenton process, to assess the effect of operating conditions,
to optimize the process, or simply for catalysts screening.
Because Fenton’s oxidation runs commonly at moderate conditions of temper-
ature and pressure, a batch reactor consists essentially of a non-pressurized stirred
device (Fig. 2a); for industrial operation it must be coupled with metering pumps
for the addition of acid, base, a ferrous sulfate catalyst solution (in the case of
homogeneous processes), and industrial strength hydrogen peroxide (35–50%)
[38]. For heterogeneous Fenton process operation, the catalyst is usually kept in
suspension (see Fig. 2b).
216 B.M. Esteves et al.

Cooling/Heating
Fluid (e.g. water)

Cooling/Heating
Fluid (e.g. water)

Fig. 1 Scheme of a typical batch reactor

a b

Wastewater
Wastewater Catalyst
H2 O2
H2 O2
2+
Fe

Fig. 2 Scheme of wastewater treatment by homogeneous (a) and heterogeneous (b) Fenton
process in batch reactors

It is recommended the coating of the reactor vessel with an acid resistant

material, as Fenton reagent is very aggressive and corrosion may become a serious
operational issue. The addition of reactants is usually performed in the following
sequence: wastewater (or solution to be treated), followed by diluted sulfuric acid
(for maintaining acidic conditions), catalyst in acidic solutions, and base or acid for
the adjustment of pH; reaction starts with the addition of the oxidant (hydrogen
peroxide solution) which can be either instantaneous (batch reactor) or progressive
over time (semicontinuous reactor). Industrially, reactants (and particularly the
H2O2) must be added slowly with proper maintenance of temperature. Downstream
Fenton’s reactor, the treated solution/wastewater is discharged into a neutralizing
tank for pH adjustment, followed by a flocculation tank and a solid liquid separation
tank, where the adjustment of TDS (total dissolved solids) content is commonly
performed. A schematic representation of the described Fenton oxidation treatment
process in discontinuous mode is presented in Fig. 3.
The batch reactor has been widely used in lab-scale studies, where homogeneous
and heterogeneous Fenton processes are applied for the treatment of model pollut-
ants and different wastewaters [39, 40]. Also, catalytic efficiency and stability tests
of solid catalysts are regularly performed in slurry reactors, due to the easiness in
operation [41, 42]. However, the use of such reactors for these applications at
industrial level has several disadvantages since effluents are normally generated
continuously, so an equalization tank is required to store the effluent prior to the
treatment. Other shortcomings such as the high concentration of intermediate
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 217

NaOH H2SO4 Fe2SO4 H2 O2 NaOH

Influent Effluent

Iron
Sludge

Fig. 3 Representative scheme of wastewater treatment by Fenton process

products formed and their long contact time with the catalyst, which may result in
its loss of longevity due to deactivation mechanisms (further discussion regarding
this subject is compiled in Sect. 3.4), are a concern regarding the slurry configura-
tion in some applications. Moreover, this type of reactors usually has high cost of
labor per unit of production as well as difficulty in maintaining large-scale
production.

2.2 Continuous Reactors

In continuous reactors, or flow reactors, the reactants are continuously fed into the
vessel at one point, reaction occurs, and then a continuous stream of end product
emerges at another point of the reactor. There are two basic (and somehow ideal)
configurations for continuous reactors: the plug flow reactor (Fig. 4a) and the
perfectly mixed flow reactor or continuous stirred-tank reactor (CSTR) – see
Fig. 4b. Plug flow reactors are commonly implemented in tubular units. Depending
on different operational parameters, namely, the velocity of the fluid phase, hetero-
geneous reactions are implemented in fixed-bed or packed-bed reactors (PBR) or in
fluidized-bed reactors (FBR); CSTRs with the catalyst in suspension (often within a
basket) are another possible configuration. A brief description of the typical oper-
ation of heterogeneous Fenton processes in such reactors is provided below.

2.2.1 Fixed-Bed Reactor

In fixed-bed reactors, the solid catalysts are deposited along the length of the
column (single-bed) (Fig. 5a) or in multi-bed column/multi-tubular reactor
(Fig. 5b); the reactants are typically fed upflow into the column, so a common
218 B.M. Esteves et al.

Fig. 4 Scheme of a plug a

flow reactor (a) and a
CSTR (b)

Fig. 5 Scheme of a single-

bed (a) and multi-bed (b)
a b
fixed-bed reactor

Catalyst Catalyst

designation for this type of reactors is UFBR (upflow fixed-bed reactor). Even if the
flow pattern is not the ideal one (i.e., is far from plug flow due to, e.g., axial
dispersion effects), oxidant is consumed and the solution/effluent is treated as they
flow along the column. In this configuration, the composition (and temperature) has
spatial variations in the axial direction and eventually also in the radial direction.
For the hypothetical and idealized plug flow pattern, it is assumed that the transfer
phenomenon is only due to convective effects, in which all molecules of the effluent
and the oxidant move at the same velocity along parallel streamlines [37].
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 219

Single-bed reactors have been used in research studies for the treatment of
pharmaceutical [43] and textile [44] wastewaters, in dye removal [44–46], and
oxidation of phenolic compounds [47–49] by heterogeneous Fenton-like processes.
In the literature it is also reported a reduced number of works dealing with the
combination of this configuration with downstream biological degradation pro-
cesses. Applications include, for example, the treatment of agrochemical wastewa-
ters, where a fixed-bed reactor is used in series with rotating biological contactors
[50], and the treatment of textile effluents, where in the first tubular reactor the
classical homogeneous process takes place and, in a second reactor coupled in
parallel, the heterogeneous Fenton-like oxidation occurs [39].
Industrially, this configuration is widely used in numerous chemical reactions
using solid catalysts, namely, in the chemical industry (e.g., steam reforming of
methane, synthesis of ammonia, sulfuric acid, and methanol), in the petrochemical
industry (e.g., in the production of ethylene oxide, vinyl acetate, and butadiene), in
petroleum refining (e.g., in isomerization, polymerization, and hydrocracking pro-
cesses), and in fermentation processes. The vast industrial application of the fixed-
bed reactor is linked with the high conversion per unit mass of catalyst attained and
the relatively low operating cost.
To the best of our knowledge, fixed-bed reactors have never been implemented
industrially for the treatment of wastewaters by the heterogeneous Fenton-like
process. This is probably related to the fact that there are no catalysts available
for such application that are commercially attractive (low cost, no leaching, stable).
Other drawbacks associated to this technology are the temperature gradients in the
reactor for exothermic reactions (e.g., oxidation of strongly polluted wastewater),
making temperature control problematic, pressure drop, and the occurrence of mass
transfer limitations – which result from the catalyst itself or from the gas bubbles,
most likely CO2 resulting from the oxidation of pollutants inside the column
[44, 46]. Also, an additional operational problem regarding their application in
continuous systems is the catalyst’s deactivation, especially for effluents with
complex composition; another issue is the fact that catalysts must be shaped as
spheres, granules, and/or extrudates for the application in fixed-bed reactors, in
order to decrease pressure drop along the column and to achieve good mechanical
strength.

2.2.2 Fluidized-Bed Reactor

Fluidized-bed reactor (FBR) operation comprises a fluid phase (liquid or gas) and a
solid phase with small particle size. In this reactor’s configuration, the fluid passes
through the catalyst bed and promotes the continuous suspension of the solid particles.
This type of reactor involves a multiphase flow system, namely, two-phase (solid-gas
or solid-liquid) or three-phase (solid-liquid-gas), with the inherent heat exchange and
mass transfer [51]. When small particles are suspended in an upward-flowing stream
of fluid, the solid presents a behavior similar to a fluid, thus improving the catalytic
220 B.M. Esteves et al.

kinetics and performance of the system. Moreover, problems related with pressure
drop are avoided in the FBR, while also improving heat and mass transfer.
The fluidization of the catalyst is achieved by the high velocity at which the fluid
passes through the catalytic bed. The fluid velocity must be sufficient to suspend the
particles but not too high to carry the catalyst out of the reactor. Depending on the
fluid velocity and solid distribution in the FBR, three different stages may occur
(see Fig. 6) [52]:
1. Fixed bed: at this stage the bed behaves similar to a packed-bed, where the fluid
flow rate is low and the catalyst is compacted;
2. Incipient fluidization: as the velocity of the fluid passing through the catalyst bed
increases, the catalyst starts dispersing in the column – this can be considered the
inflection point that indicates the minimum velocity for fluidization;
3. Fluidized bed: this stage occurs when the minimal velocity for fluidization is
surpassed and the catalyst particles expand and remain agitated.

It is possible to have several flow regimes, such as particulate fluidization,

bubbling fluidization, slugging fluidization, turbulent fluidization, and pneumatic
conveying regimes, that depend on the fluidization velocity [53].
Compared to other types of reactors (e.g., fixed-bed reactors), FBRs have a
number of advantages, namely, high degradation efficiencies, shorter reaction
times, better recirculation, and uniform temperature profiles even for highly exo-
thermal reactions, along with high mixing and liquid/solid contacting [54]. Fenton-
like FBR operation uses carriers that help in reducing the sludge formation that
occurs in the homogeneous phase, since crystallization of the target pollutant
happens in the carrier’s surface [52].
FBRs are mostly applied in catalytic cracking in the petroleum industry, com-
bustion, gasification, and catalytic processes. Also, fluidized-bed reactors have

a b c

Catalyst Catalyst Catalyst

Fig. 6 Fixed-bed (a), incipient fluidization (b), and fluidized-bed (c) stages in a FBR
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 221

benefits such as the simplicity of construction and operation, low operating cost,
and high flexibility for liquid and solid phase residence times. Recently, and
regarding their use in pollutants removal or wastewater treatment, FBRs have
been applied in:
1. Research studies by adsorption [55], biological degradation [56] and advanced
oxidation processes, namely, electro-Fenton [57], photo-Fenton [58], and homo-
geneous [59] and heterogeneous Fenton-like processes [60], as well as combi-
nation of both [61] and integration of Fenton oxidation with adsorption [62] or
ultrasound [63] processes;
2. Semi-pilot [60] and pilot-scale [64] operation for dye solutions oxidation by
Fenton-like processes;
3. Industrial application for the treatment of effluents from the textile dyeing, pulp
and paper mill, and petrochemical industries by the heterogeneous Fenton-like
process, as mentioned in the review of Garcia-Segura et al. [52].

2.2.3 Continuous Stirred-Tank Reactor

In the CSTR configuration, mechanical or hydraulic agitation is required (see

Fig. 7) in order to obtain a uniform composition and temperature inside the reactor.
The choice of agitation method is strongly influenced by process considerations.
In this reactor typology, the composition of the output mixture is considered to
be the same as the one that is inside the reactor (perfect mixing is assumed), so the
reaction’s driving force (usually the concentration of reactants) is necessarily low.
Therefore, with few exceptions (e.g., zero-order reactions), CSTRs require larger
volumes to achieve the desired conversions, when compared to plug flow reactors.
When high conversions are required, several CSTRs can be used in series or,
alternatively, a single reactor can be divided into stages while minimizing subse-
quent mixing and short circuits. The higher the number of CSTR stages, the closer
the performance approaches a tubular flow reactor (with the same residence or
contact time). CSTRs in series are (1) simpler and easier to design for isothermal
operation (i.e., when operating temperature ranges are narrower) than tubular

a b

Fig. 7 Mechanical (a) and hydraulic (b) agitation in a CSTR

222 B.M. Esteves et al.

a b

Cooling
Fluid
(e.g. water)

Cooling
Fluid
(e.g. water)

Fig. 8 Cooling/heating system out (a) and into (b) the CSTR

reactors and also (2) easier to operate in reactions where close control of reagent
concentrations is required [65].
In such reactors, if severe heat transfer is necessary, the heating or cooling
system may be incorporated into or out of the CSTR (see Fig. 8), for example,
through single or multi-tube(s), where the heating/cooling fluid circulates. Like-
wise, the contents of the reactor can be recycled through external heat exchangers.
The CSTR configuration has advantages such as the good temperature control,
cheap construction, large heat capacity, and easiness in the access to the interior of
the reactor. Moreover, for heterogeneous systems, pressure-drop issues are mini-
mized, as well as mass transfer resistances (see description above in Sect. 2.2.1).
However, the disadvantage is that the conversion per unit of volume is relatively
small when compared to other flow reactors.
CSTRs are widely used in chemical, pharmaceutical, and biofuel industrial appli-
cations and in wastewater treatment plants (i.e., activated sludge reactors). This
reactor configuration has also been used in laboratorial scale for the treatment of
industrial wastewater by anaerobic [66, 67] and aerobic [68, 69] processes. Its
application in wastewater treatment by advanced oxidation processes has been
performed mainly in lab scale. Some examples include the degradation of model
compounds (phenol [70] and dyes [71]) and the treatment of textile effluents by
heterogeneous Fenton-like processes [72], landfill leachate [73], orange II dye [74]
and industrial wastewaters containing 2,4,6-trinitrotoluene [75] by the homogeneous
Fenton process, as well as pilot-scale studies for the treatment of olive mill effluents
[76]. Other works report the application of hybrid methods, such as electro-Fenton-
like processes for landfill leachate treatment [77] and 4-nitrophenol removal [78].

3 Heterogeneous Fenton/Fenton-Like Processes

3.1 Fenton’s Oxidation: Mechanism and Characteristics

Fenton process has emerged by observing that iron species have special oxygen
transfer properties, influencing the oxidation performance of hydrogen peroxide.
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 223

This was first stated in 1984 by H. J. Fenton, when revising the oxidation of tartaric
acid with hydrogen peroxide. H. J. Fenton found that the H2O2 oxidation potential
was strongly elevated in the presence of a trace of ferrous salts (Fe2+) [79]. Later, in
1934, Haber and Weiss [80] stated that Fenton’s highly oxidative species is the
hydroxyl radical, generated by the catalytic decomposition of hydrogen peroxide in
the presence of ferrous ions, in acidic medium, according to Eq. (1).

Fe2þ þ H2 O2 ! Fe3þ þ HO • þ OH
ð1Þ

Fenton process can be applied to rapidly destroy organic compounds (RH),

which are oxidized by the nonselective HO• species in solution, according to
Eq. (2) [81, 82]. Oxidation occurs by either hydrogen abstracting, addition to the
double bonds, or electron transfer [83], originating new oxidized intermediates with
lower molecular weight, which can be further decomposed until complete miner-
alization into H2O and CO2 (Eq. 3).

HO • þ RH ! H2 O þ intermediates ð2Þ
HO þ intermediates ! H2 O þ CO2
•
ð3Þ

Although Fenton’s oxidation involves a complex free radical and chain mech-
anism, the traditionally accepted process can be simplified and described by
Eqs. (4)–(10) in addition to Eq. (1), for which reaction rates are well reported in
literature [84]. Of particular importance is the reaction associated with the ferrous
ion regeneration, responsible for the cyclic continuity of the process (Eqs. 4 and 5).
This process, commonly referred to as the Fenton-like stage, is much slower than
the one depicted in Eq. (1) and involves the formation of hydroperoxyl radicals
(HO2•). Hydroperoxyl species also attack organic molecules, but they have signif-
icantly lower oxidative potential when compared to HO• (cf. Table 1). Nonetheless,
HO2• contributes to the additional regeneration of Fe2+, according to Eq. (6).

Fe3þ þ H2 O2 $ Fe
OOH2þ þ Hþ ð4Þ

Fe
OOH 2þ
! Fe 2þ
þ HO2 •
ð5Þ
þ
Fe 3þ
þ HO2 ! Fe
• 2þ
þ O2 þ H ð6Þ

Depending on the operating conditions, a wide number of competitive reactions

may also take place; excess H2O2 or ferrous ions in solution are responsible for the
scavenging of HO• radicals, according to Eqs. (7) and (8), respectively, hindering/
decreasing the Fenton process’ overall efficiency [81].

HO • þ H2 O2 ! H2 O þ HO2 • ð7Þ


HO þ Fe
• 2þ
! Fe 3þ
þ OH ð8Þ
224 B.M. Esteves et al.

Furthermore, radical-radical reactions that negatively affect the process are also
reported to occur (Eqs. 9 and 10).

HO • þ HO2 • ! O2 þ H2 O ð9Þ
HO þ HO ! H2 O2
• •
ð10Þ

Operating at near-ambient temperature and atmospheric pressure, the Fenton

process typically runs at much smaller energy consumption requirements when
compared to alternative oxidation techniques [31], as the activation of the hydrogen
peroxide requires no energy input. Other advantages of the Fenton process include
the typically short reaction times and the use of easy-to-handle chemicals.
Several studies report the efficient application of this process for the treatment
of coking [85], olive mill [86], textile [39, 74, 87], pharmaceutical [43], pulp and
paper [88], cosmetic [89], and cork-processing wastewaters [90, 91], as well as
numerous synthetic wastewaters containing target compounds, such as phenols,
chlorobenzene, and toluene [92, 93], just to name a few.
However, despite the successful application in lab-scale tests, the process is still
to be largely implemented at industrial scale, mainly because of
1. the ineffectiveness in reducing the level of certain organic refractory pollutants
(acetic acid, carbon tetrachloride, acetone, oxalic acid, trichloroethane, etc.);
2. the high cost of the chemical reagents used (e.g., hydrogen peroxide and
chemicals for pH adjustment, as the process has limited optimum pH value of
ca. 3.0–3.5) [74];
3. the need of a subsequent process for the removal of accumulated iron sludge and
(partial) catalyst recovery, which increases the global cost and complexity of the
process; and
4. the need of high concentrations of homogeneous catalyst – concentration of iron
ions is typically in the 50–80 ppm range for batch processes [94] – clearly above
the European legal threshold of 2 ppm for safe wastewater discharge in natural
waterbodies [95].
To overcome limitations of the Fenton process toward specific pollutants and/or
to reduce costs associated with reagents, proposed methods include the coupling of
Fenton oxidation with traditional processes like coagulation/flocculation, mem-
brane filtration, and/or biological oxidation. Coupling or integration of Fenton’s
oxidation as a pretreatment stage with such processes is the most common practice
for real industrial wastewater treatment facilities, since complete mineralization via
AOPs alone is not cost-effective and often not necessary.
The enhancement of the Fenton process with the so-called hybrid methods, such
as photo-Fenton-like, electro-Fenton-like, cavitation-Fenton-like, or microwave-
Fenton-like processes, has been the focus of extensive research [96]. Also, alterna-
tives to the classical Fe2+ catalyst, including low-valence transition metals such as
Fe3+, Cu2+/Cu+, and nano-zerovalent iron, are well-known sources of HO• species
that can be used for both homogeneous and heterogeneous Fenton-like processes.
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 225

More recently, the development of heterogeneous Fenton-like systems is gaining

its importance, as the use of solid catalysts may reduce drawbacks related to the iron
loss and Fe sludge management that the homogeneous process usually entails.
Heterogeneous catalysts can be obtained from various sources, nature (natural iron-
bearing materials such as pyrite, magnetite, hematite, etc.), artificial synthesis (e.g.,
Fe/AC, Fe/ZSM-5, Fe2O3/SBA-15, Cu-MCM41, etc.), or industrial by-products (e.g.,
fly ash, sludge, etc.), and their catalytic activity may be improved by a wide range of
preparation/modification techniques [97–99].
The efforts on the development of highly active and stable catalysts as well as
their application on heterogeneous Fenton-like systems for wastewater treatment
are extensively reported in the literature. However, the vast majority of studies
report operation in discontinuous reactors, which display clear disadvantages for
industrial implementation when compared to systems operating continuously, as
addressed in Sect. 2, which are the focus of this chapter. Table 3 provides an
outlook of the studies found in the open literature in which heterogeneous materials
have been used as support of metal catalysts (typically Fe-based) for the Fenton/
Fenton-like oxidation of model compounds or wastewaters in continuous reactors.
Operational conditions that affect the process efficiency, mainly in terms of degra-
dation and/or mineralization of the model pollutant/wastewater, are also succinctly
mentioned; the phenomenological comprehension of their effects is crucial for
subsequent process optimization, although for such goal the use of statistically
based tools might be an interesting alternative.

3.2 Operational Parameters of Influence

The key operational parameters affecting Fenton/Fenton-like processes are related

with the chemicals, i.e., the catalyst and oxidant doses, in addition to the reaction
characteristics: pH, temperature, and pollutant load (concentration and character-
istics of organic and inorganic compounds present in solution). Additionally, for
heterogeneous Fenton-like processes on continuous reactors, the amount of solid
catalyst used (i.e., combination of support/matrix and low-valence transition metal)
and feed flow rate are of great importance, since they influence the effluent’s
residence/contact time (depending on the reactor’s configuration); catalyst nature/
properties are in this case also of paramount importance. The effect of such
operational conditions is discussed in the following sections, and some examples
are provided to better illustrate their impact on the overall process efficiency.

3.2.1 Reaction pH

The performance of Fenton/Fenton-like oxidation processes is strongly dependent

on the reaction medium’s pH, particularly for homogeneous systems, due to the
catalyst and oxidant speciation factors [23].
Table 3 Operational conditions and optimum catalytic performances of heterogeneous Fenton/Fenton-like systems, operating in continuous reactors, for the
226

treatment of wastewater/model pollutants

Results obtained
Type of (steady-state
Target pollutant reactor Catalyst Experimental conditions conditions) Remarks Ref.
Pharmaceutical Fixed-bed Fe2O3/SBA- pH0 ¼ 3.0, T ¼ 80 C, 59% TOC removal, Activity of the catalyst is [43]
wastewater reactor 15 nanocomposite [WW]feed ¼ 860 mg TOC L
1, 81% COD, and 71% kept constant for at least
(pellet, [H2O2]feed ¼ 10.8 g L
1, BOD5 reduction 55 h of reaction; increase
dp ¼ 1.0–1.6 mm) Wcatalyst ¼ 2.9 g, in the COD/BOD5 ratio
Fe (wt. %) ¼ 14 Qfeed ¼ 0.25 mL min
1, from 0.2 to 0.3
τ ¼ 3.8 min
Textile Packed-bed Fe/Norit RX3 Extra pH0 ¼ 2.5, T ¼ 50 C, 97% decolorization, Higher treatment effi- [44]
wastewater reactor AC (pellet, [WW]feed ¼ 174.7 mg TOC L
1, 74% TOC removal, ciencies were obtained
dp ¼ 0.8–1.6 mm) [H2O2]feed ¼ 30 mM, Wcatalyst/ 66% COD, and 73% for the real wastewater
Fe (wt. %) ¼ 7 Q ¼ 3.3 g min mL
1 BOD5 abatement, when compared to the
t¼3h dye solution used for the
parametric study; after
60 h of operation, only
1.25% cumulative Fe
loss from the catalyst
Dye solution Packed-bed Fe/Norit RX3 Extra pH0 ¼ 3.0, T ¼ 50 C, 88% decolorization, Similar treatment effi- [46]
(CSB) reactor AC (pellet, [CSB]feed ¼ 0.012 mM, 47% TOC removal, ciencies for at least three
dp ¼ 0.8–1.6 mm) [H2O2]feed ¼ 2.25 mM, Wcatalyst/ t ¼ 150 min cycles; values of iron in
Fe (wt. %) ¼ 7 Q ¼ 4.1 g min mL
1 solution after the treat-
ment were below
0.4 ppm
Phenol Fixed-bed Fe2O3/SBA-15 pH0 ¼ 5.5, T ¼ 80 C, Complete phenol degra- Increasing catalyst par- [47]
reactor mesostructured [phenol]feed ¼ 1.0 g L
1, dation, 66% TOC ticle size in the range of
(dp ¼ 1.6–2 mm) [H2O2]feed ¼ 5.1 g L
1, removal 0.35–2 mm has not pro-
Fe (wt. %) ¼ 14 Qfeed ¼ 1 cm3 min
1, moted a negative effect
Wcatalyst ¼ 2.9 g on the process efficiency
B.M. Esteves et al.
Phenol Fixed-bed Fe2O3/Al2O3 (com- pH0 ¼ 6, T ¼ 70 C, 99% phenol degrada- Leaching levels were [48]
reactor mercial alumina [pollutant]feed ¼ 5.0 g L
1, tion, 50–60% TOC reduced from 25 to 11%
spheres – 2.5 mm) [H2O2]feed ¼ 0.67 mol L
1, removal, t ¼ 6 h by combining thermal
Fe (wt. %) ¼ 4 Qfeed ¼ 5.4 mL min
1, and acidic treatments to
τ ¼ 3.4 min the catalyst; oxidant
consumption efficiency
of 80% was attained for
the optimum conditions
tested
Dye solution Recirculating Natural magnetite pH0 ¼ 5.0, T ¼ room, 84% decolorization, Comparison between the [60]
(BB3) FBR (NM) [BB3]feed ¼ 5 mg L
1, t ¼ 190 min efficiency of the FBR vs
[H2O2]feed ¼ 4 mM, batch operation, under
[BB3] ¼ 2.27 g L
1 the same conditions,
indicated that the FBR
could improve BB3
degradation
Dye solution Recirculating Natural pyrite (NP) pH0 ¼ 3.7, T ¼ room, Degradation efficiency Central composite [64]
(AY36) FBR [AY36]feed ¼ 5 mg L
1, (dye) ¼ 99.2% design has been used for
[H2O2]feed ¼ 1.7 mmol L
1, optimization of the pro-
[NP] ¼ 0.4 g L
1, Qfeed ¼ 680 L h cess. Data from the

1
model was in in good
agreement with the
experimental data (R2
¼ 0.964)
Dye solution CSTR Fe/ZSM-5 pH0 ¼ 3.0, T ¼ 70 C, 91% decolorization, Only 0.13% iron [71]
(OII) (dp ¼ 0.6–0.8 mm) [OII]feed ¼ 0.1 mM, 36% TOC removal leaching after the opti-
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . .

Fe (wt. %) ¼ 5.5 [H2O2]feed ¼ 6 mM, Wcatalyst/ mum run

Q ¼ 200 mg min mL
1,
τ ¼ 90 min
(continued)
227
Table 3 (continued)
228

Results obtained
Type of (steady-state
Target pollutant reactor Catalyst Experimental conditions conditions) Remarks Ref.
Phenol Plug flow Al-Fe-pillared clay pH0 ¼ 3.7, T ¼ 25 C, 80% phenol conversion, At recycling ratios [100]
(extrudate [pollutant]feed ¼ 5 g L
1, 60% TOC removal, higher than 10, the plug
1  5 mm) [H2O2]feed ¼ 0.1 mM, [cata- t¼4h flow reactor has the
Fe (wt. %) ¼ 3 lyst] ¼ 5 g L
1 behavior of a CSTR;
iron leaching <2% of
the initial Fe content,
after 350 h
Phenol Fixed-bed Fe2O3/γ-Al2O3 pH0 ¼ 4.5, T ¼ 80 C, 100% phenol removal, Short time to reach [101]
reactor (spheres with [PhenolI]feed ¼ 1 g L
1, 92% COD conversion steady-state conditions
dp ¼ 0.45–2.5 mm) [H2O2]feed ¼ 5.1 g L
1, (ca. 10 min); long-term
Fe (wt. %) ¼ ca. 10 Q ¼ 1.0 mL min
1, studies showed that car-
Wcatalyst ¼ 2.5 g boxylic acids formed as
intermediates are
responsible for the
reduction of active sites
on the catalyst
Phenol Fixed-bed Fe2O3/MCM-41 pH0 ¼ 6.0, T ¼ 80 C, 72.5% TOC removal, Almost no aromatic [102]
reactor mesoporous zeolite [PhenolI]feed ¼ 1 g L
1, 99% phenol conversion intermediates were
(dp ¼ 2.5 mm) [H2O2]feed ¼ 5.1 g L
1, found in the treated
Fe (wt. %) ¼ 10 Q ¼ 2 mL min
1, bed effluent when bed height
height ¼ 4 cm was over 2 cm
Dye solution (Undisclosed) Fe3O4-loaded pH0 ¼ 3.5, T ¼ room, 89% dye removal, In the 2nd run, only 74% [103]
(RB19) chitosan hollow [RB19]feed ¼ 50 mg L
1, t ¼ 150 min dye removal was
fibers (Fe3O4-CH [H2O2]feed ¼ 10 mM, achieved for the same
HFs) Qfeed ¼ 8 mL min
1 operational conditions
Phenol Fixed-bed Fe-ZSM-5 pH0 ¼ 6.0, T ¼ 80 C, 77.7% TOC conversion, High oxidant conversion [104]
reactor (dp ¼ 2 mm) [Phenol]feed ¼ 1 g L
1, 99.2% phenol (93.1%)
degradation
B.M. Esteves et al.

Fe (wt. %) ¼ 9.4 [H2O2]feed ¼ 5.1 g L
1, Q ¼ 2 mL

min
1, bed height ¼ 3.8 cm
Phenol CSTR Fe/AC (powder) pH0 ¼ 3, T ¼ 50 C, For the first 20 h of Over 170 h of operation; [105]
Fe (wt. %) ¼ 4 [Phenol]feed ¼ 100 mg L
1, operation: >90% phe- H2O2 conversion values
[H2O2]feed ¼ 500 mg L
1, nol conversion and always >90%
[Fe/AC] ¼ 5 g L
1, τ ¼ 200 min, >80% TOC reduction;
Qfeed ¼ 5 mL min
1 after that period,
increasing loss of activ-
ity until stabilization at
ca. 65% for phenol and
25% for TOC
Dyeing- Recirculating γ-FeOOH pH0 ¼ 3.5–4.0, T ¼ room, COD removal between In the 3-month long- [106]
finishing FBR (dp ¼ 0.6 mm) [COD]feed ¼ 185–210 mg L
1, 29 and 40% term operation treatment
wastewater Fe (wt. %) ¼ 3.5 [H2O2]feed ¼ 5.7–6.0 mM, [- of the real wastewater,
γ-FeOOH] ¼ 133 g L
1, the catalytic perfor-
τ ¼ 52 min mance was nearly
unaffected
Tyrosol (Undisclosed) CuNHe (copper- pH0 ¼ 5.6, T ¼ 60 C, Tyrosol and TOC con- The results obtained in [107]
supported [Tyrosol]feed ¼ 500 ppm versions ca. 85 and the continuous reactor
Al-pillared clays) [CuNHe] ¼ 0.5 g L
1, 60%, respectively were similar to the batch
Cu (wt. %) ¼ 1.93 [H2O2]feed ¼ 6.8  10
2 M, ones
Wcatalyst ¼ 1 g, Qfeed ¼ 30 mL h
1
m-cresol Fixed-bed HNO3-SW (sewage pH0 ¼ 7, T ¼ 80 C, [m- m-cresol conversion m-cresol conversion [108]
reactor sludge-derived car- cresol]feed ¼ 100 mg L
1, reached 95% reached 25% at 96 h,
bonaceous mate- [H2O2]feed ¼ 15.7 mmol L
1, increased to 80% at
rial) (dp ¼ 4–6 mm) LHSV ¼ 1 h
1, [HNO3- 360 h, and was kept at
Fe (wt. %) ¼ 1.74 SW] ¼ 0.5 g L
1 95% until 1,128 h of
operation
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . .
229
230 B.M. Esteves et al.

For homogeneous systems, optimum pH values of the Fenton process are well
known to be in the strict 3.0–3.5 range. In such conditions, maximum concentration
of Fe2+ active species is achieved at the lowest rate of H2O2 parasitic decomposition
[109]. Lower pH values are reported to slow down the formation of iron(III)-peroxo
complexes (as intermediates, cf. Eq. 4), interfering with the Fe3+/Fe2+ regeneration
cycle [35]. Increasing the pH of the reaction leads to the precipitation of relatively
inactive and insoluble ferric hydroxides (Fe(OH)3), resulting in the drop of ferric
ions’ availability; thus the reaction depicted in Eq. (4) is again the rate-limiting step
[33]. Also, hydrogen peroxide self-decomposition into molecular oxygen becomes
significant under such conditions (Eq. 11), hindering the formation of oxidizing
species [110, 111].

2H2 O2 ! O2 þ 2H2 O ð11Þ

Drawbacks associated with the narrow optimum pH range of homogeneous

systems may be avoided using solid catalysts, since heterogeneous Fenton-like
catalysts are reported to show lower sensitivity to pH than iron ions in solution
(for rather similar reaction conditions). Because iron species are restrained within
the structure and inside the pore/interlayer of the solid catalyst, precipitation of iron
hydroxide is reduced, resulting in the continuous ability for HO• formation [45, 100,
112]. For instance, Chi et al. [113] showed that the modified polyacrylonitrile
(PAN) catalyst, used on the oxidation of trace endocrine disrupting compounds
(EDCs) and pharmaceutical and personal care products (PPCPs) in a pilot-scale
continuous stirred-tank reactor, is catalytically active even at the natural pH of such
effluents (pH range 6.6–8.0). The authors suggest that the catalytic activity in this
wider pH range could be attributed to the strong ligands holding the metal ions,
preventing the iron from precipitating (which usually happens in homogeneous
systems when pH >4 – see Eq. 4). Lu et al. [101] also stated that the inexpensive
Fe2O3/γ-Al2O3 catalyst, used in the continuous Fenton-like oxidation of a phenolic
solution in a fixed-bed reactor, remained catalytically active in the pH range of 5–9.
Phenol and COD removal for those runs were >99% and >90%, respectively
(steady-state values), only dropping when pH ¼ 10 (Fig. 9).
Nonetheless, other investigations on the use of continuous heterogeneous cata-
lytic systems showed optimum pH values in a narrower acidic range. According to
the work of Duarte et al. [44] on the degradation of a dye-containing solution
(Alcian Blue-tetrakis – AB), using a fixed-bed reactor filled with an Fe on activated
carbon catalyst (Fe/AC), optimum pH was suggested to be 2.5. The authors stated
that a strongly acidified medium significantly improved discoloration and TOC
abatement of the solution, as illustrated in Fig. 10. In fact, for the 2–4 range of pH
values tested, pH ¼ 2.0 allowed reaching maximum TOC removal (48.1%), while
maintaining high discoloration percentage (>90%) at steady state. However, in
respect to the leaching of iron from the activated carbon support, after 3 h of
reaction Fe loss was ca. 5 times higher when compared to pH ¼ 2.5. Despite that,
total iron loss for that series of experiments was only 0.64% of the total Fe initially
loaded into the column. It is anticipated that leaching >1% of active ferrous iron is
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 231

100

80

Removal (%)
Phenol
60 COD

40

20

0
4 6 8 10
pH

Fig. 9 Influence of the initial pH on the degradation of phenolic solutions at steady state.
Experimental conditions: [Phenol]feed ¼ 1 g L
1, [H2O2]feed ¼ 5.1 g L
1, T ¼ 80 C,
Wcatalyst ¼ 2.5 g, and Qfeed ¼ 1.0 mL min
1. Adapted from [101]

Fig. 10 Effect of medium pH in discoloration along time (a) and TOC removal in steady state (b)
of the AB dye solution. Experimental conditions: [AB]feed ¼ 0.01 mM, [H2O2]feed ¼ 30 mM,
T ¼ 30 C, and Wcatalyst/Q ¼ 3.3 g min mL
1. Adapted from [44]

sufficient to cause catalytic activity in the homogeneous phase [114]. In such cases,
the overall catalytic activity and efficiency of the process may be affected by the
homogeneous contribution, but this depends of course on the catalyst used (namely,
content of iron), target pollutant(s), and other operating conditions.
A rather similar behavior as reported by Duarte et al. [44] was found by Queirós
et al. [71] on the oxidation studies of an azo dye solution (Orange II – OII) using an
Fe/ZSM-5 zeolite as catalyst. The optimization of the Fenton-like process under
continuous stirred-tank reactor operation (CSTR) showed that the 2–3 pH range
allowed discoloration values between 65 and 75% (Fig. 11a). Operating at higher
pH values leads to the significant reduction of the discoloration efficiency (for
232 B.M. Esteves et al.

100
Dye
a 3.0 b
TOC
Removal (%) 80 2.5

[Fe] (mg/L)
2.0
60
1.5
40
1.0
20
0.5

0 0.0
1 2 3 4 1 2 3 4
pH pH

Fig. 11 Effect of medium pH in discoloration and TOC removal at steady state (a) and
iron leaching from the catalyst support (b). Experimental conditions: [OII]feed ¼ 0.1 mM,
[H2O2]feed ¼ 6 mM, T ¼ 50 C, Wcatalyst/Q ¼ 60 mg min mL
1, and τ ¼ 30 min. Adapted from [71]

pH ¼ 4, color removal was ca. 20%); a similar decline in process performance was
observed under very low pH values. In respect to the iron loss from the zeolite
support, leaching levels were substantially higher as more acidic conditions were
applied (Fig. 11b). To assess whether the contribution of the homogeneous Fenton
process due to the iron loss from the support to the solution was influencing the
efficiency of the process, an additional experiment was performed by feeding the
reactor with the exact same Fe concentration that leached from the Fe/ZSM-5
zeolite in the run where pH ¼ 3.0. For the same operational conditions, the
homogeneous Fenton contribution was significantly less prominent than the het-
erogeneous one (9 vs 69% dye removal and 3 vs 21% TOC degradation), although
the results confirm that iron leaching is a concern in such oxidative systems,
since catalyst deactivation and homogenous oxidation coexist. This contribution
is expected to be more significant for more acidic pH conditions, due to the higher
Fe concentration in solution.
Operating at lower pH conditions entails several disadvantages, generally asso-
ciated with the cost of acidification of the initial solution, need for post-treatment
neutralization of the effluent, and the use of acid-resistant material for the reactor
coating [115]. Besides, leaching of the iron catalyst from the support also causes
secondary metal ion pollution in the treated effluent. The development of cost-
effective catalysts with high catalytic activity and long-term stability in a broader
pH range remains the greatest challenge for the effective application of Fenton-like
heterogeneous systems for wastewater treatment.

3.2.2 Temperature

The reaction temperature also plays a critical role since oxidation proceeds at a
faster rate when the reaction medium temperature is increased. This is due to the
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 233

exponential dependence of kinetic constants (k), either for radical production, for
iron regeneration, or for organics attack, from the temperature according with the
Arrhenius law (Eq. 12),
 
Ea
k ¼ k0 exp
ð12Þ
RT

where k0 is the global rate constant, R the ideal gas constant, Ea the activation
energy, and T the temperature.
This dependence, for both discontinuous and continuous processes, is particu-
larly evident between 10 and 40/50 C, as reported by several researchers [72, 116,
117]. Working with an Fe/AC catalyst for the catalytic oxidation of a dye solution in
a fixed-bed reactor, Duarte et al. [44] stated that decolorization and TOC removal in
the 10–50 C range were in accordance with the Arrhenius law dependence.
Optimum temperature of 50 C leads to 74% decolorization and 37% TOC degrada-
tion (steady-state values). For T ¼ 70 C, oxidation of the dye solution was no longer
improved by the increase of reaction’s temperature, and a slight mineralization
efficiency decrease was even observed. This is probably related to the thermal
decomposition of H2O2 into oxygen and water, promoted at higher temperatures,
which affects the HO• production, and consequently the degradation of organic
matter. Also, the formation of gas bubbles observed in the reactor’s column while
operating at T ¼ 70 C may also have played an undesirable role on the mass transfer
between the liquid and the catalyst phase, hindering the process efficiency [81].
A similar study was performed by Mesquita et al. [46], who also noticed the
formation of gas bubbles inside the fixed-bed reactor when operating in the
50–70 C range. Even so, this phenomenon was not preponderant enough to hinder
the degradation efficiency of the Chicago Sky Blue (CSB) dye solution (Fig. 12).

1.0
10 ∞C 50 ∞C
30 ∞C 70 ∞C
0.8
100

0.6 80
Dye removal (%)
C/C∞

60
0.4
40

20
0.2
0
10 20 30 40 50 60 70 80
0.0 T (∞C)
0 1000 2000 3000 4000 5000 6000
time (s)

Fig. 12 Dye concentration history at the fixed-bed reactor outlet for different reaction tempera-
tures; inset graphic shows steady-state dye conversion values. Experimental conditions:
[CSB]feed ¼ 0.012 mM, [H2O2]feed ¼ 2.25 mM, pH ¼ 3.0, and Wcatalyst/Q ¼ 1.88 g min mL
1.
Adapted from [46]
234 B.M. Esteves et al.

The study carried out by Liu et al. [102] pointed out similar results, but for the
degradation of phenol over a Fe2O3/MCM-41 mesoporous zeolite catalyst. These
results indicate that every catalytic system behaves differently depending on the
reaction conditions, thus optimization of every single operational variable is crucial
for a cost-efficient application of Fenton-like processes.
For industrial application, the reaction’s temperature could be increased (up to a
certain point) to improve degradation rates and consequently the process efficiency.
In some specific circumstances, such is the case of effluents coming from textile
industries, the heating of the system could eventually be avoided since textile
wastewaters usually present high temperatures at the time of rejection [118, 119].
Nevertheless, for most applications, the associated energy consumption costs and
the iron loss due to leaching phenomena, which is sometimes reported to be more
prominent at higher temperatures [71, 96], make the use of lower temperatures
(T ~30 C) more suitable for the majority of industrial wastewater treatment
facilities.

3.2.3 H2O2 Dosage

For the vast majority of target compounds/wastewaters and operational conditions,

an increase in the oxidant dose fed to the system leads to higher degradation rates.
However, excess oxidant may cause unwanted parallel reactions, particularly via
the so-called scavenging effect, where the HO• is being ineffectively used to
produce hydroperoxyl species (HO2•) with lower oxidation potential (Eq. 7). Addi-
tionally, the enhanced production of HO2• origins undesired radical-radical reac-
tions, also causing the parasitic consumption of HO• (Eq. 9).
Mesquita et al. [46] showed that increasing the H2O2 dose fed to a fixed-bed
reactor, which was loaded with Norit RX3 activated carbon impregnated with Fe
(7 wt.% of iron), yields an increase in the CSB dye conversion. However, this was
only true within a certain range of oxidant dosages (0.15–2.25 mM). Beyond
that range, dye removal efficiency started to decrease, as depicted in Fig. 13. The
existence of an optimum feed oxidant concentration was also reported in several
other studies [45, 71, 72, 103].
The selection of the optimum oxidant concentration in the feed usually requires
the knowledge of the H2O2 stoichiometric amount that is able to theoretically
mineralize all the organic carbon present in solution. For most cases, where the
wastewater to be treated has complex or unknown composition, this estimation can
be achieved by the reaction presented in Eq. (13).

C þ 2H2 O2 ! CO2 þ 2H2 O ð13Þ

Following the stoichiometry of the reaction, a H2O2/C molar ratio of 2, equiva-

lent to a 5.7 mass ratio, is necessary to complete carbon depletion (as TOC content)
[43]. Also, it can be referred to as the stoichiometric weight ratio between the
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 235

1.0
0.15 mM 1.50 mM 3 mM
0.90 mM 2.25 mM 12 mM
0.8
50
0.6

Dye removal (%)

∞

40
C/C

30
0.4
20

0.2 10

0
0 2 4 6 8 10 12
0.0
[H2O2] (mM)
0 500 1000 1500 2000 2500 3000
time (s)

Fig. 13 Dye concentration at the fixed-bed reactor outlet for different H2O2 feed concentrations;
the inset graphic represents dye conversion values at steady state. Experimental conditions:
[CBS]feed ¼ 0.012 mM, Wcatalyst/Q ¼ 1.88 g min mL
1, pH ¼ 3, T ¼ 30 C. Adapted from [46]

oxidant and effluent’s initial COD
R ¼ H2O2/COD ¼ 2.125 (based on H2O2

complete conversion into O2) [86]. In practice, because hydrogen peroxide partic-
ipates in unwanted parallel reactions, as previously mentioned, the H2O2 dose applied
is often higher than the theoretical stoichiometric one. For example, Queirós et al.
[71] tested a range of hydrogen peroxide feed doses corresponding to 0.42–4.76 the
stoichiometric concentration for the oxidation of an azo dye-containing solution,
using an Fe/ZSM-5 zeolite as the catalyst. The best catalytic performance was
observed at 1.42 times the stoichiometric dose. Esteves et al. [72] also reported the
use of an oxidant feed concentration of 3.52 g L
1, corresponding to two times the
calculated theoretical stoichiometric concentration (R) for the heterogeneous Fenton
oxidation of a simulated textile effluent, using an Fe/AC catalyst on a CSTR.
Melero et al. [43] tested a Fe2O3/SBA-15 nanocomposite material as a Fenton-
like heterogeneous catalyst for the treatment of a pharmaceutical wastewater in a
continuous upflow fixed-bed reactor. A stoichiometric amount of oxidant fed to the
reactor (5,400 mg L
1) yielded ca. 40% TOC degradation (steady-state value).
Twice that amount improved the catalytic activity of the system, allowing a steady-
state TOC conversion value of ca. 60%. However, further increase in the oxidant
dosage did not influenced the efficiency of the process, as Fig. 14 shows, highlight-
ing once again the existence of an optimum oxidant dose for Fenton/Fenton-like
systems.
The efficient use of hydrogen peroxide is not only important from an economical
point of view, since H2O2 is a relatively costly reactant, but also because the unused
oxidant during the process may contribute to chemical oxygen demand (COD) of
the treated effluent/solution [120]. Also, if Fenton oxidation is used as a pre-
treatment stage followed by a biological step, excess hydrogen peroxide has been
linked to cause harmful effects on microorganisms, hindering biological depuration
processes [121].
236 B.M. Esteves et al.

Fig. 14 Effect of hydrogen 100

peroxide feed concentration
in the effluent’s
80
(pharmaceutical
wastewater) TOC

XTOC (%)
degradation efficiency. 60
Experimental conditions:
[H2O2]feed ¼ square 40
16,200 mg L
1, triangle
10,800 mg L
1, circle
5,400 mg L
1; T ¼ 80 C, 20
Qfeed ¼ 0.25 mL min
1,
Wcatalyst ¼ 2.9 g, and 0
pH ¼ 3.0. Adapted 0 2 4 6 8 10
from [43] Time on stream (h)

3.2.4 Pollutant Concentration Fed

The nature and concentration of the target pollutant/wastewater also plays a key
role for the efficient application of the majority of AOPs. High or close to complete
mineralization via Fenton/Fenton-like processes is almost always favored at lower
concentrations of the target compound(s) [23, 48].
The vast majority of studies reported in literature, and cited throughout this
chapter, deal with the treatment of phenols and dye solutions. In fact, phenolic
compounds are among the most abundant pollutants present in industrial wastewa-
ters, owing to their widespread utilization in the synthesis of pesticides, solvents,
lubricating oils, dyes, and resins, just to name a few. Long-term exposure to such
compounds has been linked to cause several human health damages, as well
as toxicity toward microorganisms and plants, even at very low concentrations
[122]. Dyes and pigments are also frequently reported since they are commonly
used as coloring agents in the textile, food, and pharmaceutical industries. The
discharge of dye-containing effluents is known to cause significant environmental
hazards related to the presence of organic compounds that are not easily degraded
by conventional methods, particularly the azo dye category [123].
In the heterogeneous Fenton-like oxidation of Basic Blue 3 dye (BB3) with
natural magnetite, Aghdasinia et al. [60] found that increasing the initial BB3
concentration fed in the 5–20 mg L
1 range led to a decline of the degradation
efficiency, as illustrated in Fig. 15. Increasing the initial dye concentration may
contribute to the occupation of active sites in the natural magnetite surface, which
would deactivate accessible sites for H2O2, thus decreasing the generation of
hydroxyl radicals, as the authors enlightened. Similar results were observed by
Guo and Al-Dahhan [109] on the semicontinuous catalytic wet oxidation of phe-
nolic solutions in the feed concentration range of 100–2,000 ppm (T ¼ 70 C, in the
presence of 0.3 M of H2O2 and 6.6 g L
1 of a Al-Fe-pillared clay catalyst). The
elimination of phenol after 240 min of reaction was practically complete for feed
concentrations in the 100–1,000 ppm range, although slower oxidation rates were
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 237

Fig. 15 Effect of BB3 100

initial concentration on the 5 mg/L
10 mg/L

Degradation Efficiency (%)

BB3 degradation efficiency
80 15 mg/L
in semicontinuous
20 mg/L
operation. Experimental
conditions: 60
[H2O2]feed ¼ 4 mM,
[NM]catalyst ¼ 2.27 g L
1,
pH ¼ 5, T ¼ room. Adapted 40
from [60]
20

0
0 50 100 150 200
Time (min)

observed when increasing the initial phenol concentration in that same range. For
the maximum phenol feed dose tested (2,000 ppm), degradation efficiency was
approximately half the one obtained previously, for the same reaction time.
In summary, Fenton-like processes have proved to be effective on the degrada-
tion of most refractory compounds, but technical and economic drawbacks arise
when dealing with high organic loads, since H2O2 consumption requirements
become substantially higher for such cases and blockage of the catalyst’s surface
may occur.

3.2.5 Catalyst Load

In heterogeneous Fenton/Fenton-like processes, ferric, ferrous, or other low-

valence transition metal ions, situated in the surface sites of the solid material,
take part in the reaction scheme yielding hydroxyl radical species. Similar to
homogeneous systems, small amount of catalyst in solution will almost always
result in lower efficiency of the process, since the availability to react with H2O2 is
reduced. Also, when operating fixed-bed reactors, the catalyst load indirectly
influences the residence time (tR) of the liquid phase, according to Eq. (14),

V L EL V B
tR ¼ ¼ ð14Þ
Q Q

where the liquid holdup, EL, is the ratio between the volume of the liquid phase, VL,
and the catalyst-bed volume, VB (also referred to as catalyst bed height), and
Q stands for the total feed flow rate. The liquid holdup is calculated according to
parameters related to the packed bed, namely, porosity and external liquid
saturation [47].
238 B.M. Esteves et al.

In fact, the catalytic volume/mass can be adjusted to modify the fluid residence
time, as reported in the work of Yan et al. [104]. The influence of residence time on
the catalytic wet hydrogen peroxide oxidation of phenol was addressed by modi-
fying the catalyst bed height in the 1.1–3.8 cm range (corresponding to 2.5–9.7 g of
Fe/ZSM-5 catalyst). As anticipated, higher phenol, TOC, and H2O2 conversions
were obtained for the longer catalytic bed heights tested, either by the effect of the
higher availability of active iron species or by the increased residence time of the
solution.
In the attempt of improving the dye conversion of an azo dye-containing
solution, Mesquita et al. [46] also increased the column load with a Fe/AC catalyst
(7 wt.% of Fe) from 4.7 to 10.25 g. This increase led to ca. 70% dye conversion at
steady state (at 30 C, for a feed containing 0.012 mM of the dye and 2.25 mM
H2O2). The performance improvement, when compared to ca. 37% obtained when
applying 4.7 g of Fe/AC, was attributed to the fact that longer catalyst beds lead to
higher contact times, expressed as Wcat/Q (i.e., the amount of catalyst, Wcat,
available inside the reactor is increased for the same feed flow rate, Q).
The work of Liu et al. [102] also showed that longer catalyst bed had a positive
effect on phenol, TOC, and H2O2 conversion. By adjusting the catalytic bed height
to 2, 3, and 4 cm, under the same operating conditions, phenol degradation reached
>98% for all heights, TOC removal increased from 59 to 72.5%, and H2O2
conversion reached its higher value for 4 cm (92.1%), as shown in Fig. 16.
On the other hand, excessive loading may lead to the consumption of generated
hydroxyl radicals by the excess catalyst (see Eq. 8). For example, Aghdasinia et al.
[60] reported the existence of an optimum catalyst dose – 2.27 g L
1 of natural
magnetite – for the Fenton-like oxidation of a dye-containing solution in a FBR;
further increment in the catalyst applied to the system yields a dye conversion
efficiency decrease. Besides the scavenger effect, the formation of iron complexes
(iron + organics) is also reported to occur when excess amounts of catalyst are
present in solution [116]. Martı́nez et al. [47] also reported the existence of an
optimum dosage for the Fe2O3/SBA-15 catalyst used in the oxidation of phenolic
solutions. TOC conversion enhancement is clear when catalyst mass (and conse-
quently, the residence time) is increased from 1.4 to 2.9 g (48.1 vs 66.6% TOC
removal); applying higher catalyst mass (3.9 g) leads to little to no variation in the
mineralization degree, despite the high oxidant feed dose applied in that set of runs
([Phenol]feed ¼ 1 g L
1, [H2O2]feed ¼ 5.1 g L
1, T ¼ 80 C). The presence of
refractory compounds, formed during the oxidation of phenol, that are resistant to
mineralization (namely, formic, acetic, and oxalic acids) were detected in the
treated effluent.

3.2.6 Feed Flow Rate

Similarly to the catalyst dosage, variations in the feed flow rate also affect the
residence/contact time (note: for perfectly mixed reactors operating with constant
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 239

Fig. 16 Influence of catalyst bed height in the conversion efficiency of (a) phenol, (b) TOC,
and (c) H2O2 of a phenolic solution. Experimental conditions: [Phenol]feed ¼ 1.0 g L
1,
[H2O2]feed ¼ 5.1 g L
1, Q ¼ 2.0 mL min
1, T ¼ 80 C. Adapted from [102]

density fluids, residence time is equivalent to the space-time, τ, which is calculated

by the ratio between the total volume and the volumetric flow rate – τ ¼ V/Q).
Melero et al. [43] performed Fenton catalytic experiments for the degradation of
a pharmaceutical wastewater using Fe2O3/SBA-15 as the heterogeneous catalyst,
applying feed flow rates of 0.25, 0.5, and 1.0 mL min
1 (which provides residence
times of 3.79, 1.90, and 0.95 min, respectively). TOC and H2O2 conversion
histories at the outlet of the fixed-bed reactor are depicted in Fig. 17. Increasing
the feed flow rate from 0.5 to 1.0 mL min
1 has the most impact in conversion
profiles, as TOC degradation is almost inhibited by the greater feed flow rate tested.
Likewise, H2O2 conversion is extremely low for Qfeed ¼ 1.0 mL min
1, owning to
the lower time for oxidant/catalyst interaction. In terms of the catalytic system
performance, maximum TOC removal of ca. 60% and H2O2 conversion of ca. 90%
was attained at steady state for 0.25 and 0.5 mL min
1. The similar behavior for the
two feed flow rates could indicate the existence of refractory compounds, formed
during the oxidation of the pharmaceutical wastewater.
240 B.M. Esteves et al.

Fig. 17 Influence of the feed flow rate on TOC (a) and H2O2 (b) conversions with time on stream
of a pharmaceutical wastewater. Experimental conditions: Qfeed ¼ square 1.0, circle 0.5, and
triangle 0.25 mL min
1; [TOC]feed ¼ 860 mg L
1, [H2O2]feed ¼ 10,800 mg L
1, Wcatalyst ¼ 2.9 g,
T ¼ 80 C, pH0 ¼ 3. Adapted from [43]

Fig. 18 Feed flow rate influence in the degradation efficiency of phenolic aqueous solutions at
steady state. Experimental conditions: [Phenol]feed ¼ 1.0 g L
1, [H2O2]feed ¼ 5.1 g L
1,
Wcatalyst ¼ 2.9 g, T ¼ 80 C, particle size ¼ 1–1.6 mm. Adapted from [47]

In a previous work by the same research group [47], the same Fe2O3/SBA-15
catalyst was used for the degradation of a phenolic solution by CWHPO in the same
reactor configuration. Varying the inlet feed flow rate of the aqueous phenolic effluent
(1.0 g L
1 phenol and 5.1 g L
1 H2O2 solution) to 1.0, 2.5, and 5.0 cm3 min
1
(corresponding to residence times of 3.6, 1.2, and 0.6 min, respectively), a clear
relationship between mineralization degree and feed flow rate has been assessed,
since higher residence times promote higher TOC degradation (Fig. 18). Rather
similar results were found by Liu et al. [102] on the oxidation of phenol over a
Fe2O3/MCM-41 catalyst (operational conditions were [Phenol]feed ¼ 1.0 g L
1,
[H2O2]feed ¼ 5.1 g L
1, T ¼ 80 C, and catalyst bed height ¼ 4 cm). TOC conversion
decreased from ca. 69 to 46% with the feed flow rate increase from 2 to 8 mL min
1,
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 241

and the same trend was observed in respect to the phenol degradation efficiencies
(99.1–91.2%).

3.3 Influence of Catalyst’s Physicochemical Properties

As already mentioned, the ideal catalyst for heterogeneous Fenton/Fenton-like

processes should be a low-cost material with good catalytic activity and stability.
Numerous parameters regarding heterogeneous catalysts are reported to directly
affect the efficiency of Fenton’s oxidation and the stability of the catalyst itself,
namely, the type/source of support, catalyst’s incorporation/synthesis method (e.g.,
nature of the precursor used and metal ion selected as the active phase), and the
particle size applied to the catalytic system, among others.
Rodrı́guez et al. [124] compared the catalytic activity of Fe-based catalysts
(Fe 4.2–4.9 wt.%) prepared over nine different supports (Table 4) for the degrada-
tion of the model acid Orange II dye (OII) by the heterogeneous Fenton-like
process, although in a batch reactor. Since adsorption of organic molecules on the
solid surface of the catalysts can enhance the efficiency of the process, additional
experiments were also performed to evaluate whether adsorption or chemical
reaction was occurring under identical experimental conditions. The study showed
that overall TOC reduction of OII solutions by adsorption phenomena was more
preponderant on carbon (AC, CNT, CNF) and hydrotalcite supports than in sili-
ceous and clay mineral supports (e.g., sepiolite) – see Fig. 19. The Fe catalyst
supported on sepiolite was found to be the most viable Fenton catalyst among all
samples tested, with the overall highest color and TOC and COD conversion
percentages, being the catalyst with lowest percentage of iron leaching among all
nine materials tested.
The influence of the precursor used in the synthesis of heterogeneous Fe/AC
catalysts (Fe 7 wt.%) was also evaluated by Duarte et al. [117]; this screening was

Table 4 Nomenclature of different iron catalysts and their main textural properties
Catalyst Nomenclature SBET (m2 g
1) APS (Å)a
Hydrotalcite Fe-HT 69.7 153.5
Zeolite USY Fe-USY 172.9 19.0
Activated carbon Fe-AC 673.9 24.3
Silica Fe-S 392.7 17.7
Mesoporous silica Fe-MCM 857.4 23.2
Silica xerogel Fe-X 500.6 18.5
Carbon nanotubes Fe-CNT 106.5 169.9
Carbon nanofibers Fe-CNF 141.1 158.2
Sepiolite Fe-SEP 201.9 85.2
Adapted from Rodrı́guez et al. [124]
a
Average pore size
242 B.M. Esteves et al.

Fig. 19 (a, b) Evolution of TOC along time and (c) TOC removal after 120 min (by adsorption
and heterogeneous Fenton reaction) for different Fe-based materials. Experimental conditions:
T ¼ 30 C, Wcatalyst ¼ 0.5 g (Fe 5 wt.%), H2O2/AOII ¼ 5 w/w, H2O2/Fe2+ ¼ 3.5 w/w, pH ¼ 3.
Adapted from [124]

carried out in a slurry batch reactor. Three Fe salts were tested, iron acetate
(N-Ac2Fe), iron sulfate (N-FeSO4), and iron nitrate (N-Fe(NO3)3), and their effect
on the degradation of the model Orange II azo dye by the heterogeneous Fenton-
like process was assessed (N represents the support). It was observed that different
precursors led to different iron particle sizes and location within the AC: for the
N-Ac2-Fe catalyst, a good iron dispersion with Fe-particles located inside the
micropores was observed; with the N-FeSO4 one, larger Fe-particles were found
in the catalyst’s surface (thus on larger micropores/mesopores); finally, an inter-
mediate behavior was detected using N-Fe(NO3)3. Good iron dispersion appears to
influence the mineralization efficiency, since the catalyst prepared with iron acetate
showed the best TOC degradation percentages, while maintaining low levels of iron
loss from the support.
Leaching of the active species is also closely related to the method and conditions
of the catalyst preparation. Botas et al. [49] tested several catalysts that consisted of
iron oxide, mostly crystalline hematite particles, over different silica supports. The
authors found that samples prepared by post-synthesis incipient wetness impregnation
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 243

displayed higher leaching levels in the outlet stream of the fixed-bed reactor
(Fe concentrations above 100 mg L
1) than the ones prepared by direct incorporation
during the synthesis (i.e., co-condensation of iron and silica sources).
In another work of Duarte et al. [125], the influence of the particle size on
adsorption and heterogeneous Fenton catalysis was also addressed. A commercial
AC impregnated with iron (Fe content of 7 wt.%) was sieved and milled from the
original pellet form (cylinders of ca. 3  5 mm) to obtain particle sizes in the
intervals of 0.8–1.6, 0.25–0.8, and <0.15 mm (powder). The performance of the
catalysts was evaluated regarding TOC removal of a dye-containing solution and Fe
leaching from the AC support in batch runs. Results confirmed that the Fe-powder
catalyst reached the higher levels of mineralization; however, leaching levels were
also the highest for the smaller particle sizes tested. Taken into account the TOC
mineralization degree and the iron leaching from the supports, the authors con-
cluded that intermediate particle sizes in the 0.8–1.6 mm range were the most
adequate for the operational conditions tested (see Fig. 20).
Lu et al. [101] also tested different sets of particle sizes of a Fe2O3/γ-Al2O3
catalyst in the intervals of 0.45–0.9, 0.9–1.5, and 1.5–2 mm. The catalytic perfor-
mance of the continuous Fenton-like oxidation in a fixed-bed reactor was evaluated
by COD reduction levels and phenol degradation ([Phenol]feed ¼ 1 g L
1). Phenol
oxidation levels were ca. 100% for all particle sizes tested, and only a minor COD
conversion decrease was observed for 1.5–2 mm. Hence, for the case in study, the
effect of internal resistances to mass transfer (intraparticle diffusion) on the cata-
lytic reaction can be disregarded for the smaller particle sizes tested. Although
catalysts with smaller particle size are preferable to avoid internal diffusion prob-
lems, small particles experience a bigger pressure drop across the reactor and may
eventually be cleared away by the liquid stream, so an intermediate range was
selected as the optimum size.
The influence of the particle size was also addressed by Martı́nez et al. [47]. An
extruded Fe2O3/SBA-15 catalyst was sieved and milled to obtain particle sizes in

Fig. 20 (a) TOC reduction and (b) iron-leaching values along 24 h of reaction using Fe/AC cata-
lysts with different particle sizes. Experimental conditions: T ¼ 30 C, [Fe/AC]catalyst ¼ 0.1 g L
1
(Fe 7 wt.%), [OII] ¼ 0.1 mM, [H2O2] ¼ 0.1 g L
1, pH ¼ 3. Adapted from [125]
244 B.M. Esteves et al.

the intervals of 0.35–0.7, 0.7–1, 1–1.6, and 1.6–2 mm. By changing the catalyst
particle size within the packed bed (Wcatalyst ¼ 2.9 g), variations occur in the
porosity and liquid holdup, which eventually modifies the residence time of the
effluent in the reactor, as already addressed (higher residence times were obtained
for larger particle sizes). Thus, and contrary to the expected, TOC conversions in
steady state were slightly higher for the largest particle sizes tested (phenol degra-
dation was always >99%). The authors also suggested that the contribution of the
homogeneous Fenton oxidation reactions was significant since higher residence
times for the liquid phase were expected for that catalyst particle size range. In that
sense, the use of H2O2 as oxidant enables the degradation of phenol in the bulk
liquid phase, mediated by its own oxidation or by the OH• species (from the
catalytic decomposition of the oxidant). This suggests that the oxidation of organic
matter in the liquid phase plays an important role in the overall process efficiency.

3.4 Operational Issues Regarding Heterogeneous Catalysts:

Stability

As discussed in Sect. 3.3, different materials show different activity to promote

Fenton’s reaction. Achieving a strong anchorage of the active species on any
heterogeneous support, thus promoting extended catalytic activity and stability, is
a key operational element for upscale viability of continuous heterogeneous
Fenton-like systems.
Among all causes for catalyst deactivation, one of the most common is leaching
of metal species from the solid support to the aqueous phase. As previously
mentioned, a small concentration of the metal species in solution may act as
homogenous catalyst (therefore, the catalytic activity may not be due exclusively
to the action of the heterogeneous catalyst, but also to the effect of leached species
in solution) but, more importantly, cause secondary metal ion pollution on the
treated effluent. The most efficient way to assess the maximum productivity and
stability of a catalyst is achieved by extending the reaction time with a fixed amount
of catalyst until its complete or partial deactivation and, if necessary, elaborate
reactivation procedures according to the data obtained during the process [126].
Long-term stability experiments with an Fe/AC catalyst (Fe 4 wt.%) were
performed in a CSTR by Zazo et al. [105]. Operating with a total feed flow rate
of 5 mL min
1 (100 mg L
1 phenol and 500 mg L
1 H2O2 solutions), phenol
conversion during the initial 20 h of reaction was higher than 90%. Also, ca. 80%
TOC degradation was observed during the same period (steady-state values). From
that point on until the 170 h reaction mark, a progressive loss of activity was
observed and removal percentages dropped to ca. 65% for phenol and 25% for
TOC. Total iron loss from the AC support after the 170 h of reaction was almost
50% of the initial content.
The results of Melero et al. research team also stress out that the loss of activity
is closely related to the features of the inlet solution/wastewater. For the same
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 245

Fe2O3/SBA-15 catalyst, and under the same operational conditions, the loss of
activity reported by the parallel TOC reduction and H2O2 conversion levels was
less prominent for the treatment of an industrial pharmaceutical wastewater [43],
when compared to the degradation of a phenolic solution [47] (after 20 h of
reaction).
Other known cause for catalyst deactivation is the formation of carbonaceous
deposits that may reduce the specific surface area of the catalyst, as observed by
Zazo et al. [105]. Characterization of fresh and used catalyst after a 170 h run in
batch operation revealed a specific surface area reduction of ca. 40% (SBET of
781 vs 460 m2 g
1, respectively) and a total pore volume decrease from 0.67 to
0.36 cm3 g
1 (not only microporous but also all porous structure). Reactivation
procedures implemented by the authors included the washing of the used catalyst
with 1 N NaOH, which allowed the recovery of most of the initial pore volume and
SBET, with no further loss of Fe; nevertheless, the catalytic activity of the recovered
catalyst revealed a certain degree of irreversible deactivation, which is evidenced
by the TOC reduction curves depicted in Fig. 21.
The poisoning of active catalytic sites within the heterogeneous surface is
another known mechanism of catalyst deactivation, since the accessible active
sites for hydrogen peroxide reduction, involved in the HO• formation, become
unavailable [47]. For three consecutive runs in a batch reactor using the same
Fe-exchanged pillared beidellite catalyst, Catrinescu et al. [112] detected that the
initial rate of phenol degradation was slowly diminishing. Then, when the catalyst
was used after an intermediate calcination step, the initial oxidative capacity of the
material was almost fully restored (without significant Fe loss), indicating that the
organic species adsorbed on the active sites of the catalysts were causing the
oxidation delay for short reaction times. Catalyst’s stability investigations
performed by Di Luca et al. [48] research group indicate that the use of a high
calcination temperature (900 C), along with a step of immersion into an organic

Fig. 21 Comparison of 100

fresh vs used catalyst Fresh catalyst
regenerated with 1 N Reused after NaOH - washing
NaOH-solution in batch 80
runs. Experimental
TOC (mg/L)

conditions: 60
[Phenol]0 ¼ 100 mg L
1,
[H2O2]0 ¼ 500 mg L
1,
Wcatalyst ¼ 500 mg L
1, 40
T ¼ 50 C, pH0 ¼ 3.0.
Adapted from [105]
20

0
0 50 100 150 200 250
Time (min)
246 B.M. Esteves et al.

acid solution, enhances the stability of a Fe2O3/Al2O3 catalyst by increasing the

iron-support interactions.
Several efforts have been performed to overcome drawbacks associated with
weak anchorage of metal ions on the catalyst, such as the modification of surface
oxygenated groups by different treatment techniques [127] or the complexation of
iron with organic ligands, which are linked to extend the pH range from acidic to
basic regarding Fenton oxidation [128]; nevertheless, their deterioration occurs by
the oxidative action of the process, which gradually destroys the ligands, with the
consequent fragmentation of the structure over time.
Another major disadvantage of Fenton’s heterogeneous catalysts is that pollut-
ant’s molecules in solution must diffuse to the surface of the material to reach active
sites before they are oxidized. The detailed mechanism regarding the role of surface
interactions and adsorption/desorption of metal ions and reactants in heterogeneous
catalysts is still unclear; however, they are often considered rate-limiting steps of
the process [35, 109].

3.5 Performance of Continuous vs Batch Reactors

An overwhelming number of studies regarding homogeneous and heterogeneous

Fenton-like processes in discontinuous slurry reactors can be found in literature.
However, not only is the operation of continuous reactors preferable for industrial
applications, but it has also been demonstrated, mostly in lab-scale studies, that
degradation efficiencies of several pollutants/wastewaters are very promising in
continuous flow systems.
For example, Aghdasinia et al. [60] compared the catalytic performance of a
heterogeneous Fenton-like system operating in a FBR with a batch one, under
rather identical conditions, for the BB3-dye degradation. The higher dye removal
level attained with the fluidized-bed reactor is probably related to the enhancement
of contact between the natural magnetite catalyst particles and BB3, the high mass
transfer coefficients in FBRs, and an effective and uniform mixing of the solution
and catalyst inside the column.
The CWPO performance of sewage sludge carbonaceous materials on m-cresol
(a toxic organic compound used in the manufacture of pharmaceuticals, pesticides,
surfactants, etc.) degradation was evaluated by Yu et al. [108]. Results in batch and
continuous fixed-bed reactor experiments showed that among all materials tested,
the SW treated with HNO3 presented higher conversion of the target compound.
Conversion of m-cresol reached 98% and TOC depletion 67.1% in discontinuous
mode (experimental conditions: pH0 ¼ 7.0, T ¼ 80 C, [m-cresol] ¼ 100 mg L
1,
[H2O2] ¼ 15.7 mmol L
1, [HNO3-SW] ¼ 0.5 g L
1, 180 min of adsorption
and 210 min of oxidation); conversion of m-cresol in the long-term continuous
run (same conditions as the batch experiment and LHSV ¼ 1 h
1) was >95% from
500 to 1,200 h reaction time (Fig. 22). Nonetheless, different behavior was
observed between the two configurations. For the batch operation, after the
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 247

Fig. 22 Conversion of m- Conversion pH

cresol and pH values along
the reaction in continuous 100
12
operation with HNO3-SW

M-cresol conversion (%)

catalyst. Experimental
80
conditions: [m- 10
cresol]feed ¼ 100 mg L
1,
[H2O2]feed ¼ 15.7 mmol L
1, 60
LHSV ¼ 1 h
1, T ¼ 80 C, 8

pH
pH0 ¼ 7.0 Adapted
from [108] 40
6

20
4

0
0 200 400 600 800 1000 1200
Running time (h)

adsorption period, oxidation of m-cresol occurs almost instantly, whereas for the
continuous run m-cresol conversion dropped along time in the first 100 h of
operation, which was caused by both adsorption and oxidation phenomena. Once
adsorption equilibrium was reached, the CWPO was the key process affecting the
degradation and the efficiency of the process improved significantly. The behavior
observed could have been caused by the catalyst’s surface functional groups, since
NO2 groups (added during the HNO3 treatment) may affect negatively the adsorp-
tion process; however, the loss of such groups was verified along the reaction,
which may have led to the contact enhancement between m-cresol and the catalyst’s
active phase. Also, the lag observed could be due to the occurrence of different
mass transfer rates: for the continuous system, the oxidant and pollutant passed
through the granular catalysts; hence the mass transfer rate was lower than the one
on the batch reactor (where the powder catalyst was mixed in solution with H2O2
and m-cresol).

4 Conclusions

Undoubtedly, homogeneous Fenton and Fenton-like processes are among the most
interesting AOPs for the degradation of refractory organic compounds, increasingly
common in industrially generated wastewaters. However, the added costs associ-
ated with the recovery of the catalyst (and the treatment of the sludge formed, which
is a major concern especially for the treatment of large wastewater flow rates), the
restricted pH range of operation, and the amount of dissolved catalyst needed in
solution led to the exploration of cost-effective alternatives. The development of
heterogeneous materials, capable of supporting the Fenton’s reagent active phase
(usually iron species), with consequent high catalytic activity and stability, became
248 B.M. Esteves et al.

an interesting field of research over the last few decades. Numerous supports,
preparation methods, transition metals, and other physicochemical characteristics
regarding heterogeneous catalysts have been proposed and studied for the Fenton-
like degradation of different pollutants and wastewaters. These studies, however,
are mostly performed in discontinuous batch reactors, due to the easiness of
operation and the faster screening of the key operational parameters influencing
the oxidation process.
In recent years, more attention has been given toward the application of hetero-
geneous catalysts in continuous systems, namely, in fixed-bed reactors, fluidized-
bed reactors, and CSTRs, which are understandably preferred for upscale industrial
applications; each configuration presents its own advantages and disadvantages for
the application of heterogeneous Fenton-like process, which are explained through-
out this chapter.
Examples of the most up-to-date findings in this field of research are also
provided, along with a comprehensive review of the process operational variables
involved (e.g., pH, H2O2 feed dose, temperature, catalyst load, and properties) and
their expected effect on the overall efficiency of this technology. We believe that
such considerations provide helpful information for a faster and more effective
optimization of heterogeneous Fenton-based processes.
Moreover, an overview of the main technological issue regarding this process –
the catalysts deactivation – is made. Despite the recent progresses in this area,
developing a cost-effective and strong anchorage of the metal ions in a solid matrix
seems to be the limiting step toward the wider application of this catalytic process.
Also, it is worth mentioning that despite the more-or-less successful application of
this technology under lab-scale studies, especially for the treatment of model
compounds, the successful upscaling of the process requires the development of
more elaborated mechanisms and kinetic modeling and the study of more complex/
real wastewaters.
The final section of this chapter illustrates the potential of heterogeneous Fenton-
like continuous systems, when compared to the results obtained in batch processes
under rather identical operating conditions.

Acknowledgments This work was the result of the Project POCI-01-0145-FEDER-006939

(Laboratory for Process Engineering, Environment, Biotechnology and Energy – UID/EQU/
00511/2013) funded by the European Regional Development Fund (ERDF), through COM-
PETE2020 Programa Operacional Competitividade e Internacionalizaç~ao (POCI), and by national
funds, through Fundaç~ao para a Ciência e a Tecnologia (FCT), and Project NORTE-01-0145-
FEDER-000005 – LEPABE-2-ECO-INNOVATION, supported by the North Portugal Regional
Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through
the European Regional Development Fund (ERDF).
Carmen Rodrigues is grateful to FCT for the financial support through the postdoctoral grant
(SFRH/BPD/115879/2016).
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 249

References

1. Vandevivere PC, 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
2. Mohajerani M, Mehrvar M, Ein-Mozaffari F (2009) An overview of the integration of
advanced oxidation technologies and other processes for water and wastewater treatment.
Int J Eng 3:120–146
3. Oturan MA, Aaron J-J (2014) Advanced oxidation processes in water/wastewater treatment:
principles and applications. A review. Crit Rev Environ Sci Technol 44:2577–2641
4. Eljarrat E, Barceló D (2003) Priority lists for persistent organic pollutants and emerging
contaminants based on their relative toxic potency in environmental samples. Trends Anal
Chem 22:655–665
5. Farré M, Pérez S, Kantiani L (2008) Fate and toxicity of emerging pollutants, their metab-
olites and transformation products in the aquatic environment. Trends Anal Chem
27:991–1007
6. Durmusoglu E, Taspinar F, Karademir A (2010) Health risk assessment of BTEX emissions
in the landfill environment. J Hazard Mater 176:870–877
7. Toms L-ML, Hearn L, Mueller JF, Harden FA (2016) Assessing infant exposure to persistent
organic pollutants via dietary intake in Australia. Food Chem Toxicol 87:166–171
8. Umbuzeiro GA, Freeman HS, Warren SH, Oliveira DP, Terao Y, Watanabe T, Claxton LD
(2005) The contribution of azo dyes to the mutagenic activity of the Cristais River.
Chemosphere 60:55–64
9. White PA, Claxton LD (2004) Mutagens in contaminated soil: a review. Mutat Res
567:227–345
10. Banat IM, Nigam P, Singh D, Marchant R (1996) Microbial decolorization of textile-dye
containing effluents: a review. Bioresour Technol 58:217–227
11. Haritash AK, Kaushik CP (2009) Biodegradation aspects of polycyclic aromatic hydrocar-
bons (PAHs): a review. J Hazard Mater 169:1–15
12. Fu F, Chen R, Xiong Y (2006) Application of a novel strategy – coordination polymerization
precipitation to the treatment of Cu2+-containing wastewaters. Sep Purif Technol 52:388–393
13. Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J Environ
Manag 92:407–418
14. Cath TY, Childress AE, Elimelech M (2006) Forward osmosis: principles, applications, and
recent developments. J Membr Sci 281:70–87
15. Busca G, Berardinelli S, Resini C, Arrighi L (2008) Technologies for the removal of phenol
from fluid streams: a short review of recent developments. J Hazard Mater 160:265–288
16. Gabelman A, Hwang S-T (1999) Hollow fiber membrane contactors. J Membr Sci 159:61–106
17. Verma AK, Dash RR, Bhunia P (2012) A review on chemical coagulation/flocculation
technologies for removal of colour from textile wastewaters. J Environ Manag 93:154–168
18. Duan J, Gregory J (2003) Coagulation by hydrolysing metal salts. Adv Colloid Interf Sci
100–102:475–502
19. Kurniawan TA, Chan GYS, Lo WH, Babel S (2006) Physico-chemical treatment techniques
for wastewater laden with heavy metals. Chem Eng J 118:83–98
20. Kannan N, Sundaram MM (2001) Kinetics and mechanism of removal of methylene blue by
adsorption on various carbons – a comparative study. Dyes Pigments 51:25–40
21. Babel S, Kurniawan TA (2003) Low-cost adsorbents for heavy metals uptake from contam-
inated water: a review. J Hazard Mater 97:219–243
22. Crini G (2006) Non-conventional low-cost adsorbents for dye removal: a review. Bioresour
Technol 97:1061–1085
23. Babuponnusami A, Muthukumar K (2014) A review on Fenton and improvements to the
Fenton process for wastewater treatment. J Environ Chem Eng 2:557–572
250 B.M. Esteves et al.

24. Levec J, Pintar A (2007) Catalytic wet-air oxidation processes: a review. Catal Today
124:172–184
25. Malato S, Blanco J, Vidal A, Richter C (2002) Photocatalysis with solar energy at a pilot-
plant scale: an overview. Appl Catal B Environ 37:1–15
26. Scott JP, Ollis DF (1995) Integration of chemical and biological oxidation processes for water
treatment: review and recommendations. Environ Prog 14:88–103
27. Saharan VK, Pinjari DV, Gogate PR, Pandit B (2014) Advanced oxidation technologies for
wastewater treatment: an overview. Butterworth-Heinemann, Burlington, pp 141–191
28. Bowers AR, Gaddipati P, Eckenfelder WW, Monsen RM (1989) Treatment of toxic or
refractory wastewaters with hydrogen peroxide. Water Sci Technol 21:477–486
29. Garcı́a MT, Ribosa I, Guindulain T, Sánchez-Leal J, Vives-Rego J (2001) Fate and effect of
monoalkyl quaternary ammonium surfactants in the aquatic environment. Environ Pollut
111:169–175
30. Lapertot M, Pulgarı́n C, Fernández-Ibá~nez P, Maldonado MI, Pérez-Estrada L, Oller I,
Gernjak W, Malato S (2006) Enhancing biodegradability of priority substances (pesticides)
by solar photo-Fenton. Water Res 40:1086–1094
31. Bigda RJ (1995) Consider Fenton’s chemistry for wastewater treatment. Chem Eng Prog
12:62–66
32. Huang CP, Dong C, Tang Z (1993) Advanced chemical oxidation: its present role and
potential future in hazardous waste treatment. Waste Manag 13:361–377
33. Comninellis C, Kapalka A, Malato S, Parsons SA, Poulios I, Mantzavinos D (2008)
Advanced oxidation processes for water treatment: advances and trends for R&D. J Chem
Technol Biotechnol 83:769–776
34. Pera-Titus M, Garcı́a-Molina V, Ba~nos MA, Giménez J, Esplugas S (2004) Degradation of
chlorophenols by means of advanced oxidation processes: a general review. Appl Catal B
Environ 47:219–256
35. Pignatello JJ, Oliveros E, Mackay A (2006) Advanced oxidation processes for organic
contaminant destruction based on the Fenton reaction and related chemistry advanced
oxidation processes for organic contaminant destruction based on the Fenton. Crit Rev
Environ Sci Technol 36:1–84
36. Poyatos JM, Mu~ nio MM, Almecija MC, Torres JC, Hontoria E, Osorio F (2010) Advanced
oxidation processes for wastewater treatment: state of the art. Water Air Soil Pollut
205:187–204
37. Froment GF, Bischoff KB (1990) Chemical reactor analysis and design. 2nd edn. Wiley,
New York
38. Gogate PR, Pandit AB (2004) A review of imperative technologies for wastewater treatment
I: oxidation technologies at ambient conditions. Adv Environ Res 8:501–551
39. Karthikeyan S, Titus A, Gnanamani A, Mandal AB, Sekaran G (2011) Treatment of textile
wastewater by homogeneous and heterogeneous Fenton oxidation processes. Desalination
281:438–445
40. Punzi M, Mattiasson B, Jonstrup M (2012) Treatment of synthetic textile wastewater by
homogeneous and heterogeneous photo-Fenton oxidation. J Photochem Photobiol A Chem
248:30–35
41. Liotta LF, Gruttadauria M, Di Carlo G, Perrini G, Librando V (2009) Heterogeneous catalytic
degradation of phenolic substrates: catalysts activity. J Hazard Mater 162:588–606
42. Rey A, Zazo JA, Casas JA, Bahamonde A, Rodriguez JJ (2011) Influence of the structural and
surface characteristics of activated carbon on the catalytic decomposition of hydrogen
peroxide. Appl Catal A Gen 402:146–155
43. Melero JA, Martı́nez F, Botas JA, Molina R, Pariente MI (2009) Heterogeneous catalytic wet
peroxide oxidation systems for the treatment of an industrial pharmaceutical wastewater.
Water Res 43:4010–4018
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 251

44. Duarte F, Morais V, Maldonado-Hódar FJ, Madeira LM (2013) Treatment of textile effluents
by the heterogeneous Fenton process in a continuous packed-bed reactor using Fe/activated
carbon as catalyst. Chem Eng J 232:34–41
45. Fida H, Zhang G, Guo S, Naeem A (2016) Heterogeneous Fenton degradation of organic dyes
in batch and fixed bed using La-Fe montmorillonite as catalyst. J Colloid Interface Sci
490:859–868
46. Mesquita I, Matos LC, Duarte F, Maldonado-Hódar FJ, Mendes A, Madeira LM (2012)
Treatment of azo dye-containing wastewater by a Fenton-like process in a continuous
packed-bed reactor filled with activated carbon. J Hazard Mater 237–238:30–37
47. Martı́nez F, Melero JA, Botas JA, Pariente MI, Molina R (2007) Treatment of phenolic
effluents by catalytic wet hydrogen peroxide oxidation over Fe2O3/SBA-15 extruded catalyst
in a fixed-bed reactor. Ind Eng Chem Res 46:4396–4405
48. Di Luca C, Massa P, Fenoglio R, Cabello FM (2014) Improved Fe2O3/Al2O3 as heteroge-
neous Fenton catalysts for the oxidation of phenol solutions in a continuous reactor. J Chem
Technol Biotechnol 89:1121–1128
49. Botas JA, Melero JA, Martı́nez F, Pariente MI (2010) Assessment of Fe2O3/SiO2 catalysts for
the continuous treatment of phenol aqueous solutions in a fixed bed reactor. Catal Today
149:334–340
50. Pariente MI, Siles JA, Molina R, Botas JA, Melero JA, Martı́nez F (2013) Treatment of an
agrochemical wastewater by integration of heterogeneous catalytic wet hydrogen peroxide
oxidation and rotating biological contactors. Chem Eng J 226:409–415
51. Bello MM, Abdul Raman AA, Purushothaman M (2017) Applications of fluidized bed
reactors in wastewater treatment – a review of the major design and operational parameters.
J Clean Prod 141:1492–1514
52. Garcia-Segura S, Bellotindos LM, Huang Y-H, Brillas E, Lu M-C (2016) Fenton process as
alternative wastewater treatment technology – a review. J Taiwan Inst Chem Eng 67:211–225
53. Yang W-C (2003) Handbook of fluidization and fluid-particle systems. Marcel Dekker,
New York
54. Tisa F, Abdul Raman AA, Wan Daud WMA (2014) Applicability of fluidized bed reactor in
recalcitrant compound degradation through advanced oxidation processes: a review. J Envi-
ron Manag 146:260–275
55. Shih YJ, Huang RL, Huang YH (2015) Adsorptive removal of arsenic using a novel
akhtenskite coated waste goethite. J Clean Prod 87:897–905
56. Şen S, Demirer GN (2003) Anaerobic treatment of real textile wastewater with a fluidized bed
reactor. Water Res 37:1868–1878
57. Bocos E, Pérez-Álvarez D, Pazos M, Rodrı́guez-Arguelles MC, Sanromán MA (2016) Coated
nickel foam electrode for the implementation of continuous electro-Fenton treatment. J Chem
Technol Biotechnol 91:685–692
58. Li H, Priambodo R, Wang Y, Zhang H, Huang Y-H (2015) Mineralization of bisphenol A by
photo-Fenton-like process using a waste iron oxide catalyst in a three-phase fluidized bed
reactor. J Taiwan Inst Chem Eng 53:68–73
59. Briones RM, De Luna MDG, Su C-C, Lu M-C (2014) Factors affecting Fenton oxidation of
acetaminophen in a fluidized-bed reactor. J Environ Eng 140:77–83
60. Aghdasinia H, Khataee A, Sheikhi M, Takhtfiroozeha P (2017) Pilot plant fluidized-bed
reactor for degradation of basic blue 3 in heterogeneous Fenton process in the presence of
natural magnetite. Environ Prog Sustain Energy 2017:1–10
61. Chou S, Huang C, Huang YH (1999) Effect of Fe2+ on catalytic oxidation in a fluidized bed
reactor. Chemosphere 39:1997–2006
62. Lyu C, Zhou D, Wang J (2016) Removal of multi-dye wastewater by the novel integrated
adsorption and Fenton oxidation process in a fluidized bed reactor. Environ Sci Pollut Res
23:20893–20903
63. Hou L, Wang L, Royer S, Zhang H (2016) Ultrasound-assisted heterogeneous Fenton-like
degradation of tetracycline over a magnetite catalyst. J Hazard Mater 302:458–467
252 B.M. Esteves et al.

64. Aghdasinia H, Bagheri R, Vahid B, Khataee A (2016) Central composite design optimization
of pilot plant fluidized-bed heterogeneous Fenton process for degradation of an azo dye.
Environ Technol 37:2703–2712
65. Luyben WL (2007) Chemical reactor design and control. Wiley, New York
66. Esposito G, Frunzo L, Panico A, Pirozzi F (2011) Modelling the effect of the OLR and
OFMSW particle size on the performances of an anaerobic co-digestion reactor. Process
Biochem 46:557–565
67. Nielsen HB, Ahring BK (2006) Responses of the biogas process to pulses of oleate in reactors
treating mixtures of cattle and pig manure. Biotechnol Bioeng 95:95–105
68. Mu~ noz R, Kollner C, Guieysse B, Mattiasson B (2004) Photosynthetically oxygenated
salicylate biodegradation in a continuous stirred tank photobioreactor. Biotechnol Bioeng
87:797–803
69. Sponza DT, G€ ok O (2010) Effect of rhamnolipid on the aerobic removal of polyaromatic
hydrocarbons (PAHs) and COD components from petrochemical wastewater. Bioresour
Technol 101:914–924
70. Martı́nez F, Molina R, Pariente MI, Siles JA, Melero JA (2016) Low-cost Fe/SiO2 catalysts
for continuous Fenton processes. Catal Today 280:176–183
71. Queirós S, Morais V, Rodrigues CSD, Maldonado-Hódar FJ, Madeira LM (2015) Heteroge-
neous Fenton’s oxidation using Fe/ZSM-5 as catalyst in a continuous stirred tank reactor. Sep
Purif Technol 141:235–245
72. Esteves BM, Rodrigues CSD, Boaventura RAR, Maldonado-Hódar FJ, Madeira LM (2016)
Coupling of acrylic dyeing wastewater treatment by heterogeneous Fenton oxidation in a
continuous stirred tank reactor with biological degradation in a sequential batch reactor.
J Environ Manag 166:193–203
73. Zhang H, Choi H, Huang C (2006) Treatment of landfill leachate by Fenton’s reagent in a
continuous stirred tank reactor. J Hazard Mater 136:618–623
74. Ramirez JH, Duarte FM, Martins FG, Costa CA, Madeira LM (2009) Modelling of the
synthetic dye Orange II degradation using Fenton’s reagent: from batch to continuous reactor
operation. Chem Eng J 148:394–404
75. Barreto-Rodrigues M, Silva FT, Paiva TCB (2009) Optimization of Brazilian TNT industry
wastewater treatment using combined zero-valent iron and Fenton processes. J Hazard Mater
168:1065–1069
76. Hodaifa G, Ochando-Pulido JM, Rodriguez-Vives S, Martinez-Ferez A (2013) Optimization
of continuous reactor at pilot scale for olive-oil mill wastewater treatment by Fenton-like
process. Chem Eng J 220:117–124
77. Zhang H, Ran X, Wu X (2012) Electro-Fenton treatment of mature landfill leachate in a
continuous flow reactor. J Hazard Mater 241–242:259–266
78. Zhang H, Fei C, Zhang D, Tang F (2007) Degradation of 4-nitrophenol in aqueous medium
by electro-Fenton method. J Hazard Mater 145:227–232
79. Fenton HJH (1894) Oxidation of tartaric acid in presence of iron. J Chem Soc 65:899–910
80. Haber F, Weiss J (1934) The catalytic decomposition of hydrogen peroxide by iron salts. Proc
R Soc Lond A 147:332–351
81. Walling C (1975) Fenton’s reagent revisited. Acc Chem Res 8:125–131
82. Kuo WG (1992) Decolorizing dye wastewater with Fenton’s reagent. Water Res 26:881–886
83. Bautista P, Mohedano AF, Casas JA, Zazo JA, Rodriguez JJ (2008) An overview of the
application of Fenton oxidation to industrial wastewaters treatment. J Chem Technol
Biotechnol 83:1323–1338
84. Sychev AY, Isak VG (1995) Iron compounds and the mechanisms of the homogeneous
catalysis of the activation of O2 and H2O2 and of the oxidation of organic substrates. Russ
Chem Rev 64:1105–1129
85. Chu L, Wang J, Dong J, Liu H, Sun X (2012) Treatment of coking wastewater by an advanced
Fenton oxidation process using iron powder and hydrogen peroxide. Chemosphere 86:409–414
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 253

86. Lucas MS, Peres JA (2009) Removal of COD from olive mill wastewater by Fenton’s
reagent: kinetic study. J Hazard Mater 168:1253–1259
87. Rodrigues CSD, Madeira LM, Boaventura RAR (2009) Treatment of textile effluent by
chemical (Fenton’s reagent) and biological (sequencing batch reactor) oxidation. J Hazard
Mater 172:1551–1559
88. Tambosi JL, Di Domenico M, Schirmer WN, José HJ, Moreira RFPM (2006) Treatment of
paper and pulp wastewater and removal of odorous compounds by a Fenton-like process at
the pilot scale. J Chem Technol Biotechnol 81:1426–1432
89. Bautista P, Mohedano AF, Gilarranz MA, Casas JA, Rodriguez JJ (2007) Application of
Fenton oxidation to cosmetic wastewaters treatment. J Hazard Mater 143:128–134
90. Peres JA, Heredia JB, Domı́nguez JR (2004) Integrated Fenton’s reagent – coagulation/
flocculation process for the treatment of cork processing wastewaters. J Hazard Mater
107:115–121
91. Guedes A, Madeira LM, Boaventura RAR, Costa CA (2003) Fenton oxidation of cork
cooking wastewater – overall kinetic analysis. Water Res 37:3061–3069
92. Wang W, Liu Y, Li T, Zhou M (2014) Heterogeneous Fenton catalytic degradation of phenol
based on controlled release of magnetic nanoparticles. Chem Eng J 242:1–9
93. Watts RJ, Jones AP, Chen P-H, Kenny A (1997) Mineral-catalyzed Fenton-like oxidation of
sorbed chlorobenzenes. Water Environ Res 69:269–275
94. Idel-Aouad R, Valiente M, Yaacoubi A, Tanouti B, Lópz-Mesas M (2011) Rapid
decolourization and mineralization of the azo dye C.I. Acid Red 14 by heterogeneous Fenton
reaction. J Hazard Mater 186:745–750
95. EC Directive 2000/60/EC of the European parliament and of the council of October 23 (2000)
Establishing a framework for community action in the field of water policy
96. Rokhina EV, Virkutyte J (2010) Environmental application of catalytic processes: heteroge-
neous liquid phase oxidation of phenol with hydrogen peroxide. Crit Rev Environ Sci
Technol 41:125–167
97. Barroso-Bogeat A, Alexandre-Franco M, Fernández-González C, Gómez-Serrano V (2016)
Activated carbon surface chemistry: changes upon impregnation with Al(III), Fe(III) and Zn
(II)-metal oxide catalyst precursors from NO3
aqueous solutions. Arab J Chem, in press.
doi: 10.1016/j.arabjc.2016.02.018
98. Oliveira LCA, Silva CN, Yoshida MI, Lago RM (2004) The effect of H2 treatment on the
activity of activated carbon for the oxidation of organic contaminants in water and the H2O2
decomposition. Carbon N Y 42:2279–2284
99. Zazo JA, Bedia J, Fierro CM, Pliego G, Casas JA, Rodriguez JJ (2012) Highly stable Fe on
activated carbon catalysts for CWPO upon FeCl3 activation of lignin from black liquors.
Catal Today 187:115–121
100. Tatibouët JM, Guélou E, Fournier J (2005) Catalytic oxidation of phenol by hydrogen
peroxide over a pillared clay containing iron. Active species and pH effect. Top Catal
33:225–232
101. Lu M, Yao Y, Gao L, Mo D, Lin F, Lu S (2015) Continuous treatment of phenol over an
Fe2O3/γ-Al2O3 catalyst in a fixed-bed reactor. Water Air Soil Pollut 226:87
102. Liu P, He S, Wei H, Wang J, Sun C (2015) Catalytic wet peroxide oxidation of phenol over
Fe2O3/MCM-41 in a fixed bed reactor. Ind Eng Chem Res 54:130–136
103. Seyed Dorraji MS, Mirmohseni A, Carraro M, Gross S, Simone S, Tasselli F, Figoli A (2015)
Fenton-like catalytic activity of wet-spun chitosan hollow fibers loaded with Fe3O4
nanoparticles: batch and continuous flow investigations. J Mol Catal A Chem 398:353–357
104. Yan Y, Jiang S, Zhang H (2014) Efficient catalytic wet peroxide oxidation of phenol over
Fe-ZSM-5 catalyst in a fixed bed reactor. Sep Purif Technol 133:365–374
105. Zazo JA, Casas JA, Mohedano AF, Rodrı́guez JJ (2006) Catalytic wet peroxide oxidation of
phenol with a Fe/active carbon catalyst. Appl Catal B Environ 65:261–268
254 B.M. Esteves et al.

106. Chou S, Huang C, Huang Y (2001) Heterogeneous and homogeneous catalytic oxidation by
supported γ-FeOOH in a fluidized-bed reactor: kinetic approach. Environ Sci Technol
35:1247–1251
107. Achma RB, Ghorbel A, Dafinov A, Medina F (2008) Copper-supported pillared clay catalysts
for the wet hydrogen peroxide catalytic oxidation of model pollutant tyrosol. Appl Catal A
Gen 349:20–28
108. Yu Y, Wei H, Yu L, Wang W, Zhao Y, Gu B, Sun C (2016) Sewage-sludge-derived
carbonaceous materials for catalytic wet hydrogen peroxide oxidation of m-cresol in batch
and continuous reactors. Environ Technol 37:153–162
109. Guo J, Al-Dahhan M (2003) Catalytic wet oxidation of phenol by hydrogen peroxide over
pillared clay catalyst. Ind Eng Chem Res 42:2450–2460
110. Jung YS, Lim WT, Park J, Kim Y (2009) Effect of pH on Fenton and Fenton-like oxidation.
Environ Technol 30:183–190
111. Ramirez JH, Lampinen M, Vicente MA, Madeira LM (2008) Experimental design to opti-
mize the oxidation of Orange II dye solution using a clay-based Fenton-like catalyst. Ind Eng
Chem Res 47:284–294
112. Catrinescu C, Teodosiu C, Macoveanu M (2003) Catalytic wet peroxide oxidation of phenol
over Fe-exchanged pillared beidellite catalytic wet peroxide oxidation of phenol over
Fe-exchanged pillared beidellite. Water Res 37:1154–1160
113. Chi GT, Churchley J, Huddersman KD (2013) Pilot-scale removal of trace steroid hormones
and pharmaceuticals and personal care products from municipal wastewater using a hetero-
geneous Fenton’s catalytic process. Int J Chem Eng 2013:1–10
114. Kuznetsova EV, Savinov EN, Vostrikova LA, Parmon VN (2004) Heterogeneous catalysis in
the Fenton-type system FeZSM-5/H2O2. Appl Catal B Environ 51:165–170
115. Muruganandham M, Suri RPS, Jafari S, Sillanpää M, Lee G-J, Wu JJ, Swaminathan M (2014)
Recent developments in homogeneous advanced oxidation processes for water and waste-
water treatment. Int J Photoenergy 1:1–21
116. Ramirez JH, Maldonado-Hódar FJ, Pérez-Cadenas AF, Moreno-Castilla C, Costa CA,
Madeira LM (2007) Azo-dye Orange II degradation by heterogeneous Fenton-like reaction
using carbon-Fe catalysts. Appl Catal B 75:312–323
117. Duarte F, Maldonado-Hódar FJ, Madeira LM (2013) Influence of the iron precursor in the
preparation of heterogeneous Fe/activated carbon Fenton-like catalysts. Appl Catal A Gen
458:39–47
118. Rache ML, Garcı́a AR, Zea HR, Silva AMT, Madeira LM, Ramirez JH (2014) Azo-dye
orange II degradation by the heterogeneous Fenton-like process using a zeolite Y-Fe catalyst
– kinetics with a model based on the Fermi’s equation. Appl Catal B Environ 146:192–200
119. Rodrigues CSD, Boaventura RAR, Madeira LM (2014) Technical and economic feasibility of
polyester dyeing wastewater treatment by coagulation/flocculation and Fenton’s oxidation.
Environ Technol 35:1307–1319
120. Lin SH, Lo CC (1997) Fenton process for treatment of desizing wastewater. Water Res
31:2050–2056
121. Ito K, Jian W, Nishijima W, Baes AU, Shoto E, Okada M (1998) Comparison of ozonation
and AOPs combined with biodegradation for removal of thm precursors in treated sewage
effluents. Water Sci Technol 38:179–186
122. Nieto LM, Hodaifa G, Rodriguez S, Giménez JA, Ochando J (2011) Degradation of organic
matter in olive-oil mill wastewater through homogeneous Fenton-like reaction. Chem Eng J
173:503–510
123. Ramirez JH, Costa CA, Madeira LM (2005) Experimental design to optimize the degradation
of the synthetic dye Orange II using Fenton’s reagent. Catal Today 107–108:68–76
124. Rodrı́guez A, Ovejero G, Sotelo JL, Mestanza M, Garcı́a J (2010) Heterogeneous Fenton
catalyst supports screening for mono azo dye degradation in contaminated wastewaters. Ind
Eng Chem Res 49:498–505
Wastewater Treatment by Heterogeneous Fenton-Like Processes in Continuous. . . 255

125. Duarte F, Maldonado-Hódar FJ, Madeira LM (2012) Influence of the particle size of activated
carbons on their performance as Fe supports for developing Fenton-like catalysts. Ind Eng
Chem Res 51:9218–9226
126. Navalon S, Alvaro M, Garcia H (2010) Heterogeneous Fenton catalysts based on clays, silicas
and zeolites. Appl Catal B Environ 99:1–26
127. Figueiredo JL, Pereira MFR, Freitas MMA, Órf~ao JJM (1999) Modification of the surface
chemistry of activated carbons. Carbon 37:1379–1389
128. Yao Y, Wang L, Sun L, Zhu S, Huang Z, Mao Y, Lu W, Chen W (2013) Efficient removal of
dyes using heterogeneous Fenton catalysts based on activated carbon fibers with enhanced
activity. Chem Eng Sci 101:424–431
Disinfection by Chemical Oxidation
Methods

Luis-Alejandro Galeano, Milena Guerrero-Flórez,

Claudia-Andrea Sánchez, Antonio Gil, and Miguel-Ángel Vicente
Abstract Poor quality in drinking water is primary cause of pathogen transmission
and responsible of varied infectious diseases. Methods of water treatment for human
consumption must pay special attention on microbiological safe disinfection. Indeed,
from the past few years laws all around the world have included new, more stringent
water quality parameters. Chlorination and other mainly used conventional disin-
fection processes usually do not achieve full inactivation of all microorganisms
present in real water supplies, whereas the presence of even low concentrations of
organic matter can lead to form harmful disinfection by-products. Protozoan para-
sites Giardia sp. and Cryptosporidium sp. are some of the microorganisms that
cannot be completely inactivated via chlorination under the same contact times
typical of bacteria or virus elimination. It has increased toxicological and microbi-
ological risks as well as operational costs. Disinfection by the advanced oxidation
process more intensively studied in the past few years has been reviewed including

L.-A. Galeano (*) and Claudia-Andrea Sánchez

Grupo de Investigación en Materiales Funcionales y Catálisis (GIMFC), Departamento de
Quı́mica, Facultad de Ciencias Exactas y Naturales, Universidad de Nari~no, Pasto-Nari~
no,
Colombia
e-mail: [email protected]; [email protected]
M. Guerrero-Flórez
Grupo de Investigación en Materiales Funcionales y Catálisis (GIMFC), Departamento de
Quı́mica, Facultad de Ciencias Exactas y Naturales, Universidad de Nari~no, Pasto-Nari~
no,
Colombia
Present Address: Universidad Nacional de Colombia, Bogotá, DC, Colombia
e-mail: [email protected]
A. Gil
Departamento de Quı́mica Aplicada, Edificio de los Acebos, Universidad Pública de Navarra,
Pamplona, Spain
e-mail: [email protected]
Miguel-Ángel Vicente
GIR-QUESCAT, Departamento de Quı́mica Inorgánica, Universidad de Salamanca,
Salamanca, Spain
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 257
Water Treatment, Hdb Env Chem (2019) 67: 257–296, DOI 10.1007/698_2017_179,
© Springer International Publishing AG 2017, Published online: 9 December 2017
258 L.-A. Galeano et al.

Fenton and photo-Fenton processes and photocatalytic and electro-catalytic variants;

this vibrant topic still remains partially uncovered in the available scientific back-
ground, which has motivated many recent researches and publications. This chapter
is then devoted to briefly review the most recent reports studying the disinfecting
potential displayed by mentioned AOPs with respect to widely and currently used
conventional techniques. Revision of the inactivation of water-borne pathogens
including E. coli, total coliforms, parasites as Giardia and Cryptosporidium, and
virus such as coliphages has focused on advantages and disadvantages in application
of every particular AOP, their disinfecting mechanisms, and the main parameters
affecting the disinfection response.

Keywords Advanced oxidation processes, Chemical oxidation, Disinfection,

Drinking water, Oxidative stress, Water microbiology

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
2 Some General Issues About Pathogens and Resistance to Water Disinfection . . . . . . . . . . . 260
3 Disinfection Methods More Widely Used in Production of Drinking Water . . . . . . . . . . . . . 264
3.1 Chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
3.2 Ozone (O3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
3.3 Hydrogen Peroxide (H2O2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
4 Advanced Oxidation Processes: AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
4.1 Disinfecting Potential of AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
4.2 Fenton Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
4.3 Photo-Fenton Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
4.4 Heterogeneous TiO2 Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
4.5 Electrochemical Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285

Abbreviations

AOPs Advanced oxidation processes

BDD electrode Boron-doped diamond electrode
CoA Coenzyme A
COWPs Cryptosporidium oocyst wall proteins
CWPO Catalytic wet peroxide oxidation
DBP-Cl Chlorinated DBP
DBP-N Nitrogenated DBP
DBPs Disinfection by-products
DNA Deoxyribonucleic acid
DOC Dissolved organic carbon
EPS Exopolysaccharide
GalNAc β-1,3-linked N-acetylgalactosamine
Disinfection by Chemical Oxidation Methods 259

HAAs Haloacetic acids

IEP Isoelectric point
IR Infrared radiation
LPS Lipopolysaccharide
NOM Natural organic matter
PG Peptidoglycan
PRE Photoreactivation enzyme
RCS Reactive chlorine species
RNA Ribonucleic acid
ROS Reactive oxygen species
RPA Replication protein A
SEM Scanning electron microscopy
SOD Superoxide dismutase
SODIS Simulated solar disinfection
STP Sewage treatment plants
TEM Transmission electron microscopy
THMs Trihalomethanes
UPEC E. coli with uropathogenic characteristics
UV Ultraviolet radiation
VGs Virulence genes

1 Introduction

Water is one of the most important natural resources for human beings and ecosys-
tems. However, such a valuable resource is undergoing constant spoilage caused by
the sustained growth of population and wastes in both industry and agriculture, as
main factors responsible of the contamination exerted on the aquatic environments
[1, 2]. Entities in charge for the surveillance and protection of the environment,
social development, and health care are imposing regulations more and more strin-
gent in order to achieve extended and deeper water purification [3, 4].
Currently, one of the most significant challenges is water production with
optimal parameters of quality for human consumption. Its availability would be at
the same time a strong contribution to reduce spreading diseases related to envi-
ronmental factors. Water disinfection is a critical process for protection of public
health; either pathogen’s inactivation or elimination plays a key role on water’s
quality [5–10]. Some pathogens often transmitted by water are displayed in Table 1.
Safe disinfection of water supplies is so much important that the employment of
high-performance, top efficient methods should always be completely guaranteed.
Therefore, we share a brief revision about microbial resistance and disinfecting
potential of some chemical oxidation methods, mainly focused in AOPs, as tech-
nological alternatives currently available to achieve safer water disinfection than
traditional methods.
260 L.-A. Galeano et al.

Table 1 Pathogens commonly transmitted by water [11–13]

Bacteria Campylobacter spp., E. coli, Leptospira spp., Salmonella spp., Shigella spp., Vibrio
cholerae, Yersinia enterocolitica
Protozoa Balantidium coli, Cryptosporidium parvum, Cyclospora cayetanensis, Entamoeba
histolytica, Giardia intestinalis, Toxoplasma gondii
Virus Adenovirus, enterovirus, hepatitis virus A, hepatitis virus E, norovirus, sapovirus,
rotavirus
Helminths Ascaris lumbricoides, Enterobius vermicularis, Fasciola hepatica, Hymenolepis
nana, Taenia saginata, Taenia solium, Trichuris trichiura

2 Some General Issues About Pathogens and Resistance

to Water Disinfection

Effectiveness of any disinfectant depends on several properties of targeted water

like pH, temperature, presence of suspended particles, and chemical composition
(loading of natural organic material, agricultural and industrial chemicals). The
direct biocidal action depends on the CT value, parameter calculated as the product
of disinfectant concentration and contact time, specific for each microorganism and
disinfectant [14].
Disinfectants as chlorine can form reactive chlorine species (RCS) and reactive
oxygen species (ROS) which can cause oxidation of proteins, lipids, and nucleic
acids. In the last one either, changes in A, T, C, G, or U nitrogenous bases, breakup
of the phosphodiester bond between nucleotide chains of DNA and RNA, and
cross-linking with other molecules lead to formation of pyrimidine dimers, changes
in tridimensional structure, alteration of DNA replication process, and consequent
death as main effects on cells [11, 15, 16].
Oxidative damages accumulated in molecules as RNA can affect protein synthe-
sis and may generate lack of cultivability in vitro [16]. RNA repair is a mechanism
not well understood because it is considered that damaged RNA is degraded rather
than repaired [17]. RNA is more susceptible to oxidative damage by exposure to UV
than DNA; besides, both nucleic acids can suffer damage at the same rate [16].
In cytoplasm of eukaryotic cells, the natural formation of ROS and the important
role of enzymes superoxide dismutase (SOD), peroxidase, and catalase to keep the
balance inducing detoxification are well established. When the normal concentra-
tion of ROS in cells increases, it leads to toxic effect in response to accumulation of
reactive species; cell may lack functions, viability, and integrity, eventually causing
death [16, 18].
Microorganisms have biochemical and structural differences. The cell wall is a
complex multilayered structure based on variety of proteins, lipids, and polysac-
charides protecting the microorganism from environmental conditions [19]. Gram-
positive bacteria are surrounded by cell walls composed by PG (peptidoglycan)
and teichoic and lipoteichoic acids, whereas Gram-negative bacteria contain a thin
PG cell wall, which itself is surrounded by an outer membrane formed by lipo-
polysaccharide (LPS). Fungus cell walls instead of PG are composed by chitin,
Disinfection by Chemical Oxidation Methods 261

glucans, and proteins. Plasma membrane differs from most subcellular membranes
because high fractions of sterols, sphingolipids, and glycerophospholipids form
lipid rafts clusters into liquid-ordered domains instead of giving rise to homoge-
neous mixtures of glycerophospholipids mainly associated with proteins (e.g.,
acylated and glycosylphosphatidylinositol [GPI]-anchored proteins) [20]. Bacteria
can generate new structural macromolecules to resist hostile disinfection condi-
tions, but in fungus this process may also involve more virulence [21].
In bacteria, several mechanisms of resistance to biocides can be devised:
(1) decreasing biocide penetration (e.g., changing membrane’s composition and
porin regulation), (2) depleting intracellular biocide concentration (e.g., either
expression of efflux pumps or activation of detoxifying enzymes SOD or catalase)
[22], (3) changing metabolic pathways [23], and (4) DNA repair mechanisms [24]
helped by lyases. Other worth mentioning include EPS (exopolysaccharide) pro-
duction and cell aggregation, which allow to decrease the concentration of dispos-
able biocides and cell protection, respectively, important factors in bacterial biofilm
resistance [25].
The disinfecting potential of AOPs to produce drinking water of course should
consider the resistance mechanisms, survival potential, environmental resilience, as
well as profiles of genetic variability and distribution of microorganisms through
the water resources. Currently, these are responsible of treatment troubles and
derived risks for public health; parasites as Cryptosporidium parvum and Giardia
lamblia have developed new virulence profiles and new genotypes [26]. In the other
hand, there are also viruses capable to infect new hosts and to change their own
genomic configuration to generate new types, variants, and viral strains with high
virulence power.
The genomic variations and mechanisms of DNA repair can lead to reactivation
or regrowth of the microorganisms and subsequent low efficiency of any disinfecting
treatment. Currently there are new approaches attempting to explain the cell and
molecular response allowing some water-borne pathogens to resist mainly the UV
radiation and Fenton process [27–30].
Oocysts of Cryptosporidium have shown strong resistance to conventional chlo-
rination treatments, since they require disinfectant doses and contact times near to
four orders of magnitude higher than the ones typically used for bacteria and virus
inactivation [14, 31]. The resistance obeys in part to the outer wall, a common
structure in Apicomplexan parasites that produce environmentally stable oocysts.
The accurate erection of the oocyst’s wall and the mechanisms regulating the
process remain unclear. Cryptosporidium oocyst wall proteins (COWPs) are an
integral part of this structure, encoded by at least nine genes [32]. This composition
is related with a major resistance and survival, but other mechanisms of genomic
remodeling and response to DNA damage can be also implicated. Meanwhile, the
DNA replication machinery of C. parvum includes two unique replication protein A
(RPA) heterotrimeric complexes, expressed differentially during the parasite life
cycle in response to DNA damage [32]. This response may occur via resistance to
water disinfectants, since it has been related with response to stressing environmen-
tal conditions.
262 L.-A. Galeano et al.

Determining the changes in the gene expression profile of oocysts in response to

ultraviolet (UV) irradiation may help to understand how the parasite responds to
stress, of course with more practical relevance to UV exposure encountered in
external environment as well as UV irradiation commonly used to treat drinking
and surface waters [33]. Oocysts of Cryptosporidium exposed to UV radiation
(UV254) have shown complex and dynamic regulations in gene expression, activa-
tion of DNA repair, and intracellular trafficking mechanisms. In response to long-
time UV exposure (5 h), high activities of genes coding for protein degradation,
amino acid recycling, proteasome, ubiquitin-associated genes, and encoding hypo-
thetical or membrane proteins have been found to be displayed. Among the stress-
related genes, TCP-1 family members and some thioredoxin-associated genes
appear to play important roles in the recovery of UV-induced damages. There are
more than 1,924 genes positively expressed in oocysts after exposition to environ-
mental stress conditions, representing near 51% of the genes in C. parvum genome
[33]: 1,048 hypothetical genes with undefined functions (vs. 876 functional anno-
tated ones), actively expressed at different levels in the oocysts (e.g., cgd3_1570,
unknown, possible sporozoite antigen) and proteins containing apicomplexan-
specific domains (e.g., cgd2_200), or predicted membrane proteins (e.g.,
cgd6_780). Transcriptomic analyses have shown that CpArray15K could be used
both to study profiling of gene expression parasite oocysts as to explain responses to
UV irradiation [34]. Future research on these genes may help to elucidate their
functional roles in survival and stress resistance by parasite oocysts in the environ-
ment [33]. The effect and oxidation mechanisms on Cryptosporidium oocyst by
AOPs are still unclear.
In the case of Giardia, the host is protected outside against hypotonic lysis in the
environment by a hard cyst wall (60% carbohydrate plus 40% protein) [35]. Whereas
the walls of plants and fungi contain several sugar homopolymers (cellulose, chitin,
and β-1,3-glucans) along with dozens of proteins, the cyst wall of Giardia contains
an homopolymer of β-1,3-linked N-acetylgalactosamine (GalNAc) and at least three
cyst wall proteins (CWPs), each one composed by Leu-rich repeats and a C-terminal
Cys-rich region [36]. Then, the efficient disinfection of this parasite depends at least
in part to excystation state; during this process the fibrils of GalNAc homopolymer
and how deproteinated fibrils of GalNAc homopolymer are degraded for Giardia
cysts but not trophozoites are important. The behavior showed during excystation,
host, and Giardia proteases appear to degrade bound CWPs, exposing GalNAc
homopolymer fibrils, digested by a stage-specific glycohydrolase. In contrast, cyst
walls of Giardia treated with hot alkali to deproteinate fibrils of the GalNAc
homopolymer were thick (~1.2 μm), resistant to sonication, and permeable
[37]. These findings about a new curled fiber and lectin model of the intact Giardia
cyst wall protease and glycohydrolase model of excystation have contributed to
understand how this parasite can resist to disinfection processes and should be
carefully taken into account for future research in this field.
The regrowth of bacteria after treatment by AOPs has been reported, which has
suggested one or more possible mechanisms there involved [38–41]. Studying
various stages of sewage treatment plants (STPs), numerous virulence genes
Disinfection by Chemical Oxidation Methods 263

(VGs), resistant genes, and phylogenetic groups responsible of E. coli strain survival
have been established. When used separately either UV radiation or chlorination as
disinfecting treatment, E. coli strains carrying VGs showed better survivability
against UV treatment than chlorination [42–44]. When both disinfection methods
were combined, greater elimination efficiency of E. coli with uropathogenic char-
acteristics (UPEC) was achieved, preventing then pathogenic E. coli strains to be
released into the environment from STPs.
UV irradiation has shown to be less effective against fecal coliforms like E. coli
with capacity to repair their UV damages for both photoreactivation or light-free
mechanisms (dark repair) [27, 45–48]. In photoreactivation, a complex is formed
between the photoreactivation enzyme (PRE) and the nucleotide dimer to be
repaired followed by prereleasing and the DNA repairing; DNA repair enzymes
photo-lyases participate in the process. This process depends on the light source
(visible, IR, UV) between 380 and 480 nm in the visible spectrum and the radiant
intensity. On the other hand, the light-independent, bacterial dark repair is governed
by expression of recA protein which allows to identify damaged DNA to form
repairing complex, cleavage and elimination of defective DNA strand, filling by
polymerization of new nucleotides (by the DNA polymerase), and final binding by
corresponding ligase [38]. Other mechanism involved in disinfection resistance of
bacteria is the capacity to use and share the genetic material with other microor-
ganisms previously inactivated, as a new tool to take and recombine DNA and even
also as new source of energy to survive [16].
In studies of virus disinfection performed between the 1960s and the 1980s,
scientists used scintillation spectroscopy and electron microscopy techniques to
detect modifications in viral genomes and proteins, concluding that the virus inac-
tivation is the result of either protein damages or genome damages [49–52]. Nowa-
days, the study of the physical/chemical inactivation of virus has become simpler
than 10 years ago thanks to cornerstone advances in genomic, sequencing, protein
mass spectrometry and structural virology techniques [53]. The structure and com-
position of a virus is capable to elucidate the damage or injury by disinfection
process, but it is not enough to understand and predict the mechanism of inactivation
[11, 54].
The effect that genetic modification has on viral functions (e.g., host cell binding,
genome entry, etc.) has improved the fundamental understanding of biological
functionality of viral domains, virus-host cell interactions, virus assembly, capsid-
RNA interaction sites, and RNA release. This knowledge could also provide valu-
able insight into critical structures and biological functions that should be targeted in
virus neutralization or inactivation strategies [53].
In drinking water production, the biological safety offered by any disinfection
method and topics related with control in a context of global climate change are
fully relevant. It is also necessary to improve the surveillance on potential muta-
genicity related with either microbial regrowth or reactivation as well as potential
formation of DBPs because of the biological risk that may impose high costs on
human and animal health [55].
264 L.-A. Galeano et al.

3 Disinfection Methods More Widely Used in Production

of Drinking Water

Conventional methods for water disinfection can be divided into two categories:
physical and chemical [56, 57]. In the first case, heat and pasteurization are widely
used in household disinfection, as well as UV lamps emitting radiation at 254 nm, but
microbes differ in sensitivity to inactivation with heat and UV irradiation; in general,
heat has been established to be more effective against vegetative bacteria [13].
Chemical disinfection has been made by using oxidizing agents relatively stable
such as chlorine and its derivatives: molecular chlorine (Cl2), hypochlorite (ClO
),
monochloramine (NH2Cl), and chlorine dioxide (ClO2) with remarkable toxicity
disadvantages and formation of DBP-N and DBP-Cl [58]. Hydrogen peroxide
(H2O2) with recognized biocide effect [18], ozone (O3), as the second more
frequently used method of disinfection only after chlorination, and other agents
occasionally used are potassium permanganate (KMnO4), bromine, and iodine and
their derivatives [59, 60].

3.1 Chlorine

Chlorination features many practical advantages like simple application, high effi-
ciency, and low cost. However, its efficiency also depends on the type of microor-
ganism to be inactivated [61, 62] and a specific CT value for virus, bacteria, and
protozoa [14]. A free chlorine concentration ranging 0.1 mg/L has been estimated
to be required for inactivation of bacteria, 1.0 mg/L for virus (poliovirus 1), and
5.0 mg/L for parasites (Giardia sp. and Entamoeba histolytica) during contact times
of 0.4, 1.7, and 18 min, respectively [14]. The microbiocide effect occurs when
chlorine contacts with the pathogen’s surface; it reacts causing oxidation of lipids in
membrane changing its permeability, destabilizing the cytoplasm, inhibiting the
enzymatic activity, and causing irreversible damage at the level of the nucleic acids.
After water treatment and before the drinking water distribution systems, a
residual concentration of free chlorine is required to be dosed in order to or
minimize the risk of regrowth and formation of biofilms in the distribution pipes.
Evidences about subsequent profiles of bacterial regrowth and bacterial communi-
ties’ structure after chlorine disinfection along with using new generation sequenc-
ing technologies have allowed to realize that most chlorine-tolerant bacterial
groups belong to orders Sphingomonadales and Rizhobiales, previously reported
as inducers of biofilm formation [63]. Biofilms represent a serious problem for
water quality affecting efficiency and costs in disinfection by chlorine units, both in
pipes and distribution networks [58].
A disadvantage derived of disinfection only based in chlorine is the ability to
react with the organic matter present in most natural surface waters, conducting to
formation of halogenated, highly toxic, and hazardous disinfection by-products
Disinfection by Chemical Oxidation Methods 265

(DBPs). Increased dosages or time of contacts with chlorine used in disinfection

processes also conduces to higher potentials of formation of toxic trihalomethanes
(THMs), halo-acetic acids (HAAs), and some other emergent halogenated nitrog-
enous by-products DBPs-N, which represent till 100 times more carcinogenic risk
compared to typical chlorinated by-products of public health importance
[64]. Sequencing analysis of antibiotic resistance genes in assay of bacteria expo-
sure to different N-DBPs has shown mutagenicity of both Pseudomonas aeruginosa
PAO1 and E. coli, representing important genotoxicologic and epidemiologic risks
through treated water [55].
DBPs have cytotoxic, genotoxic, apoptotic, and even carcinogenic effects even
under very low concentrations [64, 65]. They could affect either the central nervous
system or the kidney and liver functions in humans and animals, seriously threat-
ening public health [2, 66–68]. Despite its limited efficiency to inactivate parasites
as Cryptosporidium spp., and the potential formation of toxic by-products, chlori-
nation for production of drinking water is currently accepted and widely used all
around the world [11, 69]. Since the potential toxic risk on both humans and
animal’s health derived from the use of chlorine in water facilities it has been
recently and extensively discussed in both, academic and industrial scenarios, as it
has motivated the exploration on novel technological approaches too. They must be
at least as cost-effective but safer than chlorination to decrease its use or even
substitute it completely in the mid-/long-term.

3.2 Ozone (O3)

Ozone displays high oxidation potential to decompose organic and inorganic con-
taminants, as well as also to inactivate microorganisms [67, 70, 71]. It displays a
stronger bactericidal effect than chlorine-derived agents, performs efficiently at low
concentrations, and eliminates a greater number of pathogens, including viruses,
cysts, and protozoa. One of the main species responsible for such an effect is the
hydroxyl radical (HO•), strongly oxidizing intermediate generated through the
ozonation process, that may destroy enzymes and coenzymes needed for the life
and survival of the microorganisms present in water [2, 59, 67]. Since ozone is highly
unstable, it cannot be either transported or stored in big amounts, and for practical
purposes it is produced in situ [2, 57, 59]. Production of large amounts (let’s say in
the scale of kg/h) requires the use of specialized equipment that involves expensive
operation making it difficult to be implemented at big scales [5, 11]. Other consid-
erations that must be kept in mind are both the high rate of reaction and no residual
effect; then, combined use with other oxidizing residual agents should be considered
in order to keep controlled regrowth of the pathogens along prolonged times [2, 57,
71]. A general disadvantage of ozonation is the similar behavior to chlorine once
266 L.-A. Galeano et al.

in contact with bromides, aldehydes, and ketones present in water; brominated

compounds, oxides, peroxides, and cyanides are some by-products that may be
formed, also displaying toxic and other undesired effects for humans and animals
[11, 55, 72, 73].

3.3 Hydrogen Peroxide (H2O2)

Hydrogen peroxide is extensively used as a biocide, mainly in applications where

its decomposition into nontoxic by-products is important [18]. Along with its high
disinfecting efficiency, there is still little understanding about its biocidal mecha-
nism. Hydrogen peroxide displays higher oxidizing power in comparison with
chlorine and slightly below than ozone. It can inactivate bacteria (Escherichia
coli and Salmonella spp.), bacterial spores (Bacillus anthracis, Bacillus subtilis,
and Geobacillus stearothermophilus) [74, 75], fungus (Histoplasma capsulatum,
Blastomyces dermatitidis, and Coccidioides immitis) [76, 77], viruses like bacteri-
ophage MS2 [78], and even prions [79].
In disinfection with H2O2, the cytotoxic effect has not been ascribed to the
oxidizing properties of the molecular form but to oxidizing stress caused by the
hydroxyl radicals (HO•), singlet oxygen (O2*), and superoxide species (O2
•)
coming from its natural decomposition. These species may attack a wide variety
of organic compounds as lipids, membrane proteins, and nucleic acids of cells
[74, 80]. The temperature can promote the diffusion of the hydrogen peroxide
through the cell’s membrane; once inside, it can generate reactive species of oxygen
like the hydroperoxyl and the hydroxyl radicals, which react more easily at high
temperature with a wide spectrum of organic molecules with its subsequent signif-
icant oxidative stress [61].
The effect of the pH on the bactericidal action has been also documented; H2O2
activity does not vary significantly against pH within a range of 2.0–10.0 [61, 81],
whereas other authors have mentioned that its action is higher under acidic condi-
tions [82]. Raffellini et al. [83] found the most efficient conditions to inactivate
E. coli under increased temperature and concentration together with low pH: perox-
ide concentrations close to 3.00% w/v and pH 3.0 at 25  C depleted in 5-log the
concentration of E. coli in 1–9 min of reaction. Meanwhile, Labas et al. [77] found
low levels of E. coli inactivation at pH 7.0, T ¼ 20  C, H2O2 concentrations of
15–300 mg/L, and prolonged times of exposure in comparison with other disinfec-
tion technologies. As advantage, hydrogen peroxide has associated low risk by
formation of toxic DBPs; standard side products of decomposition of any remaining
concentration once the oxidizing treatment is finished are just water and oxygen;
thus, it has been widely employed for disinfection of foods, fruits, vegetables, and
food processing equipment [74, 84]. However, its use in disinfection of surface
streams for drinking water production is more rather scarce and not extended.
Disinfection by Chemical Oxidation Methods 267

4 Advanced Oxidation Processes: AOPs

These modern technologies offer a cost-effective and high-performing response to

the challenges imposed by the current high levels of contamination in water, the
problems of public health related with the consumption of unclean water, and the
current laws on drinking water quality [9, 85–90]. AOPs could improve the systems
of treatment producing drinking water [91–94].
AOPs are a set of methods taking advantage on the high oxidizing power of the
HO• radical that basically differ one to each other in the way used to generate it
[95, 96]. Several combinations of methods to produce hydroxyl radicals have been
investigated: for example, O3/H2O2, O3/UV, catalytic peroxidation assisted by
Fenton catalysts, photocatalytic activation by semiconductors (mostly TiO2),
water sonolysis, sono-photocatalytic activation, catalytic wet peroxide oxidation
(CWPO or CWHPO), and combinations of them [57, 97–99].
The hydroxyl radicals produced by the AOPs are capable to mineralize a wide
variety of organic compounds to CO2, water, and inorganic ions, without significant
limitations exerted by concentration or phase change [86, 87, 100], whereas a high
fraction of microorganisms could be also inactivated as outstanding advantage. The
HO• radical is a ROS, and it enables processes more thermodynamically favored as
well as rates of oxidation pretty higher in comparison with most of the other known
oxidizing methods or species. They may react 102 to 103 times faster than alterna-
tive oxidizers like ozone [5, 101]. The AOPs may release significantly lower charge
of toxic DBPs in comparison with other disinfection methodologies, if some at all;
in addition, they frequently enhance organoleptic features of the so-treated waters
and show quite low selectivity in the degradation of wide variety of organic
compounds [62, 89, 100], as extensively reviewed elsewhere [91].

4.1 Disinfecting Potential of AOPs

Disinfection by AOPs has suggested high inactivation potential against a wide range
of microorganisms like spore-forming bacteria, yeasts, fungus, protozoa, and virus,
which relies primarily on the formation of ROS including singlet oxygen, triplet
oxygen, anion-radical superoxide (O2
•), hydroxyl radical (HO•), hydroperoxyl
radical (HO2•), and hydrogen peroxide itself. Altogether they may exert a toxic
effect and loss of structural integrity on such microorganisms affecting their viability
and survival [9, 11, 15, 30, 69, 74]. The mechanism of action of each ROS on every
type of microorganism is not still completely established, and it remains being an
enthusiastic seed of emerging investigations [2, 102].
The damage on microorganisms attributed to the oxidative stress caused by ROS
can take place when their concentrations are high enough to exceed the defense
capacity of the cell. ROS species like hydroxyl radical feature short half-live times.
In bacteria once got this barrier over, the components of the cell’s membrane are
268 L.-A. Galeano et al.

attacked by peroxidation of the lipid chains, oxidation of polyunsaturated fat acids

and proteins, in turn increasing the membrane’s permeability and altering the
transmembrane gradients of concentration, essential to preserve the equilibrium
and appropriate function of the cell. The long-lived endogenous ROS like the H2O2
may straightforwardly damage the cell or penetrate it giving rise to other ROS; it
may primarily lead to attack on the nucleic acids by either modifying nucleic bases
and breaking of the DNA’s double helix or simply activating cell injury processes
[9, 15, 61, 80, 86, 90, 95, 102].
The time of exposure with microorganisms may vary according with the condi-
tions of reaction of every AOP and its characteristic rate of ROS formation. During
the oxidation reaction, the microorganisms can activate their mechanisms of
defense before they truly undergo oxidative stress [103]; cells may then die by
accumulation of several damages [90, 95].
Regarding toxicity of the HO• radicals, Storz et al. [104] found that such radicals
might produce chemical modifications on the nitrogenous bases and breaks on the
DNA chains of Salmonella typhimurium; a little bit latter, Anzai et al. [105]
determined that hydroxyl radicals attack lipids of the cell’s membrane leading to
oxidative degradation. More recently, according to Spuhler et al. [90], Flores et al.
[84], and Pablos et al. [2], the action of the HO• radicals on the cell’s components is
complete and irreversible, with the pathogens unable to recover its viability.
However, the microbial resistance against an AOP treatment may sharply vary
depending on the structure and particular chemical composition of every microor-
ganism [106–108].
The kinetics of the microbial inactivation has been mostly studied by using spiked
distilled water in order to avoid the interference of ions and organic compounds
during the oxidation process. But it is still required elucidation of the mechanism of
action exerted by the AOP under real conditions, since the dissolved ionic species
often available in real aqueous influents may significantly affect the concentrations
of Ca2+ and Mg2+ between the inside and outside of the cell. It would lead to stressful
conditions of inner osmotic pressure and, then, weakening of the cell’s wall followed
by higher susceptibility to the action of the AOP [109].
Rubio et al. [96] compared the efficiency of photo-Fenton and H2O2/UV254 AOPs
in the elimination of E. coli by using three types of water. They found a rate of
bacterial inactivation in the next order as a function of the water matrix: Milli-Q
water > Leman lake water > artificial sea water. The evolution is probably due to
presence of organic material and inorganic ions such as chlorides, fluorides, sulfates,
phosphates, bromides, and bicarbonates, which may compete against hydrogen
peroxide for the binding sites on the cell’s membrane, react with the HO• radicals,
or generate other compounds making difficult the pass of light inside the water or
preventing microorganisms against the attack of ROS generated during treatment
with AOPs. Assessment of AOP’s disinfection power on real drinking water facilities
should be primarily made on the effluent of conventional physicochemical treat-
ments (coagulation-flocculation), as the much suitable stream; it might enable easier
recording of the inactivation process and the microbial elimination but also because
Disinfection by Chemical Oxidation Methods 269

this combined and sequential set of treatments – physicochemical followed by AOP –

should be more favorable than any single one.
Compared with the potential of the AOPs in the abatement of organic matter and
other highly refractory pollutants, the microbiological disinfection remains a field
more rather scarcely explored. The photocatalytic approaches have been the most
studied AOPs in microbial inactivation, but some other studies focused in simulta-
neously elucidating microorganisms inactivation and organic matter elimination
are still strongly necessary. Thus, from now on a brief description of AOPs studied
in the inactivation of microorganisms is displayed.

4.2 Fenton Process

This is a cheap and effective homogeneous catalytic system, where ROS are
produced by interaction of H2O2 and dissolved salts of Cu2+ or more often Fe2+.
In this case, the decomposition of peroxide mostly to hydroxyl and hydroperoxyl
radicals happens very fast, thanks to the catalyzed homolytic breakdown of the
peroxide bond by the dissolved metal ions in homogeneous phase [80, 84,
91]. Hence, the overall disinfecting efficiency displayed by the Fenton process
will depend on the rate of ROS generation but in turn also on the rate of reaction
between the catalyzing metal ion and the hydrogen peroxide [11]. Besides to action
of ROS, disinfection may occur by direct chemical and physical interactions
between the reagents and microorganisms, where the straightforward attack of
H2O2 is probably the most significant [110]. Microorganisms like E. coli may retain
iron into the periplasmic space but also in the intracellular spaces that allow either
Fe complexes or Fe-storing proteins to form. Once inside, iron may react with
peroxide molecules to carry out what could be so-called intracellular Fenton
process [88, 90, 111]. Since the Fe3+ formed in the very first step of reaction is
rapidly back-converted to Fe2+ in the second stage, a cyclic, sustained transforma-
tion of iron between Fe2+ and Fe3+ is verified throughout the Fenton process that in
turn enable continuous production of ROS [reactions (1) and (2)] [112]:

Fe2þ þ H2 O2 ! Fe3þ þ HO • þ OH
ð1Þ

Fe3þ þ H2 O2 ! Fe2þ þ HO2 • þ Hþ ð2Þ

Some reports related with the effects of the Fenton reaction on microorganisms
are displayed in Table 2.
Linley et al. [18] also described the mechanism of cytotoxic activity generally
reported to be based on the production of highly reactive hydroxyl radicals from the
interaction of the superoxide (O2•
) radical and H2O2, a reaction first proposed by
Haber and Weiss (Eq. 3):
270 L.-A. Galeano et al.

Table 2 Microorganisms Microorganism Reference(s)

inactivated or eliminated by
Bacteria Enterococcus sp. [113, 114]
Fenton treatment
E. coli [60, 110, 115–119]
Pseudomonas aeruginosa [117]
Salmonella sp. [90]
Virus MS2 coliphage [110, 120]
Biofilmsa [111]
a
Assemblage of microbial cells that is irreversibly associated (not
removed by gentle rinsing) with a surface and enclosed in a
matrix of primarily polysaccharide material [121]

O2 •
þ H2 O2 ! O2 þ OH
þ HO • ð3Þ

The production of extremely short-lived hydroxyl radicals within the cell by the
Haber-Weiss cycle is catalyzed in vivo by the presence of transition metal ions (iron-
II) via Fenton chemistry (Eq. 1). Investigations about DNA oxidation have suggested
that the oxidizing radical is the ferryl radical formed from DNA-associated iron but
not the hydroxyl one [18]. Before, Kim et al. [110] measured the Fenton inactivation
of MS2 coliphages hosted in E. coli resistant to antibiotics. The authors reported that
MS2 can be inactivated via the Fenton process by means of H2O2 initiated by either
Fe2+ or Fe3+. However, since the reaction with the former ion occurred faster, the
coliphages became inactivated even from the first minute, whereas for the second
form of ion, the inactivation was significantly slower. Such a higher rate of peroxide
activation by iron in its lower oxidation state has been widely reported based on the
elimination of different biorefractory organic molecules, where indeed it has been
realized that an induction period takes place when the reaction is started by Fe3+
[91]. Under several conditions of pH (6.0–8.0) and presence of Fe-chelating agents
like o-phenanthroline and bipyridine, inactivation of coliphages occurred, thanks to
hydroxyl radicals formed during the Fenton process. It is somewhat confusing to
understand the mechanism at elevated values of pH without undergoing significant
precipitation of the catalyzing metal ions. Apparently, the potential inactivating
effect exerted by the carbonate buffer on both the walls and membranes of the host
bacteria E. coli before every assay of inactivation has not been taken into account;
these factors might at least partially affect the recorded results of the process [110].
Rather scarce studies can be found about disinfection kinetics on microorgan-
isms after Fenton treatment. Among the parameters affecting the rate of reaction,
iron concentration, peroxide concentration, and pH of the reacting mixture can be
cited. Concerning the pH, alkaline conditions lead the dissolved Fe2+ to get
transformed in colloidal ferric forms, which break the peroxide primarily in water
and oxygen instead than releasing the active radicals. In other words, it more rather
promotes a parasite reaction that consumes hydrogen peroxide without production
of hydroxyl radicals, as already said the main responsible of the microbial inacti-
vation [110, 111]. The optimum reaction pH for the homogeneous Fenton process
has been reported to be below 3.0 [122–124], which is a disadvantage for use in
production of drinking water since many real polluted effluents feature pH values
Disinfection by Chemical Oxidation Methods 271

close to neutral or sometimes slightly higher. Therefore, recommended pH values

in AOPs should be near neutral [91, 125].
The pH range of operation of the Fenton process can be significantly increased
when the reaction is catalyzed in heterogeneous phase. Here, activation of hydrogen
peroxide to generate HO• radicals has been performed with various transition
metals like for instance Fe, Cu, and Mn, immobilized on several solid supports as
natural aluminosilicates, zeolites, alumina, silica, and activated carbon. This pro-
cess has been referred to by some authors as catalytic wet peroxide oxidation –
CWPO [91, 97, 100, 126, 127]. This AOP has relevant advantages in the context of
water treatment such as the high efficiency even under conditions of low, ambient
pressures and temperatures, low-energy consumption, prolonged recycling of the
catalyst, and pretty low cost for scaling up [91].
The removal of 98% of DOC after 4 h of reaction and full removal of true color
from real surface river water in less than 45 min of reaction by Al/Fe-mixed pillared
clay (Al/Fe-PILC) activated CWPO under pH 3.7 and very slight conditions of
room temperature and atmospheric pressure (291 K, 72 kPa) has been reported
[85]. Nieto-Juarez et al. [120] studied the inactivation and removal of MS2 coli-
phage by heterogeneous Fenton-like process catalyzed by iron (hydr)oxide particles
in batch reactor at circumneutral pH, containing 200 mg/L of various commercial
iron (hydr)oxide particles of similar particle size: hematite (α-Fe2O3), goethite
(α-FeOOH), magnetite (Fe3O4), and amorphous iron(III) hydroxide (Fe(OH)3).
The authors concluded that the CWPO process can inactivate and physically
remove the MS2 coliphage from water through two pathways: the particle-mediated
(photo-)Fenton-like process and the adsorption process which could be mediated by
hydrophobic interactions or Van der Waals forces. All particles showed similar
adsorption capacity, in the order FeOOH > Fe2O3 > Fe3O4  Fe(OH)3. Adsorption
on three types of the solid particles studied, α-FeOOH, Fe(OH)3 and Fe3O4, caused
virus inactivation of 7.0%, 14.0%, and 22.0%, respectively. Exposure of particle-
adsorbed viruses to sunlight and H2O2 resulted in highly efficient additional
inactivation. Only Fe3O4 caused the inactivation of MS2 coliphage via dark
Fenton-like process.

4.3 Photo-Fenton Process

The photo-Fenton process (Fe/H2O2/UV) is a photo-assisted homogeneous cata-

lytic treatment, also based in Fenton chemistry [57, 128]. Its enhanced efficiency
with respect to the process in absence of UV radiation (UV, UV-A, UV-B, or
UV-C) can be ascribed to the extra generation of active radicals by photo-reduction
of Fe3+ (see reaction 4) of course besides those taking place in reactions (1), (2), and
(3). It is noteworthy that this extra-pathway does not consume hydrogen peroxide
either [129].
272 L.-A. Galeano et al.

 III 2þ
Fe ðOHÞ þ H2 O2 þ hν ðUVÞ ! Fe2þ þ HO • ð4Þ

The outstanding performance by the photo-Fenton inactivation of several micro-

organisms has been studied on bacteria, fungi, and some protein pathogen particles
(see Table 3).
The mechanism of action of disinfection by Fe/H2O2/UV process of course is
induced by the ROS oxidative stress but also by the action of the UV radiation itself
producing peroxide and superoxide species in situ as well as by causing direct irrevers-
ible damages on the DNA of the pathogens. The ROS may be produced from H2O2
previously diffused through the cell’s membrane that may react with free dissolved iron
available into within the cell [113, 135, 139]. In absence of iron, H2O2 and O2
species
formed starting from self-oxidation of flavin adenine dinucleotide FADH2 may in turn
cause oxidation of iron sulfide clusters [4Fe-4S] releasing Fe3+ ions [147]. These ions
may promote the overall Fenton reaction, and the UV light can also attack enterobactin
or ferritin proteins, delivering Fe2+ ions [28, 90, 95].
Fe2+ ions can also induce harmful effects on the targeted microorganisms because
of its capability to diffuse across the cell’s membrane and then react with the
metabolic H2O2 [3, 28, 90, 95, 142, 148]. A diagram with several possible pathways
for generation of ROS in the photo-inactivation of E. coli and related damages is
shown in Fig. 1.
The mechanism varies according to the structure and chemical composition of
cell membranes and other organelles [114]. It was found that Fusarium solani
showed higher resistance in comparison with E. coli [95], which was attributed to
the chemical composition and structure of the fungus wall that in general is more
rigid due to presence of polysaccharides like glucans, mannans, chitin, proteins, and
glycoproteins [139]. Chitarra et al. [149] found ROS production favored during

Table 3 Some microorganisms inactivated by photo-Fenton oxidation

Microorganism Reference
Bacteria Endospores of Bacillus subtilis [130, 131]
Enterococcus faecalis [113, 132]
Enterococcus sp. [133]
E. coli [3, 60, 90, 95, 113, 114, 118, 125, 128,
134–138]
Pseudomonas aeruginosa [134]
Salmonella sp. [80, 136]
Total coliforms [3]
Fungi Fusarium solani [95, 139–143]
Phytophthora capsici [142]
Virus MS2 coliphage [120, 133]
Helminth Ascaris suum eggs [130, 144, 145]
Recombinant priona [146]
a
Pathogenic protein particles
Disinfection by Chemical Oxidation Methods 273

Fig. 1 Possible pathways involved in the photo-inactivation of E. coli in the presence of Fe2+, Fe3+,
and H2O2. Reproduced with permission of Elsevier from [90]

germination of the spores and start of the metabolic activity displayed by Fusarium
solani, since throughout that stage spores absorb water to hydrate its nucleus,
making then easier the access of iron toward the inner structure.
Polo-López et al. [142] studied the capability of the photo-Fenton system to
eliminate zoospores of Phytophthora capsici in distilled water, reaching the highest
inactivation rate with 5.0 mg/L of either Fe3+ or Fe2+ along with 10 mg/L H2O2,
under 2.5 kJ/L of solar UV dosage (60 min exposure). Under low concentrations of
iron (1.0 mg/L, 2.5 mg/L), the diffusion of H2O2 and iron inside of the cell was
limited, and it did not generate enough abundance of HO• radicals for inactivation
of the targeted zoospores. A little bit earlier, it was determined that the effect of the
photo-Fenton process strongly depends on the structure of either the cell or the
spores [107]; thereafter, optimal UV, H2O2, and Fe dosages as well as the times of
exposure are target-specific parameters for every microorganism as a function of its
intrinsic resistance against each AOP. The best photo-Fenton inactivation of E. coli
was achieved by Rodrı́guez-Chueca et al. [60] with 20 mg/L of H2O2, 5.0 mg/L of
dissolved Fe, pH 5.0, under irradiation with wavelengths in the range 320–800 nm
(light intensity of 500 W/m2); the irradiation and the interaction [Fe3+]:[H2O2] were
chosen as experimental, more influencing factors in the factorial, statistical exper-
imental design of the Fenton and photo-Fenton disinfecting treatments.
The simultaneous photo-Fenton microbial disinfection and elimination of organic
matter were also recently studied by Spuhler et al. [90]. The higher performance in
both E. coli inactivation and resorcinol degradation as model refractory molecule
274 L.-A. Galeano et al.

was found (0.6 mg/L in Fe2+ or Fe3+, 10 mg/L of H2O2, pH in the range 5.0–5.5,
radiation below 300 nm UV-C/UV-B, and radiation intensity 550 W/m2). Resorcinol
competed with bacteria for available Fe2+ or Fe3+ then limiting the contact of the
microorganism and then disfavoring intracellular diffusion. The efficiency of the
system was more affected in the presence of Fe2+ than with Fe3+. However, Fe2+ still
showed a higher bactericidal effect. Concerning similar system, Moncayo-Lasso
et al. [40] realized that upon addition of 0.6 mg/L of Fe3+ and 10 mg/L of H2O2 under
pH 6.5, the mineralization of 55% of the starting 5.3 mg/L of total dissolved organic
carbon present in a river’s water along with simultaneous E. coli inactivation without
any regrowth evidenced over 24 h later under darkness was attained.
A little bit later, Ortega-Gómez et al. [57] used photooxidation of resorcinol as a
model of natural organic matter (NOM) and inactivation of Enterococcus faecalis;
both decreased as the dosage of hydrogen peroxide and iron raised (H2O2/Fe2+:
50/20 mg/L), thanks to the subsequent production of active free radical in the
system. The photo-Fenton inactivation of the Gram-positive microorganism was
much more efficient when the temperature was increased to 37–40  C, which
apparently arose to the very close conditions of temperature with respect to the
optimal one in the growth of E. faecalis; the disinfection limits were accomplished
at 80, 65, and 40 min under 20, 30, and 40  C, respectively. Apparently under such
conditions of temperature, bacteria display complete metabolic activity, becoming
much more vulnerable to the attack by the ROS generated throughout the Fe/H2O2/
UV process.
The photo-Fenton in elimination of E. coli using two light sources (lamp for light
emission at 254 nm and SunTest simulator) has been also recently studied [96]. Under
UV254 irradiation, the presence of organic matter produced a negative effect on the rate
of disinfection ascribed to the formation of triplet-state dissolved organic matter due to
absorption of UV/visible light (UV/visible), whose deactivation should be mediated by
reaction with oxygen, leading to subsequent formation of singlet oxygen that can later
react enhancing overall photocatalytic treatment. As indicated, UV254 could be filtrated
by the NOM then decreasing the rate of E. coli inactivation. Development of Fe-NOM
complexes improved recycling of the transition metal in both oxidation states (Fe3+ and
Fe2+) as well as the rate of formation of HO• radicals.
Heaselgrave and Kilvington [150] studied the antimicrobial effect of simulated
solar disinfection-SODIS in presence and absence of riboflavin on various protozoa
and helminths: Ascaris, Giardia, Acanthamoeba, Naegleria, Entamoeba, and Cryp-
tosporidium. The authors found that SODIS can successfully disinfect water sam-
ples containing cyst of Naegleria, Entamoeba, and Giardia; they demonstrated that
inactivation of highly resistant cysts of Acanthamoeba could be significantly
enhanced by the addition of riboflavin (SODIS-R). However, Ascaris larvae con-
tinued developing inside the ova even after exposure to SODIS, whereas Crypto-
sporidium remained impermeable to propidium iodide staining, probably indicating
that it might remain infectious.
This suggests that protozoan disinfection remains being the most challenging
issue for both conventional and also modern methods of treatment. Moreover, it
also drives forward research looking for improved disinfecting conditions displayed
Disinfection by Chemical Oxidation Methods 275

by AOPs. In addition, there is still a lack of information concerning the combined

analysis of the kinetic parameters featuring both the photo-Fenton reaction itself
and the microbial growing, to more clearly establish the set of conditions able to
maximize the performance of this AOP as well as the mechanism(s) implicated in
the disinfection of a range of types and viable forms of several hazardous micro-
organisms as suspended in real water systems.

4.4 Heterogeneous TiO2 Photocatalysis

The heterogeneous photocatalysis by using titanium dioxide as catalytic active surface

has been reported as one of the most attractive AOPs for treatment of surface waters in
production of drinking water. It is mainly due to its ability, under certain conditions, for
taking direct advantage of the sunlight as primary source of energy and to carry out a
simultaneous degradation of the organic matter and the microbial inactivation without
demanding addition of other oxidizing agents [8, 62, 73, 91, 93, 151]. Probably, the
disinfecting potential of the photocatalytic oxidation was first described by Matsunaga
et al. [20]; since then many researchers have made important steps forward [152–
155]. There are now accumulated evidences about Gram-positive and Gram-negative
bacteria, protozoa, microalgae, and fungi that could be inactivated by combination of
heterogeneous photocatalysis with TiO2 [119, 156]. A wide variety of microorganisms,
whose photocatalytic inactivation has been investigated along the past three decades, is
summarized in Table 4.
The effect of the TiO2 photocatalytic treatment on cellular lines as HeLa (cervical
carcinoma) [174] and Ls-174-t (human colon carcinoma) [175] has been also
studied. Photocatalytic killing effect of the TiO2 on human colon carcinoma cells
with concentrations of TiO2 above 200 μg/mL under UV-A irradiation at room
temperature was evidenced. In the case of the HeLa cancer cells, Abdulla et al.
[174] reported removals of 20% and 25% when employing Ag metal core-TiO2 shell
composite nanocluster as photocatalytic system with 10 min of irradiation and
concentrations of 5.0 and 7.0 mM of TiO2, respectively. It was enhanced to 100%
for molar ratios Ag:TiO2 of 1:5 and 1:7. Most efficient photocatalysts were prepared
starting from AgNO3 (1 mM) and titanium (IV) (triethanolaminato)-isopropoxide
solutions in concentrations of 5.0 mM or 7.0 mM, respectively. The killing of HeLa
cells was more efficient in the presence of the Ag/TiO2 shell composite photocatalyst
than with either TiO2 or Ag alone, thanks to a synergistic response.
As displayed in Table 4, the role played by the TiO2-assisted heterogeneous
photocatalytic inactivation has been assessed for a wide range of targeted microor-
ganisms. However, their corresponding mechanisms of action have not been fully
elucidated so far [10, 15, 62, 157]. It is particularly interesting to get deeper insight in
the study of the TiO2-assisted, heterogeneous photocatalytic inactivation of hazard-
ous protozoa, mainly (oo)cyst of parasites Giardia spp. and Cryptosporidium spp.
It is proven that ROS can play a central role in fast disinfection processes.
However, linking it to the formation of superoxide anion might significantly further
276 L.-A. Galeano et al.

Table 4 Some microorganisms inactivated by TiO2 photocatalytic treatment

Microorganism Reference(s)
Bacteria Clostridium perfringens [5, 157]
Endospores of Bacillus subtilis [130, 158, 159]
Enterococcus faecalis [160]
Enterococcus sp. [86]
E. coli [5, 15, 20, 96, 108, 118, 125, 153–155, 159–167]
Listeria monocytogenes [15]
Lactobacillus acidophilus [20]
Pseudomonas aeruginosa [159]
Salmonella typhimurium [15]
Fungus Candida albicans [159]
Fusarium anthophilum [107, 108]
Fusarium equiseti [107]
Fusarium oxysporum [107]
Fusarium solani [107, 108, 141, 159, 163, 168]
Fusarium verticillioides [107]
Endospores of Aspergillus niger [169]
Yeast Saccharomyces cerevisiae [20, 59, 156]
Protozoa Acanthamoeba castellani [94, 159]
Acanthamoeba polyphaga [159]
Giardia intestinalis [94]
Cryptosporidium parvum [158]
Algae Chlorella vulgaris [59]
Virus Hepatitis B virus [170]
Herpes simplex virus [171]
MS2 coliphage [106, 172]
Poliovirus 1 [173]

improve cellular oxidative state [156]. Throughout photocatalytic processes, ROS

can oxidize lipids, proteins, and amino acids; subsequent lipid peroxidation and
formation of secondary products as for instance hydroperoxides, which carry a major
oxidative damage, secondary attack of amino acids, and lack of normal function of
membrane may also take place.
Kim et al. [176] stated almost a decade ago that DNA, RNA, proteins, and lipids
are the main biological targets of the ROS generated in the photocatalytic treatment.
An approximation to the photocatalytic generation of ROS and its consequent effect
on several microorganisms is shown in Fig. 2 [177]. As it can be seen, resistance to
oxidative damages increases from viruses to bacteria and finally yeasts and molds.
According to Kim et al. [15], ROS may damage the DNA after only 60 to 90 s of
treatment by the TiO2 – photocatalytic process.
The progressive absorption of photons by cellular envelopes may lead to the loss
of its semi-permeability, then making easier the photooxidation of the inner com-
ponents of the cell [11, 16, 86, 153]. Likewise, the direct photocatalytic oxidation of
Disinfection by Chemical Oxidation Methods 277

Fig. 2 (a) Mechanism of generation of reactive oxygen species (ROS) on the surface of photocatalyst
nanoparticles of titanium or zinc oxides and (b) effects of ROS on several infectious agents. Reproduced
with permission of Springer from [177]

the intracellular coenzyme A (CoA) to play a role in the disinfection process has
been considered, since it can involve a decrease in respiratory activities, decreasing
too in turn the cell viability [11, 20, 59, 109, 153, 178]. Dalrymple et al. [11] studied
mechanistic models based on peroxidation of the membrane’s lipid layer as well as
the interaction between the microorganisms and the photocatalyst’s particles, very
often ignored; according to this and other authors, this process can be mediated by
the orientation of the TiO2 particles, the shape and size of the microorganisms, and
the pH-controlled electric charge of the surface [16, 167].
Electron microscopy has revealed the interaction between catalyst and microor-
ganisms. For instance, in the organization of TiO2 particles on yeast Saccharomyces
cerevisiae as observed by scanning electron microscopy (SEM) and transmission
electron microscopy (TEM), yeast exposed separately to catalyst and photocatalytic
treatment was surrounded by nanoparticles causing serious structural damages on
yeast’s cells, but no direct contact between catalyst and cell wall neither entry of
nanoparticles into the cellular compartments was observed. In other study [16], TEM
showed the structural damages caused by TiO2 and photocatalytic treatment on
E. coli; after 30 min of contact, E. coli envelope demonstrated lower resistance in
comparison to yeast S. cerevisiae; it was attributed to polysaccharides and glyco-
proteins forming a reticular tridimensional structure surrounding yeasts capable of
generating protection against stress conditions [179] (see more details in Fig. 3).
TiO2 is for sure the most widely used active solid in photocatalytic studies
because of its high activity, stability, and safety [86, 180]. The most used is the
commercial form Degussa P-25 (mixture of approx. 70% of the anatase phase and
30% of the rutile phase), which has exhibited the highest efficiency in degradation of
organic pollutants [72, 151, 181]. The phase content of the TiO2 photocatalyst has
been a variable considered in evaluation of disinfecting capability. Gumy et al. [182]
studied the catalytic activity of 13 commercial powders of TiO2 with specific surface
areas varying from 9 to 335 m2/g and isoelectric points (IEP) from 3.0 to 7.5 in E. coli
inactivation. The most efficient material in the photocatalytic disinfection was TiO2
278 L.-A. Galeano et al.

Fig. 3 TEM pictures of E. coli cells in aqueous suspension: (Left) (a) In the dark without TiO2 (the
insert is a zoom picture in the bacterial envelope); (b) after 30 min of contact with TiO2 P-25 (0.25 g/L)
in the dark. (Right) Exposed to UV-A photocatalysis with TiO2 P-25 (0.25 g/L) and IUV-A ¼ 3.45 mW/
cm2: (a) after 80 min of exposure, (b) and (c) after 180 min of exposure. Reproduced with permission
of Elsevier from [16]

Degussa P-25. Likewise, minor bacterial inactivation for lower IEP values was
observed, whereas the disinfection showed to be somehow independent of the
catalyst’s specific surface area, behavior observed with most catalyst tested. Guillard
et al. [153] also compared two catalysts in disinfection of two strains of E. coli (K12
PHL849 and K12 PHL1273) differing in the number of bacterial fimbriae: one
commercial TiO2 Degussa P-25 (anatase/rutile ¼ 80/20, SBET ¼ 50 m2/g, size
particle ¼ 30 nm) and one industrial named Millennium PC500 from Millennium
Inorganic Chemicals (anatase, SBET higher than 300 m2/g, size particle  5 nm, IEP
lower than TiO2 P-25). In the presence of Degussa P-25, both strains were inactivated
in a similar way, but without significant effects, mainly due to alterations in bacteria
surface with respect to fimbriae number. Likewise, with the second catalyst, the
bacterial strain PHL1273, containing a higher fimbriae number, was inactivated
Disinfection by Chemical Oxidation Methods 279

faster than strain PHL849, probably due to stronger adherence of first strain to
catalyst’s surface.
Thus, the selection of active catalyst in photocatalytic inactivation of microor-
ganisms should consider particle size, crystalline phase, isoelectric point, and
surface area, but mainly surface charge and particular electrostatic interaction of
targeted infectious agent with TiO2 particles. More investigations are still required
in order to improve the understanding about the effects exerted by the main
operational parameters (type of catalyst, type of catalysis reaction) in the
photocatalytic inactivation of wide diversity of water-borne pathogens.
Regarding inactivation kinetics, Agulló-Barceló et al. [5] recently studied the
heterogeneous photocatalytic reaction in presence of 100 mg/L of TiO2 on four
microbial indicators: E. coli, spores of sulfite-reducing clostridia, somatic coli-
phages, and F-specific RNA bacteriophages. These authors realized several disin-
fection kinetics for every target. The viral indicators were those more susceptible to
the treatment, followed by E. coli that showed similar behavior, whereas the higher
relative resistance was exhibited by the spores of sulfite-reducing clostridia, in
similar trend latter reported elsewhere [177]. Nevertheless, viruses had shown to be
more resistant to the action of either H2O2, UV (>295 nm), or UV/H2O2 in
comparison with bacteria [183]; apparently TiO2 leads to increase susceptibility
of the virus as advantage of this AOP. It must be stressed that anyway the effect
strongly depends on the size and type of virion, as well as on the type of nucleic acid
[172]. The relatively high resistance exhibited by the microbial spores could be
caused by structural components of multiple layers covering them, mainly com-
posed by proteins, glycoproteins, PG, calcium, and dipicolinic acid that provide
them enhanced impermeability against toxic molecules and greater resistance under
hostile conditions [169, 184]. In this regard, Cho et al. [106] previously showed the
biocidal modes of action of ROS to be very different depending on the specific
microorganism involved; whereas the MS-2 phage was inactivated mainly by the
free hydroxyl radical in the solution bulk, E. coli was inactivated by both the free
and the surface-bound hydroxyl radicals, but probably also by other ROS species
generated along the TiO2 photocatalytic reaction.
Similar to bacterial endospores, (oo)cystic forms of protozoa parasites have displayed
significantly higher resistance to disinfection [185, 186]. Sokmen et al. [94] assessed
inactivation of cysts of two protozoans by the TiO2/UV system (titanium dioxide as
anatase 99.9%, low-pressure Hg lamp, 300 W, 254 nm, and light intensity 5.8 W/m2). In
the case of Giardia intestinalis, 52.5% of the cysts were inactivated after 25 min of
reaction, while the complete disinfection of the effluent was achieved over 30 min;
irreversible damages on the cell’s wall were evidenced and hence no chances of regrow-
ing. However, the same system was not effective in the elimination of Acanthamoeba
castellani. Meanwhile, the increase in concentration of H2O2 in the range of 25–100 mg/L
did not produce any significant effect on the inactivation of E. coli [181]. These evidences
have allowed to elucidate the composition of walls playing a central role involved in
generating resistance to disinfection by (oo)cystic forms of protozoa parasites [187].
Along with the particular type of targeted microorganism, experimental param-
eters of the TiO2-assisted heterogeneous photocatalytic disinfection such as pH,
280 L.-A. Galeano et al.

type, and intensity of UV radiation, phase of the TiO2 photocatalyst, initial con-
centration of microorganism, temperature, turbidity, and presence of either elec-
trolytes and/or organic compounds have shown to participate in overall inactivation
of pathogens [5, 154, 161–163, 182].
External sources of UV radiation or dope-sensitizing by various ways have
increased the absorption of low-energy UV or visible-photons by the catalysts
toward only solar-driven photocatalytic treatment of real streams [167, 188,
189]. The photo-response of TiO2 in the visible region has been varied by the
doping of the photocatalyst with metal and nonmetals: e.g., N-doped TiO2 [190], N,
S co-doped TiO2 [191], and carbon-sensitized TiO2
xNx [103]. Using external
sources of UV irradiation, the efficiency of the catalytic disinfection process can
be modified. UV-A radiation induces less deleterious effects than UV-B and UV-C
on cell’s survival [119, 155], whereas UV-C radiation is capable to generate the
lack of integrity in cell’s envelope after only 10 min of exposure, but it was also
observed that the lack of total bacterial cultivability is faster in the presence of
UV-C with respect to UV-A radiation. Pigeot-Rémy et al. [155] and Kim et al. [176]
determined by independent studies that UV-C range of radiation is more efficient
than UV-A and UV-B fractions in elimination of pathogenic microorganisms.
Likewise, the ability of UV-C to affect essential functions of the cells such as the
DNA replication, due to induced formation of ROS, is well-known.
Regarding the way the UV light is applied, it can be continuous, intermittent,
average irradiation, direct, or diffuse. This parameter must be carefully considered
for comparisons between results obtained by employing different photoactivated
systems [12, 15, 73, 154, 192]. High values of pH (7.31  0.30) disfavor the
interaction of the microorganisms with the particles of the photocatalyst, whereas
under pH values below 6.5 the proteins of the cell’s membrane get destabilized
along with increasing both ROS concentration and then disinfecting performance.
Throughout the process, the reaction mixture tends to acidify as a product of
carboxylic functionalities as intermediates on the oxidizing treatment. This induces
positive charges on the catalyst’s surface facilitating electrostatic interaction of
catalyst pathogens to accelerate the microbial inactivation [5, 182].
In real water sources, ions introduced by anthropogenic activities may exert an
important effect on the disinfection kinetics; phosphate anions, carbonates, or
bicarbonates may inhibit the adsorption of amino acids on the TiO2 particles. The
chloride anion (Cl
) increases the time required for photocatalytic bacterial inac-
tivation, because it slows down oxidation mediated by radical species like HO• and
HO2• and blocks photoactivation of sites on the catalyst’s surface [154]. Other
oxidizable species establish a competition with microorganisms, reducing overall
disinfecting efficiency of the photocatalytic system [5, 60, 109]. Rincon et al. [154]
found that even low concentrations (~ 0.2 mmol/L) of SO42
or HCO3
can affect
bacteria inactivation. Finally, the time of reaction required for full disinfection is a
proper indirect parameter in order to compare the efficiency of several AOPs;
prolonged time of treatment may suppose very often complete elimination of the
microorganisms, but if partial, some undesirable events of microbial resistance or
genetic modifications could be also involved, leading to reactivation or persistence
Disinfection by Chemical Oxidation Methods 281

of the microorganisms in water. There is scarce knowledge about the mutagenic and
cytotoxic potential of AOPs.

4.5 Electrochemical Oxidation

This AOP has claimed recent interest as an alternative treatment of various water
matrices including drinking water, ballast water, and wastewaters [87, 193–
199]. Some related advantages are environmental friendly, easily automated, sim-
ple operation, lower consumption of additional reagents, fast treatment, and more
severe injuries compared with chlorination [198, 200]. Among the disadvantages,
high costs of operation compared with other AOPs in terms of energy consumption,
short life cycle of the required electrodes, and possible formation of hazardous
DBPs like the THMs must be cited [196, 201]. Thus, it is important to determine
how cost-effective could be this family of processes in the real-scale application on
every type of targeted influent streams. Studies about the electrochemical disinfec-
tion on microorganisms have been reported (see Table 5).
The bactericidal properties of the electrooxidation techniques arise to the syn-
ergistic effect of the oxidizing species directly produced on the anode’s surface
together with the indirect oxidation by substances in the fluid aqueous phase
[208]. Hence, as a function of the conditions of reaction and the chemical compo-
sition of the electrodes, several reactive species of oxygen can be produced like
molecular hydrogen peroxide (H2O2), ozone (O3), hydroxyl radicals (HO•), free
chlorine Cl2 (in the presence of chlorides), peroxodisulfate S2O82
(in the presence
of sulfates), and peroxydicarbonate C2O62
(in the presence of carbonates)
[87, 115, 193, 196, 197, 199]. The role of every oxidizing species during the
operation of this AOP is in some cases still scarcely understood, and then there
are clear efforts motivating more investigations in order to explain it [203, 204].
Diao et al. [115] compared the effects of chlorination, ozonation, Fenton reac-
tion, and electrooxidation in the inactivation of E. coli (Fig. 4). Similar damages can
be observed on the cells treated by Fenton and electrooxidation, along with sub-
stantial leakage of intracellular materials, less evident upon ozonation and almost
imperceptible after chlorination. Both results involve the action of chemical species
with comparable oxidizing power to the hydroxyl radicals of the Fenton reaction; it
means higher oxidizing potential compared to chlorine. Thus, probably the mech-
anism involved in the electrochemical disinfection was primarily related with the
action of ROS; it could be linked with the hypothesis of dissolved chloride ions
being not only precursors to form free chlorine Cl2 but also catalyzing a set of
reactions believed to increase the lifetime of the hydroxyl radicals, consequently
enhancing their disinfecting action.
Concerning the short-lived ROS, in order to enhance the efficiency of their
production and hence their effectiveness destroying pathogen cells, it would be
better to use a direct electrocatalyst instead of the electrochemical generation of the
oxidizing species in solution [203, 204].
282 L.-A. Galeano et al.

Table 5 Microorganisms inactivated or eliminated by electrochemical oxidation

Microorganisms Reference(s)
Bacteria Bacillus subtilis [202]
Endospores of Bacillus subtilis [203]
Enterococcus faecalis [193, 196, 204]
E. coli [87, 115, 193–196, 198, 200, 202, 204–206]
Legionella [207]
Pseudomonas aeruginosa [199]
Staphylococcus aureus [202]
Virus MS2 coliphage [195, 196]
Recombinant adenovirus serotype 5 [196]

The mechanism proposed to explain the high disinfecting potential of the

electrooxidation claims that it is strongly related with the increased membrane’s
permeability caused by the exposure to the electric field that facilitates the diffusion
of the oxidizing species into the cell, in turn leading to alterations of the enzymes,
oxidation of the N-terminal groups in the cell-wall proteins, lysis, and final cellular
death. It has been also found that throughout the electrochemical treatment, the
oxidation of the coenzyme A may take place, even without prior rupture of the
membrane, seriously modifying the metabolism of the cell [115, 193, 200, 204,
208].
Several factors that must be accounted for to increase the efficiency of the
electroch4emical disinfection include the material of the electrode, electrolyte
composition, applied current, pH, temperature, and type of electrolysis [199, 197,
204–206, 209]. High temperature is a condition under which the microbial metab-
olism responds faster to the oxidizing action of chlorine [209], and then it should
display the same trend in the presence of ROS generated by the AOPs.
Electric current presents an inverse relationship with the contact time required for
the disinfection process. Electrochemical treatment of E. coli under 25 mA/cm2
yields complete inactivation of this microorganism in only 0.5 min of contact,
whereas disinfection reached 99.98% for 2 min of reaction under 16 mA/cm2
(Fig. 4, [115]). These results showed a clearly superior performance of the electro-
chemical oxidation in comparison with the conventional disinfection treatments by
chlorination, which in 30 min of reaction attained 88.94% of efficiency measured
under identical experimental conditions. In the other hand, the material of the
electrodes used in the electrochemical oxidation has been considered one of the
more relevant factors on microbial inactivation. The materials more frequently used
thanks to their high oxygen overpotential have been lead dioxide, dimension-stable
anodes based on SnO2, and boron-doped diamond BDD electrodes [197, 198]. The
BDD electrodes display great electrochemical stability along with high overpotential
for water oxidation, allowing the efficient electro-generation of hydroxyl radicals
and other ROS directly into the aqueous solution, but are significantly less effective
producing free chlorine from the dissolved chlorides available in the target stream.
Accordingly, such a type of electrodes is more suitable for treatment of water with
Disinfection by Chemical Oxidation Methods 283

Fig. 4 SEM micrographs of E. coli in (a) fresh culture and after either (b) chlorination at 5 mg/L
for 30 min, (c) ozonation at 10 mg/L for 5 min, (d) Fenton reaction (8.5 mg/L H2O2 and 0.85 mg/L
Fe2+ at pH 4.0) for 10 min, (e) electrochemical disinfection (16 mA/cm2) for 2 min, or (f)
electrochemical disinfection at 25 mA/cm2 for 2 min. Reproduced with permission of Elsevier
from [115]

low contents of chloride [87, 204, 207]. In contrast, Pt and RuO2 electrodes exhibit
higher effectiveness to treat water containing this anion [204, 209]. From the results
reported by Jeong et al. [197], the production of active chlorine as a function of the
electrode’s material decreases in the following order: Ti/IrO2 > Ti/RuO2 > Ti/Pt-
IrO2 > BDD > Pt; it is a trend quite different to that observed for electrochemical
production of ROS. In this sense, BDD electrode produced tenfold the amount of
hydroxyl radicals formed with the Ti/RuO2 and the Pt electrodes. BDD electrode was
284 L.-A. Galeano et al.

also much more efficient in the production of O3, effect attributed to the distinct
electrostatic activities of the materials. Finally, it must be stressed that the study and
application of this AOP at big scale is still very incipient. Then, further studies to
figure out other factors favoring its entire efficiency and to clarify the disinfectant
potential are both interesting issues in the field to be addressed in the very short-term.
The disinfecting potential of other AOPs and their combinations with either other
AOPs or different disinfection systems is focus of a vibrant, currently developing
field of research in water science. The literature reports are still incipient, and for this
reason this review is circumscribed to the most studied AOPs so far.

5 Conclusions

The disinfection process plays an essential role in the production of drinking water.
According with the most up-to-date available references, AOPs are technological
alternatives to conventional disinfection methods widely used in drinking water
facilities that have not been still fully developed and exploited. Those AOPs acti-
vated by catalytic routes probably are going to play the central role in the short term.
Moreover, in order to speed up their applicability at real scale, at least the following
aspects should be considered:
1. The mechanisms of inactivation and/or elimination of the main and more
hazardous water-borne microorganisms must be elucidated taking into
account not only the attack by the powerful radical oxidizing species but also
their particular interaction with either the surface of the solid (photo)-catalyst/
electrocatalyst (in the case of the heterogeneously activated) and the implicated
radiation (photoactivated processes).
2. The increasing variability of species, types, or strains of parasites, virus, and
bacteria, as well as phages or prions present in water, must be carefully accounted
in the analysis; besides, their evolutionary and adaptive mechanisms to environ-
mental conditions and capability to form new structures with varied composition
under determined stressing conditions must also be considered.
3. The presence of spores, cyst forms, endospores, plasmids, and other genomic
rearrangements, aggregations, or biofilms are featured by high resistance to
disinfection.
4. Potential formation of intermediate metabolites alongside the oxidizing process.
5. Presence and type of NOM that may affect the overall performance or delay the
oxidation and contribute to the pathogen’s resistance.
6. Dosage, particle size, type, and surface charge of solid catalyst.
7. Realistic potential for the scaling up of the process in terms of both technical and
economic issues. Finally, other critical aspects concern the biological safety
displayed by every AOP; in this regard, potential cytotoxic and/or genotoxic
effects produced by AOPs on every type of microorganisms including cyst,
Disinfection by Chemical Oxidation Methods 285

oocyst, spores, endospores, and plasmids that can be present in varied surface
waters must be carefully examined.
Acknowledgment Authors acknowledge funding received from Nari~ no University (VIPRI),
EMPOPASTO S.A. E.S.P. – Specific Cooperation Agreement 09/2012 and Research project
Agua Potable Nari~no – SGR, CT&I Fund of the SGR, Departamento de Nari~ no, Colombia
(BPIN 2014000100020). C.A. Sánchez also thanks Young Researchers scholarship granted by
COLCIENCIAS (2012). MAV and AG thank the support from the Spanish Ministry of Economy
and Competitiveness (MINECO) and the European Regional Development Fund (FEDER) (pro-
jects MAT2013-47811-C2-R and MAT2016-78863-C2-R).

References

1. Bichai F, Polo-Lopez MI, Fernandez Ibanez P (2012) Solar disinfection of wastewater to

reduce contamination of lettuce crops by Escherichia coli in reclaimed water irrigation.
Water Res 46(18):6040–6050
2. Pablos C, Marugan J, van Grieken R, Serrano E (2013) Emerging micropollutant oxidation
during disinfection processes using UV-C, UV-C/H2O2, UV-A/TiO2 and UV-A/TiO2/H2O2.
Water Res 47(3):1237–1245
3. Ortega-Gomez E, Esteban Garcia B, Ballesteros Martin MM, Fernandez Ibanez P, Sanchez
Perez JA (2014) Inactivation of natural enteric bacteria in real municipal wastewater by solar
photo-Fenton at neutral pH. Water Res 63:316–324
4. Primo Martı́nez O (2008) Mejoras en el tratamiento de lixiviados de vertedero de RSU
mediantes procesos de oxidación avanzada. PhD thesis. Universidad de Cantabria, Spain
5. Agulló-Barceló M, Polo-López MI, Lucena F, Jofre J, Fernández-Ibá~ nez P (2013) Solar
advanced oxidation processes as disinfection tertiary treatments for real wastewater: impli-
cations for water reclamation. Appl Catal B-Environ 136:341–350
6. Gomez-Couso H, Fontan-Sainz M, Navntoft C, Fernandez-Ibanez P, Ares-Mazas E (2012)
Comparison of different solar reactors for household disinfection of drinking water in developing
countries: evaluation of their efficacy in relation to the waterborne enteropathogen Cryptosporid-
ium parvum. Trans R Soc Trop Med Hyg 106(11):645–652
7. Guzzella L, Di Caterino F, Monarca S, Zani C, Feretti D, Zerbini I, Nardi G, Buschini A,
Poli P, Rossi C (2006) Detection of mutagens in water-distribution systems after disinfection.
Mutat Res 608(1):72–81
8. Malato S, Fernández-Ibá~nez P, Maldonado MI, Blanco J, Gernjak W (2009) Decontamination
and disinfection of water by solar photocatalysis: recent overview and trends. Catal Today
147(1):1–59
9. McGuigan KG, Conroy RM, Mosler H-J, Md P, Ubomba-Jaswa E, Fernandez-Iba~ nez P
(2012) Solar water disinfection (SODIS): a review from bench-top to roof-top. J Hazard
Mater 235:29–46
10. McLoughlin OA, Kehoe SC, McGuigan KG, Duffy EF, Touati FA, Gernjak W, Alberola IO,
Rodrı́guez SM, Gill LW (2004) Solar disinfection of contaminated water: a comparison of
three small-scale reactors. Sol Energy 77(5):657–664
11. Dalrymple OK, Stefanakos E, Trotz MA, Goswami DY (2010) A review of the mechanisms
and modeling of photocatalytic disinfection. Appl Catal B-Environ 98(1):27–38
12. Méndez-Hermida F, Ares-Mazás E, McGuigan KG, Boyle M, Sichel C, Fernández-Ibá~ nez P
(2007) Disinfection of drinking water contaminated with Cryptosporidium parvum oocysts
under natural sunlight and using the photocatalyst TiO2. J Photochem Photobiol B 88
(2):105–111
13. Guidelines for drinking-water quality (2011) 4th edn. WHO Press, Geneva, Switzerland
286 L.-A. Galeano et al.

14. Hoff JC, Akin EW (1986) Microbial resistance to disinfectants: mechanisms and significance.
Environ Health Perspect 69:7–13
15. Kim S, Ghafoor K, Lee J, Feng M, Hong J, Lee D-U, Park J (2013) Bacterial inactivation in
water, DNA strand breaking, and membrane damage induced by ultraviolet-assisted titanium
dioxide photocatalysis. Water Res 47(13):4403–4411
16. Pigeot-Rémy S, Simonet F, Errazuriz-Cerda E, Lazzaroni JC, Atlan D, Guillard C (2011)
Photocatalysis and disinfection of water: identification of potential bacterial targets. Appl
Catal B-Environ 104(3):390–398
17. Emadoldin F, Ottar S, Marianne Pedersen W, Per Arne A, Cathrine BV, Marit O, Geir S,
Hans EK (2007) RNA base damage and repair. Curr Pharm Biotechnol 8(6):326–331
18. Linley E, Denyer SP, McDonnell G, Simons C, Maillard J-Y (2012) Use of hydrogen
peroxide as a biocide: new consideration of its mechanisms of biocidal action. J Antimicrob
Chemother 67(7):1589–1596
19. Silhavy TJ, Kahne D, Walker S (2010) The bacterial cell envelope. Cold Spring Harb Perspect
Biol 2(5):a000414
20. Matsunaga T, Tomoda R, Nakajima T, Wake H (1985) Photoelectrochemical sterilization of
microbial cells by semiconductor powders. FEMS Microbiol Lett 29(1–2):211–214
21. Alvarez FJ, Douglas LM, Konopka JB (2007) Sterol-rich plasma membrane domains in
fungi. Eukaryot Cell 6(5):755–763
22. Maillard JY (2007) Bacterial resistance to biocides in the healthcare environment: should it
be of genuine concern? J Hosp Infect 65:60–72
23. Webber MA, Randall LP, Cooles S, Woodward MJ, Piddock LJV (2008) Triclosan resistance
in Salmonella enterica serovar Typhimurium. J Antimicrob Chemother 62(1):83–91
24. Finnegan M, Linley E, Denyer SP, McDonnell G, Simons C, Maillard JY (2010) Mode of
action of hydrogen peroxide and other oxidizing agents: differences between liquid and gas
forms. J Antimicrob Chemother 65(10):2108–2115
25. Martin NL, Bass P, Liss SN (2015) Antibacterial properties and mechanism of activity of a
novel silver-stabilized hydrogen peroxide. PLoS One 10(7):e0131345
26. Abdou AG, Harba NM, Afifi AF, Elnaidany NF (2013) Assessment of Cryptosporidium
parvum infection in immunocompetent and immunocompromised mice and its role in
triggering intestinal dysplasia. Int J Infect Dis 17(8):e593–e600
27. Hallmich C, Gehr R (2010) Effect of pre- and post-UV disinfection conditions on photore-
activation of fecal coliforms in wastewater effluents. Water Res 44(9):2885–2893
28. Imlay JA (2008) Cellular defenses against superoxide and hydrogen peroxide. Annu Rev
Biochem 77:755–776
29. Coulon C, Collignon A, McDonnell G, Thomas V (2010) Resistance of Acanthamoeba spp.
cysts to disinfection treatments used in health care settings. J Clin Microbiol 48(8):2689–2697
30. Zhang Y, Zhang Y, Zhou L, Tan C (2014) Factors affecting UV/H2O2 inactivation of Bacillus
atrophaeus spores in drinking water. J Photochem Photobiol B 134:9–15
31. Okoh A, Odjadjare EE, Igbinosa EO, Osode AN (2007) Wastewater treatment plants as a
source of microbial pathogens in receiving watersheds. Afr J Biotechnol 6(25):2932–2944
32. Rider SD Jr, Zhu G (2010) Cryptosporidium: genomic and biochemical features. Exp Parasitol
124(1):2–9
33. Zhang H, Guo F, Zhou H, Zhu G (2012) Transcriptome analysis reveals unique metabolic
features in the Cryptosporidium parvum Oocysts associated with environmental survival and
stresses. BMC Genomics 13:647
34. Rider SD Jr, Zhu G (2008) Differential expression of the two distinct replication protein a
subunits from Cryptosporidium parvum. J Cell Biochem 104(6):2207–2216
35. Ankarklev J, Jerlstr€om-Hultqvist J, Ringqvist E, Troell K, Svärd SG (2010) Behind the smile:
cell biology and disease mechanisms of Giardia species. Nat Rev Microbiol 8(6):413–422
36. Sun C-H, McCaffery JM, Reiner DS, Gillin FD (2003) Mining the Giardia lamblia genome
for new Cyst Wall proteins. J Biol Chem 278(24):21701–21708
Disinfection by Chemical Oxidation Methods 287

37. Chatterjee A, Carpentieri A, Ratner DM, Bullitt E, Costello CE, Robbins PW, Samuelson J (2010)
Giardia cyst wall protein 1 is a lectin that binds to curled fibrils of the GalNAc homopolymer. PLoS
Pathog 6(8):e1001059
38. Giannakis S, Darakas E, Escalas-Ca~nellas A, Pulgarin C (2014) Elucidating bacterial
regrowth: effect of disinfection conditions in dark storage of solar treated secondary effluent.
J Photoch Photobio A 290:43–53
39. Gilboa Y, Friedler E (2008) UV disinfection of RBC-treated light greywater effluent:
kinetics, survival and regrowth of selected microorganisms. Water Res 42(4–5):1043–1050
40. Moncayo-Lasso A, Sanabria J, Pulgarin C, Benitez N (2009) Simultaneous E. coli inactivation and
NOM degradation in river water via photo-Fenton process at natural pH in solar CPC reactor.
A new way for enhancing solar disinfection of natural water. Chemosphere 77(2):296–300
41. Sanabria J, Wist J, Pulgarin C (2011) Photocatalytic disinfection treatments: viability, cultivability
and metabolic changes of E. coli using different measurements methods. Dyna 78(166):150–157
42. Anastasi EM, Wohlsen TD, Stratton HM, Katouli M (2013) Survival of Escherichia coli in
two sewage treatment plants using UV irradiation and chlorination for disinfection. Water
Res 47(17):6670–6679
43. Anastasi EM, Matthews B, Gündogdu A, Vollmerhausen T, Ramos NL, Stratton H,
Ahmed W, Katouli M (2010) Prevalence and persistence of Escherichia coli strains with
uropathogenic virulence characteristics in sewage treatment plants. Appl Environ Microbiol
76(17):5882–5886
44. Anastasi EM, Matthews B, Stratton HM, Katouli M (2012) Pathogenic Escherichia coli found in
sewage treatment plants and environmental waters. Appl Environ Microbiol 78(16):5536–5541
45. Guo M, Huang J, Hu H, Liu W, Yang J (2012) UV inactivation and characteristics after
photoreactivation of Escherichia coli with plasmid: health safety concern about UV disin-
fection. Water Res 46(13):4031–4036
46. Guo M, Huang J, Hu H, Liu W (2011) Growth and repair potential of three species of bacteria
in reclaimed wastewater after UV disinfection. Biomed Environ Sci 24(4):400–407
47. Hijnen WA, Beerendonk EF, Medema GJ (2006) Inactivation credit of UV radiation for
viruses, bacteria and protozoan (oo)cysts in water: a review. Water Res 40(1):3–22
48. Locas A, Demers J, Payment P (2008) Evaluation of photoreactivation of Escherichia coli and
enterococci after UV disinfection of municipal wastewater. Can J Microbiol 54(11):971–975
49. Dennis WH, Olivieri VP, Krusé CW (1979) The reaction of nucleotides with aqueous hypochlorous
acid. Water Res 13(4):357–362
50. Kim CK, Gentile DM, Sproul OJ (1980) Mechanism of ozone inactivation of bacteriophage
f2. Appl Environ Microbiol 39(1):210–218
51. O’Brien RT, Newman J (1979) Structural and compositional changes associated with chlo-
rine inactivation of polyviruses. Appl Environ Microbiol 38(6):1034–1039
52. Roy Y, Wong PKY, Engelbrecht RS, Chian ESK (1981) Mechanism of enteroviral inactiva-
tion by ozone. Appl Environ Microbiol 41(3):718–723
53. Wigginton KR, Kohn T (2012) Virus disinfection mechanisms: the role of virus composition,
structure, and function. Curr Opin Virol 2(1):84–89
54. Page MA, Shisler JL, Marinas BJ (2010) Mechanistic aspects of adenovirus serotype 2 inac-
tivation with free chlorine. Appl Environ Microbiol 76(9):2946–2954
55. Lv X, Lu Y, Yang X, Dong X, Ma K, Xiao S, Wang Y, Tang F (2015) Mutagenicity of
drinking water sampled from the Yangtze River and Hanshui River (Wuhan section) and
correlations with water quality parameters. Sci Rep 5:9572
56. Hindiyeh M, Ali A (2010) Investigating the efficiency of solar energy system for drinking
water disinfection. Desalination 259(1–3):208–215
57. Ortega-Gómez E, Fernández-Ibá~nez P, Ballesteros Martı́n MM, Polo-López MI, Esteban
Garcı́a B, Sánchez Pérez JA (2012) Water disinfection using photo-Fenton: effect of tem-
perature on enterococcus faecalis survival. Water Res 46(18):6154–6162
58. Lin W, Yu Z, Zhang H, Thompson IP (2014) Diversity and dynamics of microbial commu-
nities at each step of treatment plant for potable water generation. Water Res 52:218–230
288 L.-A. Galeano et al.

59. Venieri D, Fraggedaki A, Kostadima M, Chatzisymeon E, Binas V, Zachopoulos A,

Kiriakidis G, Mantzavinos D (2014) Solar light and metal-doped TiO2 to eliminate water-
transmitted bacterial pathogens: photocatalyst characterization and disinfection performance.
Appl Catal B-Environ 154:93–101
60. Rodrı́guez-Chueca J, Mosteo R, Ormad MP, Ovelleiro JL (2012) Factorial experimental
design applied to Escherichia coli disinfection by Fenton and photo-Fenton processes. Sol
Energy 86(11):3260–3267
61. Raffellini S, Schenk M, Guerrero S, Alzamora SM (2011) Kinetics of Escherichia coli
inactivation employing hydrogen peroxide at varying temperatures, pH and concentrations.
Food Control 22(6):920–932
62. Pariente MI, Martı́nez F, Melero JA, Botas JÁ, Velegraki T, Xekoukoulotakis NP,
Mantzavinos D (2008) Heterogeneous photo-Fenton oxidation of benzoic acid in water:
effect of operating conditions, reaction by-products and coupling with biological treatment.
Appl Catal B-Environ 85(1):24–32
63. Acharya SM, Kurisu F, Kasuga I, Furumai H (2016) Chlorine dose determines bacterial
community structure of subsequent regrowth in reclaimed water. J Water Environ Technol 14
(1):15–24
64. Chu W, Li X, Gao N, Deng Y, Yin D, Li D, Chu T (2015) Peptide bonds affect the formation
of haloacetamides, an emerging class of N-DBPs in drinking water: free amino acids versus
oligopeptides. Sci Rep 5:14412
65. Zhang SH, Miao DY, Liu AL, Zhang L, Wei W, Xie H, WQ L (2010) Assessment of the
cytotoxicity and genotoxicity of haloacetic acids using microplate-based cytotoxicity test and
CHO/HGPRT gene mutation assay. Mutat Res Genet Toxicol Environ Mutagen 703
(2):174–179
66. Ye B, Wang W, Yang L, Wei J, Xueli E (2009) Factors influencing disinfection by-products
formation in drinking water of six cities in China. J Hazard Mater 171(1–3):147–152
67. Molnar JJ, Agbaba JR, Dalmacija BD, Klasnja MT, Dalmacija MB, Kragulj MM (2012)
A comparative study of the effects of ozonation and TiO2-catalyzed ozonation on the selected
chlorine disinfection by-product precursor content and structure. Sci Total Environ 425:169–175
68. Tian C, Liu R, Liu H, Qu J (2013) Disinfection by-products formation and precursors
transformation during chlorination and chloramination of highly-polluted source water:
significance of ammonia. Water Res 47(15):5901–5910
69. Sciacca F, Rengifo-Herrera JA, Wéthé J, Pulgarin C (2011) Solar disinfection of wild
Salmonella sp. in natural water with a 18L CPC photoreactor: detrimental effect of
non-sterile storage of treated water. Sol Energy 85(7):1399–1408
70. Chin A, Berube PR (2005) Removal of disinfection by-product precursors with ozone-UV
advanced oxidation process. Water Res 39(10):2136–2144
71. Yang X, Peng J, Chen B, Guo W, Liang Y, Liu W, Liu L (2012) Effects of ozone and ozone/
peroxide pretreatments on disinfection byproduct formation during subsequent chlorination
and chloramination. J Hazard Mater 239–240:348–354
72. Coleman HM, Marquis CP, Scott JA, Chin SS, Amal R (2005) Bactericidal effects of titanium
dioxide-based photocatalysts. Chem Eng J 113(1):55–63
73. Guillard C, Pigeot-Rémy S, Simonet F, Atlan D, Lazzaroni JC (2012) Antimicrobial activity
and mode of action of photochemistry and photocatalysis. Book of abstracts, 7th international
conference on environmental catalysis. Lyon, France
74. Malik DJ, Shaw CM, Rielly CD, Shama G (2013) The inactivation of Bacillus subtilis spores
at low concentrations of hydrogen peroxide vapour. J Food Eng 114(3):391–396
75. Rogers JV, Sabourin CL, Choi YW, Richter WR, Rudnicki DC, Riggs KB, Taylor ML,
Chang J (2005) Decontamination assessment of Bacillus anthracis, Bacillus subtilis, and
Geobacillus stearothermophilus spores on indoor surfaces using a hydrogen peroxide gas
generator. J Appl Microbiol 99(4):739–748
Disinfection by Chemical Oxidation Methods 289

76. Hall L, Otter JA, Chewins J, Wengenack NL (2008) Deactivation of the dimorphic fungi
Histoplasma capsulatum, Blastomyces dermatitidis and Coccidioides immitis using hydrogen
peroxide vapor. Med Mycol 46(2):189–191
77. Labas MD, Zalazar CS, Brandi RJ, Cassano AE (2008) Reaction kinetics of bacteria
disinfection employing hydrogen peroxide. Biochem Eng J 38(1):78–87
78. Pottage T, Richardson C, Parks S, Walker JT, Bennett AM (2010) Evaluation of hydrogen
peroxide gaseous disinfection systems to decontaminate viruses. J Hosp Infect 74(1):55–61
79. Fichet G, Antloga K, Comoy E, Deslys JP, McDonnell G (2007) Prion inactivation using a
new gaseous hydrogen peroxide sterilisation process. J Hosp Infect 67(3):278–286
80. Sciacca F, Rengifo-Herrera JA, Wethe J, Pulgarin C (2010) Dramatic enhancement of solar
disinfection (SODIS) of wild Salmonella sp. in PET bottles by H2O2 addition on natural water
of Burkina Faso containing dissolved iron. Chemosphere 78(9):1186–1191
81. Block SS (2001) Disinfection, sterilization, and preservation, 5th edn. Lippincott Williams &
Wilkins, Philadelphia
82. Cords BR, Burnett SL, Hilgren J, Finley M, Magnuson J (2005) Sanitizers: halogens, surface-
active agents, and peroxides. In: Davidson PM, Sofos JN, Branen AL (eds) Antimicrobials in
food. Taylor & Francis, Boca Raton, FL
83. Raffellini S, Guerrero S, Alzamora SM (2008) Effect of hydrogen peroxide concentration and
pH on inactivation kinetics of Escherichia coli. J Food Saf 28(4):514–533
84. Flores MJ, Brandi RJ, Cassano AE, Labas MD (2012) Chemical disinfection with H2O2
the
proposal of a reaction kinetic model. Chem Eng J 198–199:388–396
85. Galeano LA, Bravo PF, Luna CD, Vicente MÁ, Gil A (2012) Removal of natural organic
matter for drinking water production by Al/Fe-PILC-catalyzed wet peroxide oxidation: effect
of the catalyst preparation from concentrated precursors. Appl Catal B-Environ
111–112:527–535
86. Lanao M, Ormad MP, Mosteo R, Ovelleiro JL (2012) Inactivation of Enterococcus sp. by
photolysis and TiO2 photocatalysis with H2O2 in natural water. Sol Energy 86(1):619–625
87. Lopez-Galvez F, Posada-Izquierdo GD, Selma MV, Perez-Rodriguez F, Gobet J, Gil MI,
Allende A (2012) Electrochemical disinfection: an efficient treatment to inactivate Escherichia
coli O157:H7 in process wash water containing organic matter. Food Microbiol 30(1):146–156
88. Ndounla J, Spuhler D, Kenfack S, Wéthé J, Pulgarin C (2013) Inactivation by solar photo-
Fenton in pet bottles of wild enteric bacteria of natural well water: absence of re-growth after
one week of subsequent storage. Appl Catal B-Environ 129:309–317
89. Primo O, Rivero MJ, Ortiz I (2008) Photo-Fenton process as an efficient alternative to the
treatment of landfill leachates. J Hazard Mater 153(1–2):834–842
90. Spuhler D, Andrés Rengifo-Herrera J, Pulgarin C (2010) The effect of Fe2+, Fe3+, H2O2 and
the photo-Fenton reagent at near neutral pH on the solar disinfection (SODIS) at low
temperatures of water containing Escherichia coli K12. Appl Catal B-Environ 96(1):126–141
91. Galeano L-A, Vicente MÁ, Gil A (2014) Catalytic degradation of organic pollutants in
aqueous streams by mixed Al/M-pillared clays (M ¼ Fe, Cu, Mn). Catal Rev 56(3):239–287
92. Mohajerani M, Mehrvar M, Ein-Mozaffari F (2009) An overview of the integration of
advanced oxidation technologies and other processes for water and wastewater treatment. Int
J Eng 3(2):120–146
93. Rincón A-G, Pulgarin C (2007) Absence of E. coli regrowth after Fe3+ and TiO2 solar
photoassisted disinfection of water in CPC solar photoreactor. Catal Today 124(3):204–214
94. Sokmen M, Degerli S, Aslan A (2008) Photocatalytic disinfection of Giardia intestinalis and
Acanthamoeba castellani cysts in water. Exp Parasitol 119(1):44–48
95. Garcı́a-Fernández I, Polo-López MI, Oller I, Fernández-Ibá~nez P (2012) Bacteria and fungi
inactivation using Fe3+/sunlight, H2O2/sunlight and near neutral photo-Fenton: a comparative
study. Appl Catal B-Environ 121:20–29
96. Rubio D, Nebot E, Casanueva JF, Pulgarin C (2013) Comparative effect of simulated solar
light, UV, UV/H2O2 and photo-Fenton treatment (UV-Vis/H2O2/Fe2+,3+) in the Escherichia
coli inactivation in artificial seawater. Water Res 47(16):6367–6379
290 L.-A. Galeano et al.

97. Galeano LA, Gil A, Vicente MA (2010) Effect of the atomic active metal ratio in Al/Fe-,
Al/Cu- and Al/(Fe–Cu)-intercalating solutions on the physicochemical properties and cata-
lytic activity of pillared clays in the CWPO of methyl orange. Appl Catal B-Environ 100
(1–2):271–281
98. Joseph CG, Li Puma G, Bono A, Krishnaiah D (2009) Sonophotocatalysis in advanced
oxidation process: a short review. Ultrason Sonochem 16(5):583–589
99. Malato S, Blanco J, Alarcón DC, Maldonado MI, Fernández-Ibá~ nez P, Gernjak W (2007)
Photocatalytic decontamination and disinfection of water with solar collectors. Catal Today
122(1–2):137–149
100. Galeano LA, Gil A, Vicente MA (2011) Strategies for immobilization of manganese on expanded
natural clays: catalytic activity in the CWPO of methyl orange. Appl Catal B-Environ 104
(3–4):252–260
101. Li B, Xu X, Zhu L, Ding W, Mahmood Q (2010) Catalytic ozonation of industrial wastewater
containing chloro and nitro aromatics using modified diatomaceous porous filling. Desalina-
tion 254(1–3):90–98
102. Flores MJ, Brandi RJ, Cassano AE, Labas MD (2012) Chemical disinfection with H2O2
the
proposal of a reaction kinetic model. Chem Eng J 198:388–396
103. Liu Y, Li J, Qiu X, Burda C (2007) Bactericidal activity of nitrogen-doped metal oxide
nanocatalysts and the influence of bacterial extracellular polymeric substances (EPS).
J Photoch Photobio A 190(1):94–100
104. Storz G, Christman MF, Sies H, Ames BN (1987) Spontaneous mutagenesis and oxidative
damage to DNA in Salmonella typhimurium. Proc Natl Acad Sci U S A 84:8917–8921
105. Anzai K, Hamasuna M, Kadono H, Lee S, Aoyagi H, Kirino Y (1991) Formation of ion
channels in planar lipid bilayer membranes by synthetic basic peptides. Biochim Biophys
Acta-Biomembr 1064(2):256–266
106. Cho M, Chung H, Choi W, Yoon J (2005) Different inactivation behaviors of MS-2 phage and
Escherichia coli in TiO2 photocatalytic disinfection. Appl Environ Microbiol 71(1):270–275
107. Sichel C, de Cara M, Tello J, Blanco J, Fernández-Ibá~ nez P (2007) Solar photocatalytic
disinfection of agricultural pathogenic fungi: Fusarium species. Appl Catal B-Environ 74
(1):152–160
108. Sichel C, Tello J, de Cara M, Fernández-Ibá~nez P (2007) Effect of UV solar intensity and
dose on the photocatalytic disinfection of bacteria and fungi. Catal Today 129(1):152–160
109. Ubomba-Jaswa E, Navntoft C, Polo-López MI, Fernández-Ibá~ nez P, McGuigan KG (2009)
Solar disinfection of drinking water (SODIS): an investigation of the effect of UV-A dose on
inactivation efficiency. Photochem Photobiol Sci 8(5):587–595
110. Kim JY, Lee C, Sedlak DL, Yoon J, Nelson KL (2010) Inactivation of MS2 coliphage by
Fenton’s reagent. Water Res 44(8):2647–2653
111. Gosselin F, Madeira LM, Juhna T, Block JC (2013) Drinking water and biofilm disinfection
by Fenton-like reaction. Water Res 47(15):5631–5638
112. Benatti CT, Tavares CR, Guedes TA (2006) Optimization of Fenton’s oxidation of chemical
laboratory wastewaters using the response surface methodology. J Environ Manage 80
(1):66–74
113. Rodrı́guez-Chueca J, Polo-López MI, Mosteo R, Ormad MP, Fernández-Ibá~ nez P (2014)
Disinfection of real and simulated urban wastewater effluents using a mild solar photo-
Fenton. Appl Catal B-Environ 150:619–629
114. Rodrı́guez-Chueca J, Ormad MP, Mosteo R, Ovelleiro JL (2015) Kinetic modeling of
Escherichia coli and Enterococcus sp. inactivation in wastewater treatment by photo-Fenton
and H2O2/UV–vis processes. Chem Eng Sci 138:730–740
115. Diao HF, Li XY, JD G, Shi HC, Xie ZM (2004) Electron microscopic investigation of the
bactericidal action of electrochemical disinfection in comparison with chlorination, ozona-
tion and Fenton reaction. Process Biochem 39(11):1421–1426
Disinfection by Chemical Oxidation Methods 291

116. Mackulak T, Nagyova K, Faberova M, Grabic R, Koba O, Gal M, Birosova L (2015)

Utilization of Fenton-like reaction for antibiotics and resistant bacteria elimination in differ-
ent parts of WWTP. Environ Toxicol Pharmacol 40(2):492–497
117. Park SC, Kim NH, Yang W, Nah JW, Jang MK, Lee D (2016) Polymeric micellar
nanoplatforms for Fenton reaction as a new class of antibacterial agents. J Control Release
221:37–47
118. Rincón A-G, Pulgarin C (2006) Comparative evaluation of Fe3+ and TiO2 photoassisted
processes in solar photocatalytic disinfection of water. Appl Catal B-Environ 63(3):222–231
119. Rodriguez C, Di Cara A, Renaud FNR, Freney J, Horvais N, Borel R, Puzenat E, Guillard C
(2014) Antibacterial effects of photocatalytic textiles for footwear application. Catal Today
230:41–46
120. Nieto-Juarez JI, Kohn T (2013) Virus removal and inactivation by iron (hydr)oxide-mediated
Fenton-like processes under sunlight and in the dark. Photochem Photobiol Sci 12(9):1596–1605
121. Donlan RM (2002) Biofilms: microbial life on surfaces. Emerg Infect Dis 8(9):881–890
122. Bozzi A, Yuranova T, Mielczarski E, Mielczarski J, Buffat PA, Lais P, Kiwi J (2003) Superior
biodegradability mediated by immobilized Fe-fabrics of waste waters compared to Fenton homo-
geneous reactions. Appl Catal B-Environ 42(3):289–303
123. Rodriguez ML, Timokhin VI, Contreras S, Chamarro E, Esplugas S (2003) Rate equation for
the degradation of nitrobenzene by “Fenton-like” reagent. Adv Environ Res 7(2):583–595
124. Garrido-Ramı́rez EG, Theng BKG, Mora ML (2010) Clays and oxide minerals as catalysts
and nanocatalysts in Fenton-like reactions – a review. Appl Clay Sci 47(3–4):182–192
125. Ruales-Lonfat C, Benı́tez N, Sienkiewicz A, Pulgarı́n C (2014) Deleterious effect of homogeneous
and heterogeneous near-neutral photo-Fenton system on Escherichia coli. Comparison with photo-
catalytic action of TiO2 during cell envelope disruption. Appl Catal B-Environ 160:286–297
126. Rey A, Faraldos M, Casas JA, Zazo JA, Bahamonde A, Rodrı́guez JJ (2009) Catalytic wet
peroxide oxidation of phenol over Fe/AC catalysts: influence of iron precursor and activated
carbon surface. Appl Catal B-Environ 86(1–2):69–77
127. Bautista P, Mohedano AF, Menéndez N, Casas JA, Rodriguez JJ (2010) Catalytic wet peroxide
oxidation of cosmetic wastewaters with Fe-bearing catalysts. Catal Today 151(1–2):148–152
128. Moncayo-Lasso A, Torres-Palma RA, Kiwi J, Benı́tez N, Pulgarin C (2008) Bacterial
inactivation and organic oxidation via immobilized photo-Fenton reagent on structured silica
surfaces. Appl Catal B-Environ 84(3–4):577–583
129. Tokumura M, Morito R, Hatayama R, Kawase Y (2011) Iron redox cycling in hydroxyl radical
generation during the photo-Fenton oxidative degradation: dynamic change of hydroxyl radical
concentration. Appl Catal B-Environ 106(3–4):565–576
130. Bandala ER, Corona-Vasquez B, Guisar R, Uscanga M (2009) Deactivation of highly resistant
microorganisms in water using solar driven photocatalytic processes. Int J Chem React Eng 7:
A7
131. Bandala ER, Perez R, Velez-Lee AE, Sanchez-Salas JL, Quiroz MA, Méndez-Rojas MA
(2011) Bacillus Subtilis spore inactivation in water using photo-assisted Fenton reaction.
Sustain Environ Res 21(5):285–290
132. Ortega-Gómez E, Martı́n MMB, Garcı́a BE, Pérez JAS, Ibá~ nez PF (2016) Wastewater disin-
fection by neutral pH photo-Fenton: the role of solar radiation intensity. Appl Catal B-Environ
181:1–6
133. Ortega-Gómez E, Ballesteros Martı́n MM, Carratala A, Fernández Iba~ nez P, Sánchez Pérez
JA, Pulgarı́n C (2015) Principal parameters affecting virus inactivation by the solar photo-
Fenton process at neutral pH and μM concentrations of H2O2 and Fe2+/3+. Appl Catal
B-Environ 174:395–402
134. Bandala ER, González L, de la Hoz F, Pelaez MA, Dionysiou DD, Dunlop PSM, Byrne JA,
Sanchez JL (2011) Application of azo dyes as dosimetric indicators for enhanced photocatalytic
solar disinfection (ENPHOSODIS). J Photoch Photobio A 218(2):185–191
292 L.-A. Galeano et al.

135. Barreca S, Velez Colmenares JJ, Pace A, Orecchio S, Pulgarin C (2015) Escherichia coli
inactivation by neutral solar heterogeneous photo-Fenton (HPF) over hybrid iron/montmo-
rillonite/alginate beads. J Environ Chem Eng 3(1):317–324
136. Ndounla J, Pulgarin C (2014) Evaluation of the efficiency of the photo Fenton disinfection of
natural drinking water source during the rainy season in the Sahelian region. Sci Total Environ
493:229–238
137. Ruales-Lonfat C, Barona JF, Sienkiewicz A, Bensimon M, Vélez-Colmenares J, Benı́tez N,
Pulgarı́n C (2015) Iron oxides semiconductors are efficients for solar water disinfection: a
comparison with photo-Fenton processes at neutral pH. Appl Catal B-Environ 166:497–508
138. Ruales-Lonfat C, Barona JF, Sienkiewicz A, Vélez J, Benı́tez LN, Pulgarı́n C (2016)
Bacterial inactivation with iron citrate complex: a new source of dissolved iron in solar
photo-Fenton process at near-neutral and alkaline pH. Appl Catal B-Environ 180:379–390
139. Aurioles-López V, Polo-López MI, Fernández-Ibá~nez P, López-Malo A, Bandala ER (2016)
Effect of iron salt counter ion in dose–response curves for inactivation of Fusarium solani in
water through solar driven Fenton-like processes. Phys Chem Earth A/B/C 91:46–52
140. Dubey JP, Huong LT, Sundar N, Su C (2007) Genetic characterization of toxoplasma gondii isolates
in dogs from Vietnam suggests their South American origin. Vet Parasitol 146(3–4):347–351
141. Polo-López MI, Castro-Alférez M, Oller I, Fernández-Ibá~ nez P (2014) Assessment of solar
photo-Fenton, photocatalysis, and H2O2 for removal of phytopathogen fungi spores in syn-
thetic and real effluents of urban wastewater. Chem Eng J 257:122–130
142. Polo-López MI, Oller I, Fernández-Ibá~nez P (2013) Benefits of photo-Fenton at low concen-
trations for solar disinfection of distilled water. A case study: Phytophthora capsici. Catal
Today 209:181–187
143. Polo-López MI, Garcı́a-Fernández I, Velegraki T, Katsoni A, Oller I, Mantzavinos D,
Fernández-Ibá~nez P (2012) Mild solar photo-Fenton: an effective tool for the removal of
Fusarium from simulated municipal effluents. Appl Catal B-Environ 111:545–554
144. Ramı́rez Zamora RM, Galván Garcı́a M, Gallardo IR, Rigas F, Durán-Moreno A (2006)
Viability reduction of parasites (Ascaris spp.) in water with photo-Fenton reaction via
response surface methodology. Water Pract Technol 1(2):wpt2006043
145. Bandala ER, Gonzalez L, Sanchez-Salas JL, Castillo JH (2012) Inactivation of Ascaris eggs
in water using sequential solar driven photo-Fenton and free chlorine. J Water Health 10
(1):20–30
146. Paspaltsis I, Berberidou C, Poulios I, Sklaviadis T (2009) Photocatalytic degradation of
prions using the photo-Fenton reagent. J Hosp Infect 71(2):149–156
147. Imlay JA (2003) Pathways of oxidative damage. Annu Rev Microbiol 57:395–418
148. Cartron ML, Maddocks S, Gillingham P, Craven CJ, Andrews SC (2006) Feo – transport of
ferrous iron into bacteria. Biometals 19(2):143–157
149. Chitarra GS, Breeuwer P, Rombouts FM, Abee T, Dijksterhuis J (2005) Differentiation inside
multicelled macroconidia of Fusarium culmorum during early germination. Fungal Genet
Biol 42(8):694–703
150. Heaselgrave W, Kilvington S (2011) The efficacy of simulated solar disinfection (SODIS)
against Ascaris, Giardia, Acanthamoeba, Naegleria, Entamoeba and Cryptosporidium. Acta
Trop 119(2–3):138–143
151. Rubio D, Casanueva JF, Nebot E (2013) Improving UV seawater disinfection with
immobilized TiO2: study of the viability of photocatalysis (UV254/TiO2) as seawater disin-
fection technology. J Photoch Photobio A 271:16–23
152. Dunlop PSM, Byrne JA, Manga N, Eggins BR (2002) The photocatalytic removal of bacterial
pollutants from drinking water. J Photoch Photobio A 148(1):355–363
153. Guillard C, Bui T-H, Felix C, Moules V, Lina B, Lejeune P (2008) Microbiological disin-
fection of water and air by photocatalysis. C R Chim 11(1–2):107–113
154. Rincón A-G, Pulgarin C (2004) Bactericidal action of illuminated TiO2 on pure Escherichia
coli and natural bacterial consortia: post-irradiation events in the dark and assessment of the
effective disinfection time. Appl Catal B-Environ 49(2):99–112
Disinfection by Chemical Oxidation Methods 293

155. Pigeot-Remy S, Simonet F, Atlan D, Lazzaroni JC, Guillard C (2012) Bactericidal efficiency
and mode of action: a comparative study of photochemistry and photocatalysis. Water Res 46
(10):3208–3218
156. Thabet S, Simonet F, Lemaire M, Guillard C, Cotton P (2014) Impact of photocatalysis on
fungal cells: depiction of cellular and molecular effects on Saccharomyces cerevisiae. Appl
Environ Microbiol 80(24):7527–7535
157. Dunlop PSM, McMurray TA, Hamilton JWJ, Byrne JA (2008) Photocatalytic inactivation of
Clostridium perfringens spores on TiO2 electrodes. J Photoch Photobio A 196(1):113–119
158. Cho M, Yoon J (2008) Measurement of OH radical CT for inactivating Cryptosporidium
parvum using photo/ferrioxalate and photo/TiO2 systems. J Appl Microbiol 104(3):759–766
159. Lonnen J, Kilvington S, Kehoe SC, Al-Touati F, McGuigan KG (2005) Solar and photocatalytic
disinfection of protozoan, fungal and bacterial microbes in drinking water. Water Res 39(5):877–883
160. van Grieken R, Marugán J, Pablos C, Furones L, López A (2010) Comparison between the
photocatalytic inactivation of Gram-positive E. faecalis and Gram-negative E. coli faecal
contamination indicator microorganisms. Appl Catal B-Environ 100(1):212–220
161. Benabbou AK, Derriche Z, Felix C, Lejeune P, Guillard C (2007) Photocatalytic inactivation
of Escherichia coli: effect of concentration of TiO2 and microorganism, nature, and intensity
of UV irradiation. Appl Catal B-Environ 76(3):257–263
162. Castillo-Ledezma JH, Sánchez Salas JL, López-Malo A, Bandala ER (2011) Effect of pH,
solar irradiation, and semiconductor concentration on the photocatalytic disinfection of
Escherichia coli in water using nitrogen-doped TiO2. Eur Food Res Technol 233(5):825–834
163. Garcı́a-Fernández I, Fernández-Calderero I, Polo-López MI, Fernández-Ibá~ nez P (2015) Disin-
fection of urban effluents using solar TiO2 photocatalysis: a study of significance of dissolved
oxygen, temperature, type of microorganism and water matrix. Catal Today 240:30–38
164. Khraisheh M, Wu L, Al-Muhtaseb AH, Al-Ghouti MA (2015) Photocatalytic disinfection of
Escherichia coli using TiO2 P25 and Cu-doped TiO2. J Ind Eng Chem 28:369–376
165. Pratap Reddy M, Phil HH, Subrahmanyam M (2008) Photocatalytic disinfection of
Escherichia coli over titanium (IV) oxide supported on Hβ zeolite. Catal Lett 123(1):56–64
166. Rincón AG, Pulgarin C, Adler N, Peringer P (2001) Interaction between E. coli inactivation
and DBP-precursors – dihydroxybenzene isomers – in the photocatalytic process of drinking-
water disinfection with TiO2. J Photoch Photobio A 139(2):233–241
167. Rizzo L, Sannino D, Vaiano V, Sacco O, Scarpa A, Pietrogiacomi D (2014) Effect of solar
simulated N-doped TiO2 photocatalysis on the inactivation and antibiotic resistance of an
E. coli strain in biologically treated urban wastewater. Appl Catal B-Environ 144:369–378
168. Fernández-Ibá~nez P, Sichel C, Polo-López MI, de Cara-Garcı́a M, Tello JC (2009) Photocatalytic
disinfection of natural well water contaminated by Fusarium solani using TiO2 slurry in solar CPC
photo-reactors. Catal Today 144(1):62–68
169. Pigeot-Remy S, Real P, Simonet F, Hernandez C, Vallet C, Lazzaroni JC, Vacher S, Guillard
C (2013) Inactivation of Aspergillus niger spores from indoor air by photocatalytic filters.
Appl Catal B-Environ 134–135:167–173
170. Zan L, Fa W, Peng T, Gong ZK (2007) Photocatalysis effect of nanometer TiO2 and TiO2-
coated ceramic plate on hepatitis B virus. J Photochem Photobiol B 86(2):165–169
171. Hajkova P, Spatenka P, Horsky J, Horska I, Kolouch A (2007) Photocatalytic effect of TiO2
films on viruses and bacteria. Plasma Processes Polym 4(S1):S397–S401
172. Misstear DB, Gill LW (2012) The inactivation of phages MS2, PhiX174 and PR772 using UV
and solar photocatalysis. J Photochem Photobiol B 107:1–8
173. Watts RJ, Kong S, Orr MP, Miller GC, Henry BE (1995) Photocatalytic inactivation of
coliform bacteria and viruses in secondary wastewater effluent. Water Res 29(1):95–100
174. Abdulla-Al-Mamun M, Kusumoto Y, Zannat T, Islam MS (2011) Synergistic cell-killing by
photocatalytic and plasmonic photothermal effects of Ag@TiO2 core–shell composite nanoclusters
against human epithelial carcinoma (HeLa) cells. Appl Catal A-Gen 398(1):134–142
175. Zhang A-P, Sun Y-P (2004) Photocatalytic killing effect of TiO2 nanoparticles on Ls-174-t
human colon carcinoma cells. World J Gastroenterol 10(21):3191–3193
294 L.-A. Galeano et al.

176. Kim TY, Lee Y-H, Park K-H, Kim SJ, Cho SY (2005) A study of photocatalysis of TiO2
coated onto chitosan beads and activated carbon. Res Chem Intermediat 31(4):343–358
177. Bogdan J, Zarzyńska J, Pławińska-Czarnak J (2015) Comparison of infectious agents suscep-
tibility to photocatalytic effects of nanosized titanium and zinc oxides: a practical approach.
Nanoscale Res Lett 10(1):1023
178. Cheng YW, Chan RC, Wong PK (2007) Disinfection of legionella pneumophila by photocatalytic
oxidation. Water Res 41(4):842–852
179. Klis FM, Boorsma A, De Groot PW (2006) Cell wall construction in Saccharomyces cerevisiae.
Yeast 23(3):185–202
180. Gogate PR, Pandit AB (2004) A review of imperative technologies for wastewater treatment
I: oxidation technologies at ambient conditions. Adv Environ Res 8(3):501–551
181. Paleologou A, Marakas H, Xekoukoulotakis NP, Moya A, Vergara Y, Kalogerakis N,
Gikas P, Mantzavinos D (2007) Disinfection of water and wastewater by TiO2 photocatalysis,
sonolysis and UV-C irradiation. Catal Today 129(1):136–142
182. Gumy D, Morais C, Bowen P, Pulgarin C, Giraldo S, Hajdu R, Kiwi J (2006) Catalytic
activity of commercial of TiO2 powders for the abatement of the bacteria (E. coli) under solar
simulated light: influence of the isoelectric point. Appl Catal B-Environ 63(1):76–84
183. Mamane H, Shemer H, Linden KG (2007) Inactivation of E. coli, B. subtilis spores, and MS2,
T4, and T7 phage using UV/H2O2 advanced oxidation. J Hazard Mater 146(3):479–486
184. Dunlop PSM, Sheeran CP, Byrne JA, McMahon MAS, Boyle MA, McGuigan KG (2010)
Inactivation of clinically relevant pathogens by photocatalytic coatings. J Photochem Photobiol
A 216(2):303–310
185. Ali MA, Al-Herrawy AZ, El-Hawaary SE (2004) Detection of enteric viruses, Giardia and
Cryptosporidium in two different types of drinking water treatment facilities. Water Res 38
(18):3931–3939
186. Castro-Hermida JA, Gonzalez-Warleta M, Mezo M (2015) Cryptosporidium spp. and Giardia
duodenalis as pathogenic contaminants of water in Galicia, Spain: the need for safe drinking
water. Int J Hyg Environ Health 218(1):132–138
187. Jenkins MB, Eaglesham BS, Anthony LC, Kachlany SC, Bowman DD, Ghiorse WC (2010)
Significance of wall structure, macromolecular composition, and surface polymers to the survival
and transport of Cryptosporidium parvum oocysts. Appl Environ Microbiol 76(6):1926–1934
188. Chen E, Su H, Tan T (2011) Antimicrobial properties of silver nanoparticles synthesized by
bioaffinity adsorption coupled with TiO2 photocatalysis. J Chem Technol Biotechnol 86(3):421–427
189. Zhang N, Hu K, Shan B (2014) Ballast water treatment using UV/TiO2 advanced oxidation
processes: an approach to invasive species prevention. Chem Eng J 243:7–13
190. Li Q, Xie R, Li YW, Mintz EA, Shang JK (2007) Enhanced visible-light-induced
photocatalytic disinfection of E. coli by carbon-sensitized nitrogen-doped titanium oxide.
Environ Sci Technol 41(14):5050–5056
191. Rengifo-Herrera JA, Pierzchała K, Sienkiewicz A, Forró L, Kiwi J, Pulgarin C (2009)
Abatement of organics and Escherichia coli by N, S co-doped TiO2 under UV and visible
light. Implications of the formation of singlet oxygen (1O2) under visible light. Appl Catal
B-Environ 88(3–4):398–406
192. Merwald H, Klosner G, Kokesch C, Der-Petrossian M, Honigsmann H, Trautinger F (2005)
UVA-induced oxidative damage and cytotoxicity depend on the mode of exposure. J Photochem
Photobiol B 79(3):197–207
193. Chen S, Hu W, Hong J, Sandoe S (2016) Electrochemical disinfection of simulated ballast
water on PbO2/graphite felt electrode. Mar Pollut Bull 105(1):319–323
194. Cui X, Quicksall AN, Blake AB, Talley JW (2013) Electrochemical disinfection of Escherichia
coli in the presence and absence of primary sludge particulates. Water Res 47(13):4383–4390
195. Hong X, Wen J, Xiong X, Hu Y (2016) Silver nanowire-carbon fiber cloth nanocomposites
synthesized by UV curing adhesive for electrochemical point-of-use water disinfection.
Chemosphere 154:537–545
Disinfection by Chemical Oxidation Methods 295

196. Huang X, Qu Y, Cid CA, Finke C, Hoffmann MR, Lim K, Jiang SC (2016) Electrochemical
disinfection of toilet wastewater using wastewater electrolysis cell. Water Res 92:164–172
197. Jeong J, Kim C, Yoon J (2009) The effect of electrode material on the generation of oxidants
and microbial inactivation in the electrochemical disinfection processes. Water Res 43
(4):895–901
198. Lacasa E, Tsolaki E, Sbokou Z, Rodrigo MA, Mantzavinos D, Diamadopoulos E (2013)
Electrochemical disinfection of simulated ballast water on conductive diamond electrodes.
Chem Eng J 223:516–523
199. Rajab M, Heim C, Letzel T, Drewes JE, Helmreich B (2015) Electrochemical disinfection
using boron-doped diamond electrode – the synergetic effects of in situ ozone and free
chlorine generation. Chemosphere 121:47–53
200. Long Y, Ni J, Wang Z (2015) Subcellular mechanism of Escherichia coli inactivation during
electrochemical disinfection with boron-doped diamond anode: a comparative study of three
electrolytes. Water Res 84:198–206
201. Schaefer CE, Andaya C, Urtiaga A (2015) Assessment of disinfection and by-product
formation during electrochemical treatment of surface water using a Ti/IrO2 anode. Chem
Eng J 264:411–416
202. Li H, Zhu X, Ni J (2011) Comparison of electrochemical method with ozonation, chlorination
and monochloramination in drinking water disinfection. Electrochim Acta 56(27):9789–9796
203. Jeong J, Kim JY, Cho M, Choi W, Yoon J (2007) Inactivation of Escherichia coli in the
electrochemical disinfection process using a Pt anode. Chemosphere 67(4):652–659
204. Polcaro AM, Vacca A, Mascia M, Palmas S, Pompei R, Laconi S (2007) Characterization of a stirred
tank electrochemical cell for water disinfection processes. Electrochim Acta 52(7):2595–2602
205. Cano A, Ca~ nizares P, Barrera-Dı́az C, Sáez C, Rodrigo MA (2012) Use of conductive-
diamond electrochemical-oxidation for the disinfection of several actual treated wastewaters.
Chem Eng J 211:463–469
206. Hussain SN, de Las Heras N, Asghar HM, Brown NW, Roberts EP (2014) Disinfection of
water by adsorption combined with electrochemical treatment. Water Res 54:170–178
207. Furuta T, Tanaka H, Nishiki Y, Pupunat L, Haenni W, Rychen P (2004) Legionella inacti-
vation with diamond electrodes. Diamond Relat Mater 13(11):2016–2019
208. Feng C, Suzuki K, Zhao S, Sugiura N, Shimada S, Maekawa T (2004) Water disinfection by
electrochemical treatment. Bioresour Technol 94(1):21–25
209. Schmalz V, Dittmar T, Haaken D, Worch E (2009) Electrochemical disinfection of biolog-
ically treated wastewater from small treatment systems by using boron-doped diamond
(BDD) electrodes – contribution for direct reuse of domestic wastewater. Water Res 43
(20):5260–5266
Inactivation of Cryptosporidium by
Advanced Oxidation Processes

Abidelfatah M. Nasser

Abstract Cryptosporidium, a protozoan parasite, was found responsible for numer-

ous water- and foodborne outbreaks. The high risk introduced by the presence of
Cryptosporidium in water is attributed to its low infectious dose and its resistance to
environmental stress and conventional disinfection processes. Since Cryptosporidium
oocysts are highly resistant to chlorine, the most applied water disinfectant, alterna-
tive disinfectants were proposed and applied to reduce the health risks of Cryptospo-
ridium in water, among them advanced oxidation processes (AOPs), based on highly
reactive oxidants, mainly hydroxyl radicals. AOPs proved to be efficient in reducing
the concentration of micropollutants. The data presented here proved also that AOPs
are effective in the inactivation of Cryptosporidium and other waterborne pathogens.
Therefore AOPs can be applied as a barrier for reducing the health risks of waterborne
Cryptosporidium.

Keywords Advanced oxidation processes, Cryptosporidium, Disinfection,

Inactivation, Water

Contents
1 Importance of Cryptosporidium for Public Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
2 Challenges in Determining the Viability and Infectivity of Cryptosporidium . . . . . . . . . . . . 299
3 Inactivation of Cryptosporidium by Chlorine, Monochloramine, Chlorine Dioxide,
and Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
4 Sequential Inactivation of Cryptosporidium by Ozone as Primary and by Chlorine or
Monochloramine as Secondary Disinfectants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300

A.M. Nasser (*)

Institute of Natural Sciences, Beit Berl Academic College of Education, Kfar Saba, Israel
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 297
Water Treatment, Hdb Env Chem (2019) 67: 297–308, DOI 10.1007/698_2017_85,
© Springer International Publishing AG 2017, Published online: 17 October 2017
298 A.M. Nasser

5 Photocatalytic and Advanced Oxidation Processes for the Inactivation

of Cryptosporidium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306

1 Importance of Cryptosporidium for Public Health

Cryptosporidium is an enteric protozoan parasite which causes severe diarrhea in

human and domestic animals. Although Cryptosporidium was first recognized as a
waterborne pathogen during an outbreak in Braun station, Texas, in 1984, in which
more than 2,000 individuals have developed cryptosporidiosis, only 10 years later,
following the largest waterborne outbreak in Milwaukee, Wisconsin, its importance
as waterborne pathogen was recognized worldwide [1, 2]. The occurrence of the
outbreaks which involved thousands of individuals stimulated research for the
development of sensitive and specific methods for monitoring drinking water and
drinking water sources for the presence of low levels of Cryptosporidium. On the
other hand, intensive efforts were allocated for the development of efficient treat-
ment methods for the reduction of Cryptosporidium from drinking water sources.
Cryptosporidium is an intracellular protozoan parasite with an infectious dose of
as low as 120 oocysts [3]. The thick outer wall of the oocysts enables the persistence
of Cryptosporidium for long time in the environment which may facilitate its
transmission by contaminated water and food [4]. Additional routes of transmission
of Cryptosporidium may include person to person and exposure to infected animals
and to recreational waters [5, 6]. Numerous waterborne outbreaks of Cryptospo-
ridium have been reported in developed countries [4]. Most of the waterborne
outbreaks resulted from the consumption of drinking water, contaminated either
by anthropogenic or animal wastes, which received inadequate treatment. It is
worth noting that in some cryptosporidiosis outbreaks, the suspected drinking
water complied with the fecal coliform guideline, since Cryptosporidium oocysts
are very resistant to chlorine [7].
The source of Cryptosporidium oocysts in the environment can be from the
discharge of untreated human and animal wastes. Studies have shown that Crypto-
sporidium oocysts are highly prevalent in raw wastewater and often poorly removed
by wastewater treatment processes [8, 9]. Therefore, surface-water sources have
been found to be contaminated with various levels of Cryptosporidium oocysts
[10, 11]. The thick wall surrounding the oocysts of Cryptosporidium makes them
resistant to natural decay. Oocysts of Cryptosporidium may survive for months in
soil at cold temperature in dark [11]. Fayer et al. have shown that oocysts of
Cryptosporidium remained infectious for up to 24 weeks in water at 20
C; the
low infectious dose of Cryptosporidium and its high persistence in natural water
may result in the occurrence of cryptosporidiosis [12]. Therefore, efficient water
treatment processes must be applied to prevent the transmission of Cryptosporid-
ium oocysts by drinking water.
Inactivation of Cryptosporidium by Advanced Oxidation Processes 299

2 Challenges in Determining the Viability and Infectivity

of Cryptosporidium

The difference between the inactivation of Cryptosporidium and bacteria or viruses

by oxidizers stem from that the disinfectant must penetrate through oocysts wall to
inactivate the sporozoites. To measure the inactivation efficiency of Cryptosporid-
ium, the analysis should be able to determine whether the sporozoites are alive
or dead. Viability assays for Cryptosporidium oocysts based on the inclusion or
exclusion of fluorogenic vital dyes, 40 ,6-diamidino-2-phenylindole (DAPI), and
propidium iodide (PI) were reported by Campbell et al. [13] (Table 1). Inclusion
of DAPI and/or PI indicated that oocysts of Cryptosporidium lost their viability. In
addition to the dye inclusion-exclusion method, differential interphase contrast
(DIC) is also applied to distinguish between empty and full oocysts [14]. An
additional method for viability measurement of Cryptosporidium is by in vitro
excystation (the ability of oocysts to release sporozoites) which was found to be
highly correlated with the dye inclusion-exclusion method [13]. Both dye-based
methods and in vitro excystation cannot measure infectivity.
Assessment of the infectivity of Cryptosporidium oocysts relayed initially on
animal hosts, which is time consuming and very costly [15]. The development of an
in vitro method for the detection of infectious Cryptosporidium in cell culture
enables accurate evaluation of the persistence of the parasites in environmental
settings and its inactivation by disinfection methods [16]. Rochelle et al. compared
the sensitivity of in vitro cell culture with mouse assay for measuring the infectivity
of Cryptosporidium [17]. These authors demonstrated good correlation between the
infectivity for HCT-8 cells and the results for CD-1 mice for untreated oocysts and
oocysts exposed to ozone and UV irradiation. Consequently, the authors concluded
that in vitro cell culture is equivalent to the “gold standard” mouse infectivity and
should be considered as practical and accurate method to assess oocysts’ infectivity

Table 1 Detection of Cryptosporidium oocysts by viability and infectivity methods

Detection viability/
Method infectivity Parameter detected Reference
DAPIa Viability Permeability of oocysts wall and [13]
membrane
PIb Viability Permeability of oocysts wall and [13]
membrane
DICc Viability Empty or full oocyst [14]
Excystation Viability Ability to release sporozoites [13]
Animal Infectivity Ability to multiply in animal [15]
intestine
Cell culture Infectivity Ability to multiply in cell culture [16, 17]
Cell culture PCR Infectivity Ability to multiply in cell culture [18, 19]
a
DAPI 40 ,6-diamidino-2-phenylindole
b
PI propidium iodide
c
DIC differential interphase contrast
300 A.M. Nasser

and inactivation. An improved sensitivity was accomplished by integrating cell

culture real-time polymerase chain reaction (CC-RT-PCR), where single infectious
oocyst was detected [18, 19].

3 Inactivation of Cryptosporidium by Chlorine,

Monochloramine, Chlorine Dioxide, and Ozone

Chlorine is the most commonly used disinfectant in water and wastewater treat-
ment. Studies using mouse infectivity to measure the inactivation rate of Crypto-
sporidium oocysts by free chlorine demonstrated low reduction efficiency [20–
22]. Korich et al. compared the inactivation efficiency of Cryptosporidium by
ozone, chlorine dioxide, chlorine, and monochloramine using mouse infectivity to
determine oocysts’ viability [20]. A C  T (concentration  time) of five of ozone
was sufficient to cause 90% inactivation of Cryptosporidium, whereas a C  T of
7,200 was required to reach the same inactivation level for chlorine and
monochloramine (Table 2). A CT of up to 7,200 mg min/L of free chlorine was
required to obtain an inactivation of 2 log of Cryptosporidium (Table 2). Inactiva-
tion of Cryptosporidium oocysts by monochloramine was inefficient also, and a CT
of 80,000 mg min/L of monochloramine was required for the inactivation of 2 log
[22]. Chlorine dioxide was found more efficient than free chlorine and chloramine
for the inactivation of Cryptosporidium, where a CT of 111 mg min/L resulted in
2-log inactivation as measured by mouse infectivity [23]. However, Chauret et al.
reported a CT of 1,000 mg min/L to obtain 2-log inactivation of Cryptosporidium
using cell culture to determine infectivity [24]. Ozone was found the most efficient
disinfectant compared to monochloramine, free chlorine, and chlorine dioxide, and
a CT of 5 mg min/L resulted in 2-log inactivation of Cryptosporidium. It is worth
noting that an agreement was observed between the inactivation results measured
by mouse infectivity and excystation (Table 2).

4 Sequential Inactivation of Cryptosporidium by Ozone

as Primary and by Chlorine or Monochloramine
as Secondary Disinfectants

Since the CT values required for the inactivation of Cryptosporidium are large, free
chlorine may not be suitable for disinfecting drinking water under most treatment
sittings. Therefore, sequential inactivation using two disinfectants was proposed, in
an attempt to improve pathogens inactivation efficiency in drinking water treatment
plants [26–28]. Sequential disinfection using ozone as a primary disinfectant and
either free chlorine or monochloramine as secondary disinfectants have been
studied (Table 3). Corona-Vasquez et al. reported that ozone pretreatment results
Inactivation of Cryptosporidium by Advanced Oxidation Processes 301

Table 2 Inactivation of Cryptosporidium by chlorine, monochloramine, chlorine dioxide, and

ozone
CT
(mg min/ Method of Log/%
Matrix Disinfectant L) detection inactivation Reference
DFa 0.01 M Free chlorine 7,200 Mouse 2.0 [20]
PBSb infectivity
ODFc PBS Free chlorine 1,200 Mouse 1.5 [21]
infectivity
DF water, pH 6, Free chlorine 3,200 Mouse 1.0 [22]
22
C infectivity
DF 0.01 M PBS Monochloramine 7,200 Mouse 1.0 [20]
infectivity
DF water Monochloramine 80,000 Mouse 2.0 [23]
infectivity
DF water Monochloramine 11,400 Excystation 2.0 [25]
DF 0.01 M PBS Chlorine dioxide 78 Mouse 90% [20]
infectivity
DF water Chlorine dioxide 111 Mouse 2.0 [22]
infectivity
Deionized Chlorine dioxide 1,000 Cell culture 99% [24]
water
Ozone DF Ozone 5 Mouse 99% [20]
water infectivity
DF 0.01 M PBS Ozone 5 Mouse 1.5 [22]
infectivity
DF 0.01 M PBS Ozone 5 Excystation 2.0 [26]
a
DF demand free
b
PBS phosphate-buffered saline
c
ODF oxidant demand free

in the disappearance of the lag phase often observed when free chlorine is
used to inactivate Cryptosporidium [26]. Although temperature dependent, after
pretreatment with 1.8 mg min/L ozone, only a CT of 40 mg min/L of free chlorine
was required to inactivate 2 log of Cryptosporidium at 20
C. Similar results were
observed for the sequential inactivation of Cryptosporidium by chloramine. After
pretreatment of ozone at CT of 22.5 mg min/L, a CT of 900 of chloramine was
required to inactivate 2 log of Cryptosporidium at 20
C. Sequential inactivation using
ozone and either free chlorine or monochloramine was found to be temperature
dependent, increasing temperature, in the range 1–25
C, resulting in decreased
inactivation efficiency of Cryptosporidium. Li et al. determined the sequential inac-
tivation of ozone as primary disinfectant and free chlorine as secondary disinfectant
by animal infectivity using neonatal CD-1 mice [22] (Table 3). The same authors
reported also that temperature is critical for both single and sequential inactivation.
After a primary kill of 1.6 log by ozone, the free chlorine (Cavg T products) for
inactivation of 3.0 log units were 1,000, 2,000, and 3,300 mg min/L for 22
C, 10
C,
and 1
C, respectively [22].
302 A.M. Nasser

Table 3 Sequential inactivation of Cryptosporidium by ozone as primary and chlorine or

monochloramine as secondary disinfectants
Disinfectant
(CT ¼ mg min/L) Detection Log/%
Matrix Primary Secondary method inactivation Reference
0.01 M PBS, pH 7.0, Ozone F. chlorinea Excystation 1.0 [25]
5
C (28) (20)
0.01 M PBS, pH 7.0, Ozone F. chlorine Excystation 2.0 [25]
20
C (1.8) (40)
0.01 M PBS, pH 8.0, Ozone MCAb (900) Excystation 2.0 [30]
20
C (22.5)
0.01 M PBS, pH 8.0, Ozone MCA (1400) Excystation 2.0 [30]
5
C (11.5)
0.01 M PBS, pH 6.0, Ozone F. chlorine Excystation 2.0 [28]
20
C (1.4) (600)
0.01 M PBS, pH 8.0, Ozone MCA (2000) Excystation 2.0 [28]
20
C (1.4)
0.05 M PB, pH 6, Ozone F. chlorine Mouse 4.6 [22]
22
C (5) (1000) infectivity
a
F. chlorine free chlorine
b
MCA monochloramine

No synergy was observed in the inactivation rate of Cryptosporidium when

sequential inactivation of chlorine dioxide and free chlorine or monochloramine
was applied [29]. The authors explained that the absence of synergy for chlorine
dioxide/free chlorine and chlorine dioxide/monochloramine could be the result of
chlorine dioxide reacting with oocyst chemical groups that are mostly different
from those reacting with ozone, free chlorine, and monochloramine. Driedger et al.
proposed that secondary inactivation step may be the result of permeation within
the oocyst wall layers, whereas primary disinfection may be a permeation process
within more reactive oocyst wall layers [27].

5 Photocatalytic and Advanced Oxidation Processes

for the Inactivation of Cryptosporidium

Titanium dioxide (TiO2) photocatalysis is an advanced oxidation process (AOP)

which can be used for water treatment. When irradiated with supra band gap
energy, electron-hole pairs are generated within the titanium dioxide particles.
Redox reactions with water and dissolved oxygen at the particle solution interface
can result in the formation of reactive oxygen species (ROS). ROS formed by
photocatalysis include the hydroxyl radical, a powerful indiscriminate oxidant, and
superoxide anions, formed by reduction of dissolved oxygen [30, 31]. Photocatalysis
can degrade a wide range of organic compounds and inactivate pathogens in water
[32]. The ROS generated at the TiO2 surface have been proposed to be the
Inactivation of Cryptosporidium by Advanced Oxidation Processes 303

responsible agent for the disruption of cell membranes leading to loss of respiration
and microbial inactivation [33]. DNA damage has also been reported following
exposure of cells to superoxide anions and/or hydroxyl radicals [34].
Holes in the valence band are strongly oxidizing agents able to oxidize water to
highly aggressive hydroxyl radicals as well as superoxide, and other active oxygen
species are responsible for disinfection in water by attacking cellular membranes as
well as cytoplasmic proteins. When UV energy is combined with ozone, it creates a
chemical reaction resulting in hydroxyl radicals, short lived, but very powerful
oxidizer that can kill pathogens as well as destroy inorganic contaminants in the
water. The more ozone molecules in the system, the more hydroxyl radicals are
created [35].
King et al. used cell culture infectivity to measure solar inactivation of Crypto-
sporidium [36]. A reduction of 90% of Cryptosporidium infectivity was recorded
within 1 h on a high UV index summer day, whereas up to 6.4 h were needed to
obtain 90% inactivation on an overcast day of low UV index rating. Cryptosporid-
ium inactivation was attributed to the UV-B and UV-A fractions of the solar
radiation. These results are in agreement with those reported by Connelly et al.,
who also used cell culture infectivity to evaluate the inactivation of Cryptosporid-
ium by solar radiation [37]. These authors reported that exposures of Cryptospo-
ridium to 32 and 66 kJ/m2 artificial UV-B significantly decreased oocyst infectivity
by an average of 58 and 98%, respectively. Exposure of oocysts to approximately
half and full intensity of solar spectrum (all wavelengths) for a period of less than
1 day (10 h) in midsummer reduced mean infectivity by an average of 67% and of
>99.99%, respectively [37]. McGuigan et al. observed that after 6 h of solar
disinfection system (SODIS) exposure 60% of infective Cryptosporidium parvum
were permeable to DAPI and from 10 h, all oocysts were PI positive [38] (Table 4).
Ten hours of SODIS exposure was also sufficient to fully inactivate Cryptosporid-
ium oocysts as measured by Swiss CD-1 mice. Inactivation of Cryptosporidium by
sunlight may be the result of optical and thermal process, and a strong synergistic
effect occurs at temperatures exceeding 45
C [38, 39]. Sunlight may be absorbed by
photosensitizers present in water which reacts with oxygen and then produce highly
reactive superoxide and hydrogen peroxide.
To enhance the inactivation efficiency of waterborne pathogenic microorganisms
by SODIS, semiconductor photocatalysis is used to produce highly reactive species
[40]. As indicated above, ROS formed by photocatalysis include hydroxyl radical and
superoxide anions [41]. The generation of OH radicals by photo/ferrioxalate and
photo/TiO2 systems was evaluated for the inactivation of C. parvum [42] (Table 4). In
vitro excystation of Cryptosporidium was used to evaluate the inactivation efficiency.
The study revealed that CT values of OH radicals to achieve 2-log C. parvum
inactivation were 9.3  105 and 7.9  105 mg min/L from photo/ferrioxalate
and photo/TiO2 systems, respectively [42] (Table 4). OH radical is one of the most
effective oxidants (oxidation potential: OH radical 2.7 V, ozone 2.07 V, chlorine
dioxide 1.91 V, and free chlorine) 1.36 V [32]. Sunnotel et al. demonstrated a
reduction of 78.4 and 73.7% after 180 min exposure to photocatalytic activity of
using TiO2 films [30]. These authors assessed the oocysts viability by dye exclusion,
304 A.M. Nasser

Table 4 Photocatalytic and AOP inactivation of Cryptosporidium

Cryptosporidium detection Inactivation efficiency
Treatment method (log/%) Reference
1 h high UV index summer Cell culture 90% [36]
day
6.4 h low UV index rating Cell culture 90% [36]
SODISa, 10 h Mouse infectivity 100% [38]
SODISa, 6 h DAPI 60% [38]
Photo/TiO2, In vitro excystation 2 log [42]
CT ¼ 7.9  105
Photo/ferrioxalate, In vitro excystation 2 log [42]
CT ¼ 9.3  105
Photocatalysis with TiO2 Dye exclusion and in vitro 78.4% [30]
film excystation
10% H2O2, 2 h Cell culture 99% [44]
TiO2 and UV 4 mJ/cm2 CC-PCR 2 log [44]
TiO2 and UV 11 mJ/cm2 CC-PCR 3 log [44]
SODIS and 8 mg/L FAC Cell culture >2 log [46]
a
SODIS solar disinfection system

excystation, and a gene expression assay based on lactate dehydrogenase 1 (LDH1)

expression level. Scanning electron microscopy analysis showed a large number of
empty oocysts following treatment confirming rupture of the oocyst wall suture line
[30]. The ROS generated at the TiO2 surface have been proposed to be the responsible
agents for the disruption of the cell membrane leading to loss of respiration and
microbial inactivation [33].
Although the evaluation of Cryptosporidium viability was performed by the
inclusion/exclusion of the fluorogenic vital dye propidium iodide (PI), it has been
demonstrated that the effectiveness of solar disinfection against C. parvum was
enhanced when TiO2 was incorporated. Incorporation of TiO2 resulted in decreas-
ing the time needed for Cryptosporidium inactivation by solar radiation [43].
Reduction of dissolved oxygen generates additional reactive oxygen species
including superoxide radical anion (O2•), hydroperoxyl radical (HO2•), and
hydrogen peroxide (H2O2). These species can feed into the radical attack mecha-
nisms responsible for the oxidation of organic matter and inactivation of pathogenic
microorganisms present in the water. Delling et al. reported that exposure of
Cryptosporidium for 2 h to 10% H2O2 resulted in 99% inactivation as measured
by CC-PCR [44] (Table 4).
Ryu et al. studied the inactivation efficiency of Cryptosporidium by the syner-
gistic effect of UV irradiation and TiO2 [45]. Whereas low inactivation (<0.28 log)
was recorded by long-wave UV radiation, the synergistic effect of germicidal UV
and TiO2 resulted in 2-log and 3-log oocysts inactivation with 4.0 and 11.0 mJ/cm2,
respectively.
Zhou et al. demonstrated that solar radiation of water containing free available
chlorine (FAC) dramatically enhances the inactivation of C. parvum compared to
Inactivation of Cryptosporidium by Advanced Oxidation Processes 305

solar radiation and FAC alone [46]. Exposure to simulated sunlight for 60 min in
the presence of 8 mg/L free chlorine resulted in photo decomposition of free
chlorine to 1 mg/L and inactivation of >2 log of Cryptosporidium. The enhanced
Cryptosporidium inactivation was due to in situ ROS and ozone production via
FAC photolysis.
Kniel et al. recorded 50% inhibition of protease activity by treatment of
C. parvum with H2O2 [47]. These authors proposed several mechanisms for the
inhibition of infectivity and excystation of Cryptosporidium oocysts by H2O2.
These mechanisms include oxidation of cell wall proteins or lipids, chelation of
cations necessary for infection or hydroxyl radical-induced DNA damage in spo-
rozoites, or both.
Abeledo-Lameiro et al. demonstrated enhancement in the effectiveness of solar
disinfection procedures against C. parvum, when TiO2 or TiO2/H2O2 were incor-
porated, decreasing the time needed for oocysts inactivation and resulting in 97.7%
and 99.1% inactivation, respectively [48].
Cho and Yoon used Bacillus subtilis spores as surrogate for Cryptosporidium
inactivation by O3/H2O2 followed by Cl2 [49]. The authors demonstrated a 2.7 log
inactivation in system of O3/H2O2 followed by Cl2 at 20
C which was induced
by OH radical enhancement and synergistic effect of sequential disinfection. The
presence of OH radical achieved 1-log inactivation. In addition, the sequential
treatment with O3/H2O2 followed by Cl2 achieved an additional 1.4 log inactivation
with the extra synergistic effect.
Barbee et al. reported that exposure of Cryptosporidium to 3% H2O2 for 20 min
at 20
C, resulted in 1-log inactivation, whereas exposure to 6% resulted in over
3-log inactivation [50].
Rodrı́guez-Chueca et al. demonstrated high inactivation efficiency of Escherichia
coli by peroxone system (O3/H2O2) and catalytic ozonation (O3/TiO2) [51]. Inacti-
vation of 6.80 log after 10 min of contact time was observed for the peroxone system
and 6.22 log for the catalytic ozonation.

6 Conclusions

Disinfection is an important barrier to prevent the infection of Cryptosporidium by

water consumption. Since Cryptosporidium oocysts are highly resistant to chlorine,
alternative disinfection methods are applied to efficiently inactivate Cryptosporidium.
Advanced oxidation processes, especially reactive oxygen species and hydroxyl
radicals, have been shown to be efficient for the inactivation of Cryptosporidium
oocysts and other waterborne pathogens.
306 A.M. Nasser

References

1. D’Antonio RG, Winn RE, Taylor JP, Gustafson TL, Current WL, Rhodes MM, Gary GW Jr,
Zajac RA (1985) A waterborne outbreak of cryptosporidiosis in normal hosts. Ann Intern Med
103(6_Part_1):886–888
2. MacKenzie W, Hoxie N, Proctor M, Gradus M, Blari K, Peterson D, Kazmierczak J, Davis J
(1994) A massive outbreak in Milwaukee of Cryptosporidium infection transmitted through
the public water supply. N Engl J Med 331(3):161–167
3. DuPont HL, Chappell CL, Sterling CR, Okhuysen PC, Rose JB, Jakubowski W (1995)
The infectivity of Cryptosporidium parvum in healthy volunteers. N Engl J Med 332:855–859
4. Baldursson S, Karanis P (2011) Waterborne transmission of protozoan parasites: review of
worldwide outbreaks – an update 2004-2010. Water Res 45(20):6603–6614
5. Rose JB, Huffman DE, Gennaccaro A (2002) Risk and control of waterborne cryptosporidi-
osis. FEMS Microbiol Rev 26(2):113–123
6. Long SM, Adak GK, O’Brien SJ, Gillespie IA (2002) General outbreaks of infectious intestinal
disease linked with salad vegetables and fruit, England and Wales, 1992-2000. Commun Dis
Public Health 5(2):101–105
7. Craun GF, Hubbs SA, Frost F, Calderon RL, Via SH (1998) Waterborne outbreaks of
cryptosporidiosis. J Am Water Works Assoc 90(9):81–91
8. Benshoshan M, Vaizel-Ohayon D, Aharoni A, Nitzan Y, Rebhun M, Nasser AM (2015)
Prevalence and fate of Cryptosporidium genotypes in two wastewater treatment plants.
J Environ Sci Health A 50(12):1265–1273
9. Nasser AM (2016) Removal of Cryptosporidium by wastewater treatment processes, a review.
J Water Health 14(1):1–13
10. Robertson LJ, Campbell AT, Smith HV (1992) Survival of Cryptosporidium parvum oocysts
under various environmental pressures. Appl Environ Microbiol 58(11):3494–3500
11. Nasser AM, Tweto E, Nitzan Y (2007) Die-off of C. parvum in soil and wastewater effluents.
J Appl Microbiol 102:169–176
12. Fayer R, Trout JM, Jenkins MC (1998) Infectivity of Cryptosporidium parvum oocysts stored
in water at environmental temperatures. J Parasitol 84:1165–1169
13. Campbell AT, Robertson LJ, Smith HV (1992) Viability of Cryptosporidium parvum oocysts:
correlation of in vitro excystation with inclusion or exclusion of fluorogenic vital dyes.
Appl Environ Microbiol 58:3488–3493
14. U.S. Environmental Protection Agency Method 1623.1: Cryptosporidium and Giardia in water
by IFA/IMS/FA (2012) EPA 821-R-01-025. Office of Water, U.S. Environmental Protection
Agency, Washington
15. Tzipori S, Angus KW, Campbell I, Gray EW (1982) Experimental infection of lambs with
Cryptosporidium isolated from a human patient with diarrhea. Gut 23(1):71–74
16. Slifko TR, Friedman D, Rose JB, Jakubowski W (1997) An in vitro method for detecting
infectious Cryptosporidium oocysts with cell culture. Appl Environ Microbiol 63(9):3669–3675
17. Rochelle PA, Marshall MM, Mead JR, Johnson AM, Korich DG, Rosen JS, De Leon R (2002)
Comparison of in vitro cell culture and a mouse assay for measuring infectivity of Cryptospo-
ridium parvum. Appl Environ Microbiol 68(8):3809–3817
18. Rochelle PA, Ferguson DM, Handojo TJ, De Leon R, Stewart MH, Wolfe RL (1997) An assay
combining cell culture with reverse transcriptase PCR to detect and determine the infectivity of
waterborne Cryptosporidium parvum. Appl Environ Microbiol 63:2029–2037
19. Di Giovanni GD, Hashemi FH, Shaw NJ, Abrams FA, LeChevallier MW, Abbaszadegan M
(1999) Detection of infectious Cryptosporidium parvum oocysts in surface and filter backwash
water samples by immunomagnetic separation and integrated cell culture-PCR. Appl Environ
Microbiol 65(8):3427–3432
20. Korich DG, Mead JR, Madore MS, Sinclair NA, Sterling CR (1990) Effects of ozone, chlorine
dioxide, chlorine, and monochloramine on Cryptosporidium parvum oocyst viability. Appl
Environ Microbiol 56(5):1423–1428
Inactivation of Cryptosporidium by Advanced Oxidation Processes 307

21. Venczel LV, Arrowood M, Hurd M, Sobsey MD (1997) Inactivation of Cryptosporidium

parvum oocysts and Clostridium perfringens spores by a mixed-oxidant disinfectant and by
free chlorine. Appl Environ Microbiol 63(4):1598–1601
22. Li H, Finch GR, Smith DW, Belosevic M (2001) Sequential inactivation of Cryptosporidium
parvum using ozone and chlorine. Water Res 35(18):4339–4348
23. Gyurek LL, Finch GR, Belosevic M (1997) Modeling chlorine inactivation of Cryptosporid-
ium parvum oocysts. J Environ Eng 9:865–875
24. Chauret CP, Radziminski CZ, Lepuil M, Creason R, Andrews RC (2001) Chlorine dioxide
inactivation of Cryptosporidium parvum oocysts and bacterial spore indicators. Appl Environ
Microbiol 67(7):2993–3001
25. Driedger AM, Rennecker JL, Mari~nas BJ (2001) Inactivation of Cryptosporidium parvum
oocysts with ozone and monochloramine at low temperature. Water Res 35(1):41–48
26. Corona-Vasquez B, Samuelson A, Rennecker JL, Mari~ nas BJ (2002) Inactivation of Crypto-
sporidium parvum oocysts with ozone and free chlorine. Water Res 36(16):4053–4063
27. Driedger AM, Rennecker JL, Mari~nas BJ (2000) Sequential inactivation of Cryptosporidium
parvum oocysts with ozone and free chlorine. Water Res 34(14):3591–3597
28. Rennecker JL, Driedger AM, Rubin SA, Mari~nas BJ (2000) Synergy in sequential inactivation
of Cryptosporidium parvum with ozone/free chlorine and zone/monochloramine. Water Res
34(17):4121–4130
29. Corona-Vasquez B, Rennecker JL, Driedger AM, Mari~nas BJ (2002) Sequential inactivation of
Cryptosporidium parvum oocysts with chlorine followed by free chlorine or monochloramine.
Water Res 36:178–188
30. Sunnotel O, Verdoold R, Dunlop PS, Snelling WJ, Lowery CJ, Dooley JS, Moore JE, Byrne JA
(2010) Photocatalytic inactivation of Cryptosporidium parvum on nanostructured titanium
dioxide films. J Water Health 8(1):83–91
31. Cho M, Lee Y, Chung H, Yoon J (2004) Inactivation of Escherichia coli by photochemical
reaction of ferrioxalate at slightly acidic and near-neutral pHs. Appl Environ Microbiol 70
(2):1129–1134
32. Egerton TA, Kosa SA, Christensen PA (2006) Photoelectrocatalytic disinfection of E. coli
suspensions by iron doped TiO2. Phys Chem Chem Phys 21(3):398–406
33. Maness P-C, Smolinski S, Blake DM, Huang Z, Wolfrum EJ, Jacoby WA (1999) Bactericidal
activity of photocatalytic TiO2 reaction: toward an understanding of its killing mechanism.
Appl Environ Microbiol 65:4094–4098
34. Su M, Yang Y, Yang G (2006) Quantitative measurement of hydroxyl radical induced DNA
double-strand breaks and the effect of N-acetyl-L-cysteine. FEBS Lett 580(17):4136–4142
35. Rincón A-G, Pulgarin C (2004) Field solar E. coli inactivation in the absence and presence of
TiO2: is UV solar dose an appropriate parameter for standardization of water solar disinfec-
tion? Solar Energy 77(5):635–648
36. King BJ, Hoefel D, Daminato DP, Fanok S, Monis PT (2008) Solar UV reduces Cryptosporidium
parvum oocyst infectivity in environmental waters. J Appl Microbiol 104(5):1311–1323
37. Connelly SJ, Wolyniak EA, Williamson CE, Jellison KL (2007) Artificial UV-B and solar
radiation reduce in vitro infectivity of the human pathogen Cryptosporidium parvum. Environ
Sci Technol 41(20):7101–7106
38. McGuigan KG, Méndez-Hermida F, Castro-Hermida JA, Ares-Mazás E, Kehoe SC, Boyle M,
Sichel C, Fernández-Ibá~nez P, Meyer BP, Ramalingham S, Meyer EA (2006) Batch solar
disinfection inactivates oocysts of Cryptosporidium parvum and cysts of Giardia muris in
drinking water. J Appl Microbiol 101(2):453–463
39. Theitler DJ, Nasser A, Gerchman Y, Kribus A, Mamane H (2012) Synergistic effect of heat
and solar UV on DNA damage and water disinfection of E. coli and bacteriophage MS2.
J Water Health 10(4):605–618
40. Byrne JA, Fernandez-Iba~nez PA, Dunlop PSM, Alrousan DMA, Hamilton JWJ (2011)
Photocatalytic enhancement for solar disinfection of water: a review. Int J Photoenergy
2011:12. Article ID: 798051
308 A.M. Nasser

41. Ireland JC, Klostermann P, Rice EW, Clark RM (1993) Inactivation of Escherichia coli by
titanium dioxide photocatalytic oxidation. Appl Environ Microbiol 59(5):1668–1670
42. Cho M, Yoon J (2008) Measurement of OH radical CT for inactivating Cryptosporidium
parvum using photo/ferrioxalate and photo/TiO2 systems. J Appl Microbiol 104:759–766
43. Abeledo-Lameiro MJ, Ares-Mazás E, Gómez-Couso H (2016) Evaluation of solar photo-
catalysis using TiO2 slurry in the inactivation of Cryptosporidium parvum oocysts in water.
J Photochem Photobiol B 163:92–99
44. Delling C, Holzhausen I, Daugschies A, Lendner M (2016) Inactivation of Cryptosporidium
parvum under laboratory conditions. Parasitol Res 115(2):863–866
45. Ryu H, Gerrity D, Crittenden JC, Abbaszadegan M (2008) Photocatalytic inactivation of
Cryptosporidium parvum with TiO2 and low-pressure ultraviolet irradiation. Water Res 42
(6–7):1523–1530
46. Zhou P, Di Giovanni GD, Meschke JS, Dodd MC (2014) Enhanced inactivation of Crypto-
sporidium parvum oocysts during solar photolysis of free available chlorine. Environ Sci
Technol Lett 1(11):453–458
47. Kniel KE, Sumner SS, Pierson MD, Zajac AM, Hackney C, Fayer RR, Lindsay DS (2004)
Effect of hydrogen peroxide and other protease inhibitors on Cryptosporidium parvum
excystation and in vitro development. J Parasitol 90(4):885–888
48. Abeledo-Lameiro MJ, Reboredo-Fernández A, Polo-López MI, Fernández-Ibá~ nez P, Ares-
Mazás E, Gómez-Couso H (2017) Photocatalytic inactivation of the waterborne protozoan
parasite Cryptosporidium parvum using TiO2/H2O2 under simulated and natural solar condi-
tions. Catal Today 280:132–138
49. Cho M, Yoon Y (2006) Enhanced bactericidal effect of O3/H2O2 followed by Cl2. J Ozone Sci
Eng 28(5):335–340
50. Barbee SL, Weber DJ, Sobsey MD, Rutala WA (1999) Inactivation of Cryptosporidium
parvum oocyst infectivity by disinfection and sterilization processes. Gastrointest Endosc 49
(5):605–611
51. Rodrı́guez-Chueca J, Ormad Melero MP, Mosteo Abad R, Esteban Finol J, Ovelleiro Narvión
JL (2015) Inactivation of Escherichia coli in fresh water with advanced oxidation processes
based on the combination of O3, H2O2 and TiO2. Kinetic modeling. Environ Sci Pollut Res Int
22(13):10280–10290
Cost-Effective Catalytic Materials for AOP
Treatment Units

Shahryar Jafarinejad

Abstract Catalysts (homogeneous or heterogeneous) can be utilized to improve

the performance of conventional advanced oxidation processes (AOPs). In general,
catalyst activity, selectivity, stability, simplicity of preparation, preparation time,
cost, nontoxicity, availability, recycling capability, environmental suitability, etc.
can be the important parameters in the catalyst selection. High costs, cumbersome
preparations, and environmental unsuitability can usually hinder the industrial
applicability of a catalyst. In this chapter, catalytic AOPs (Fenton-based processes,
catalytic ozonation, heterogeneous photocatalysis, catalytic wet air oxidation, and
catalytic supercritical water oxidation), related catalytic materials, and cost-
effective catalytic materials used in these processes are discussed.

Keywords Advanced oxidation processes (AOPs), Catalyst, Cost, Treatment

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
2 Overview of AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3 Catalytic AOPs and Related Catalytic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
3.1 Fenton-Based Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
3.2 Catalytic Ozonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
3.3 Heterogeneous Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
3.4 Catalytic Wet Air Oxidation (CWAO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
3.5 Catalytic Supercritical Water Oxidation (CSCWO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330

S. Jafarinejad (*)
Chemical Engineering Division, College of Environment, UoE, Karaj, Iran
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 309
Water Treatment, Hdb Env Chem (2019) 67: 309–344, DOI 10.1007/698_2017_77,
© Springer International Publishing AG 2017, Published online: 24 August 2017
310 S. Jafarinejad

1 Introduction

Generally, various techniques have been applied for treatment of industrial and
municipal wastewaters, purification of drinking water, ultrapurification of water for
particular applications, etc. In some cases, conventional methods are not suitable to
attain the degree of purity needed by international or local regulations or by the
subsequent utilization of the effluent. In these situations, advanced oxidation
processes (AOPs) can be useful as novel techniques for water and wastewater
treatment that allow the total or partial degradation of compounds resistant to
conventional treatment methods [1]. In real, AOPs can cause a total mineralization,
converting recalcitrant compounds into inorganic substances (CO2 and H2O), or
partial mineralization, converting them into more biodegradable substances [2]. In
other words, they not only destruct pollutants but also prevent consequent genera-
tion of toxic residues, whereas conventional methods (i.e., nondestructive physical
separation methods) only eliminate the contaminants, transferring them to other
phases, thereby producing concentrated residues [3, 4].
AOPs have appeared as powerful processes and are extensively applied in
drinking water purification for the destruction of all kinds of constituents, including
endocrine disrupting chemicals [5, 6]. Also, they are largely utilized for the
elimination of recalcitrant organic compounds from industrial and domestic
wastewaters [7].
The existence of other water and wastewater contaminants such as natural
organic matter, dissolved and suspended solids, alkalinity, pH, and temperature
can affect the performance of AOPs [6, 8]. The operational cost of many AOPs can
be relatively high [9]. Therefore, the costs of materials and equipment, energy
requirements, and efficiency should be considered when evaluating the overall
performance of AOPs [6].
In this chapter, overview of AOPs, catalytic AOPs (Fenton-based processes,
catalytic ozonation, heterogeneous photocatalysis, catalytic wet air oxidation, and
catalytic supercritical water oxidation), related catalytic materials, and cost-
effective catalytic materials used in these processes are discussed.

2 Overview of AOPs

AOPs were first proposed for drinking water treatment by Glaze [10] in 1987 [11],
which are referred to clean technologies based on physicochemical processes to
generate the extremely reactive and nonselective hydroxyl radicals (HO•), with
very high oxidative power (E0 ¼ 2.8 V) for toxic organic compounds degradation in
a medium [1, 3, 4, 12–14]. AOPs may be applied for various purposes [1, 3, 8–22].
According to Litter and Quici [1], Mota et al. [3], and Jafarinejad [4], the
electrophilic addition of a hydroxyl radical (HO•) to π systems (unsaturated or
aromatic) leading to the formation of organic radicals (Eq. 1), the hydrogen
Cost-Effective Catalytic Materials for AOP Treatment Units 311

abstraction by reacting the hydroxyl radical (HO•) with a saturated aliphatic

compound (Eq. 2), and electron transfer reactions (Eq. 3) may be the possible
reaction pathway in the AOPs [1, 3, 4]. It is necessary to note that some chemical
species in water such as carbonate and bicarbonate ions may react with the hydroxyl
radicals, hence competing with the organic compounds through the hydroxyl
radicals [3, 4].

HO • þ Unsaturated or Aromatic ! Unsaturated  OH or Aromatic  OH ð1Þ

HO þ R  H ! R þ H2 O
• •
ð2Þ
þ•
HO • þ R  X ! ½R  X þ HO ð3Þ

Depending on the number of phases involved, the AOPs can be divided into
homogeneous and heterogeneous processes [3, 4, 23, 24]. They can be also cate-
gorized based on light usage in them as non-photochemical and photochemical
processes [3, 4, 24]. According to these classifications, the types of AOPs are listed
in Table 1.

3 Catalytic AOPs and Related Catalytic Materials

A catalyst is a material which can be added in the balance of a chemical reaction to

speed up the attainment of the chemical equilibrium between reactants and products
without affecting the thermodynamic equilibrium of the process. In most cases, the
rate of chemical reactions can be increased by lowering their activation energy with a
catalyst. Generally, consumption of catalysts does not occur during the reaction, and
they can be found unchanged after completion of the reaction (deactivation of the
catalyst may occur). In homogeneous catalysis, the catalyst, reactants, and products
are in the same phase, usually the liquid phase. If the catalyst and reactants are in
different phases, usually the catalyst is a solid and the reactants and the products are
in the liquid or vapor phase; this catalyst will be called heterogeneous [34].
Nowadays, due to the environmental issues, catalysis seems to be even more
important than before and to constitute one of the main sources of developments in
our society [35–37]. Improvements in the catalytic activity and selectivity are
essential to make catalytic processes more efficient [37].
Due to the very short lifetime of hydroxyl radicals, they are only in situ
generated during AOPs, including a combination of oxidizing agents, irradiation,
and/or catalysts [14, 23]. Large consumption of chemicals, acidic pH, high cost of
oxidizing agents, generation of sludge (e.g., iron sludge), and necessity of
posttreatment can be some limitations of the homogeneous AOPs. Thus, heteroge-
neous catalysts should be used to improve the performance of conventional AOPs
[38]. In real, catalysts can be applied in combination with some of AOPs to enhance
the oxidation process [2, 39]. Activity, selectivity, stability [40], recycling capabil-
ity [11], cost, etc. of catalysts are important. In addition, the use of suitable catalysts
312 S. Jafarinejad

Table 1 Various advanced oxidation processes (AOPs) [1, 3, 4, 22, 25–33]

Non-photochemical processes Photochemical processes
Homogeneous processes
Ozonation in alkaline media (O3/ Photolysis of water in vacuum ultraviolet (VUV)
HO)
Ozonation with hydrogen peroxide US/UV
(O3/H2O2)
Fenton (Fe2+ or Fe3+/H2O2) UV/H2O2
Electro-Fenton UV/O3
Electrochemical oxidation UV/O3/H2O2
Electrohydraulic discharge – ultra- Photo-Fenton (Fe2+ or Fe3+/H2O2/UV)
sound (US)
US/Fenton US/photo-Fenton
O3/US
H2O2/US
Microwave (MW)/H2O2
Gamma-radiolysis and electron
beam treatment
Nonthermal plasma (surface corona
discharge)
Ferrate(VI) oxidation
Wet air oxidation (WAO)
Supercritical water oxidation
(SCWO)
Heterogeneous processes
Catalytic wet air oxidation (CWAO) Heterogeneous photocatalysis: ZnO/UV, SnO2/UV,
TiO2/UV, TiO2/H2O2/UV
Zerovalent iron (ZVI) and related ZVI/UV
processes
Catalytic ozonation Photocatalytic ozonation (O3/TiO2/UV)
Heterogeneous Fenton Heterogeneous photo-Fenton
Catalytic supercritical water oxida-
tion (CSCWO)
US/H2O2/catalyst
O3/TiO2/electron beam irradiation

for AOPs not only decreases the severity of reaction conditions but also more easily
destructs even the most refractory contaminants, thereby diminishing capital and
operational cost [21, 41]. In this section, catalytic AOPs (Fenton-based processes,
catalytic ozonation, heterogeneous photocatalysis, catalytic wet air oxidation, and
catalytic supercritical water oxidation), related catalytic materials, and cost-
effective catalytic materials used in these processes are discussed.
Cost-Effective Catalytic Materials for AOP Treatment Units 313

3.1 Fenton-Based Processes

3.1.1 Principles

The Fenton process is one of the cost-effective and environmentally friendly

oxidation methods, which was discovered by Henry J. Fenton in 1894 when he
strongly improved tartaric acid oxidation by the use of ferrous ion (Fe2+) and H2O2
[4, 12, 42, 43]. This process was not utilized for the degradation of organic
pollutants until late 1960s [43, 44]; nowadays, it is widely used in wastewater
treatment. In real, Fenton’s reagent is a solution of H2O2 and ferrous ions and this
process has a complex mechanism, which primarily can involve the following
reactions [3, 4, 12–14, 45, 46]:

H2 O2 þ Fe2þ ! Fe3þ þ OH þ HO • ð4Þ

Organic matter þ HO ! Oxidation intermediates
•
ð5Þ
Oxidation intermediates þ HO ! CO2 þ H2 O •
ð6Þ
þ
H2 O2 þ Fe 3þ
! Fe 2þ
þH þ HO2• ð7Þ
H2 O2 þ HO ! H2 O þ •
HO2• ð8Þ

Fe 2þ
þ HO ! Fe • 3þ
þ HO ð9Þ
þ
Fe 3þ
þ HO2• ! Fe 2þ
þ O2 H ð10Þ
þ
Fe 2þ
þ HO2• þ H ! Fe 3þ
þ H2 O2 ð11Þ
HO þ HO ! H2 O2
• •
ð12Þ
2HO2• ! H2 O2 þ O2 ð13Þ

Briefly, the reaction between ferrous ions and H2O2 generates hydroxyl radicals
with high oxidative power (Eq. 4), which attack the organic compounds present in
the water (Eq. 5). Unfortunately, some parallel reactions take place, and so the
hydroxyl radicals are not only consumed to degrade the organic matter but also to
produce other radicals, with less oxidative power, or other species (scavenging effect
of HO•). Besides, this leads to the undesired consumption of H2O2 (Eq. 8) [4, 12,
13]. Thus, a suitable molar ratio of iron ion to H2O2 requires to be experimentally
determined for minimization of the unwanted scavenging [14]. According to Mota
et al., although a [Fe2+]/[H2O2] ratio of 1/2 has a higher destruction rate of organic
matters, it is generally recommended to use the 1/5 ratio, which yields similar results
and requires fewer reagents [3]. Besides, the ideal pH in Fenton’s reaction is at an
acidic pH condition (3) [3, 4]. Fe3+ can generate iron sludge at typical water and
wastewater treatment situations [14]. In other words, the generation of a substantial
amount of Fe(OH)3, which precipitates and causes additional water pollution, by the
homogeneous catalyst added as an iron salt that cannot be retained in the process, can
restrict the application of this system [4, 14, 47].
314 S. Jafarinejad

On the other hand, Eqs. (14) and (15) demonstrate a production of Fe2+ by the
reaction between H2O2 and Fe3+ (Fenton-like process); this way ferrous ion is
restored, acting as catalyst in the overall process [4, 12, 13, 48].
 2þ
Fe3þ þ H2 O2 $ FeIII ðHO2 Þ þ Hþ ð14Þ
 III 2þ
Fe ðHO2 Þ ! Fe2þ þ HO2• ð15Þ

In real, according to Andreozzi et al., and Ribeiro et al., the reduction of Fe3+ to
2+
Fe is often called “Fenton-like” process [48, 49]. This concept is also extensively
used to refer to variants of the Fenton process. For example, in the Fe /H2O2/H2SO4
Fenton-like process, zerovalent iron (Fe ) is applied directly, and the efficiency of
the process can rely on the gradual production of Fe2+ from Fe (Eq. 16), followed
by Fenton reaction (Eq. 4) [48, 50].

Feo þ H2 SO4 ! Fe2þ þ SO2

4 þ H2 ð16Þ

The Fenton-based processes can be divided into homogeneous and heteroge-

neous [1, 38, 43, 48, 51–55]. Generally, there are many variations of the Fenton
process [55] and Fenton-based processes may be classified as:
• Classical Fenton process [48]
• Photo-Fenton-like processes
• Electro-Fenton-like processes [48, 53]
• Cavitation-Fenton-like processes
• Microwave (another physical field)-Fenton-like processes [53]
• Fenton-like reactions using nano-zerovalent iron (nZVI) [52]
In the photo-Fenton-like systems, UV and/or visible light may be used to
decrease the catalyst loading and/or to enhance the catalytic capacity of the catalyst
in both heterogeneous and homogeneous Fenton-like processes with a major goal of
increasing the UV-induced reduction of dissolved Fe3+ to Fe2+ [14, 48, 53]. In the
electro-Fenton-like processes, either or both of the Fenton reagents may be pro-
duced by electrochemical methods [14]. An effective alternative for organic deg-
radation may be provided by acoustic cavitation (produced by the passage of high-
frequency sound waves, i.e., ultrasonic) and hydrodynamic cavitation (generated by
the pressure variations in the fluid because of a sudden alteration in the linear flow
rate of the fluid). The utilization of microwave irradiation in the Fenton-like
processes has offered evident superiority in comparison with the Fenton-like
process alone [53].
   
Zerovalent state metals (such as Fe , Zn , Sn , and Al ) can be effective agents
for the treatment of polluted water [53, 56, 57]. In heterogeneous Fenton reaction,
an alternative mean of inducing Fenton oxidation can be supplied by oxidation of
nZVI [53, 58, 59] as shown in Eq. (17) to overcome the disadvantages of homoge-
neous Fenton processes [53]:
Cost-Effective Catalytic Materials for AOP Treatment Units 315

Feo þ O2 þ 2Hþ ! Fe2þ þ H2 O2 ð17Þ

Ferrous ion concentration, H2O2 concentration, operating pH [52, 53], catalyst

type and dosage [53], initial concentration of pollutant, and operating temperature
[52] are parameters which may affect the efficiency of the Fenton-based processes.

3.1.2 Catalytic Materials Used in Fenton-Like Processes

Despite its high performance and simplicity [53, 60, 61] and its low toxicity [53, 62]
(H2O2 can decompose into environmentally friendly compounds such as water and
oxygen), Fenton process has some drawbacks such as high operating cost, narrow
optimum pH range, large volume of metal-containing sludge generation, difficulties
in recycling of the homogeneous catalyst (Fe2+) [53, 63], and the required iron ion
concentration range of 50–80 ppm for batch processes which is above the standards
(e.g., 2 ppm limit forced by the European Union (EU) directives for direct discharge
of wastewater into the environment) [53, 64]. To resolve some of the above
disadvantages, heterogeneous Fenton-like processes have been developed [65].
Replacing Fe2+ in the Fenton reagent with a solid catalyst can establish hetero-
geneous Fenton-like systems, while homogeneous Fenton-like systems are because
of a combination of other metal ions/metal ion-organic ligand complexes and H2O2
[53, 66]. In the homogeneous process, the catalysis can take place in the whole
liquid phase; meanwhile in the heterogeneous process, the catalysis always takes
place on the surface of the catalyst [53, 67, 68]. The surface characteristics and the
pore structure of the solid catalyst [33], stability, reusability, diffusion, and adsorp-
tion processes of H2O2 and other reactants to the surface of catalyst [53, 67, 68] are
important in the solid catalyzed Fenton reactions.
The removal rate of the organics in the wastewater can sometimes be improved
by enhancing the catalyst dosage. The excessive loading of catalyst in both hetero-
and homogeneous Fenton-like systems may have a negative effect on the waste-
water treatment due to the consumption of the generated hydroxyl radicals by the
excess catalyst. In addition, it may increase the treatment cost. Therefore, optimi-
zation of the catalyst loading in both hetero- and homogeneous Fenton-like systems
is essential [53].
In recent years, the application of solid catalysts in the so-called catalytic wet
peroxide oxidation (CWPO) or heterogeneous Fenton oxidation has extensively
been investigated [43]. Heterogeneous Fenton-like catalysts can be solids including
cations of transition metals [65, 69, 70]. The catalytic activity can be directly influ-
enced by metals and the selected support because they are important parameters in
the stability of the supported metal and its dispersion [65, 71, 72]. Various solid
catalysts such as metal oxide (CuO and Cu/Al2O3) [73], Fe-clay [74], metal oxide
impregnated activated carbon (Fe2MO4, M:Fe and Mn) [75], iron molybdate Fe2
(MoO4)3 [76], CuFeZSM-5 zeolite [77], Fe exchanged/supported on zeolite

[78–80], goethite [81], Fe /Fe3O4 composites [82, 83], nanomagnetite [84],
316 S. Jafarinejad

iron-containing SBA-15 [85–87], Al-Fe-pillared clays [88–90], Fe3O4 supported on

γ-Al2O3 and activated carbon as well as bare carbon materials (graphite) [91, 92],
and nZVI [93] manganese functionalized mesoporous molecular sieves Ti-HMS
[20] have been tested in Fenton reactions.
Different supports such as nafion [94], zeolite [95–99], silica [100], clay [101],
resins, and activated carbon [102, 103] have been applied to prepare heterogeneous
Fenton catalysts [33]. In real, carbon materials such as activated carbon, MWCNTs,
and reduced graphene oxide ((r)GO) and silicate materials such as mesoporous
silica, quartz, zeolite, and saponite may be applied as support for efficient hetero-
geneous Fenton catalysts because of the good chemical stability, high mechanical
strength, and low cost [54].
Munoz et al. reviewed magnetite-based catalysts and their application in het-
erogeneous Fenton oxidation [43]. In addition, Ezzatahmadi et al. [104] recently
reviewed clay-supported nZVI composite materials for the remediation of contam-
inated aqueous solutions. Besides, Wang et al. [53] reviewed catalyst types for
organic wastewater treatment in various Fenton-like processes.
Based on the reactive content and physicochemical properties, the iron-based
heterogeneous Fenton catalysts may be divided into five primary categories:
(1) zerovalent iron, (2) iron minerals and iron (hydr)oxides [magnetite (Fe3O4),
goethite (α-FeOOH), etc.], (3) multimetallic iron-based materials, (4) supported
iron-based materials (carbon-based materials as support, silicate-based materials as
support, and organic compound as support), and (5) horseradish peroxidase (HRP)-
based materials. Interfacial mechanisms of heterogeneous Fenton reactions cata-
lyzed by iron-based materials have been reviewed by He et al. [54].
Some researches have been carried out to develop non-Fe catalysts (e.g. Mn-,
Co-containing materials) as the substitute for Fe-based catalysts in Fenton reactions
[105–108]. For example, according to Song et al. [20], Mn contained (Ti-)HMS
catalyst may introduce a new type of Fenton-like catalyst, which can be environ-
mentally friendly and cost-effective and has superior efficiency for the reactive
hydroxyls generated in AOPs [20].

3.1.3 Cost-Effective Catalytic Materials Used in Fenton-Like Processes

Heterogeneous Fenton-like processes are cost-effective in overcoming the draw-

backs of homogeneous Fenton process [38]. The development of efficient and
low-cost catalytic materials to promote sufficient treatment in heterogeneous
Fenton-like systems is essential [7, 109]. The wastewater treatment cost can be
influenced by the source (nature, industrial waste, and artificial synthesis), prepara-
tion and modification method, activity, and stability of the heterogeneous catalysts.
On the other hand, prevention of precipitation/flocculation of the homogeneous
catalyst is critical due to the deactivation of the catalyst that can adversely affect
the decreasing of the wastewater treatment cost [53].
High Fenton activity, low cost, negligible toxicity, and easy recovery are
advantages of iron-based materials [54, 110, 111]. The use of natural minerals as
Cost-Effective Catalytic Materials for AOP Treatment Units 317

catalysts in CWPO is interesting because of their wide availability and low cost
[43]. Among iron-oxide minerals, magnetite is extensively used as catalyst in
heterogeneous Fenton oxidation because of its relatively high abundance, low
cost, and easy magnetic separation from the reaction medium [43, 110]. In addition,
ZVI can be applied as low-cost catalytic material in Fenton reaction [112]. High
production cost of ZVI is an important drawback which can be reduced by produc-
ing ZVI from waste iron oxide generated in steel works [113]. For example, Martins
et al. [112] tested low-cost materials such as red volcanic rock, sepiolite, and iron
shavings (coming from Fe processing industries) without modification as catalysts
during the Fenton-like process on the treatment of simulated and actual olive mill
wastewaters. They claimed that iron shavings can be promising low-cost catalytic
materials applied in Fenton’s reaction for the treatment of bio-refractory effluents in
batch or continuous operations [112]. In other works, Pereira and Freire [114] used
the recycled waste ZVI powder (iron particles discarded from a manufacturing
process) as an environmentally friendly and low-cost material for azo dye degra-
dation. Reduction in color and total organic carbon were reported to be 95% and
70%, respectively, under the optimum operational conditions (pH ¼ 3, [Fe] ¼ 5 g/
L, and iron particle size 250 μm) [114].
Manu et al. applied a novel iron catalyst source laterite soil as a cost-effective
material to degrade paracetamol in aqueous solutions by Fenton oxidation process.
At [H2O2]:[Laterite iron] ¼ 40:1, pH of 3, 10 mg/L initial concentration of paracet-
amol, and a reaction time of 60 min, the paracetamol and chemical oxygen demand
(COD) removals were reported to be 75 and 63, respectively. In addition, paracet-
amol degradation of 100% was reported with HPLC analysis in 240 min [115].
Due to the wide availability of clay minerals in nature, they can be considered as
low-cost alternatives to zeolites in many applications [116]. In recent years, the
pillared clays have been widely applied as catalysts for Fenton-like advanced
oxidation, specifically wet hydrogen peroxide catalytic oxidation (WHPCO) of
organic contaminants due to their high activity, reusability, easy recovery, envi-
ronmental compatibility, low cost, high stability of the active phase in the reaction
medium, and conducting oxidation at room temperature and atmospheric pressure.
According to Sanabria et al. [65], the combination of the biological and catalytic
oxidation with AlFe-pillared interlayered clays (PILCs) could attain a 96.7%
reduction of COD in coffee wet processing wastewater.
Song et al. [20] claimed that manganese functionalized mesoporous molecular
sieves Ti-HMS (Mn contained (Ti-)HMS) catalyst is a novel Fenton-like catalyst
that could be environmentally friendly and cost-effective and has superior effi-
ciency for the reactive hydroxyls generated in AOPs [20].
Because of high surface area, well-developed porous structure, variable surface
composition, good chemical resistance, and acceptable cost, activated carbon has
mostly been used as support [43, 117, 118]. Also, alumina (Al2O3) is extensively
used as catalyst support because of its mechanical, electrical, and chemical stability
and relatively low cost. Alumina-supported catalysts have demonstrated a consid-
erably higher stability in CWPO in comparison with carbon-based ones [43, 119].
318 S. Jafarinejad

3.2 Catalytic Ozonation

3.2.1 Principles

Because of the strong oxidative properties of ozone (O3), it can oxidize organic
compounds in aqueous solution by direct or indirect pathways [4, 120, 121]. Despite
the high demand of energy to generate ozone (high production cost) [3, 4, 13, 17,
121, 122] and efficiency dependence of ozone on gas-liquid mass transfer [3, 4, 13,
17, 123], its use in wastewater treatment has numerous advantages such as no
sludge remaining, minimal danger, easy performance, little space requirement,
one-step degradation, and easy conversion of residual ozone to oxygen and water
[121]. Having a high reduction potential (2.07 V), it can react with an organic
substrate (R in Eq. 18) [3, 4, 13, 17, 121, 124]. However, the application of ozone is
only defined as an AOP when it can decompose for hydroxyl radical generation
(Eq. 19) and can be catalyzed by hydroxyl ions in alkaline medium or by transition
metal cations (indirect type of ozonation) [3, 4, 13, 17, 120, 122, 124].

O3 þ R ! RO þ O2 ð18Þ
2O3 þ 2H2 O ! 2HO þ •
2HO2• þ O2 ð19Þ

The ozone decomposition mechanism in water is very complicated which may

be explained by the chain mechanism of Weiss as follows [120, 125, 126]:

O3 þ H2 O ! 2HO • þ O2 ð20Þ

O3 þ OH ! O2•  þ HO2• ð21Þ
O3 þ HO ! •
HO2• þ O2 ð22Þ
O3 þ HO2• ! HO •
þ 2O2 ð23Þ
2HO2• ! H2 O2 þ O2 ð24Þ

The efficiency of ozone in destructing organic pollutants can be enhanced in

combination with catalyst, H2O2, radiolysis, UV radiation, or ultrasound [3, 4, 13,
127, 128].
Ozonation reactions can be improved by applying heterogeneous or homoge-
neous catalysts [4, 127]. Homogeneous catalytic ozonation is based on ozone
activation by metal ions present in the reaction medium (aqueous solution), while
in heterogeneous catalytic ozonation, the major catalysts are metal oxides or
metals/metal oxide on supports [120, 128]. The possible mechanisms for homoge-
neous and heterogeneous catalytic ozonation have been given in some references
[120, 128, 129]. The removal of organic compounds from aqueous solutions can be
improved by homogeneous catalytic ozonation, but the costs of water treatment can
be enhanced due to the introduction of ions which result in the secondary pollution.
Heterogeneous catalytic ozonation can extensively be applied in water treatment
due to the higher stability, reusability, and lower loss of heterogeneous catalysts
Cost-Effective Catalytic Materials for AOP Treatment Units 319

that improve the efficiency of ozone decomposition [129]. In the heterogeneous

system, ozonation can occur not only in the bulk solution but also in all the
interfaces involved between the different phases present in the reaction media
[116, 120, 130]. Simplified scheme of the catalytic ozonation pilot is shown in
Fig. 1, which includes an ozone generator, a continuous stirred tank reactor
containing the suspended catalyst powder with an ozone distribution system, a
recirculation loop with a membrane module for the catalyst separation from the
treated effluent, and residual ozone destruction unit (an oven at 475  C)
[131, 132]. The catalyst, its surface properties, the pH of the solution (influences
the characteristics of the surface active sites and ozone decomposition reactions in
wastewater), etc. can affect the efficiency of the catalytic ozonation process
[129]. Selection of catalysts is the most important parameter for heterogeneous
systems [120].
Addition of hydrogen peroxide to ozone (this mixture is called peroxone pro-
cess) can start the decomposition cycle of ozone [4, 127], in which hydroxyl
radicals can be formed as follows [3, 4]:

O3 þ H2 O2 ! HO • þ HO2• þ O2 ð25Þ

UV radiation can readily be absorbed at 254 nm wavelength by ozone, generat-

ing as an intermediate hydrogen peroxide (Eq. 26), which can then be decomposed
to hydroxyl radicals under exposure of UV radiation as shown by Eq. (27) [3, 4,
127]:

Fig. 1 Simplified schematic of the catalytic ozonation pilot (modified from [131, 132])
320 S. Jafarinejad

hv
O3 þ H2 O ! H2 O2 þ O2 ð26Þ
hv
H2 O2 ! 2HO • ð27Þ

The production of hydroxyl radicals may also be accelerated by combined use of

ultrasound and ozone due to the reduction of mass transfer limitations resulting
from the turbulence generation by the acoustic current induced by ultrasound [3, 4,
123].

3.2.2 Catalytic Materials Used in Catalytic Ozonation

In homogeneous catalytic ozonation, several transition metals such as Fe2+, Fe3+,

Mo6+, Mn2+, Ni2+, Co2+, Cd2+, Cu2+, Ag+, Cr3+, and Zn3+ have been used as
homogeneous solutions in ozonation media [4, 116, 120, 127–129, 133], whose
nature determines the reaction rate, selectivity of ozone oxidation system, ozone
consumption, and the efficiency of ozone application [120, 134, 135]. The highest
catalytic performances have been demonstrated by bivalent cations and more
especially by Fe2+ions [116, 136, 137].
In heterogeneous catalytic ozonation, metal oxides (MnO2, TiO2, Al2O3,
FeOOH, ZnO, Fe2O3, WO3, CuO, Ni2O3, CoO, V2O5, Cr2O3, MoO3, CeO, and
CeO2), metals (Cu, Ru, Pt, Pb, Pd, Co, etc.) or metal oxides (Fe2O3, TiO2, Co3O4,
CuO, etc.) on supports (SiO2, Al2O3, TiO2, CeO2, ZrO2, activated carbon, clay,
silica gel, ceramic honeycomb, and so on), zeolites and related catalysts, carbon-
based materials as catalysts or catalyst supports (activated carbon, granulated
activated carbon (GAC), carbon black powder and graphite, multiwalled carbon
nanotubes (MWCNTs), etc.), modified activated carbon, mixed hydroxide cata-
lysts, and natural minerals have been applied as catalysts [4, 116, 120, 127–129,
133, 135, 138–141].
Shahidi et al. reviewed oxidative water treatments with emphasis on catalytic
ozonation [116]. In addition, Fe-based catalysts for heterogeneous catalytic ozon-
ation of emerging pollutants in water and wastewater have been reviewed by Wang
and Bai [142]. Besides, Xiao et al. [138] and Mehrjouei et al. [143] reviewed
heterogeneous photocatalytic ozonation for the removal of contaminants from
wastewater.

3.2.3 Cost-Effective Catalytic Materials Used in Catalytic Ozonation

Catalyst activity, simplicity of preparation, preparation time, cost [144], nontoxicity,

availability, environmental suitability [145], etc. can be important parameters in the
catalyst selection. High costs, cumbersome preparations, and environmental
unsuitability can usually hinder the industrial applicability of a catalyst [145]. TiO2
is a common and low-cost catalyst extensively applied in photo-oxidative processes,
Cost-Effective Catalytic Materials for AOP Treatment Units 321

especially photocatalytic ozonation [116, 146]. Due to relatively low-cost,

nontoxicity, and availability of WO3, it may be an interesting alternative to TiO2
for the photocatalytic ozonation under visible or solar light radiation [147]. Fe2O3
has been proposed as an attractive and efficient catalyst for treatment, especially for
the removal of color from distillery wastewater, due to its cost-effectiveness and
nontoxicity [148]. High catalytic capacity, low cost, and low toxicity of ZnO make it
promising catalyst for catalytic ozonation [149, 150]. Copper oxide may be cost-
competitive, chemically stable, and nontoxic in the catalytic ozonation
process [151].
Clay minerals with extensive abundance in nature can be low-cost alternatives to
zeolites in different applications, especially in catalytic ozonation [116, 152,
153]. Natural raw mixtures of clay minerals, volcanic ashes, silicas, carbonates,
and miscellaneous are different types of clays [116, 152]. The clays from smectite
mineral family, more specifically montmorillonite, the major component of ben-
tonites, are attractive and low-cost aluminosilicates [116].
Recycling/reusing of particular wastes to manufacture a catalyst for the ozona-
tion process can be cost-effective and “wastes-treat-wastes” or “green” strategy
[145, 154]. Cobalt doped red mud (Co/RM) (RM from the alumina industry waste
as the catalyst supporter) has been applied in the catalytic ozonation for bezafibrate
destruction in water; better performance and detoxification than using un-doped
RM has been reported. The higher catalytic activity in Co/RM can be due to the
presence of Fe, Al, Si, and Ti oxides and oxyhydroxides in RM as potential reaction
sites and the surface modification by cobalt oxide [155, 156]. Sewage sludge was
reused as a catalyst in the ozonation process by Wen et al. [157]. Sludge-based
catalyst (SBC) was prepared with ZnCl2 as activation agent. The removal efficiency
of oxalic acid was reported to be improved by 45.4% with simultaneous application
of ozone and SBC in comparison with that of single SBC adsorption plus ozone
alone, which demonstrates a strong synergistic effect [157]. The spent fluid cata-
lytic cracking catalysts (sFCCc), a typical petrochemical waste, were recycled and
applied for the advanced treatment of petrochemical wastewater by Chen et al.
[145]. Al2O3 and various types of zeolites are the main components of sFCCc that
can have excellent adsorptive and catalytic performance. In addition, the metal
oxides in the waste which poisoned FCCc could be the active components of
catalytic ozonation. Hydroxyl radical generation and hydroxyl radical-mediated
oxidation could be promoted by multivalent vanadium (V4+ and V5+), iron (Fe2+
and Fe3+), and nickel (Ni2+) oxides which were highly distributed on the surface of
sFCCc. The sFCCc assisted catalytic ozonation (sFCCc-O) showed high potential
for the treatment of bio-refractory wastewaters and enhanced to threefold the COD
removal compared to single ozonation. Besides, nonbiodegradable polar contami-
nants were remarkably destructed [145]. Wu et al. used recycled waste iron
shavings as a catalyst for the catalytic ozonation of organic pollutants from actual
bio-treated dyeing and finishing wastewater (BDFW) [158]. The effluent COD level
reported to meet the discharge limitation of 80 mg/L. The iron shavings with their
high stability and excellent reusability at a low cost and without the requirement for
322 S. Jafarinejad

separation from the treated effluent can be appropriate for both successive batch
process and continuous (flow) process [158].

3.3 Heterogeneous Photocatalysis

3.3.1 Principles

For the first time, the term photocatalysis was introduced in the 1930s as a new
branch of catalysis [4, 37, 159]. Promotion or acceleration of a chemical reaction
under the action of light in the presence of photocatalysts which absorb light quanta
and are involved in the chemical transformations of the reaction components is
called photocatalysis [37, 160, 161]. In the heterogeneous photocatalysis, the
catalyst occurs in a different phase than the reaction medium [162]. Since 1972,
when Fujishima and Honda [163] reported the photochemical splitting of water into
hydrogen and oxygen in the presence of TiO2, heterogeneous photocatalysis has
been interestingly investigated [4, 159, 164–166]. Since the 1980s, this process has
been evaluated and examined with great success by various scientists for environ-
mental (air, water, and soil) applications [3, 4, 13, 159, 167].
According to Mota et al. [3], heterogeneous photocatalysis principle (Fig. 2) is
based on the activation of a semiconductor material such as TiO2 by the action of
radiation with a suitable wavelength (e.g., with the light of λ < 390 nm). With the
absorption of photons by the semiconductor particulate possessing enough energy
to promote the conduction of an electron (e) from its valence band (VB) to the
conduction band (CB) (a transition called band gap energy), activation is attained
generating holes in the valence band (h+) that will act as oxidizing sites [3, 4, 13]. In
other words, illumination onto a photocatalyst excites to produce electron and hole
pair (e/h+) with high-energy state, which move to the particle surface, where they
take part in redox reactions with adsorbed species and, thus, form superoxide
radical anion (O2•) and hydroxyl radical as follows [4, 121, 159, 168–172]:

TiO2 ! TiO2 ðe þ hþ Þ

hv
ð28Þ

e þ O2 ! O2•  ð29Þ
hþ þ H2 O ! OH þ Hþ•
ð30Þ
þ 
h þ OH ! OH •
ð31Þ

The generated radicals are applied as powerful oxidizing agents to transform

organic contaminants into H2O, CO2, and less toxic by-products [4, 13, 18, 168,
169, 171]. The generated hydroxyl radical attacks organic compounds as follows
[173]:
Cost-Effective Catalytic Materials for AOP Treatment Units 323

Fig. 2 Typical mechanism of TiO2 in solar photocatalysis process (modified from [4, 166, 171])

OH • þ Organic ðRÞ ! Intermediates ! CO2 þ H2 O ð32Þ

According to Bockelmann et al. [174] and Mota et al. [3], the heterogeneous
photocatalytic process may also be favored by the addition of H2O2, given that, like
O2, it may act as the acceptor of electrons present in the system, producing hydroxyl
radicals as follows [3, 4, 174]:

e þ H2 O2 ! HO • þ HO ð33Þ

In the photocatalytic systems, artificial sources (e.g., UV polychromatic lamps)

or the sun may be utilized as radiation sources. Solar light-based photocatalytic
degradation systems are of interest because of economical aspects [4, 121, 170,
175].
The major factors that can affect the performance of heterogeneous
photocatalytic process in water and wastewater treatment are the initial organic
load or initial concentration of substrate, catalyst and state of catalyst, amount of
catalyst, reactor’s design, irradiation source, UV irradiation time, temperature,
solution’s pH, light intensity, and the presence of ionic species [4, 7, 121, 170].
Wastewater treatment photocatalytic reactors can be classified based on their
design characteristics such as the state of the photocatalyst, type of illumination,
and position of the irradiation source [4, 170]. The reactors may be categorized
according to the state of the photocatalyst into two main groups: (1) a suspension/
slurry type and (2) thin film type [4, 18, 165, 170]. The slurry reactor needs an
additional downstream separation unit for the photocatalyst particles’ recovery
while the second one permits a continuous operation [176]. Efficient illumination
of the catalyst can be the major challenge in the design of a photocatalytic reactor
[4, 166]. The annular slurry photoreactor, cascade photoreactor, downflow
324 S. Jafarinejad

contactor reactor, etc. have been applied in the photocatalytic water and waste-
water treatment [176].

3.3.2 Catalytic Materials Used in Heterogeneous Photocatalysis

An ideal photocatalyst should be photoactive, biologically and chemically inert,

stable toward photo-corrosion, suitable for visible or near UV light energy
harnessing, low cost, nontoxic, and environmentally friendly [4, 166].
Various materials such as oxides (TiO2, ZnO, SiO2, SnO2, WO3, ZrO2, CeO,
Nb2O3, Fe2O3, MgO, etc.) [4, 121, 165, 177, 178], mixed oxides (SrTiO3, Co-TiO2
nanocatalysts [179], FeTiO3 [180]), sulfides (CdS, ZnS, etc.), GaP [177],
semiconductor-conjugated CP composites [e.g., AgI/UiO-66 (zirconium-based
metal-organic framework) photocatalyst] [177, 181], Ag/BiVO4 composite [182],
10:100 (w/w) of oxidized multiwalled carbon nanotube (MWCNTox)-anatase
(10-MWCNTox-TiO2) composite [183], graphitic carbon nitride (g-C3N4)/semicon-
ductor (CNS) nanocomposites [184], etc. have been applied in photocatalysis.
TiO2 is an excellent photocatalyst due to its high resistance to photo-corrosion
and desirable bandgap energy, availability in the market, chemical inertness and
durability, and nontoxicity [4, 165]. Anatase and rutile are the most common
crystalline forms of TiO2, while brookite is an uncommon form which is unstable.
Having more open structure in comparison with rutile, anatase is more efficient than
rutile in photocatalytic utilizations. The commercially available form of TiO2 is
Degussa P25 which includes two forms of ca. 25% rutile and 75% anatase [4, 166].
Supports can play a major role in immobilizing active catalyst, increasing the
surface area of catalytic material, sintering reduction, and improving hydrophobic-
ity, thermal, hydrolytic, and chemical stability of the catalytic material [4, 166]. Acti-
vated carbon, fiber-optic cables, fiberglass, glass, glass beads, glass wool,
membranes, quartz sand, zeolites, silica gel, stainless steel, Teflon, clays, polymeric
materials, pumice stone, monoliths, cellulose, and others have been studied as TiO2
supports [4, 170, 176, 185].

3.3.3 Cost-Effective Catalytic Materials Used in Heterogeneous

Photocatalysis

If the photocatalyst is nonrecyclable, cost efficiency will be a concern. Photocatalysts

which apply rare metals can be expensive due to their low abundance. Treatment cost
can be low when photocatalysts are recyclable [186, 187].
Among the photocatalysts studied for photodegradation, TiO2 and ZnO have
intensively been used due to their low cost, high efficiency and quantum yield,
resistance to photo-corrosion, and safe handling [188, 189]. TiO2 is the most
extensively applied catalyst in heterogeneous photocatalysis to destruct a large
range of contaminants due to its wide bandgap (3.03 eV for rutile, 3.18 eV for
anatase) [183, 190], spectral overlap with sunlight emission (about 5%) [183],
Cost-Effective Catalytic Materials for AOP Treatment Units 325

photostability, nontoxicity, low cost [183, 191], availability, high photoactivity,

environmentally friendly [192], and water insolubility under most environmental
conditions [191].
Natural clays (bentonite, sepiolite, montmorillonite, and kaolinite) and zeolites
have been widely reported in the literature as supports for TiO2 due to their high
adsorption capacity and cost-effectiveness [176].
Singh et al. developed an effective and low-cost TiO2/polystyrene floating
photocatalyst using solvent-cast method for environmental application and the
color removal efficiency by the optimized photocatalyst on reuse reported to be
in the range of 99–100% [193].
Garcı́a-Mu~noz et al. assessed ilmenite mineral (FeTiO3) as low-cost catalyst in
different AOPs (photocatalysis, CWPO, and CWPO-photoassisted processes) using
phenol as target compound. Results revealed a scarce activity of ilmenite in
photocatalytic process. But, ilmenite mineral has demonstrated to be active and
highly stable catalyst for CWPO-photoassisted process; a complete phenol and
H2O2 conversion and a TOC conversion higher than 95% were reported to be
attained at pH 3 and 25  C with 500 mg/L of ilmenite and the stoichiometric
amount of H2O2 [180].

3.4 Catalytic Wet Air Oxidation (CWAO)

3.4.1 Principles

Zimmermann [194] originally developed the WAO process and the first industrial
utilizations of WAO appeared in the late 1950s [195–198]. Generally, the oxidation
of soluble or suspended organic or inorganic substances in an aqueous solution by
means of oxygen or air as the oxidizing agent at elevated temperatures and
pressures is called WAO process [4, 197, 199–201]. The temperature usually varies
from approximately 175 to 320  C [4, 199] or 150 to 320  C [4, 200]. Hydroxyl
radicals are formed in this process [3, 4]. The products of WAO system can be
determined by the degree of oxidation. For high degrees of oxidation, organic
matter can mainly be transformed to CO2 and H2O [4, 199]. The following reaction
can explain the typical material balance for the WAO process where the heat value
is close to 435 kJ/(mole O2 reacted) [4, 202]:

Cm Hn Ok Clw Nx Sy Pz þ ½m þ 0:25ðn  3xÞ  0:5k þ 2ðy þ zÞO2 !

ð34Þ
mCO2 þ 0:5ðn  3xÞH2 O þ xNH3 þ wCl þ ySO2 4 þ zPO4 þ heat
3

Temperature, pressure, inert gas flow rate, pH evolution during oxidation, etc.
are factors which can affect the efficiency of a WAO system and should be
considered during reactor design [4, 202].
More than 200 WAO treatment plants have been built around the world, the
majority to treat sewage sludge. Other major fields of utilization include the
326 S. Jafarinejad

regeneration of activated carbon and the treatment of industrial wastewater (e.g.,

petrochemical, chemical, and pharmaceutical wastewaters) [197, 198, 203].
Application of WAO units can be very useful for the treatment of a variety of
refractory organic contaminants in wastewater, but the need of high pressure and
high temperature for its operation restricts their practical utilization; thus, CWAO
has been suggested to relax the oxidation conditions [204, 205]. CWAO is an
improvement over the WAO process by the introduction of a catalyst (homoge-
neous or heterogeneous) in the reaction [3, 4, 201, 206].
The development of commercial CWAO units began as early as the mid-1950s
in the USA [198, 207, 208]. In Japan, several companies developed CWAO
technologies based on heterogeneous catalysts including precious metals deposited
on titania or titania-zirconia oxides. In Europe, the interest was more on homoge-
neous CWAO. In recent years, various homogeneous CWAO processes based on
this concept (e.g., Ciba-Geigy, LOPROX, WPO, ORCAN, and ATHOS processes)
have been developed [198, 208, 209]. A scheme of the Bayer LOPROX process
(with Fe2+ ions as catalyst) is shown in Fig. 3. NS-LC (with Pt-Pd/TiO2-ZrO2
honeycomb catalyst), Osaka gas (with ZrO2 or TiO2 with noble or base metal
catalyst), Kurita (with supported Pt catalyst), and CALIPHOX (with a metal
oxide catalyst, e.g., CuO-ZnO-Al2O3) processes are examples of industrial hetero-
geneous CWAO processes [198, 210].

Fig. 3 Schematic of the Bayer LOPROX process (modified from [211])

Cost-Effective Catalytic Materials for AOP Treatment Units 327

3.4.2 Catalytic Materials Used in CWAO

Homogeneous and heterogeneous catalysts can be applied in CWAO process.

Selection of the suitable catalyst for CWAO system not only can reduce the severity
of reaction conditions, but it can also increase the degradation of refractory organic
contaminants, resulting in diminishing investment and operational cost [209, 212,
213]. Homogeneous catalysts such as dissolved salts of Cu, Fe, Ni, Co, Mn, etc.
have successfully been applied in CWAO process [214, 215]. Generally, the
homogeneous catalysts, such as dissolved copper salts, are regarded as effective,
but an additional separation step (e.g., precipitation or membrane separation) is
required for the removal or recovery of metal ions from the treated effluent because
of their toxicity, which substantially enhances operational costs [213, 216]. Note
that homogeneous catalyst utilization should be assessed in the early process design
stage based on the existing discharge standards or regulations either in the liquid or
solid phases [198, 208].
Various heterogeneous catalysts including supported noble metals and metal
oxides (as well as mixed metal oxides) have been widely studied to enhance the
efficiency of CWAO [4, 21, 198, 211, 217–220]. Heterogeneous catalysts show
very high activity and stability. They can be easily separated by filtration from the
treated solution [216]. However, deactivation phenomena and leaching of active
metals to the liquid phase can exist. For this reason, metal-free carbon materials
have been evaluated as catalysts in various CWAO utilizations, including activated
carbons [220–222], carbon xerogels [223, 224], multiwalled carbon nanotubes
[225–227], carbon foams and fibers enriched with nitrogen [220, 228], and
graphene oxide (GO) and chemically reduced graphene oxides [229]. Stuber et al.
reviewed the application of carbon materials as catalytic supports or direct catalyst
in CWAO of organic pollutants [221]. The employed heterogeneous catalysts in
CWAO are listed in Table 2.
Tailoring of catalyst for each particular application is essential and inexpensive
materials should be used for its preparation. Oxides of Zr, Ce, and Ti may be
applied as stable supports. Metal oxide catalysts can be very active but unstable due
to leaching. The catalytically active compounds must be incorporated into a lattice
of catalyst support to decrease leaching. If this is not practicable, precious metals
should be applied in the catalytic active phase [208].

3.4.3 Cost-Effective Catalytic Materials Used in CWAO

Soluble transition metal catalysts based on iron or copper salts have been used in
various commercial WAO plants, which were successfully employed in the treat-
ment of industrial effluents and sludge [198, 208].
High catalytic activity, long life cycle, and strong adaptability are demonstrated
by precious metals such as Pt and Pd; however, their utilizations are restricted due
to high cost [231, 232]. Thus, a catalyst for CWAO comparable to noble metal
328 S. Jafarinejad

Table 2 Some of the employed heterogeneous catalysts in CWAO process [4, 21, 198, 211, 217–
230]
Type of catalyst Description
Noble metals Pt supported on γ-Al2O3; Ru, Ir, Pd, Ag, base metals supported
on CeO2, TiO2, ZrO2; Pt supported on C; Pt supported on resin;
Pt supported on SDB resin; Rh supported on TiO2, CeO2, C;
Pt-Ru supported on C; Pd, Pd-Pt supported on ALONTM; Pd-Pt-
Ce supported on γ-Al2O3
Metal oxides (as well as Cu/Cr oxides; Cu/Cr/Ba/Al oxides; Co, Fe, Mn, Zn oxides with
mixed metal oxides) Cu oxides supported on γ-Al2O3; CuO supported on γ-Al2O3;
Cu/Ni/Al oxides; CuO/ZnO/CoO supported on cement;
CuO/ZnO supported on γ-Al2O3; CuO/CeO2; K-MnO2/CeO2;
MnO2/CeO2; CuO supported on C; MnO2, Co2O3; Ni-oxide;
Cu/Zn/Cr/Ba/Al oxides; Fe2O3; Cu/Mn/La supported on
ZnO-Al2O3; Ce/Zr/Cu oxides or Ce/Zr/Mn; Cu-Fe-La
supported on γ-Al2O3
Carbon materials Activated carbons; carbon xerogels; multiwalled carbon
nanotubes; carbon foams and fibers enriched with nitrogen;
graphene oxide and chemically reduced graphene oxides

catalysts is highly wanted. Transition metal catalysts are low cost, and introduction
and removal of the lattice oxygen in transition metal oxides can be easily done.
They are extensively employed due to their high catalytic activity [230, 233–
235]. In other words, according to Kim and Ihm [21], with regard to cost and
resistance to poisoning by halogen-containing compound, base metal oxide cata-
lysts can be more desirable than noble metals, though their catalytic activities are
still lower than noble metals. The most futuristic species of them to challenge with
noble metals can be Cu, Mn, and Ce [21].

3.5 Catalytic Supercritical Water Oxidation (CSCWO)

3.5.1 Principles

A promising process which takes place in an aqueous medium at temperatures and

pressures above the critical point of water (Tc ¼ 374  C and Pc ¼ 22.1 MPa) is
called SCWO [4, 15, 16, 19, 236–245]. A smaller amount of hydrogen bonds, a
lower dielectric constant, a lower viscosity, and a higher diffusion coefficient
compared to normal water are characteristics of supercritical water [4, 240]. Having
unique properties under these conditions, supercritical water can be utilized as a
reaction medium to produce nanoparticles, destruct organic compounds, etc. In
general, operational temperature and pressure ranges in SCWO process are
400–600  C and of 24–28 MPa, respectively [4, 16, 19].
Degradation of organic wastes is the primary use of SCWO technology [4, 16,
246]. Formation of a single phase environment by dissolving organic substances
and oxidants (such as air, or pure oxygen, or H2O2) into supercritical water can
Cost-Effective Catalytic Materials for AOP Treatment Units 329

overcome the interphase mass transfer resistance and enhance the whole reaction
rate. In this process, organic matter can be destructed into small molecular com-
pounds such as CO2, N2, H2O, etc., and heteroatoms may also be converted into
their mineral acids [4, 240]. Removal rates higher than 99% can be attained with
residence times shorter than 1 min. This technology will not generate a secondary
pollution [4, 237, 246].
The technology of waste treatment by SCWO was suggested by Medoll in the
1980s [247]. Since then, a wide variety of toxic and hazardous industrial wastes has
been successfully treated by SCWO which has been reviewed by some researchers
[4, 237, 240, 246]. In real, commercial-scale SCWO plants have been employed in
the USA, the UK, Japan, China, Sweden, etc. [4, 237, 240, 246]. The main
disadvantages of SCWO which still exist and even make some commercial-scale
SCWO plants inactive are corrosion, plugging, and high running costs [4, 237, 240,
248].
The oxidation rate enhancement, the residence time and operational temperature
reduction, and possibly a better selectivity for competing reaction pathways can be
attained by catalysts [244, 249]. CSCWO is an amelioration over the SCWO system
by the introduction of a catalyst (homogeneous or heterogeneous) in the reaction.
Effective use of a catalyst in CSCWO process has the ability to reduce reactor
temperature and the energy consumption of the device and oxidant concentration
and improve the CO2 formation efficiency, which makes this process to be much
more feasible for practical use in the aspects of device safety, durability, and
economy [241, 250, 251].

3.5.2 Catalytic Materials Used in CSCWO

The applied catalysts in CSCWO may be generally divided into noble metals, metal
oxides, and transition metal salts [241]. In real, H4Si12O40 [252], activated carbon
[31, 253], CuO/ZnO/CoO supported on porous cement [254], MnO2/CeO2, V2O5/
Al2O3 [255], Carulite 150, a commercial catalyst [256], TiO2 [257], MnO2
[244, 258], CuO, CuO/Al2O3 [30], MnO2/CuO [259], Mn2O3/Ti-Al oxide compos-
ite catalyst [245], Ni/Al2O3 [260], Pt/γ-Al2O3 [261], NaOH [262], CuSO4
[241, 263], CuNO3, FeCl3, (Fe)2(SO4)3, V2O5, MnSO4, FeSO4 [263], ZnSO4
[264], etc. have been studied as catalysts in the CSCWO of organic components.

3.5.3 Cost-Effective Catalytic Materials Used in CSCWO

Some frequently used homogeneous catalysts in CSCWO such as Cu2+ have shown
to be an efficient catalyst [241, 265, 266]. Transition metal catalysts can be
generally low cost [230, 233–235].
330 S. Jafarinejad

4 Conclusions

In this chapter, overview of AOPs, catalytic AOPs (Fenton-based processes, cata-

lytic ozonation, heterogeneous photocatalysis, catalytic wet air oxidation, and
catalytic supercritical water oxidation), related catalytic materials, and cost-
effective catalytic materials used in these processes have been discussed.
The use of natural minerals as catalysts in CWPO is interesting because of their
wide availability and low cost. In addition, ZVI can be applied as low-cost catalytic
material in Fenton reaction. Activated carbon has mostly been used as support.
Also, alumina-supported catalysts have demonstrated a considerably higher stabil-
ity in CWPO in comparison with carbon-based ones.
TiO2 is a common and low-cost catalyst extensively applied in photo-oxidative
processes, especially photocatalytic ozonation. Due to relatively low cost,
nontoxicity, and availability of WO3, it may be an interesting alternative to TiO2
for the photocatalytic ozonation under visible or solar light radiation. Clay minerals
with extensive abundance in nature can be low-cost alternatives to zeolites in
different applications, especially in catalytic ozonation. Recycling/reusing of par-
ticular wastes (such as SBC, sFCCc, etc.) to manufacture a catalyst for the ozon-
ation process can be cost-effective and “wastes-treat-wastes” or “green” strategy.
Among the photocatalysts studied for photodegradation, TiO2 and ZnO have
intensively been used due to their low cost, high efficiency and quantum yield,
resistance to photo-corrosion, and safe handling. Natural clays (bentonite, sepiolite,
montmorillonite, and kaolinite) and zeolites have been widely reported in the
literature as supports for TiO2 due to their high adsorption capacity and cost-
effectiveness.
Soluble transition metal catalysts based on iron or copper salts have been used in
various commercial WAO plants, which were successful in the treatment of indus-
trial effluents and sludge.
Some frequently used homogeneous catalysts in CSCWO such as Cu2+ have
shown to be an efficient catalyst. Transition metal catalysts can be generally low cost.

References

1. Litter MI, Quici N (2010) Photochemical advanced oxidation processes for water and
wastewater treatment. Rec Pat Eng 4:217–241
2. Covinich LG, Bengoechea DI, Fenoglio RJ, Area MC (2014) Advanced oxidation processes
for wastewater treatment in the pulp and paper industry: a review. Am J Environ Eng 4
(3):56–70
3. Mota ALN, Albuquerque LF, Beltrame LTC, Chiavone-Filho O, Machulek A Jr, Nascimento
CAO (2008) Advanced oxidation processes and their application in the petroleum industry: a
review. Brazil J Petrol Gas 2(3):122–142
4. Jafarinejad S (2017) Petroleum waste treatment and pollution control. 1st edn. Elsevier Inc.,
Butterworth-Heinemann, USA
Cost-Effective Catalytic Materials for AOP Treatment Units 331

5. Badriyha BN, Song W, Ravindran V, Pirbazari M (2007) Advanced oxidation processes for
destruction of endocrine disrupting chemicals in water treatment: comparison of free-radical
reaction mechanisms, pathways and kinetics. 2007 AIChE Annual Meeting
6. Hofman-Caris CHM, Harmsen DJH, Beerendonk EF (2010) Advanced oxidation processes,
degradation of priority compounds by UV and UV-oxidation. TECHNEAU, deliverable
number D 2.4.1.2b, Dec 2010
7. Stasinakis AS (2008) Use of selected advanced oxidation processes (AOPs) for wastewater
treatment – a mini review. Global NEST J 10(3):376–385
8. Ikehata K, Jodeiri Naghashkar N, Gamal El-Din M (2006) Degradation of aqueous pharma-
ceuticals by ozonation and advanced oxidation processes: a review. Ozone Sci Eng 28
(6):353–414
9. Remya N, Lin JG (2011) Current status of microwave application in wastewater treatment – a
review. Chem Eng J 166:797–813
10. Glaze WH (1987) Drinking-water treatment with ozone. Environ Sci Technol 21(3):224–230
11. Fu J, Kyzas GZ (2014) Wet air oxidation for the decolorization of dye wastewater: an
overview of the last two decades. Chin J Catal 35:1–7
12. Santos MSF, Alves A, Madeira LM (2011) Paraquat removal from water by oxidation with
Fenton’s reagent. Chem Eng J 175:279–290
13. Jafarinejad S (2015) Recent advances in determination of herbicide paraquat in environmen-
tal waters and its removal from aqueous solutions: a review. Inter Res J Appl Basic Sci 9
(10):1758–1774
14. Deng Y, Zhao R (2015) Advanced oxidation processes (AOPs) in wastewater treatment. Curr
Pollution Rep 1:167–176
15. Jafarinejad S, Abolghasemi H, Golzary A, Moosavian MA, Maragheh MG (2010) Fractional
factorial design for the optimization of hydrothermal synthesis of lanthanum oxide under
supercritical water condition. J Super Fluid 52:292–297
16. Jafarinejad S (2014) Supercritical water oxidation (SCWO) in oily wastewater treatment.
National e-conference on advances in basic sciences and engineering (AEBSCONF), Iran
17. Jafarinejad S (2015) Ozonation advanced oxidation process and place of its use in oily sludge
and wastewater treatment. 1st international conference on environmental engineering
(eiconf), Tehran, Iran
18. Jafarinejad S (2015) Heterogeneous photocatalysis oxidation process and use of it for oily
wastewater treatment. 1st international conference on environmental engineering (eiconf),
Tehran, Iran
19. Sabet JK, Jafarinejad S, Golzary A (2014) Supercritical water oxidation for the recovery of
dysprosium ion from aqueous solutions. Inter Res J Appl Basic Sci 8(8):1079–1083
20. Song H, You JA, Chen C, Zhang H, Ji XZ, Li C, Yang Y, Xu N, Huang J (2016) Manganese
functionalized mesoporous molecular sieves Ti-HMS as a Fenton-like catalyst for dyes
wastewater purification by advanced oxidation processes. J Environ Chem Eng 4:4653–4660
21. Kim KH, Ihm SK (2011) Heterogeneous catalytic wet air oxidation of refractory organic
pollutants in industrial wastewaters: a review. J Hazard Mater 186:16–34
22. Mahamuni NN, Adewuyi YG (2010) Advanced oxidation processes (AOPs) involving
ultrasound for waste water treatment: a review with emphasis on cost estimation. Ultrason
Sonochem 17:990–1003
23. Huang CP, Dong C, Tang Z (1993) Advanced chemical oxidation: its present role and
potential future in hazardous waste treatment. Waste Manag 13:361–377
24. Loures CCA, Alc^antara MAK, Filho HJI, Teixeira ACSC, Silva FT, Paiva TCB, Samanamud
GRL (2013) Advanced oxidative degradation processes: fundamentals and applications. Inter
Rev Chem Eng 5(2):102–120
25. Jelonek P, Neczaj E (2012) The use of advanced oxidation processes (AOP) for the treatment
of landfill leachate. Inżynieria i Ochrona Środowiska 15(2):203–217
26. Trapido M (2008) Ozone-based advanced oxidation processes, ozone science and technol-
ogy. Encyclopedia of Life Support Systems (EOLSS), Developed under the Auspices of
UNESCO, 1–17. http://www.eolss.net/sample-chapters/c07/e6-192-07a-00.pdf
332 S. Jafarinejad

27. Kalra SS, Mohan S, Sinha A, Gurdeep Singh G (2011) Advanced oxidation processes for
treatment of textile and dye wastewater: a review. 2nd international conference on environ-
mental science and development IPCBEE, vol 4. IACSIT Press, Singapore, pp 271–275
28. Burgos AJ, Rodriguez PU, Lopez JS (2015) Advanced oxidation processes (AOPs), series:
advanced treatments, technology fact sheets for effluent treatment plants of textile industry,
INDITEX, FS-AVA-001, 1-27
29. Sharma S, Ruparelia JP, Patel ML (2011) A general review on advanced oxidation processes
for waste water treatment. Institute of Technology, Nirma University, Ahmedabad – 382 481,
08-10 December, 1–7
30. Yu J, Savage PE (2000) Phenol oxidation over CuO/Al2O3 in supercritical water. Appl Catal
Environ 28(3–4):275–288
31. Matsumura Y, Urase T, Yamamoto K, Nunoura T (2002) Carbon catalyzed supercritical
water oxidation of phenol. J Super Fluids 22(2):149–156
32. Adewuyi YG, Peters RW (2013) Fundamental developments and economic feasibility of
AOPs involving ultrasound for environmental remediation. Core Programming Area at the
2013 AIChE Annual Meeting: Global Challenges for Engineering a Sustainable Future, San
Francisco, CA, USA, 3–8 Nov 2013. https://www3.aiche.org/Proceedings/content/Annual-
2013/extended-abstracts/P342115.pdf
33. Blanco M, Martinez A, Marcaide A, Aranzabe E, Aranzabe A (2014) Heterogeneous Fenton
catalyst for the efficient removal of Azo dyes in water. Am J Anal Chem 5:490–499
34. Sahu O, Paul D, Chaudhari PK (2014) A comparatively study on thermal and advance
oxidation wastewater treatment process: review. J Chem Eng Chem Res 1(6):353–364
35. Corma A (1997) From microporous to mesoporous molecular sieve materials and their use in
catalysis. Chem Rev 97:2373–2420
36. Somorjai GA, Rioux RM (2005) High technology catalysts towards 100% selectivity.
Fabrication, characterization and reaction studies. Catal Today 100:201–215
37. Fechete I, Wang Y, Vedrine JC (2012) The past, present and future of heterogeneous
catalysis. Catal Today 189:2–27
38. Buthiyappan A, Aziz ARA, Daud WMAW (2016) Recent advances and prospects of catalytic
advanced oxidation process in treating textile effluents. Rev Chem Eng 32(1):1–47
39. Abramov VO, Abramov OV, Gekhman AE, Kuznetsov VM, Price GJ (2006) Ultrasonic
intensification of ozone and electrochemical destruction of 1,3-dinitrobenzene and
2,4-dinitrotoluene. Ultrason Sonochem 13:303–307
40. Arena F, Chio RD, Gumina B, Spadaro L, Trunfio G (2015) Recent advances on wet air
oxidation catalysts for treatment of industrial wastewaters. Inorg Chim Acta 431:101–109
41. Luck F (1996) A review of industrial catalytic wet air oxidation processes. Catal Today
27:195–202
42. Fenton HJH (1894) Oxidation of tartaric acid in presence of iron. J Chem Soc Trans
65:899–910
43. Munoz M, de Pedro ZM, Casas JA, Rodriguez JJ (2015) Preparation of magnetite-based
catalysts and their application in heterogeneous Fenton oxidation – a review. Appl Catal
Environ 176–177:249–265
44. Eisenhauer HR (1964) Oxidation of phenolic wastes. J Water Pollut Control Fed
36:1116–1128
45. Sun JH, Sun SP, Fan MH, Guo HQ, Qiao LP, Sun RX (2007) A kinetic study on the
degradation of p-nitroaniline by Fenton oxidation process. J Hazard Mater 148:172–177
46. Jiang C, Pang S, Ouyang F, Ma J, Jiang J (2010) A new insight into Fenton and Fenton like
processes for water treatment. J Hazard Mater 174:813–817
47. Awaleh MO, Soubaneh YD (2014) Waste water treatment in chemical industries: the concept
and current technologies. Hydrol Current Res 5(1):1–12
48. Ribeiro AR, Nunes OC, Pereira MFR, Silva AMT (2015) An overview on the advanced
oxidation processes applied for the treatment of water pollutants defined in the recently
launched directive 2013/39/EU. Environ Int 75:33–51
Cost-Effective Catalytic Materials for AOP Treatment Units 333

49. Andreozzi R, Caprio V, Insola A, Marotta R (1999) Advanced oxidation processes (AOP) for
water purification and recovery. Catal Today 53:51–59
50. Mackul’ak T, Prousek J, Švorc LU (2011) Degradation of atrazine by Fenton and modified
Fenton reactions. Monatsh Chem 142:561–567
51. Muruganandham M, Suri RPS, Jafari S, Sillanpää M, Lee GJ, Wu JJ, Swaminathan M (2014)
Recent developments in homogeneous advanced oxidation processes for water and waste-
water treatment. Int J Photoenergy 2014:21 p, Article ID 821674. Hindawi Publishing
Corporation. http://dx.doi.org/10.1155/2014/821674
52. Babuponnusami A, Muthukumar K (2014) A review on Fenton and improvements to the
Fenton process for wastewater treatment. J Environ Chem Eng 2:557–572
53. Wang N, Zheng T, Zhang G, Wang P (2016) A review on Fenton-like processes for organic
wastewater treatment. J Environ Chem Eng 4:762–787
54. He J, Yang X, Men B, Wang D (2016) Interfacial mechanisms of heterogeneous Fenton
reactions catalyzed by iron-based materials: a review. J Environ Sci 39:97–109
55. Luiz DB, Jose HJ, Moreira RFPM (2012) A discussion paper on challenges and proposals for
advanced treatments for potabilization of wastewater in the food industry. In: Valdez B
(ed) Scientific, health and social aspects of the food industry. InTech, Rijeka, Croatia
56. Powell RM, Puls RW, Hightower SK, Sabatini DA (1995) Coupled iron corrosion and
chromate reduction: mechanisms for subsurface remediation. Environ Sci Technol
29:1913–1922
57. Warren KD, Arnold RG, Bishop TL, Lindholm LG, Betterton EA (1995) Kinetics and
mechanism of reductive dehalogenation of carbon tetrachloride using zerovalence metals. J
Hazard Mater 41:217–227
58. Joo SH, Feitz AJ, Waite TD (1995) X oxidative degradation of the carbothioate herbicide,
molinate using nanoscale zero-valent iron. Environ Sci Technol 38:2242–2247
59. Babuponnusami A, Muthukumar K (2012) Removal of phenol by heterogenous photo electro
Fenton-like process using nano-zero valent iron. Separ Purif Tech 98:130–135
60. Bigda RJ (1995) Consider Fenton’s chemistry for wastewater treatment. Chem Eng Prog
91:62–66
61. Mesquita I, Matos LC, Duarte F, Maldonado-Hódar FJ, Mendes A, Madeira LM (2012)
Treatment of azo dye-containing wastewater by a Fenton-like process in a continuous
packed-bed reactor filled with activated carbon. J Hazard Mater 237–238:30–37
62. Duarte F, Maldonado-Hódar FJ, Madeira LM (2011) Influence of the characteristics of carbon
materials on their behaviour as heterogeneous Fenton catalysts for the elimination of the azo
dye Orange II from aqueous solutions. Appl Catal B 103:109–115
63. Yuan SH, Gou N, Alshawabkeh AN, Gu AZ (2013) Efficient degradation of contaminants of
emerging concerns by a new electro-Fenton process with Ti/MMO cathode. Chemosphere
93:2796–2804
64. Sabhi S, Kiwi J (2001) Degradation of 2,4-dichlorophenol by immobilized iron catalysts.
Water Res 35:1994–2002
65. Sanabria NR, Molina R, Moreno S (2012) Development of pillared clays for wet hydrogen
peroxide oxidation of phenol and its application in the posttreatment of coffee wastewater. Int
J Photoenergy 2012:17 p. Article ID 864104. Hindawi Publishing Corporation. doi: 10.1155/
2012/864104
66. Zhou T, Lim TT, XH W (2011) Sonophotolytic degradation of azo dye reactive black 5 in an
ultrasound/UV/ferric system and the roles of different organic ligands. Water Res
45:2915–2924
67. Yang XJ, Tian PF, Zhang XM, Yu X, Wu T, Xu J, Han YF (2014) The generation of hydroxyl
radicals by hydrogen peroxide decomposition on FeOCl/SBA-15 catalysts for phenol degra-
dation. AIChE J 61:166–176
68. Zhang C, Zhou MH, Ren GB, Yu XM, Ma L, Yang J, Yu FK (2015) Heterogeneous electro-
Fenton using modified iron-carbon as catalyst for 2,4-dichlorophenol degradation: influence
factors, mechanism and degradation pathway. Water Res 70:414–424
334 S. Jafarinejad

69. Soon AN, Hameed BH (2011) Heterogeneous catalytic treatment of synthetic dyes in aqueous
media using Fenton and photo-assisted Fenton process. Desalination 269(1–3):1–16
70. Moreno S, Sanabria N, Molina R (2008) Chapter 4. Recent tendencies in the synthesis of
pillared clays for phenol oxidation. In: Heikkine E (ed) Focus on water resource research.
Nova Science Publisher, New York, NY, USA, pp 185–209
71. Rao TSRP, Dhar GM (1998) Recent advanced in basic and applied aspects of industrial
catalysis. Elsevier Science B.V., Amsterdam, The Netherlands
72. Sanabria NR, Molina R, Moreno S (2012) Raschig rings based on pillared clays: efficient
reusable catalysts for oxidation of phenol. J Advan Oxid Technol 15(1):117–124
73. Kim JK, Martinez F, Metcalfe IS (2007) The beneficial role of use of ultrasound in hetero-
geneous Fenton-like system over supported copper catalysts for degradation of
p-chlorophenol. Catal Today 124(3–4):224–231
74. Hassan H, Hameed BH (2011) Fe-clay as effective heterogeneous Fenton catalyst for the
decolorization of reactive blue 4. Chem Eng J 171(3):912–918
75. Nguyen TD, Phan NH, Do MH, Ngo KT (2011) Magnetic Fe2MO4 (M:Fe, Mn) activated
carbons: fabrication, characterization and heterogeneous Fenton oxidation of methyl orange.
J Hazard Mater 185(2–3):653–661
76. Tian SH, YT T, Chen DS, Chen X, Xiong Y (2011) Degradation of acid Orange II at neutral
pH using Fe2(MoO4)3 as a heterogeneous Fenton-like catalyst. Chem Eng J 169(1–3):31–37
77. Dukkanci M, Gunduz G, Yilmaz S, Prihod’ko RV (2010) Heterogeneous Fenton-like degra-
dation of Rhodamine 6G in water using CuFeZSM-5 zeolite catalyst prepared by hydrother-
mal synthesis. J Hazard Mater 181(1–3):343–350
78. Idel-aouad R, Valiente M, Yaacoubi A, Tanouti B, Lopez-Mesas M (2011) Rapid
decolourization and mineralization of the azo dye C.I. Acid red 14 by heterogeneous Fenton
reaction. J Hazard Mater 186(1):745–750
79. Kuˇsi’c H, Koprivanac N, Selanec I (2006) Fe-exchanged zeolite as the effective heteroge-
neous Fenton-type catalyst for the organic pollutant minimization: UV irradiation assistance.
Chemosphere 65(1):65–73
80. Kuznetsova EV, Savinov EN, Vostrikova LA, Parmon VN (2004) Heterogeneous catalysis in
the Fenton-type system FeZSM-5/H2O2. Appl Catal B 51(3):165–170
81. de la Plata GBO, Alfano OM, Cassano AE (2010) Decomposition of 2-chlorophenol
employing goethite as Fenton catalyst II: reaction kinetics of the heterogeneous Fenton and
photo-Fenton mechanisms. Appl Catal B 95(1–-2):14–25
82. Costa RCC, Moura FCC, Ardisson JD, Fabris JD, Lago RM (2008) Highly active heteroge-
neous Fenton-like systems based on Fe0/Fe3O4 composites prepared by controlled reduction
of iron oxides. Appl Catal B 83(1–-2):131–139
83. Moura FCC, Araujo MH, Costa RCC et al (2005) Efficient use of Fe metal as an electron
transfer agent in a heterogeneous Fenton system based on Fe0/Fe3O4 composites.
Chemosphere 60(8):1118–1123
84. Sun SP, Lemley AT (2011) P-Nitrophenol degradation by a heterogeneous Fenton-like
reaction on nano-magnetite: process optimization, kinetics, and degradation pathways. J
Molec Catal A 349(1–2):71–79
85. Mart’ınez F, Calleja G, Melero JA, Molina R (2005) Heterogeneous photo-Fenton degrada-
tion of phenolic aqueous solutions over iron-containing SBA-15 catalyst. Appl Catal B 60
(3–4):181–190
86. Molina R, Mart’ınez F, Melero JA, Bremner DH, Chakinala AG (2006) Mineralization of
phenol by a heterogeneous ultrasound/Fe-SBA-15/H2O2 process: multivariate study by
factorial design of experiments. Appl Catal B 66(3–4):198–207
87. Shukla P, Wang S, Sun H, Ang HM, Tad’e M (2010) Adsorption and heterogeneous advanced
oxidation of phenolic contaminants using Fe loaded mesoporous SBA-15 and H2O2. Chem
Eng J 164(1):255–260
Cost-Effective Catalytic Materials for AOP Treatment Units 335

88. Galeano LA, Vicente MA, Gil A (2011) Treatment of municipal leachate of landfill by
fenton-like heterogeneous catalytic wet peroxide oxidation using an Al/Fe-pillared montmo-
rillonite as active catalyst. Chem Eng J 178:146–153
89. Luo M, Bowden D, Brimblecombe P (2009) Catalytic property of Fe-Al pillared clay for
Fenton oxidation of phenol by H2O2. Appl Catal B 85(3–-4):201–206
90. Molina CB, Casas JA, Zazo JA, JJ R’ı (2006) A comparison of Al-Fe and Zr-Fe pillared clays
for catalytic wet peroxide oxidation. Chem Eng J 118(1–-2):29–35
91. Munoz M, Dominguez CM, de Pedro ZM, Quintanilla A, Casas JA, Rodriguez JJ (2016)
Degradation of imidazolium-based ionic liquids by catalytic wet peroxide oxidation with
carbon and magnetic iron catalysts. J Chem Technol Biotechnol 91(11):2882–2887
92. Munoz M, de Pedro ZM, Menendez N, Casas JA, Rodriguez JJ (2013) Appl Catal Environ
136–137:218–224
93. Xu L, Wang J (2011) A heterogeneous Fenton-like system with nanoparticulate zero-valent
iron for removal of 4-chloro-3-methyl phenol. J Hazard Mater 186:256–264
94. Parra S, Henao L, Mielczarski E, Mielczarski J, Albers P, Suvorova E (2004) Synthesis,
testing, and characterization of a novel nafion membrane with superior performance in photo
assisted immobilized Fenton catalysis. Langmuir 20:5621–5629. http://dx.doi.org/10.1021/
la049768d
95. Aleksić M, Kušić H, Koprivanac N, Leszczynska D, Božić AL (2010) Heterogeneous Fenton
type processes for the degradation of organic dye pollutant in water-the application of zeolite
assisted AOPs. Desalination 257:22–29. http://dx.doi.org/10.1016/j.desal.2010.03.016
96. Gonzalez-Olmos R, Holzer F, Kopinke FD, Georgi A (2011) Indications of the reactive
species in a heterogeneous Fenton-like reaction using Fe-containing zeolites. Appl Catal A
Gen 398:44–53. http://dx.doi.org/10.1016/j.apcata.2011.03.005
97. Gonzalez-Olmos R, Martin MJ, Georgi A, Kopinke FD, Oller I, Malato S (2012) Fe-zeolites
as heterogeneous catalysts in solar Fenton-like reactions at neutral pH. Appl Catal Environ
125:51–58. http://dx.doi.org/10.1016/j.apcatb.2012.05.022
98. Tekbas M, CengizYatmaz H, Bektas N (2008) Heterogeneous photo-Fenton oxidation of
reactive Azo dye solutions using iron exchanged zeolite as a catalyst. Micropor Mesopor Mat
115:594–602. http://dx.doi.org/10.1016/j.micromeso.2008.03.001
99. Pirkanniemi K, Sillanpää M (2002) Heterogeneous water phase catalysis as an environmental
application: a review. Chemosphere 48:1047–1060. http://dx.doi.org/10.1016/S0045-6535
(02)00168-6
100. Soon AN, Hameed BH (2013) Degradation of acid blue 29 in visible light radiation using iron
modified mesoporous silica as heterogeneous photo-Fenton catalyst. Appl Catal A Gen
450:96–105. http://dx.doi.org/10.1016/j.apcata.2012.10.025
101. Ramirez JH, Vicente MA, Madeira LM (2010) Heterogeneous photo-Fenton oxidation with
pillared clay-based catalysts for wastewater treatment: review. Appl Catal Environ 98:10–26.
http://dx.doi.org/10.1016/j.apcatb.2010.05.004
102. Martı́nez F, Pariente MI, Ángel J, Botas JA, Melero JA, Rubalcaba A (2012) Influence of
preoxidizing treatments on the preparation of iron-containing activated carbons for catalytic
wet peroxide oxidation of phenol. J Chem Technol Biotechnol 87:880–886. http://dx.doi.org/
10.1002/jctb.2744
103. Santos A, Yustos P, Rodrı́guez S, Garcia-Ochoa F, de Gracia M (2007) Decolorization of
textile dyes by wet oxidation using activated carbon as catalyst. Ind Eng Chem Res
46:2423–2427. http://dx.doi.org/10.1021/ie0614576
104. Ezzatahmadi N, Ayoko GA, Millar GJ, Speight R, Yan C, Li J, Li S, Zhu J, Xi Y (2017) Clay-
supported nanoscale zero-valent iron composite materials for the remediation of contami-
nated aqueous solutions: a review. Chem Eng J 312:336–350
105. Tušar NN, Maucec D, Rangus M, Arcon I, Mazaj M, Cotman M, Pintar A, Kaucic V (2012)
Manganese functionalized silicate nanoparticles as a Fenton-type catalyst for water purifica-
tion by advanced oxidation processes (AOP). Adv Funct Mater 22:820–826
336 S. Jafarinejad

106. Yao Y, Cai Y, Wu G, Wei F, Li X, Chen H, Wang S (2015) Sulfate radicals induced from
peroxymonosulfate by cobalt manganese oxides (CoxMn3-xO4) for Fenton-like reaction in
water. J Hazard Mater 296:128–137
107. Rhadfi T, Piquemal JY, Sicard L, Herbst F, Briot E, Benedetti M, Atlamsani A (2010) Polyol-
made Mn3O4 nanocrystals as efficient Fenton-like catalysts. Appl Catal A Gen 386:132–139
108. Karthikeyan S, Boopathy R, Sekaran G (2015) In situ generation of hydroxyl radical by
cobalt oxide supported porous carbon enhance removal of refractory organics in tannery
dyeing wastewater. J Colloid Interface Sci 448:163–174
109. Comninellis C, Kapalka A, Malato S, Parsons SA, Poulios I, Mantzavinos D (2008)
Advanced oxidation processes for water treatment: advances and trends for R&D. J Chem
Technol Biotechnol 83:769–776
110. Pereira MC, Oliveira LCA, Murad E (2012) Iron oxide catalysts: Fenton and Fenton-like
reactions – a review. Clay Miner 47:285–302
111. Rahim Pouran S, Abdul Raman AA, Wan Daud WMA (2014) Review on the application of
modified iron oxides as heterogeneous catalysts in Fenton reactions. J Clean Prod 64:24–35
112. Martins RC, Henriques LR, Quinta-Ferreira RM (2013) Catalytic activity of low cost
materials for pollutants abatement by Fenton’s process. Chem Eng Sci 100:225–233
113. Lee H, Kim BH, Park YK, Kim SJ, Jung SC (2015) Application of recycled zero-valent iron
nanoparticle to the treatment of wastewater containing nitrobenzene. J Nanomater 2015:8
p. Article ID 392537. Hindawi Publishing Corporation. http://dx.doi.org/10.1155/2015/
392537
114. Pereira WS, Freire RS (2006) Azo dye degradation by recycled waste zero-valent iron
powder. J Braz Chem Soc 17(5):832–838
115. Manu B, Mahamood S, Vittal H, Shrihari S (2011) A novel catalytic route to degrade
paracetamol by Fenton process. Int J Res Chem Environ 1(1):157–164
116. Shahidi D, Roy R, Azzouz A (2015) Advances in catalytic oxidation of organic pollutants-
prospects for thorough mineralization by natural clay catalysts. Appl Catal Environ
174:277–292
117. Zazo JA, Casas JA, Mohedano AF, Rodriguez JJ (2006) Catalytic wet peroxide oxidation of
phenol with a Fe/active carbon catalyst. Appl Catal Environ 65:261–268
118. Rey A, Faraldos M, Casas JA, Zazo JA, Bahamonde A, Rodriguez JJ (2009) Catalytic wet
peroxide oxidation of phenol over Fe/AC catalysts: influence of iron precursor and activated
carbon surface. Appl Catal Environ 86:69–77
119. Bautista P, Mohedano AF, Menendez N, Casas JA, Rodriguez JJ (2010) Catalytic wet
peroxide oxidation of cosmetic wastewaters with Fe-bearing catalysts. Catal Today
151:148–152
120. Guo Y, Yang L, Cheng X, Xiangtao Wang X (2012) The application and reaction mechanism
of catalytic ozonation in water treatment. J Environ Anal Toxicol 2:150. doi:10.4172/2161-
0525.1000150
121. Krzemińska D, Neczaj E, Borowski G (2015) Advanced oxidation processes for food
industrial wastewater decontamination. Rev Article J Ecol Eng 16(2):61–71
122. Pera-Titus M, Garcia-Molina V, Banos MA, Gimenez J, Esplugas S (2004) Degradation of
chlorophenols by means of advanced oxidation processes: a general review. Appl Catal
Environ 47:219–256
123. Gogate PR, Pandit AB (2004) A review of imperative technologies for wastewater treatment
I: oxidation technologies at ambient conditions. Adv Environ Res 8(3–4):501–551
124. Augugliaro V, Litter M, Palmisano L, Soria J (2006) The combination of heterogeneous
photocatalysis with chemical and physical operations: a tool for improving the photoprocess
performance. J Photochem Photobiol C Photochem Rev 7(4):127–144
125. Weiss J (1935) Investigations on the radical HO2 in solution. Trans Faraday Soc 31:668–681
126. Masschelein WJ (1992) Unit processes in drinking water treatment. Marcel Dekker,
New York
Cost-Effective Catalytic Materials for AOP Treatment Units 337

127. Munter R (2001) Advanced oxidation processes – current status and prospects. Proc Est Acad
Sci Chem 50(2):59–80
128. Wang JL, LJ X (2012) Advanced oxidation processes for wastewater treatment: formation of
hydroxyl radical and application. Crit Rev Environ Sci Tech 42:251–325
129. Kasprzyk-Hordern B, Ziółek M, Nawrocki J (2003) Catalytic ozonation and methods of
enhancing molecular ozone reactions in water treatment. Appl Catal Environ 46:639–669
130. Legube B, Leitner NKV (1999) Catalytic ozonation: a promising advanced oxidation tech-
nology for water treatment. Catal Today 53:61–72
131. Abouzlam M, Ouvrard R, Mehdi D, Pontlevoy F, Gombert B, Leitner NKV, Boukari S (2013)
An optimal control of a wastewater treatment reactor by catalytic ozonation. Control Eng
Practice 21:105–112
132. Abouzlam M, Ouvrard R, Mehdi D, Pontlevoy F, Gombert B, Leitner NKV, Boukari S (2015)
A H1 control for optimizing the advanced oxidation processes-case of a catalytic ozonation
reactor. Control Eng Practice 44:1–9
133. Pirgalıoglu S, Ozbelge TA (2009) Comparison of non catalytic and catalytic ozonation
processes of three different aqueous single dye solutions with respect to powder copper
sulfide catalyst. Appl Catal A: General 363:157–163
134. Munoz MSG (2010) Catalytic ozonation of pharmaceuticals in aqueous solution, PhD thesis,
Alcala University
135. Nawrocki J, Kasprzyk-Hordern B (2010) The efficiency and mechanisms of catalytic ozon-
ation. Appl Catal Environ 99:27–42
136. Azzouz A, Kotbi A, Niquette P, Sajin T, Ursu AV, Rami A, Monette F, Hausler R (2010)
Ozonation of oxalic acid catalyzed by ion-exchanged montmorillonite in moderately acidic
media. React Kinet Mech Catal 99:289–302
137. Liotta LF, Gruttadauria M, DiCarlo G, Perrini G, Librando V (2009) Heterogeneous catalytic
degradation of phenolic substrates: catalysts activity. J Hazard Mater 162:588–606
138. Xiao J, Xie Y, Cao H (2015) Organic pollutants removal in wastewater by heterogeneous
photocatalytic ozonation. Chemosphere 121:1–17
139. Pocostales P, Álvarez P, Beltrán FJ (2011) Catalytic ozonation promoted by alumina-based
catalysts for the removal of some pharmaceutical compounds from water. Chem Eng J
168:1289–1295
140. Liu Y, Wang S, Gong W, Chen Z, Liu H, Bu Y, Zhang Y (2017) Heterogeneous catalytic
ozonation of p-chloronitrobenzene (pCNB) in water with iron silicate doped hydroxylation
iron as catalyst. Catal Commun 89:81–85
141. Li B, Xu X, Zhu L, Ding W, Mahmood Q (2010) Catalytic ozonation of industrial wastewater
containing chloro and nitro aromatics using modified diatomaceous porous filling. Desalina-
tion 254:90–98
142. Wang J, Bai Z (2017) Fe-based catalysts for heterogeneous catalytic ozonation of emerging
contaminants in water and wastewater. Chem Eng J 312:79–98
143. Mehrjouei M, Müller S, M€oller D (2015) A review on photocatalytic ozonation used for the
treatment of water and wastewater. Chem Eng J 263:209–219
144. Orge CA, Órf~ao JJM, Pereira MFR (2012) Carbon xerogels and ceria–carbon xerogel
materials as catalysts in the ozonation of organic pollutants. Appl Catal Environ 126:22–28
145. Chen C, Yu J, Yoza BA, Li QX, Wang G (2015) A novel “wastes-treat-wastes” technology:
role and potential of spent fluid catalytic cracking catalyst assisted ozonation of petrochem-
ical wastewater. J Environ Manage 152:58–65
146. Gilbert E (2002) Influence of ozone on the photocatalytic oxidation of organic compounds.
Ozone Sci Eng 24:75–82
147. Rey A, Mena E, Chávez AM, Beltrán FJ, Medina F (2015) Influence of structural properties
on the activity of WO3 catalysts for visible light photocatalytic ozonation. Chem Eng Sci
126:80–90
148. Sreethawong T, Chavadej S (2008) Color removal of distillery wastewater by ozonation in
the absence and presence of immobilized iron oxide catalyst. J Hazard Mater 155:486–493
338 S. Jafarinejad

149. Jung H, Choi H (2006) Catalytic decomposition of ozone and parachlorobenzoic acid (pCBA)
in the presence of nanosized ZnO. Appl Catal Environ 66:288–294
150. Gharbani P, Mehrizad A (2014) Heterogeneous catalytic ozonation process for removal of
4-chloro-2-nitrophenol from aqueous solutions. J Saudi Chem Soc 18:601–605
151. Hu E, Wu X, Shang S, Tao X, Jiang S, Gan L (2016) Catalytic ozonation of simulated textile
dyeing wastewater using mesoporous carbon aerogel supported copper oxide catalyst. J Clean
Prod 112:4710–4718
152. Bergaya F, Theng BKG, Lagaly G (2006) Handbook of clay science. Elsevier, Oxford, pp
541–546
153. Shahidi D, Roy R, Azzouz A (2014) Total removal of oxalic acid via synergistic parameter
interaction in montmorillonite catalyzed ozonation. J Environ Chem Eng 2:20–30
154. Aly AA, Hasan YNY, Al-Farraj AS (2014) Olive mill wastewater treatment using a simple
zeolite-based low-cost method. J Environ Manage 145:341–348
155. Li H, Xu B, Qi F, Sun D, Chen Z (2014) Degradation of bezafibrate in wastewater by catalytic
ozonation with cobalt doped red mud: efficiency, intermediates and toxicity. Appl Catal
Environ 152:342–351
156. Xu B, Qi F, Zhang J, Li H, Sun D, Robert D, Chen Z (2016) Cobalt modified red mud
catalytic ozonation for the degradation of bezafibrate in water: catalyst surface properties
characterization and reaction mechanism. Chem Eng J 284:942–952
157. Wen G, Pan ZH, Ma J, Liu ZQ, Zhao L, Li JJ (2012) Reuse of sewage sludge as a catalyst in
ozonation – efficiency for the removal of oxalic acid and the control of bromate formation. J
Hazard Mater 239–240:381–388
158. Wu J, Ma L, Chen Y, Cheng Y, Liu Y, Zha X (2016) Catalytic ozonation of organic pollutants
from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a
catalyst: removal and pathways. Water Res 92:140–148
159. Kamboj ML (2009) Studies on the degradation of industrial wastewater using heterogeneous
photocatalysis master thesis. Thapar University, Patiala
160. Braslavsky SE, Houk KN (1988) Glossary of terms used in photochemistry. Pure Appl Chem
60:1055–1106
161. Verhoven JW (1996) Glossary of terms used in photochemistry. Pure Appl Chem
68:2223–2286
162. Cesaro A, Belgiorno V (2015) Removal of endocrine disruptors from urban wastewater by
advanced oxidation processes (AOPs): a review. Open Biotechnol J 9:1–28
163. Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor
electrode. Nature 238:37–38
164. Renge VC, Khedkar SV, Thanvi NJ (2012) Photocatalytic oxidation and reactors – a review.
Int J Adv Eng Technol 3(4):31–35
165. Kaan CC, Aziz AA, Ibrahim S, Matheswaran M, Saravanan P (2012) Heterogeneous
photocatalytic oxidation an effective tool for wastewater treatment – a review, studies on
water management issues, Dr. Muthukrishnavellaisamy Kumarasamy (ed) ISBN: 978-953-
307-961-5, InTech. [Online] http://www.intechopen.com/books/studies-on-water-
managementissues/heterogeneous-photocatalytic-oxidation-an-effective-tool-for-wastewa
ter-treatment-a-review
166. Ibhadon AO, Fitzpatrick P (2013) Heterogeneous photocatalysis: recent advances and appli-
cations. Catalysts 3:189–218
167. Fujishima A, Zhang X, Tryk DA (2007) Heterogeneous photocatalysis: from water photolysis
to applications in environmental cleanup. Int J Hydro Energy 32:2664–2672
168. Hoffmann HR, Martin ST, Choi W, Bahnemann DW (1995) Environmental applications of
semiconductor photocatalysis. Chem Rev 69:95–101
169. Lee JC, Kim MS, Kim CK, Chung CH, Cho SM, Han GY, Yoon KJ, Kim BW (2003)
Removal of paraquat in aqueous suspension of TiO2 in an immersed UV photoreactor.
Korean J Chem Eng 20(5):862–868
Cost-Effective Catalytic Materials for AOP Treatment Units 339

170. Mok NB (2009) Photocatalytic degradation of oily wastewater: effect of catalyst concentra-
tion load, irradiation time and temperature. Bachelor thesis, Faculty of Chemical & Natural
Resources Engineering, University Malaysia Pahang
171. Zhang T, Wang X, Zhang X (2014) Recent progress in TiO2-mediated solar photocatalysis
for industrial wastewater treatment. Int J Photoenergy 12 p. Article ID 607954. Hindawi
Publishing Corporation. [Online] http://dx.doi.org/10.1155/2014/607954
172. Khataee AR, Zarei M, Ordikhani-Seyedlar R (2011) Heterogeneous photocatalysis of a dye
solution using supported TiO2 nanoparticles combined with homogeneous
photoelectrochemical process: molecular degradation products. J Molec Catal A Chem
338:84–91
173. Ahmed S, Rasul MG, Brown R, Hashi MA (2011) Influence of parameters on the heteroge-
neous photocatalytic degradation of pesticides and phenolic contaminants in wastewater: a
short review. J Environ Manage 92:311–330
174. Bockelmann D, Weichgrebe D, Goslich R, Bahnemann D (1995) Concentrating versus
non-concentrating reactors for solar water detoxication. Sol Energ Mater Sol Cell
38:441–251
175. Banu JR, Anandan S, Kaliappan S, Yeom IY (2008) Treatment of dairy wastewater using
anaerobic and solar photocatalytic methods. Sol Energy 82:812–819
176. Chong MN, Jin B, Chow CWK, Saint C (2010) Recent developments in photocatalytic water
treatment technology: a review. Water Res 44:2997–3027
177. Zhang H, Liu G, Shi L, Liu H, Wang T, Ye J (2016) Engineering coordination polymers for
photocatalysis. Nano Energy 22:149–168
178. Kumar P, Kumar S, Bhardwaj NK, Kumar S (2011) Titanium dioxide photocatalysis for the
pulp and paper industry wastewater treatment. Ind J Sci Technol 4(3):327–332
179. Chen Q, Ji F, Guo Q, Fan J, Xu X (2014) Combination of heterogeneous Fenton-like reaction
and photocatalysis using Co-TiO2 nanocatalyst for activation of KHSO5 with visible light
irradiation at ambient conditions. J Environ Sci 26:2440–2450
180. Garcı́a-Mu~ noz P, Pliego G, Zazo JA, Bahamonde A, Casas JA (2016) Ilmenite (FeTiO3) as
low cost catalyst for advanced oxidation processes. J Environ Chem Eng 4:542–548
181. Sha Z, Sun J, Chan HSO, Jaenicke S, Wu J (2015) Enhanced photocatalytic activity of the
AgI/UiO-66(Zr) composite for Rhodamine B degradation under visible-light irradiation.
Chem Plus Chem 80(8):1321–1328. http://dx.doi.org/10.1002/cplu.201402430
182. Booshehri AY, Polo-Lopez MI, Castro-Alférez M, He P, Xu R, Rong W, Malato S,
Fernández-Ibá˜nez P (2017) Assessment of solar photocatalysis using Ag/BiVO4 at pilot
solar compound parabolic collector for inactivation of pathogens in well water and secondary
effluents. Catal Today 281:124–134
183. Martı́nez C, Canle LM, Fernández MI, Santaballa JA, Faria J (2011) Aqueous degradation of
diclofenac by heterogeneous photocatalysis using nanostructured materials. Appl Catal
Environ 107:110–118
184. Lam SM, Sin JC, Mohamed AR (2016) A review on photocatalytic application of g-C3N4/
semiconductor (CNS) nanocomposites towards the erasure of dyeing wastewater. Mater Sci
Semicond Process 47:62–84
185. Shan AY, Ghaz TIM, Rashid SA (2010) Immobilisation of titanium dioxide onto supporting
materials in heterogeneous photocatalysis: a review. Appl Catal A General 389:1–8
186. Rajeshwar K, Chenthamarakshan CR, Goeringer S, Djukic M (2001) Titania based hetero-
geneous photocatalysis: materials mechanistic issues and implications for environmental
remediation. Pure Appl Chem 73(12):1849–1860
187. Murphy S (2012) Photocatalytic degradation of pharmaceuticals in aqueous solutions and
development of new dye sensitised photocatalytic materials, PhD thesis, Dublin City
University
188. Osarumwense JO, Amenaghawn NA, Aisien FA (2015) Heterogeneous photocatalytic deg-
radation of phenol in aqueous suspension of periwinkle shell ash catalyst in the presence of
UV from sunlight. J Eng Sci Technol 10(12):1525–1539
340 S. Jafarinejad

189. Ahmed S, Rasul MG, Martens WN, Brown R, Hashib MA (2011) Advances in heterogeneous
photocatalytic degradation of phenols and dyes in wastewater: a review. Water Air Soil Pollut
215(1–4):3–29
190. Jin YX, Li GH, Zhang Y, Zhang YX, Zhang LD (2001) Photoluminescence of anatase TiO2
thin films achieved by the addition of ZnFe2O4. J Phys Condens Matter 13:L913–L918
191. Belgiorno V, Rizzo L, Fatta D, Rocca CD, Lofrano G, Nikolaouc A, Naddeo V, Meric S
(2007) Review on endocrine disrupting-emerging compounds in urban wastewater: occur-
rence and removal by photocatalysis and ultrasonic irradiation for wastewater reuse. Desa-
lination 215:166–176
192. Hassan M, Zhao Y, Xie B (2016) Employing TiO2 photocatalysis to deal with landfill
leachate: current status and development. Chem Eng J 285:264–275
193. Singh S, Singh PK, Mahalingam H (2015) An effective and low-cost TiO2/polystyrene
floating photocatalyst for environmental remediation. Int J Environ Res 9(2):535–544
194. Zimmermann FJ (1954) Waste disposal. US Patent No. 2 665 249, US Patent Office 6
(10):630–631
195. Zimmermann FJ, Diddams DG (1960) The Zimmermann process and its application in the
pulp and paper industry. TAPPI 43:710–715
196. Zou LY, Li Y, Hung YT (2007) Wet air oxidation for waste treatment. In: Wang LK, Hung
YT, Shammas NK (eds) Advanced physicochemical treatment technologies. Handbook of
Environmental Engineering, vol 5. Humana Press. https://doi.org/10.1007/978-1-59745-173-
4_13
197. Zou L, Zhu B (2006) Literature review report for smart water project “improving recycled
water aesthetic quality by removing colour and trace organics.” Oxidation processes for
degradation of organic pollutants in water. Institute of Sustainability and Innovation Victoria
University
198. Roy S, Vashishtha M, Saroha AK (2010) Catalytic wet air oxidation of oxalic acid using
platinum catalysts in bubble column reactor: a review. J Eng Sci Technol Rev 3(1):95–107
199. Copa WM, Dietrich MJ (1988) Wet air oxidation of oils, oil refinery sludges, and spent
drilling muds. ZIMPRO/PASSAVANT INC., Apr 1988. [Online] http://infohouse.p2ric.org/
ref/25/24892.pdf
200. Siemens Water Technologies Corp (2011) Can you treat the most difficult wastewater with
only air?, Zimpro® wet air oxidation systems: the cleanest way to treat the dirtiest water,
answers for industry, Siemens Water Technologies Corp, GIS-WAO-BR-0111. [Online]
http://www.energy.siemens.com/hq/pool/hq/industries-utilities/oil-gas/water-solutions/
Zimpro-Wet-Air-Oxidation-System-The-Cleanest-Way.pdf
201. Gaikwad RW, Malik I, Kulkarni V, Mhaske S, Badadhe S (2016) Review on catalytic wet air
oxidation. Int J Environ Natural Sci 9:1–8
202. Debellefontaine H, Foussard JN (2000) Wet air oxidation for the treatment of industrial
wastes. Chemical aspects, reactor design and industrial applications in Europe. Waste Manag
20:15–25
203. Kolaczkowski ST, Plucinski P, Beltran FJ, Rivas FJ, McLurgh DB (1999) Wet air oxidation:
a review of process technologies and aspects in reactor design. Chem Eng J 73:143–160
204. Ovejero G, Sotelo JL, Garcia J, Rodrıguez A (2005) Catalytic removal of phenol from
aqueous solutions in a trickle bed reactor. J Chem Technol Biotechnol 80:406–412
205. Rodr’ıguez A, Ovejero G, Romero MD, Diaz C, Barreiro M, Garcia J (2008) Catalytic wet air
oxidation of textile industrial wastewater using metal supported on carbon nanofibers. J Super
Fluids 46:163–172
206. Hong TY (2013) Catalytic wet air oxidation of wastewater containing acetic acid. BSc thesis,
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang
207. Moses DV, Smith EA (1954) Wet air oxidation of aqueous wastes, US Patent 2,690,425
208. Levec J, Pintar A (2007) Catalytic wet-air oxidation processes: a review. Catal Today
124:172–184
209. Luck F (1999) Wet air oxidation: past, present and future. Catal Today 53:81–91
Cost-Effective Catalytic Materials for AOP Treatment Units 341

210. Hosseini AM (2013) Intensification of wet oxidation of industrial process wastewater.

Department of Chemical and Environmental Process Engineering of BME and Centre of
Energy Research of Hungarian Academy of Sciences
211. Trunfio G Catalyst development for the catalytic wet air oxidation (CWAO) of phenol. Thesis
for the degree of Doctor of Philosophy in “Chemical Technologies and Innovative Pro-
cesses,” University of Messina, Area 03-Scienze Chimiche (CHIM 04), CYCLE XXI
(2006–2008)
212. Oliviero L, Barbier J, Duprez D (2003) Wet air oxidation of nitrogen-containing organic
compounds and ammonia in aqueous media. Appl Catal Environ 40:163–184
213. Erjavec B, Kaplana R, Djinovic P, Pintar A (2013) Catalytic wet air oxidation of bisphenol a
model solution in a trickle-bed reactor over titanate nanotube-based catalysts. Appl Catal
Environ 132-133:342–352
214. Modi RR, Vyas DS, Patel SM (2016) Catalytic wet air oxidation of dye industry wastewater
using metallic catalyst. IJARIIE 2(3):461–469
215. Jani HR (2008) Catalytic wet air oxidation of pulp and paper mills effluent. PhD thesis,
School of Applied Sciences, Science, Engineering, and Technology Portfolio, RMIT
University
216. Gomes HT, Figueiredo JL, Faria JL (2007) Catalytic wet air oxidation of olive mill waste-
water. Catal Today 124:254–259
217. Imamura S (1999) Catalytic and noncatalytic wet oxidation. Ind Eng Chem Res
38:1743–1753
218. Matatov-Meytal Y, Sheintuch M (1998) Catalytic abatement of water pollutants. Ind Eng
Chem Res 37:309–326
219. Eftaxias A (2002) Catalytic wet air oxidation of phenol in a trickle bed reactor: kinetics and
reactor modelling, PhD thesis, Escola T’ecnica Superior de Enginyeria Qu’ımica,
Departament d’Enginyeria Qu’ımica, Universitat Rovira i Virgili, Tarragona
220. Katsoni A, Gomes HT, Pastrana-Martı́nez LM, Faria JL, Figueiredoc JL, Mantzavinos D,
Silva AMT (2011) Degradation of trinitrophenol by sequential catalytic wet air oxidation and
solar TiO2 photocatalysis. Chem Eng J 172:634–640
221. Stüber F, Font J, Fortuny A, Bengoa C, Eftaxias A, Fabregat A (2005) Carbon materials and
catalytic wet air oxidation of organic pollutants in wastewater. Topics Catal 33:3–50
222. Morales-Torres S, Silva AMT, Pérez-Cadenas AF, Faria JL, Maldonado-Hódar FJ, Figuei-
redo JL, Carrasco-Marı́n F (2010) Wet air oxidation of trinitrophenol with activated carbon
catalysts: effect of textural properties on the mechanism of degradation. Appl Catal Environ
100:310–317
223. Gomes HT, Machado BF, Ribeiro A, Moreira I, Rosário M, Silva AMT, Figueiredo JL, Faria
JL (2008) Catalytic properties of carbon materials for wet oxidation of aniline. J Hazard
Mater 159:420–426
224. Apolinário AC, Silva AMT, Machado BF, Gomes HT, Araújo PP, Figueiredo JL, Faria JL
(2008) Wet air oxidation of nitro-aromatic compounds: reactivity on single- and multi-
component systems and surface chemistry studies with a carbon xerogel. Appl Catal Environ
84:75–86
225. Yang S, Zhu W, Li X, Wang J, Zhou Y (2007) Multi-walled carbon nanotubes (MWNTs) as
an efficient catalyst for catalytic wet air oxidation of phenol. Catal Commun 8:2059–2063
226. Yang S, Li X, Zhu W, Wang J, Descorme C (2008) Catalytic activity, stability and structure
of multi-walled carbon nanotubes in the wet air oxidation of phenol. Carbon 46:445–452
227. Rocha RP, Sousa JP, Silva AMT, Pereira MFR, Figueiredo JL (2011) Catalytic activity and
stability of multiwalled carbon nanotubes in catalytic wet air oxidation of oxalic acid: the role
of the basic nature induced by the surface chemistry. Appl Catal Environ 104:330–336
228. Sousa JPS, Silva AMT, Pereira MFR, Figueiredo JL (2010) Wet air oxidation of aniline using
carbon foams and fibers enriched with nitrogen. Sep Sci Technol 45:1546–1554
229. Yang S, Cui Y, Sun Y, Yang H (2014) Graphene oxide as an effective catalyst for wet air
oxidation of phenol. J Hazard Matter 280:55–62
342 S. Jafarinejad

230. Zhang Y, Peng F, Zhou Y (2016) Structure, characterization, and dynamic performance of a
wet air oxidation catalyst Cu-Fe-La/γ-Al2O3. Chin J Chem Eng 24:1171–1177
231. Nakatsuji T, Kunishige M, Li J, Hashimoto M, Matsuzono Y (2013) Effect of CeO2 addition
into Pd/Zr–Pr mixed oxide on three-way catalysis and thermal durability. Catal Comm
35:88–94
232. Bernardi M, ML D, Dodouche I, Descorme C, Deleris S, Blanchet E, Besson M (2012)
Selective removal of the ammonium-nitrogen in ammonium acetate aqueous solutions by
catalytic wet air oxidation over supported Pt catalysts. Appl Catal Environ 128:64–71
233. Wang C, Wang GR, Wang JF (2014) A bi-component Cu catalyst for the direct synthesis of
methylchlorosilane from silicon and methyl chloride. Chin J Chem Eng 22:299–304
234. Massa P, Ivorra F, Haure P, Fenoglio R (2011) Catalytic wet peroxide oxidation of phenol
solutions over CuO/CeO2 systems. J Hazard Mater 190:1068–1073
235. Fazlollahi F, Sarkari M, Gharebaghi H, Atashi H, Zarei MM, Mirzaei AA, Hecker WC (2013)
Preparation of Fe–Mn/K/Al2O3 Fischer–Tropsch catalyst and its catalytic kinetics for the
hydrogenation of carbon monoxide. Chin J Chem Eng 21:507–519
236. Wenbing M, Hongpeng L, Xuemei M (2013) Study on supercritical water oxidation of oily
wastewater with ethanol. Res J Appl Sci Eng Technol 6(6):1007–1011
237. Bambang V, Jae-Duck K (2007) Supercritical water oxidation for the destruction of toxic
organic wastewaters: a review. J Environ Sci 19:513–522
238. Fourcault A, Garcia-Jarana B, Sanchez-Oneto J, Mariasa F, Portela JR (2009) Supercritical
water oxidation of phenol with air. Experimental results and modeling. Chem Eng J
152:227–233
239. Paraskeva P, Diamadopoulos E (2006) Technologies for olive mill wastewater (OMW)
treatment: a review. J Chem Technol Biotechnol 81:1475–1485
240. Xu D, Wang S, Tang X, Gong Y, Guo Y, Wang Y, Zhang J (2012) Design of the first pilot
scale plant of China for supercritical water oxidation of sewage sludge. Chem Eng Res Des
90:288–297
241. Han D, Zhang H, Fang L, Lin C (2015) Continuous monitoring of total organic carbon based
on supercritical water oxidation improved by CuSO4 catalyst. J Anal Bioanal Tech S13:002.
doi:10.4172/2155-9872.S13-002
242. Marrone PA (2013) Supercritical water oxidation-current status of full-scale commercial
activity for waste destruction. J Super Fluids 79:283–288
243. Li X, Li G (2015) A review: pharmaceutical wastewater treatment technology and research in
China. Asia-Pacific energy equipment engineering research conference (AP3ER 2015), pp
345–348
244. Youngprasert B, Poochinda K, Ngamprasertsith S (2010) Treatment of acetonitrile by
catalytic supercritical water oxidation in compact-sized reactor. J Water Resource Protect
2:222–226
245. Dong X, Gan Z, Lu X, Jin W, Yu Y, Zhang M (2015) Study on catalytic and non-catalytic
supercritical water oxidation of p-nitrophenol wastewater. Chem Eng J 277:30–39
246. Yu L, Han M, He F (2017) A review of treating oily wastewater. Arabian J Chem 10:S1913–
S1922
247. Medoll M (1982) Processing methods for the oxidation of organics in supercritical water. US
Patent 4,338,199
248. Abelleira J, Sánchez-Oneto J, Portela JR, Martı́nez de la Ossa EJ (2013) Kinetics of
supercritical water oxidation of isopropanol as an auxiliary fuel and co-fuel. Fuel
111:574–583
249. Ding ZY, Frisch MA, Li L, Gloyna EF (1996) Catalytic oxidation in supercritical water. Ind
Eng Chem Res 35:3257–3279
250. Tomita K, Oshima Y (2004) Stability of manganese oxide in catalytic supercritical water
oxidation of phenol. Ind Eng Chem Res 43:7740–7743
Cost-Effective Catalytic Materials for AOP Treatment Units 343

251. Silva CLD, Garlapalli RK, Trembly JP (2017) Removal of phenol from oil/gas produced
water using supercritical water treatment with TiO2 supported MnO2 catalyst. J Environ
Chem Eng 5:488–493
252. Arslan-Alaton I, Ferry JL (2002) H4SiW12O40-catalyzed oxidation of nitrobenzene in super-
critical water: kinetic and mechanistic aspects. Appl Catal B-Environ 38:283–293
253. Nunoura T, Lee G, Matsumura Y, Yamamoto K (2003) Reaction engineering model for
supercritical water oxidation of phenol catalyzed by activated carbon. Ind Eng Chem Res
42:3522–3531
254. Krajnc M, Levec J (1997) Oxidation of phenol over a transition-metal oxide catalyst in
supercritical water. Ind Eng Chem Res 36:3439–3445
255. Ding ZY, Aki SN, Abraham MA (1995) Catalytic supercritical water oxidation: phenol
conversion and product selectivity. Environ Sci Technol 29:2748–2753
256. Zhang X, Savage PE (1998) Fast catalytic oxidation of phenol in supercritical water. Catal
Today 40:333–342
257. Yu J, Savage PE (2000) Kinetics of catalytic supercritical water oxidation of phenol over
TiO2. Environ Sci Technol 34:3191–3198
258. Yu J, Savage PE (1999) Catalytic oxidation of phenol over MnO2 in supercritical water. Ind
Eng Chem Res 38:3793–3801
259. Angeles-Hernández MJ, Leeke GA, Santos RC (2008) Catalytic supercritical water oxidation
for the destruction of quinoline over MnO2/CuO mixed catalyst. Ind Eng Chem Res
48:1208–1214
260. Civan F, Özaltun DH, Kıpcak E, Akgün M (2015) The treatment of landfill leachate over
Ni/Al2O3 by supercritical water oxidation. J Super Fluids 100:7–14
261. Aki SNVK, Abraham MA (1998) An economic evaluation of catalytic supercritical water
oxidation: comparison with alternative waste treatment technologies. Environ Prog Sustain
Energy 17(4):246–255
262. Lee G, Nunoura T, Matsumura Y, Yamamoto K (2002) Comparison of the effects of the
addition of NaOH on the decomposition of 2-chlorophenol and phe-nol in supercritical water
and under supercritical water oxidation conditions. J Super Fluids 24:239–250
263. Qi XH, Zhuan YY, Yuan YC, WX G (2002) Decomposition of aniline in supercritical water. J
Hazard Mater B 90:51–62
264. Kazemi N, Tavakoli O, Seif S, Nahangi M (2015) High-strength distillery wastewater
treatment using catalytic sub- and supercritical water. J Super Fluids 97:74–80
265. Chen JH, Ma CY, Xi DL, Li Q (2011) Study on catalytic supercritical water oxidation process
for treating the perfume waste water. Environ Eng 29:36–39
266. Lin KS, Wang HP (2000) Supercritical water oxidation of 2-chlorophenol catalyzed by Cu2+
cations and copper oxide clusters. Environ Sci Technol 34:4849–4854
Impact on Disinfection Byproducts Using
Advanced Oxidation Processes
for Drinking Water Treatment

Brooke K. Mayer and Donald R. Ryan

Abstract Since the inception of drinking water treatment systems, ensuring the
production of microbiologically safe drinking water has been a primary objective.
While chemical oxidants are often successfully employed to mitigate microbial
risks, the chemical reactions that occur between oxidants and the dissolved or
particulate constituents present in source waters, e.g., natural organic matter
(NOM), can produce byproducts associated with unintended health consequences.
These disinfection byproducts (DBPs) are potentially carcinogenic, mutagenic,
genotoxic, and/or teratogenic. Since the discovery of DBPs in the early 1970s,
considerable effort has been afforded to develop regulations or guidelines striving
to simultaneously control microbial pathogens and DBPs. As advanced oxidation
processes (AOPs) gain traction as an integral part of advanced treatment trains in
water, wastewater, and water reuse scenarios, their impact on DBPs, in terms of
both formation and destruction, is an increasingly important consideration and is
the focus of this chapter.
This chapter begins with a brief overview of major drinking water disinfection
processes, followed by an introduction to common classes of disinfection
byproducts (DBPs) and their precursors, and concludes with discussion of the
influence of AOPs on DBP formation, formation potential, and removal.

Keywords Disinfection byproducts (DBP), Haloacetic acids (HAA), Natural

organic matter (NOM), Oxidation, Trihalomethanes (THM)

B.K. Mayer (*) and D.R. Ryan

Department of Civil, Construction and Environmental Engineering, Marquette University,
Milwaukee, WI 53151, USA
e-mail: [email protected]; [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 345
Water Treatment, Hdb Env Chem (2019) 67: 345–386, DOI 10.1007/698_2017_82,
© Springer International Publishing AG 2017, Published online: 25 October 2017
346 B.K. Mayer and D.R. Ryan

Contents
1 Brief Introduction to Disinfection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
1.1 Common Disinfectants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
1.2 Advanced Oxidation Process-Based Disinfection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
2 Disinfection Byproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
2.1 Disinfection Byproduct Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
2.2 Conventional Disinfection Byproducts: Trihalomethanes, Haloacetic Acids,
and Oxyhalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
2.3 Emerging Disinfection Byproducts, Including Brominated, Iodinated,
and Nitrogenous Species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
2.4 Non-halogenated Organic Disinfection Byproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
3 Disinfection Byproduct Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
3.1 Bulk Organic Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
3.2 Natural Organic Matter Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
3.3 Structure and Reactivity of Natural Organic Matter (NOM) Fractions . . . . . . . . . . . . . 364
3.4 Synthetic Organic Disinfection Byproduct Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
4 Disinfection Byproduct Formation in Relation to Advanced Oxidation Processes . . . . . . . 366
4.1 Disinfection Byproduct Formation in Advanced Oxidation Processes . . . . . . . . . . . . . . 367
4.2 The Impact of Advanced Oxidation Processes on Disinfection Byproduct (DBP)
Formation Potential: Influence of Oxidation on Precursor Organic Matter
and Subsequent DBP Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
5 Mitigation of Disinfection Byproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
5.1 Alternative Disinfectants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
5.2 Removal of Precursor Natural Organic Matter Prior to Disinfection . . . . . . . . . . . . . . . 374
5.3 Mitigation of Preformed Disinfection Byproducts Using Advanced Oxidation
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379

1 Brief Introduction to Disinfection

The five most commonly used drinking water disinfection strategies are free
chlorine, combined chlorine, chlorine dioxide, ozone, and ultraviolet (UV) light.
Figure 1 shows the relative distribution of the use of these disinfectants in the
United States based on surveys conducted by the American Water Works Associ-
ation (AWWA).
UV inactivates microorganisms on the basis of electromagnetic radiation, which
primarily disrupts nucleic acids. Each of the other four common disinfection
processes involves additions of oxidizing chemicals. These oxidizers damage
microbial proteins (amino acids) and genomes (nucleic acids) [3], thereby
preventing microbial replication, i.e., causing inactivation. However, these oxidants
are relatively nonselective, so they also react with other materials in the water (such
as natural organic matter, NOM), and can produce disinfection byproducts (DBPs),
which are potentially carcinogenic, mutagenic, genotoxic, and/or teratogenic. This
is represented by the generalized reaction:
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 347

100%

Relative usage of disinfectant

80%

60%

40%

20%

0%
1978 1989 1998 2007
Free chlorine Chloramines Chlorine dioxide
Ozone Ultraviolet

Fig. 1 Temporal summary of relative disinfectant use in municipal drinking water treatment in
the United States. Adapted from [1, 2]. The cited surveys reported the use of multiple types of
disinfectants for some systems (yielding totals in excess of 100% of the number of systems
surveyed); here the relative distribution of type of disinfectant used is shown, resulting in a
maximum of 100%

Oxidant ðe:g:; HOClÞ þ Precursor ðe:g:; NOMÞ ! DBP ðe:g:; CHCl3 Þ

The extent of DBP formation is a function of the type of disinfectant used,

disinfectant dose, system parameters (e.g., contact time), and water quality (e.g.,
quantity and character of NOM, pH, and temperature).

1.1 Common Disinfectants

Free chlorine (primarily in the form of HOCl and OCl [Eo ¼ 1.49 V for HOCl/Cl])
is typically added as gaseous Cl2 or NaOCl. It is the most commonly used disinfec-
tant for water treatment as it is broadly effective against microbial pathogens and is
comparatively inexpensive. Although free chlorine remains the dominant drinking
water disinfectant, concerns over chlorine-resistant microbes (e.g., Cryptosporidium
and Giardia) and formation of halogenated DBPs have increased interest in alterna-
tive disinfection strategies. Free chlorine is associated with the production of clas-
sically regulated DBPs such as trihalomethanes (THMs) and haloacetic acids
(HAAs), as well as emerging DBPs, including chloral hydrate, chlorophenols,
formaldehyde, haloketones, halogenated furanones, and haloacetonitriles. In gen-
eral, the production of organochlorine compounds during chlorination is caused by
reactions between chlorine and humic substances [4]. There are three general
pathways through which free chlorine reacts with water constituents: oxidation,
addition, and substitution [5]. When organic compounds have double bonds, the
chlorine can undergo an addition reaction, but this reaction is often too slow to be
of importance in water treatment. Thus, most chlorinated DBPs are formed via
348 B.K. Mayer and D.R. Ryan

oxidation and substitution reactions, with reactions occurring much more rapidly at
high pH than at low pH [4].
Combined chlorine is the sum of the species formed through the reaction of
chlorine and ammonia: monochloramine (NH2Cl), dichloramine (NHCl2), and
trichloramine (NCl3). Combined chlorine, or chloramines, is not as effective as
free chlorine for inactivation of pathogens and is thus not commonly used as a
primary disinfectant. However, its longer residual makes it a common choice for
secondary disinfection to avoid biological regrowth in the distribution system.
Chloramines reduce the amount of THMs and HAAs formed in comparison to
free chlorine; however, they introduce concerns for nitrosamine and cyanogen
chloride DBP formation. Reactions of chloramines with humic materials and
amino acids produce haloacetonitriles and non-halogenated acetonitriles, following
a pathway similar to that for chlorine [4].
Chlorine dioxide (ClO2) is a powerful disinfecting agent (Eo ¼ 0.95 V for ClO2/
ClO2) but is volatile, typically requiring onsite generation. It is widely used as a
disinfectant in continental Europe but is not as commonly used in the United States.
At the dosages typically used in drinking water treatment, ClO2 (which is more
selective than free chlorine) does not react with NOM, so it avoids formation of
THMs and HAAs, and produces almost no identifiable organic byproducts
(although low levels of some aldehydes and ketones can result) [6]. Chlorine
dioxide reacts only by oxidation, which explains the lack of organochlorine com-
pound formation [4]. Although stable in pure water, ClO2 decomposes in drinking
water as it is photoreactive and can also undergo disproportionation to produce the
inorganic DBPs chlorite (ClO2) and chlorate (ClO3), the kinetics and degree of
which depend on ambient water quality parameters [7].
Of the common chemical disinfectants, ozone (O3, Eo ¼ 2.07 V for O3/O2) is the
strongest oxidizing agent and must be generated on-site as it is unstable. Ozone
provides effective oxidation of many chemical contaminants as well as inactivation
of microbial pathogens. Ozonation itself does not produce halogenated DBPs and
has thus become increasingly common. However, when bromide is present in
waters, ozone can produce brominated DBPs such as bromate (BrO3). In general,
bromate forms through a combination of molecular ozone attack and reactions of
bromide with free radicals, which are formed as ozone decomposes during water
treatment [4]. The radical pathway may play a more important role than the
molecular ozone pathway [4]. Ozone can also react with bromide to form bromi-
nated organics such as bromoform, dibromoacetonitrile, and dibromoacetone
[4, 8]. As ozone progressively degrades complex organics, non-halogenated
DBPs such as formaldehyde (CH2O) may also result.
In the case of UV disinfection, microorganisms are inactivated via disruption of
their genetic material (DNA or RNA) rather than via chemical oxidation. For the
fluences (i.e., UV dose, which is a function of intensity and exposure time) typically
used in drinking water treatment (<200 mJ/cm2), there is no evidence of DBP
formation, nor are DBP levels exacerbated using post-UV disinfection [9].
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 349

1.2 Advanced Oxidation Process-Based Disinfection

Recalcitrant contaminants, such as endocrine-disrupting compounds (EDCs), phar-

maceuticals and personal care products (PPCPs), pesticides, etc., are typically the
primary targets for AOPs, and there are numerous reports of this application.
However, the hydroxyl radicals (HO•, Eo ¼ 2.70 V) or sulfate radicals (SO4•, Eo
¼ 2.5–3.1 V) generated from AOPs or sulfate-radical-based AOPs (SR-AOPs),
respectively, may also provide some degree of disinfection [10]. The use of AOPs
for disinfection is far less frequently reported in comparison to chemical degradation
(e.g., for UV/TiO2 [11–14]) but may be realized as a secondary outcome of the use of
AOP treatments in drinking water. Disinfection using solar irradiation-based AOPs
may be of particular interest for use in developing countries [15]. Hydroxyl radicals
may oxidize and disrupt cell walls and membranes, thereby lysing the cell, or they
may diffuse into the cells and react with intracellular components. AOP-based
disinfection may be limited by mass transfer through the cell walls or membranes
as HO• reacts with most biological molecules at diffusion-controlled rates. Although
there may be some oxidative enhancement in virus inactivation due to HO•, UV
appears to be primarily responsible for microbial inactivation using UV-based
AOPs [10].
Since the oxidation pathway in AOPs relies on radicals rather than halogens,
halogenated DBP production during AOP treatments is generally less of a concern
in comparison to traditional oxidative disinfectants. However, ozone-associated
DBPs may be generated during ozone-based AOPs, and non-halogenated organic
DBPs can occur as complex organic matter is degraded. DBP formation during
AOP treatments is discussed in greater detail in Sect. 4.1.

2 Disinfection Byproducts

Reactions between oxidizing disinfectants and the organic or inorganic precursor

material found in water can lead to the generation of potentially harmful DBPs, as
depicted in the generalized illustration in Fig. 2.
The range of DBPs produced via reactions between oxidants and organic pre-
cursors (NOM or anthropogenic organic pollutants) or inorganic precursors (i.e.,
bromide or iodide) include halogenated organics, organic oxidation byproducts, and
inorganics. Table 1 lists several important classes of DBPs, their main causative
agents, and examples of established drinking water regulations.
The formation of DBPs during drinking water disinfection has been recognized
since the 1970s [23, 24], but advances in analytical techniques and risk assessment
continue to facilitate discovery and better characterization of the more than 600 cur-
rently identified DBPs. Of note, the number of DBPs identified and quantified in
water to date is only a small fraction of those potentially formed. As illustrated for
 350

Fig. 2 Examples of disinfection byproducts (DBPs) produced from reactions between oxidizing disinfectants and precursor material, in accordance with the
general reaction: Oxidant + Precursor ! DBP. All chemical structures are from the ChemSpider website (http://www.chemspider.com/)
B.K. Mayer and D.R. Ryan
Table 1 Examples of classical and emerging drinking water disinfection byproducts (DBPs) produced by conventional oxidative disinfection processes and
advanced oxidation processes (AOPs) (all concentrations in μg/L)
Primarily a byproduct of Selected drinking water regulations
O3- Non-O3- European Health US Environmental World Health
Chemical Free based based Union Canada Protection Agency Organization
a
Species formula chlorine Chloramines ClO2 O3 AOP AOP Australia (EU)b (HC)c (USEPA)d (WHO)e
g
Trihalomethanes (THM) TTHMf 250 100 100 80
Chloroform CHCl3 X X 300
Bromodichloromethane CHBrCl2 X X 60
Dibromochloromethane CHBr2Cl X X 100
Bromoform CHBr3 X X X X 100
Dichloroiodomethane CHICl2 X X
Chlorodiiodomethane CHI2Cl X X
Bromochloroiodomethane CHBrICl X X
Dibromoiodomethane CHBr2I X
Bromodiiodomethane CHBrI2 X
Triiodomethane CHI3 X
Haloacetic acids (HAA) HAA5h 80 60
Monochloroacetic acid C2H3ClO2 X X 150 20
Dichloroacetic acid C2H2Cl2O2 X X 100 50
Trichloroacetic acid C2HCl3O2 X X 100 200
Monobromoacetic acid C2H3BrO2 X X --
Dibromoacetic acid C2H2Br2O2 X X
Bromochloroacetic acid C2H2BrClO2 X X
Dibromochloroacetic acid C2HBr2ClO2 X X
Bromodichloroacetic acid C2HCl3O2 X X
Tribromoacetic acid C2HBr3O2 X X
Oxyhalides
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . .

Bromate BrO3 X X 20 10 10 10 10
Chlorite ClO2 X 800 1,000 1,000 700
Chlorate ClO3 X 1,000 700
Haloketones (HK)
1,1-Dichloro-2-propanone C3H4Cl2O X X
351

(continued)
Table 1 (continued)
352

Primarily a byproduct of Selected drinking water regulations

O3- Non-O3- European Health US Environmental World Health
Chemical Free based based Union Canada Protection Agency Organization
a
Species formula chlorine Chloramines ClO2 O3 AOP AOP Australia (EU)b (HC)c (USEPA)d (WHO)e
1,1,1-Trichloro-2-propanone C3H3Cl3O X X
Chlorophenols
2-Chlorophenol C6H5ClO X X 300
2,4-Dichlorophenol C6H4Cl2O X X 200
2,4,6-Trichlorophenol C6H3Cl3O X X 20 5 200
Chloral hydrate C2H3Cl3O2 X X 100
(trichloroacetaldehyde)
Haloacetonitriles (HANs) X X
Dichloroacetonitrile C2HCl2N X X 20
Dibromoacetonitrile C2HBr2N X X 70
Trichloroacetonitrile C2Cl3N X X
Bromochloroacetonitrile C2HBrClN X X
Nitrosamines
N-Nitrosodimethylamine C2H6N2O X X X 0.1 0.04 0.1
(NDMA)
Trihalonitromethanes
Trichloronitromethane CCl3NO2 X X
(chloropicrin)
Bromodichloronitromethane CBrCl2NO2 X X
Dibromochloronitromethane C2Br2ClNO2 X X
Tribromonitromethane CBr3NO2 X X
Cyanogen halides (CNX)
Cyanogen chloride CNCl X 80 70
(as cyanogen)
Cyanogen bromide CNBr X X
Aldehydes
Formaldehyde CH2O X X X X X 500
Acetaldehyde C2H4O X X X X X
Glyoxal C2H2O2 X X X X X
B.K. Mayer and D.R. Ryan
 Methylglyoxal C3H4O2 X X X X X
Carboxylates
Formate CHO2 X X X
Acetate C2H3O2 X X X
Oxalate C2O42 X X X
Keto acids
Glyoxylic acid C2H2O3 X X X
Pyruvic acid C3H4O3 X X X
Ketomalonic acid C3H2O5 X X X

Updated and adapted from [16, 17]

a
[18]
b
[19]
c
[20]
d
[21]
e
[22]
f
TTHM ¼ sum of four THMs: chloroform, bromodichloromethane, dibromochloromethane, and bromoform
g
The sum of the ratio of the concentration of each to its respective guideline value should not exceed 1
h
HAA5 ¼ sum of five HAAs: monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . .
353
354 B.K. Mayer and D.R. Ryan

chlorinated drinking water in Fig. 3, more than half of the total organic halide
(TOX) formed during chlorination has yet to be chemically identified [25, 26].

2.1 Disinfection Byproduct Regulations

Since their discovery in the 1970s, DBPs have been widely regulated as drinking
water contaminants, as demonstrated by the list of select DBPs and applicable
regulations/guidelines shown in Table 1. For historical context, a brief description
of the regulatory basis for DBPs in the United States is provided here. Next, the
most commonly regulated, or classical, DBPs are introduced, including trihalo-
methanes, haloacetic acids, chlorate, chlorite, and bromate. This section concludes
with brief descriptions of several classes of emerging DBPs.
In the United States, DBPs were first regulated in 1979, beginning with the
TTHM (total trihalomethanes) Rule, which set a maximum contaminant level
(MCL) of 100 μg/L TTHM based on a running annual average of distribution
system samples. In 1986, amendments to the Safe Drinking Water Act (SDWA)
noted that disinfectants and DBPs should be regulated [28]. Thus, to simultaneously
control microbial pathogens, residual disinfectants, and DBPs, three related rules
were developed: the Information Collection Rule (ICR), the Disinfectants/DBP
Rule (D/DBPR, implemented in two stages), and the Enhanced Surface Water
Treatment Rule (ESWTR, implemented in stages, e.g., Long-Term 2 Enhanced
Surface Water Treatment Rule or LT2). In Stage 1 of the D/DBPR, the USEPA
reduced the existing TTHM standard to 80 μg/L and expanded regulations to
include haloacetic acids (HAA5s ¼ 60 μg/L), bromate (BrO3 ¼ 10 μg/L), and
chlorite (ClO2 ¼ 1,000 μg/L). In Stage 2 of the D/DBPR, the DBP MCLs were
maintained, but compliance was amended to a locational running annual average
basis (rather than the previous approach of averaging concentrations across distri-
bution system sampling points).

Fig. 3 Distribution of
characterized total organic
halides (TOX) in THMs, 13.5%
chlorinated drinking water,
including unknown TOX, Unknown TOX, HAAs, 11.8%
trihalomethanes (THMs), 69.9%
haloacetic acids (HAAs),
and several classes of
emerging halogenated
disinfection byproducts
(DBPs) which account for
<5% of the total DBPs.
Adapted from [27] ∑(Iodo THMs, Halofuranones, Haloacetonitriles,
Halogenated Aldehydes, Haloketones, Haloacetates,
Halonitromethanes), 4.8%
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 355

In addition to these established federal regulations, the USEPA also periodically

reviews the status of unregulated DBPs (and other drinking water contaminants) as
part of the Contaminant Candidate List (CCL) and Unregulated Contaminant
Monitoring Rule (UCMR). The CCL is a list of currently unregulated contaminants
that are known or believed to occur in public water systems and are thus identified
as research priorities in order to better inform determinations of risks and regula-
tions. The USEPA’s 4th version of the CCL (CCL4, announced in 2016) includes
several additional DBPs: acetaldehyde (an O3-DBP), chlorate (formed during ClO2
and hypochlorite disinfection), formaldehyde (O3 based), bromochloromethane, N-
nitrosodiethylamine (NDEA), N-nitrosodimethylamine (NDMA), N-nitrosodi-n-
propylamine (NDPA), N-nitrosodiphenylamine (NDPhA), and N-
nitrosopyrrolidine (NPYR) [29]. The state of California’s Department of Public
Health has already set a notification level of 10 ng/L for NDEA, NDMA, and NDPA
and a public health goal for NDMA of 3 ng/L [30]. Monitoring results from public
water systems collected as part of the USEPA’s UCMR program suggest that more
than 10% of the US’ chloraminated systems could be affected if a NDMA MCL was
introduced at the California action level of 10 ng/L [31].

2.2 Conventional Disinfection Byproducts:

Trihalomethanes, Haloacetic Acids, and Oxyhalides

The trihalomethanes (THMs) were the first DBPs to be discovered and are one of
the most prevalent classes of DBPs resulting from chlorine disinfection
[25]. Together with haloacetic acids, THMs account for approximately 25% of
the halogenated DBPs from chlorination [32]. Chloramination can also generate
THMs, albeit typically to a much lesser extent, as can ozone through production of
bromoform. Many DBP regulations are based on total trihalomethanes (TTHMs),
which are calculated as the sum of four THMs: chloroform, bromoform,
bromodichloromethane, and chlorodibromomethane, of which chloroform is often
found at the highest concentrations [25]. All of the TTHM species demonstrate
carcinogenicity in rodents [25].
Surface water typically contains higher concentrations of precursor NOM and,
as such, is associated with higher DBP production, as shown in Fig. 4. Other
commonly used indicators of THM formation include chlorine dose, pH, temper-
ature, bromide concentration, and disinfection contact time. In general, as these
parameters increase, so does DBP formation (although DBP responses to increasing
pH are mixed). A number of empirical and semi-mechanistic DBP formation
models have been used to predict DBP concentrations based on these and other
parameters, often using a multiple linear or nonlinear regression approach. When
applied to the treatment scenarios for which they were specifically developed, these
models can be helpful indicators of operation, risk assessment, etc. [33], although
they tend to overpredict DBPs for conditions least conducive to formation while
356 B.K. Mayer and D.R. Ryan

250
TTHMs
HAA5s
DBP Concentration (μg/L)
200

150

100
US TTHM MCL

50 US HAA5 MCL

0
Surface Water Groundwater Mixed Waters

Fig. 4 Formation of TTHMs and HAA5s in finished water surveyed in 1992 at more than 100 US
drinking water treatment plants with varying source waters. The bars represent average values,
while the error bars illustrate the range in values reported, and the lines denote regulatory
maximum contaminant levels (MCLs) in the US. Data from [36]

underpredicting for the conditions most conducive for DBPs [8, 16, 34, 35]. How-
ever, Mayer et al. [16] reported that TTHM and HAA5 models generally performed
poorly when applied to DBP data not used to directly develop the model, regardless
of the use and extent of AOP treatment and type of source water. This suggests that
bulk indicators and/or models should be used cautiously as metrics for AOP
mitigation of DBP formation potential.
The main haloacetic acids (HAAs) include nine different halogenated com-
pounds, as shown in Table 1. When regulated, the HAAs are sometimes dealt with
on the basis of individual compounds but are sometimes grouped together, for
example, as HAA5, or the sum of five of the HAAs: bromoacetic acid, dibromoacetic
acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid, all five of
which are mutagenic [25]. The remaining four main HAAs were more difficult to
quantify when the US regulation was promulgated and so were excluded from
regulation. Like THMs, chlorination generally produces the highest levels of
HAAs, although lower levels can result from chloramination, ClO2, and O3 [37].
The oxyhalides chlorite (ClO2) and chlorate (ClO3) are the inorganic DBPs
produced through reactions of NOM with ClO2. Chlorine dioxide rapidly reacts
with NOM and inorganic matter, degrading to chlorite, chlorate, and chloride [25].
When bromide is present in source water, brominated DBPs including inorganic
bromate (BrO3) and organic brominated DBPs may pose a concern. Bromate is of
particular concern for ozonation processes when bromide is present in source
waters at high levels (>50–100 μg/L) [25, 38]. Bromate is both genotoxic and
carcinogenic, and of the DBPs regulated in the United States, it is the most potent
carcinogen in laboratory animals [25]. It is formed by a series of oxidations
mediated by O3 or a combination of O3 and HO• reacting with natural bromide,
where O3 sequentially oxidizes bromide to hypobromite (BrO), followed by
bromite (BrO2), and finally to bromate [39]. The HO• produced as part of the
ozonation process also participates in the intermediate reactions [39].
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 357

2.3 Emerging Disinfection Byproducts, Including

Brominated, Iodinated, and Nitrogenous Species

To date, the greatest emphasis in DBP research and mitigation has been on a subset
of more conventionally regulated DBPs including THMs, HAAs, and BrO3.
However, there are a large number of “emerging” DBPs, including those not
currently widely regulated. As the majority of TOX often consists of unidentified
compounds (see Fig. 3), developing a better understanding of emerging DBPs is an
important area of research. In this section, several major classes of emerging DBPs
are introduced.

2.3.1 Organic Brominated and Iodinated Disinfection Byproducts

Bromide and iodide are naturally occurring inorganic DBP precursors for a variety
of DBPs. These ions may be present, and of concern, in source waters impacted by
seawater intrusion and natural salt deposits, e.g., coastal cities or areas affected by
oil and gas brines. When bromide is present, organic brominated DBPs (B-DBPs)
are primarily produced by chlorination in the same manner as the classical DBPs. In
contrast, iodinated DBPs (I-DBPs) are primarily produced by chloramination of
iodide-containing waters. Both B-DBPs and I-DBPs are more toxic and carcino-
genic than their chlorine analogs, in order of greatest health risk:
chlorinated < brominated < iodinated [40].
Although iodo-THMs and iodo-HAAs are among the most toxic unregulated
DBPs, iodate (IO3) is generally not problematic and is readily reduced to iodide
(I) after consumption [41]. In processes that use strong oxidizing disinfectants,
e.g., ozone or chlorine, I is readily oxidized to IO3 (as shown below), which
results in very low amounts of organic I-DBPs remaining in solution.

I ! IO =HIO ! IO2  ! IO3 

For example, 90% of naturally occurring I was converted to IO3 during

ozonation [42]. This stems from the higher activity of hypoiodous acid (HIO)
with strong oxidizing disinfectants in comparison to reactivity with NOM. Thus,
the oxidation reactions can be optimized as a sink to form IO3 rather than organic
I-DBPs when I reacts with NOM [43].
The smaller oxidative potential of chloramines yields ineffective oxidation of
HIO to IO3, which can increase formation of I-DBPs during chloramination
[42]. Iodide can be oxidized prior to ammonia additions during chloramination
using prechlorination or preozonation; however, this approach could increase the
formation of B-DBPs and chlorinated DBPs [40, 42].
358 B.K. Mayer and D.R. Ryan

2.3.2 Halogenated Furanones

Halogenated furanones, including MX (3-chloro-4-(dichloromethyl)-5-hydroxy-2

(5H)-furanone) and its brominated analogues (BMX), are highly mutagenic DBPs.
Weinberg et al. [26] found that MX and BMX analogues are generally found at
concentrations of 60 ng/L or less, but they have also been found at concentrations as
high as 80 ng/L [44]. These species can account for more than 50% of the mutage-
nicity in bioassays of chlorinated drinking waters [45, 46]. The formation pathway
for MX may be similar to that for THMs and HAAs as occurrence of MX analogues
is positively correlated with occurrence of chloroform, and MX analogues have been
found in effluent from chlorine and chlorine dioxide disinfection processes which
also contained THMs and HAAs [47]. Chloramine disinfection processes yield
comparatively smaller concentrations of MX and BMX analogues [47].

2.3.3 Nitrogenous Disinfection Byproducts

Nitrogenous DBPs (N-DBPs) are a subset of the classical carbonaceous DBPs

(C-DBPs) [27]. They may result when sufficient levels of nitrogen are present for
DBP incorporation, e.g., using source waters impaired by algal blooms, during
chloramination, in the presence of certain polymers, or at water reuse facilities.
Nitrosamines are one of the most widely studied N-DBPs. They are a family of
emerging DBPs often found at ng/L concentrations but associated with serious
health risks as they have been reported to be carcinogenic, mutagenic, and/or
teratogenic [48, 49]. N-Nitrosodimethylamine (NDMA) is the most common nitro-
samine and is a probable human carcinogen, with 0.7 ng/L NDMA correlating to a
lifetime cancer risk of 106 [50].
The NDMA formation potential varies as a function of source water and
treatment process. It is primarily produced during chloramination of water [51],
which directly adds nitrogen during disinfection. Low molar yields of NDMA may
be generated by reacting precursors with either chloramines or ozone, but most
precursors are more reactive with just one of the disinfectants (i.e., chlorine- or
ozone-reactive NDMA precursors) [52]. Some studies have shown that
preozonation increases NDMA formation potential in water [53], but others have
found decreased NDMA formation potential [54].
In general, NDMA precursors comprise secondary, tertiary, or quaternary
amines, with sources including PPCPs, pesticides, water or wastewater treatment
chemicals, and industrial chemicals [52]. As wastewater effluent may contain more
of these N-rich compounds in comparison to many drinking water sources, NDMA
is of particular concern in wastewater effluent and water reuse scenarios. Naturally
occurring bromide can also contribute to NDMA formation by catalyzing reactions
with precursors [55]. Padhye et al. [56] found that NDMA formation tripled in the
presence of 100 μM bromide.
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 359

In addition to NOM, polymers may serve as NDMA precursors. As shown in

Fig. 5, cationic amine-based polymers, such as polyamine and poly-DADMAC,
used to enhance coagulation and dewatering can contain dimethylamine (DMA)
and other small amine moieties which serve as significant NDMA precursors
[48, 51, 57]. When dosed at optimal levels, minimal polymer residual remains in
solution following physicochemical treatment. Accordingly, it is unlikely that
sufficient concentrations of polymer will be present to react with chloramines to
form NDMA. Rather, the primary concern lies in degradation of the polymers and
release of NDMA precursors. Polyamine is generally more susceptible to degrada-
tion and DMA release than poly-DADMAC and therefore is more closely linked to
DBP formation [57]. Alternative polymers produced from natural products may
perform as well as poly-DADMAC while limiting nitrosamine formation
potential [58].

2.4 Non-halogenated Organic Disinfection Byproducts

When condensed aromatic compounds are oxidized, low molecular weight,

non-halogenated organic DBPs may result. These products may include aldehydes,
carboxylic acids, and keto acids, all of which can enhance biodegradability and can
even be toxic. The most commonly observed organic byproducts are aldehydes
such as formaldehyde and acetaldehyde [59]. Other common organic byproducts
include formate, acetate, and oxalate [17].

3 Disinfection Byproduct Precursors

DBP precursors include both organic matter (e.g., NOM) and inorganic compounds
(e.g., bromide and iodide). Increases in the ratio of bromide ion relative to chlorine
or organic matter can shift speciation of THMs and HAAs toward more bromine-

Fig. 5 N-Nitrosodimethylamine (NDMA) and common polymers acting as NDMA disinfection

byproduct (DBP) precursors, with the dimethylamine (DMA)-related moiety (primary component
serving as NDMA precursor) highlighted in each molecule
360 B.K. Mayer and D.R. Ryan

substituted species, which are associated with more significant health risks com-
pared to chlorinated DBPs [60].
Natural organic matter is ubiquitous in drinking water sources and serves as the
primary organic DBP precursor. Its enigmatic character derives from a complex
mixture of numerous compounds ranging from aromatic phenolic compounds and
aliphatic carboxylic acids to nitrogenous compounds such as proteins, sugars,
amino acids, and large biopolymers, e.g., lignin [61]. Understanding the quantity
and character of NOM is essential for water treatment design to effectively mitigate
NOM-related problems such as DBP formation; greater coagulant dose require-
ments; increased bioavailability of organics in the water; and aesthetic concerns
such as color, taste, and odor [62]. Multiple approaches can be used to provide
indications of the quantity and quality of complex mixtures of NOM, including bulk
organic measurements and fractionation on the basis of fluorescence excitation/
emissions, size, or operational behavior (e.g., hydrophilic, acid, etc.).

3.1 Bulk Organic Measurements

Total organic carbon (TOC), dissolved organic carbon (DOC), ultraviolet absor-
bance at a wavelength of 254 nm (UV254), and specific ultraviolet absorbance
(SUVA) are bulk parameters often used as indicators of NOM quantity and general
character. These parameters are also commonly used as surrogates for estimating
DBP formation potential, although they do have limitations. They do not always
correlate to DBP concentrations in finished drinking water since other factors such
as disinfectant type and dose, as well as water pH, temperature, bromide concen-
trations, etc. all strongly influence DBP formation [16, 36]. However, bulk organic
parameters are still commonly used as they offer an easy, rapid, and inexpensive
approach to gauging NOM.
Natural waters used as drinking water sources typically contain low levels of
synthetic organic contaminants, so TOC is often considered synonymous with
NOM [61]. The DOC fraction is classified as the organic carbon that passes through
a 0.45 μm filter, whereas the fraction that is retained is the particulate organic matter
(POM, often accounting for <10% of TOC) [63, 64].
Spectrophotometric analysis in the wavelength range of 220–280 nm is also
commonly used as an indicator of the presence of organics. Molar absorptivities
vary widely due to the diversity of chromophores present in NOM; for example,
carboxylic acids and aromatic compounds are associated with a wavelength of
220 nm [65], with maximum absorption at 254 nm for most aromatic groups.
Accordingly, absorbance at 254 nm (UV254) is primarily used to indicate the
presence of the dense, aromatic, hydrophobic portion of NOM [66] and is also
used as a rough indicator of overall NOM content [61].
SUVA is another helpful correlation parameter for DBP formation potential [67]
as it is indicative of the relative aromaticity of the NOM. The SUVA value
normalizes UV254 relative to the DOC concentration.
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 361

UV254
SUVA ¼ , ðL=mg mÞ
DOC

High SUVA values (>4) indicate largely aromatic, hydrophobic, high molecular
weight compounds, whereas low SUVA values (<4) represent small molecular
weight, hydrophilic compounds [68].
These bulk organic parameters are useful in describing the quantity of NOM and
providing an indication of its character, which can provide an indication of water
quality through treatment stages as well as DBP formation potential (as bulk
organic matter parameters increase, DBP formation potential generally increases).
However, bulk parameters do not always correlate to DBPs, nor do they provide
information regarding specific NOM constituents such as amino acids, sugars, and
carbohydrates.

3.2 Natural Organic Matter Fractionation

To better characterize the array of diverse compounds present in NOM, fraction-

ation techniques based on parameters such as absorbance, size, hydrophobicity, etc.
may be employed.

3.2.1 Fluorescence Absorption and Emission-Based Fractionation

Analysis using a 3-D fluorescence excitation emission matrix (EEM) can be useful
for understanding NOM fractions [69]. In water, fluorophores are generally divided
into humic-like fluorophores and protein-like fluorophores [70, 71]. The NOM can
be fractionated prior to analysis in order to express characteristic peaks, locations of
which are illustrated in the EEM matrix in Fig. 6 [72–75]. Each fraction is
characterized by its own potential for DBP production. The humic-like peak
correlates strongly with TTHM formation potential, and the tryptophan-like peak
correlates well with NDMA formation potential [76]. EEM analysis may provide
better correlation to NDMA formation potential compared to UV254 and SUVA
indicators [76–78].

3.2.2 Size-Based Fractionation

Size exclusion chromatography (SEC) and high-performance liquid chromatography-

SEC (HPLC-SEC) can be used to characterize NOM samples on the basis of molec-
ular size. Although molecular size can provide an indication of DBP formation
potential, there is a great deal of variation in observed correlations between size of
precursor NOM and resulting DBP formation. While some studies have found the
hydrophobic NOM fraction with an apparent molecular weight (AMW) of 1–10 kDa
362 B.K. Mayer and D.R. Ryan

410
Humic acid-like range
390
Humic-like
Excitation (nm)

370
350
330 Protein-like

310 Tryptophan-like
Tyrosine-like range Fulvic acid-like range
290 range
270
250
300 350 400 450 500
Emission (nm)

Fig. 6 Excitation emission matrix (EEM) wavelengths associated with natural organic matter
(NOM) fractions. Adapted from [79, 80]

to be the primary DBP precursor [81], hydrophilic and lower molecular weight
fractions may also generate significant DBPs [16, 82–84]. For example, the bulk
portion of NDMA precursors consists of small molecular weight compounds
(<3,000 Da) [85, 86]. Similarly, Zhao et al. [87] found that low molecular weight
dissolved organic matter serves as a significant THM precursor.
Figure 7 shows several example datasets from disinfected surface waters illus-
trating the relative contribution of different NOM size fractions to C-DBP, N-DBP,
and I-DBP formation potential. As exemplified here, there is no clear trend between
NOM molecular weight fractions and DBP formation; therefore, size fractionation
by itself is a less important predictor for DBP formation compared to chemical
composition of the NOM and water quality parameters [88, 89].
Thus, while using UV detectors for HPLC-SEC provides helpful information for
evaluating the potential for removal of high molecular weight organic matter via
coagulation or other processes, their use for understanding DBP formation potential
may still be limited. Alternatively, coupling UV detectors in tandem with DOC
analyzers or fluorospectrometers can be used to provide more informative datasets
by detecting aromatic and nonaromatic datasets as a function of molecular weight,
both of which parameters are important for predicting DBP formation potential
[90, 91]. Compound classes and their respective apparent molecular weights are
shown in Table 2.

3.2.3 Resin Fractionation

To better understand complex organic matter, resin fractionation methods can be

used to classify NOM in accordance with behavior during different water treatment
processes. The predominant properties of organic matter can be characterized as
hydrophobic, hydrophilic, acidic, basic, and neutral (although distinctions are not
always clear, e.g., a great deal of dissolved organic matter is recognized as both
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 363

Fig. 7 Disinfection byproduct formation relative to natural organic matter (NOM) molecular
weight (MW) size fraction for C-DBPs, N-DBPs, and I-DBPs in chlorinated and chloraminated
water from the (a) Huangpu River, China, and (b) the Yangtze River, China. Data from [89]
364 B.K. Mayer and D.R. Ryan

Table 2 Size characterization using a combination of high-performance liquid chromatography-

size exclusion chromatography (HPLC-SEC) with (ultraviolet) UV and online dissolved organic
carbon (DOC) detectors to characterize natural organic matter (NOM) by apparent molecular
weight (AMW)
Compound class Apparent molecular weight (AMW)
Polysaccharide- and protein-like substances High (>10,000 g/mol)
Highly aromatic and fulvic substances Medium (1,000–5,000 g/mol)
Aliphatic-like substances Low (<680 g/mol)
Adapted from [92]

amphiphilic and amphoteric) [61]. Each of these fractions, or subsets thereof, can
be isolated using sequential resin-based separation.
The hydrophobic portion of NOM is composed of densely aromatic structures,
conjugated double bonds, and high molecular weight compounds. The hydrophobic
fraction is also characterized by a high specific surface charge, making it more
amenable to removal via coagulation [93]. The hydrophobic fraction can account
for more than half of the DOC in water [64, 93, 94], although there is great variation
in fractionation among different source waters. This can be problematic for drink-
ing water treatment since the hydrophobic portions of NOM serve as significant
precursors for DBPs and produce greater amounts of unidentified total organic
halogen products (TOX) [95–97].
The hydrophilic fraction of NOM contains low molecular weight polar com-
pounds such as carboxylic acids, as well as nitrogenous compounds including sugars,
peptides, and amino acids [61]. The hydrophilic NOM fraction is also a significant
precursor for DBPs and generally forms more NDMA than the hydrophobic fractions
[98]. The hydrophilic fraction has been observed to be more reactive with bromine
and iodine than the hydrophobic NOM fraction [95], as illustrated in Fig. 8a, b, which
shows DBP formation potential from different NOM fractions in several waters.
As shown in Fig. 8, although the presence of different fractions can provide an
indication of DBP formation potential, actual DBP production can vary widely with
source water and operational parameters in the disinfection process.

3.3 Structure and Reactivity of Natural Organic Matter

(NOM) Fractions

The physicochemical properties (Kow, pKa, and molecular weight) of individual

NOM species do not correlate well to DBP formation potential [101]. However,
halogen substitution efficiency is an effective indicator of DBP formation potential.
As shown in Fig. 9, compounds exhibiting high halogen substitution efficiency, and
which produce substantial THMs and HAAs, include ferulic acid, L-tryptophan, and
resorcinol [101]. These compounds are considered activated aromatics because the
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 365

Fig. 8 Disinfection byproduct (DBP) formation potential associated with natural organic matter
(NOM) fractions in variable source waters. C-DBPs, N-DBPs, and I-DBPs formed during chlori-
nation or chloramination of water from (a) the Huangpu River, China, and (b) the Yangtze River,
China [89]. (c) Shows chloroform [99], total trihalomethane (TTHM), and haloacetic acid (HAA)
formation following chlorination [100]
366 B.K. Mayer and D.R. Ryan

Ferulic acid L-tryptophan Resorcinol

L-aspartic acid

Fig. 9 Compounds exhibiting high halogen substitution efficiency and which produce substantial
trihalomethanes (THMs) and/or haloacetic acids (HAAs)

constituents on the ring are electron donors. Although not an activated aromatic
species, L-aspartic acid also has many electron donating functional groups, has a
high substitution efficiency, and serves as a significant precursor for HAA species.

3.4 Synthetic Organic Disinfection Byproduct Precursors

In addition to NOM, synthetic organic compounds can serve as precursor material

for DBP formation. For example, the active compounds in sunscreens can be
transformed to halogenated DBPs when swimming pools are disinfected with
chlorine [102]. Understanding of DBPs produced by oxidation of the activated
aromatic rings in synthetic compounds is a relatively new undertaking in compar-
ison to their NOM-derived relatives. However, research is progressing, often
stemming from studies of oxidative degradation of compounds such as pesticides
(e.g., S-triazine herbicides and isoproturon), pharmaceuticals (e.g., carbamazepine
and acetaminophen), antibacterial agents (e.g., triclosan and carbadox), textile dyes
(e.g., azo), bisphenol A, alkylphenol ethoxylate surfactants, etc. [25].

4 Disinfection Byproduct Formation in Relation

to Advanced Oxidation Processes

Advanced oxidation processes primarily impact DBP formation in two different

ways: directly through in situ DBP formation and indirectly by influencing the DBP
formation potential of the organics in the water matrix. In the first case, DBPs may
be generated during the operation of AOPs themselves, particularly when using
AOPs with direct inputs of chemical oxidants, e.g., ozone or hydrogen peroxide.
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 367

Additionally, organic oxidation byproducts may result during AOPs as complex

organics are progressively degraded. In addition to direct formation during AOP
treatments, AOPs may influence subsequent DBP formation potential as the DBP
precursor organic material undergoes dramatic transformations during AOPs,
which can serve to either decrease or increase DBP formation during subsequent
disinfection processes.

4.1 Disinfection Byproduct Formation in Advanced

Oxidation Processes

Hydroxyl radicals can attack organic molecules by radical addition, hydrogen

abstraction, electron transfer, and radical combination. Select kinetic rate constants
for reactions of HO• with organic matter, with and without radical scavengers (i.e.,
dissolved organic matter [DOM]), are shown in Table 3. The rate constants are
generally greater for benzene-based compounds (44–120  108/M s) in comparison
to carboxylic acid-based compounds (1–120  108/M s; at 190/M s, cysteine
appears to be an outlier, perhaps based on its thiol properties). However, there are
no distinct correlations between structure, molecular weight, and reactivity [103].
Westerhoff et al. [105] analyzed the reactivity of ozone and HO• with hydro-
phobic organic acids isolated from a variety of source waters. Although NOM
characteristics varied among samples, there were strong correlations between
SUVA values and the rate constants for O3 and HO• interactions, as shown in
Fig. 10. The data demonstrate ozone’s strong preference for densely conjugated
aromatic NOM, whereas HO• reactions with NOM were rapid and nonselective.
The general progression of oxidation using AOPs follows the pathway:

organic pollutant ! aldehydes ! carboxylic acids

! carbon dioxide and mineral acids

Accordingly, although AOPs can effectively mitigate organic precursors to limit

downstream formation of DBPs, they can also directly generate their own suite of
DBPs in the event of incomplete oxidation, wherein the products do not completely
mineralize due to insufficient chemical and/or energy inputs. DBPs produced
during AOP treatments may include BrO3, NDMA, and small molecular weight
organic compounds, e.g., acetaldehyde and formaldehyde [59, 106].
368 B.K. Mayer and D.R. Ryan

Table 3 Hydroxyl radical (HO•) kinetic rate constants with various organic compounds, with and
without dissolved organic matter (DOM)
kHO• kHO•, DOM
Chemical Compound (108/ (108/
Compound formula class M s) Mcarbon s)
Benzaldehyde C7H6O Benzene-based 44 6
Hydroquinone C6H6O2 Benzene-based 52 9
Catechol C6H6O2 Benzene-based 110 18
Phthalic acid C8H6O4 Benzene- 59 7
based, carbox-
ylic acid
Salicylic acid C7H6O3 Benzene- 120 17
based, carbox-
ylic acid
Oxalic acid C2H2O4 Carboxylic 1 0.2
acid
Citric acid C6H8O7 Carboxylic 3 1
acid
Tartaric acid C4H6O6 Carboxylic 14 4
acid
Cysteine C3H7NO2S Carboxylic 190 63
acid, thiol
Mean value for hydrophobic organic Organic acids 3.6
acids isolated from a variety of
sources
Data from [103–105]

4.1.1 Bromate and Organic Brominated Disinfection Byproducts

Bromate (BrO3) formation stems from ozonation, wherein O3 directly oxidizes Br
to BrO3:

Br ! BrO =HBrO ! BrO2  ! BrO3 

Consequently, O3-based AOPs such as O3/UV and O3/H2O2 can directly generate
BrO3, the extent of which depends on water quality and process operation. During
O3-based AOPs, the synergistic effect of O3 and HO• may oxidize Br to BrO3 as
HO• can participate in intermediate steps by producing radical species (e.g., Br•,
BrO•) [107]. Relative to O3-only processes, O3/UV may produce similar amounts of
BrO3 [108]. However, O3/H2O2 can produce less BrO3 than O3/UV, and O3-only
processes since H2O2 can reduce BrO to Br; hence optimized H2O2 doses can
mitigate BrO3 formation [109, 110]. Although HO• is involved in BrO3 formation
during ozonation processes, non-O3-based AOPs such as UV/H2O2 and TiO2
photocatalysis (UV/TiO2), which rely on the production of HO• radicals, have not
been shown to form significant amounts of BrO3 [109].
The production of organic B-DBPs can be much less prominent than BrO3
during ozonation and AOPs due to competing kinetics between HBrO and HO•.
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 369

16
14 Ozone
Reaction rate constant, k
12 Hydroxyl Radicals

10
8
6
4
2
0
0 0.02 0.04 0.06 0.08 0.1 0.12
SUVA (L/mg/m)

Fig. 10 Reactivity of natural waters with ozone (k in units of 103 per second) and hydroxyl
radicals (k in units of 108 L/mol C s). Data from [105]

Hypobromous acid reacts more readily with O3 and HO• compared to the precursor
NOM necessary to form B-DBP haloorganics [111].

4.1.2 N-Nitrosodimethylamine (NDMA)

The use of AOP treatments can have variable results in terms of NDMA formation,
as a function of influent water quality parameters. This is demonstrated in Fig. 11,
where Zhao et al. [112] analyzed seven different source waters and found that
UV/H2O2 yielded the highest amount of NDMA for some waters but lower NDMA
for other waters. Interestingly, there was no correlation with bulk organic pre-
cursors (DOC, UV254, SUVA), although the two waters yielding the most nitrosa-
mines using UV/H2O2 had high UV254 values. In contrast, the water with the
highest TOC and UV254 yielded small amounts of NDMA relative to others [112].

4.1.3 Non-halogenated Organic Disinfection Byproducts

AOPs can produce non-halogenated organic DBPs, primarily due to oxidation of

condensed aromatic compounds, which produces low molecular weight organics.
These byproducts can enhance biodegradability and can even be toxic. Wert et al.
[113] compared organic byproduct formation during O3 treatment to O3/H2O2 AOP
treatment and showed that O3/H2O2 produced more organic byproducts than ozon-
ation alone. This indicated greater organic degradation using the AOP, leading to
incomplete oxidation. Incomplete oxidation can be problematic in distribution sys-
tems as it increases assimilable organic carbon (AOC), which can enhance down-
stream biological growth. Moreover, incomplete oxidation can actually increase
DBP formation potential, as described in the following section.
370 B.K. Mayer and D.R. Ryan

Fig. 11 Comparison of N-nitrosodimethylamine (NDMA) formation during disinfection of var-

iable quality untreated source water. The disinfection strategies tested include conventional
approaches as well as advanced treatments such as the UV/H2O2 advanced oxidation process
(AOP). Data from [112]

4.2 The Impact of Advanced Oxidation Processes

on Disinfection Byproduct (DBP) Formation Potential:
Influence of Oxidation on Precursor Organic Matter
and Subsequent DBP Formation

Although AOPs have the ability to mineralize NOM and recalcitrant synthetic
organic compounds, variations in chemical and energy inputs as well as process
configuration can lead to incomplete oxidation. Incomplete oxidation products can
include small organics such as carboxylates, ketones, and aldehydes. These com-
pounds are formed when HO• oxidizes the hydrophobic, densely conjugated por-
tions of NOM, thus opening ring structures and decreasing aromaticity. This is
illustrated for the photo(electro)catalytic degradation pathways of phenol shown in
Fig. 12. As the ring structures open, the NOM becomes more hydrophilic, and the
exposed ring structure can exhibit greater halogen substitution efficiency, thereby
serving as an active site for halogenated DBP formation [114].
In many drinking water systems, an oxidizing disinfectant such as free or
combined chlorine is added prior to releasing the water to the distribution system
to provide residual disinfectant to inactivate pathogens, maintain water quality, and
protect against biological regrowth. The use of this type of secondary disinfection
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 371

Fig. 12 Photo(electro)catalytic degradation pathways of phenol mineralization using BiVO4 as

the catalyst with visible light irradiation. Based on [115]

after AOP treatments wherein incomplete oxidation occurs can potentially exacer-
bate DBP production, depending on the type and dose of residual disinfectant.
Incomplete oxidation leads to conversion of the humic fraction toward the fulvic
fraction, which can increase THM and HAA formation potential as the structural
properties of NOM change to resemble significant precursors, such as resorcinol.
Structural changes in NOM due to reactions with HO• can particularly affect the
formation of B-DBPs and I-DBPs because, in comparison to chlorine, bromine and
iodine are more reactive with hydrophilic fractions of NOM produced by HO• [95].
AOP-derived chemical changes in NOM can also significantly impact NDMA
formation as the hydrophilic NOM fraction produced during incomplete oxidation
generally forms more NDMA than the hydrophobic fraction [98]. Additionally,
AOPs can degrade residual polymer, which can potentially exacerbate the release of
NDMA precursors, thereby greatly increasing NDMA formation when downstream
chloramines are used as the residual disinfectant [56].
The extent to which DBP formation potential increases or decreases following
AOP treatment is a function of numerous parameters and can thus vary widely
across systems as well as within systems. The variation in AOPs’ impact on DBP
formation potential for selected studies is shown in Table 4.
372 B.K. Mayer and D.R. Ryan

As oxidation progresses toward NOM mineralization using greater energy

and/or chemical AOP inputs, DBP formation potential decreases, as illustrated in
Fig. 13, for TiO2 photocatalysis AOP treatment followed by free chlorine addition.
Complete mineralization, and the resultant reduction in DBP formation poten-
tial, is energy and/or chemically intensive, perhaps making combinations of AOP
treatment together with processes such as filtration more feasible for implementa-
tion in multi-barrier drinking water treatment trains. For example, dual barriers
using AOPs followed by biological activated carbon (BAC) filtration can be used to
more effectively mitigate DBP concerns using more feasible energy inputs. Toor
and Mohseni [120] showed that using UV/H2O2 AOP followed by BAC signifi-
cantly reduced DBP formation potential, whereas using the AOP as a stand-alone
treatment required extremely high initial H2O2 concentrations and UV fluences to
effectively reduce DBP formation (>23 mg/L H2O2 and >1,000 mJ/cm2; for
perspective, <200 mJ/cm2 is typical for drinking water treatment).

5 Mitigation of Disinfection Byproducts

To mitigate DBPs, the recommended course of action is to prevent DBP formation

in the first place. Several strategies are employed for this purpose, including
employing alternative disinfectants and removing precursor material prior to dis-
infection. An additional option is to remove/destroy DBPs after they have formed.

5.1 Alternative Disinfectants

Free chlorine remains the most commonly used disinfectant, but concerns over
DBP production have led to implementation of alternative disinfectants, including
other chemical oxidants such as chloramines, chlorine dioxide, and ozone, as well
as non-oxidant-based strategies. It is also possible to move the point of chlorination
further downstream in the treatment process to allow reductions in NOM precursor
material prior to disinfection [124].
As described in Sect. 2.1, each of the oxidizing disinfectants is characterized by
varying degrees of effectiveness against different microbial pathogens and also has
potential to produce DBPs, although they may impact the magnitude of DBP
formation or the type of DBP produced. For example, monochloramine reduces
production of THMs and HAAs; however, it can increase formation of iodo-acids,
which are considered one of the most toxic DBPs [40]. Likewise, chlorine dioxide
introduces concerns for chlorite and chlorate production, while ozonation can
increase bromate formation.
Heat (e.g., boiling or pasteurization) and electromagnetic radiation (e.g., gamma
and UV radiation) offer non-oxidant-based disinfection strategies. For water disin-
fection, the only one of these approaches in routine practice is UV radiation [17]. A
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 373

Table 4 Impact of advanced oxidation processes (AOPs) on disinfection byproduct (DBP)

formation potential reported in select studies
Trend in DBP formation
Process potential (FP) following
AOP Source water description AOP treatment Reference
O3 River Ruhr, Germany 1.5 mg O3/mg # TTHMFP and AOXFPa [116]
DOC
O3 Indoor swimming pool 6 mg/L O3 # TTHMFP, AOXFP, [117]
TOC, AOX
O3/ Indoor swimming pool 6 mg/L O3, " TTHMFP [117]
H2O2 1.5 mg/L H2O2 # AOXFP, TOC, AOX
O3/ Indoor swimming pool 6 mg/L O3, " TTHMFP [117]
UV 2.93 W # AOXFP, TOC, AOX
low-pressure UV
lamp
O3/ Seymour reservoir, 0.620.019 mg # TTHMFP and HAA5FP [118]
UV Canada O3/mL, UV
fluence ¼ 1.61 J/
cm2
UV/ Ohio river sample from 5–10 mg/L H2O2, " TTHM yield following [119]
H2O2 water treatment plant medium- and post-chlorination
high-pressure UV
lamps
UV/ River Ruhr, Germany 15 W low-pressure " TTHMFP prior to [116]
H2O2 UV lamp, 8 mg/L 1,050 min of irradiation
H2O2 initially # TTHMFP after
1,050 min of irradiation
and 5.6 mg/L H2O2
consumed
UV/ Vancouver reservoir 5–15 mg/L H2O2, # TTHMFP for fluences [114]
H2O2 low-pressure high- >1,500 mJ/cm2
output UV lamp
UV/ Raw surface water 0–23 mg/L H2O2, # DBP formation potential [120]
H2O2 low-pressure UV for >1,000 mJ/cm2 and
fluence ¼ initial H2O2 concentrations
0–3,500 mJ/cm2 >23 mg/L
UV Indoor swimming pool 2.93 W " TTHMFP [117]
low-pressure UV # AOXFP, TOC, AOX
lamp
UV/ Arizona surface water 7 mW/cm2 " TTHMFP using 5–20 [121]
TiO2 low-pressure UV, kWh/m3
400 mg/L TiO2 # TTHMFP for energy
inputs >20 kWh/m3
UV/ Myponga reservoir, Blacklight blue # TTHMFP [122]
TiO2 Australia fluorescent UV " HAA5FP before 30 min
lamp, 0.1 g/L TiO2 of irradiation
# HAA5FP after 30 min
of irradiation
(continued)
374 B.K. Mayer and D.R. Ryan

Table 4 (continued)
Trend in DBP formation
Process potential (FP) following
AOP Source water description AOP treatment Reference
UV/ Hillsborough river 450–1,200 W # THMFP [123]
TiO2 water, Florida; high-pressure UV
Sacramento-San lamps, 1.0 g/L
Joaquin Estuary, TiO2
California
a
AOX represents the organically bound halogens adsorbable on activated carbon

major advantage of UV disinfection is that at the fluences typically used in drinking

water treatment (<200 mJ/cm2), there is no evidence of DBP formation, nor are
DBP levels exacerbated using post-UV disinfection [9]. However, UV provides no
residual disinfection, so an oxidant such as chlorine or chloramines is typically
applied prior to release of the water in the drinking water distribution system to
protect against pathogen regrowth.
While AOPs can provide some degree of disinfection, they are unlikely to be
used explicitly for this purpose. Moreover, increased reactivity of the NOM due to
the production of small organic compounds during AOP-based incomplete oxida-
tion can exacerbate DBP formation and also lead to challenges in the distribution
system. Enhanced biodegradability of the small organics in the effluent can lead to
increased corrosion, nitrification, taste and odor compound formation, and
enhanced microbial growth that can impair the microbial safety of the drinking
water [62, 114, 125].
To simultaneously mitigate concerns related to a wide spectrum of microbial
pathogens, DBPs, and contaminants of emerging concern, water treatment plants
may use dual barriers including an alternative disinfectant such as ozone or
chloramination alongside advanced treatment (e.g., AOP-BAC) [126].

5.2 Removal of Precursor Natural Organic Matter Prior

to Disinfection

Given the trade-offs associated with the use of alternative disinfectants, the most
common strategy to mitigate DBPs is to avoid formation by removing precursor
NOM prior to disinfection [127].
Physicochemical unit operations including enhanced coagulation or softening,
granular activated carbon adsorption, and membrane processes are considered best
available techniques for physical removal of NOM from water [83, 128]. These
processes are often sufficient to control DBP formation, but alternatives such as
ozonation or AOP treatments have also been investigated [16, 84, 121, 129].
Coagulation processes preferentially remove the humic and higher molecular
weight portions of NOM. Removal of 15–50% TOC is commonly achieved using
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 375

200
CAP Canal
180 Salt River1
Salt River2
TTHM Formation Potential (μg/L)

160
Settled
140 GAC Filtered
Distribution System
120

100

80

60

40

20

0
Source Water 0, Dark 5 kWh/m3 10 kWh/m3 20 kWh/m3 40 kWh/m3 80 kWh/m3 160 kWh/m3
Adsorption

Level of Photocatalytic Energy Input

Fig. 13 Total trihalomethane (THM) formation potential in various source waters resulting from
UV/TiO2 advanced oxidation process (AOP) treatment followed by free chlorine addition. The
data show that TTHM formation potentials increase in some source waters following incomplete
oxidation with relatively low-energy inputs (5 kWh/m3). In all waters tested, high-energy inputs
approached more complete natural organic matter (NOM) mineralization, and TTHM formation
potential decreased. Adapted from [84, 121]

enhanced coagulation (which relies on the use of higher coagulant doses and/or pH
adjustment to target NOM removal) or enhanced softening [17]. Since the hydro-
phobic portion of NOM, which generally consists of humic substances, is primarily
removed by coagulation, further treatment may be necessary to remove the hydro-
philic, fulvic portion of NOM, which can also contribute to DBP formation.
Adsorption of NOM is possible using activated carbon (granular [GAC] or
powdered [PAC]) or ion-exchange resins. However, the use of activated carbon
for NOM can be costly as a significant fraction of the NOM, comprised of large
molecular weight organics, is poorly adsorbed, meaning that large amounts of
activated carbon are used to remove relatively small amounts of NOM. With
more selective ion-exchange media, e.g., MIEX resin, much greater NOM removal
can be achieved more quickly [17].
In some cases, membrane filtration can effectively remove DBP precursors,
although results vary for different types of membranes. For example, ultrafiltration
with a molecular weight cutoff (MWCO) of 100,000 Da was not effective for
controlling DBP formation in pilot studies, whereas nanofiltration with a MWCO
of 400–800 Da was effective when little-to-no bromide was present
[130]. Microfiltration and ultrafiltration are not effective at removing NDMA pre-
cursors, but 57–98% of precursors were removed using nanofiltration and reverse
376 B.K. Mayer and D.R. Ryan

osmosis [131]. Reverse osmosis has been effectively used for NOM removal,
rejecting >90% NOM and DBP precursors [132].
The use of O3 or AOP treatments in combination with BAC filtration can provide
an effective means for removing NOM to both reduce DBP formation potential and
decrease AOC in the distribution system. Using AOPs or ozonation can break
carbon-carbon double bonds in NOM, which transforms the NOM into more readily
biodegradable organic matter (higher AOC or biodegradable dissolved organic
carbon – BDOC), which is particularly amenable to biofiltration. By combining
ozonation with biologically active filtration, 35–40% DOC removal can be
achieved [17]. This sequential AOP-biological process treatment train concept is
depicted in Fig. 14.

5.3 Mitigation of Preformed Disinfection Byproducts Using

Advanced Oxidation Processes

Another strategy to mitigate DBPs is to remove them from water following DBP
generation during disinfection processes. While the use of phase-transfer processes
or redox chemistry may offer options to accomplish this, DBP removal is typically a
less effective and economical approach compared to avoiding DBP formation in the
first place via removal of precursors prior to disinfection processes, as described in
Sect. 5.2.
Phase-transfer processes such as activated carbon adsorption and air stripping
can be used to remove DBPs from water. However, these approaches may
introduce elevated operation and maintenance costs that limit feasibility of imple-
mentation. For example, GAC is characterized by low THM adsorption capacity,
meaning that large amounts of GAC would be required for adequate DBP removal
[134, 135]. Additionally, while volatile THMs will readily be removed by air
stripping, HAAs will remain [136].
The hydroxyl radicals produced during AOPs can degrade organic DBPs, as
illustrated by the kinetic rate constants of several different types of DBPs shown in
Table 5.
AOPs have been used to mitigate DBPs in swimming pool water, where O3/UV
and O3/H2O2 generally improved removal of TOC precursors and DBPs (quantified
as AOX) beyond levels achieved by O3 alone. For THM formation potential, O3
provided a slight advantage over the AOPs due to O3 oxidation selectivity in
comparison to the small reactive molecules produced via HO• reactions, which
are more easily transformed to THMs [117].
NDMA readily penetrates reverse osmosis membranes and is poorly adsorbed
and stripped, so UV-AOPs have been used to meet regulatory guidelines for potable
water reuse [137, 141]. Notably, NDMA is photodegradable using direct UV
irradiation (λ<260 nm), so additions of H2O2, O3, or TiO2 to provide advanced
oxidation would not be necessary if other recalcitrant compounds were not also
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 377

Fig. 14 Conceptual sequential advanced oxidation process (AOP)/biological process (e.g., BAC)
approach to treatment, taking advantage of the efficiency of each process for degrading organic
matter. The breakpoint between AOPs and biological processes is illustrated, where biological
treatment becomes more attractive in terms of rate and efficiency as incomplete oxidation
byproducts can be easily biodegraded. Modified after [133]

being targeted, e.g., 1,4-dioxane [141]. Degradation of NDMA during UV treat-

ments can proceed via three pathways: hemolytic cleavage of N-NO bonds, het-
erolytic cleavage of N-NO bonds, and photooxidation [142]. During UV/H2O2 AOP
treatment, HO•-based degradation of NDMA occurs by hydrogen atom abstraction
from the methyl groups in NDMA [137, 143].
Using a UV dose of 1,000 mJ/cm2 together with 3 mg/L H2O2, 1 log removal
of NDMA can typically be achieved [141]. As noted previously, additions of H2O2
do not substantially improve NDMA degradation beyond UV alone. However,
direct photolysis of NDMA can produce DMA as a major byproduct, and as
DMA reacts with chloramines to produce NDMA, care must be taken to avoid
regeneration of NDMA [141].
The electrical energy per order (EEO) of reduction is a metric used to evaluate
electrical efficiency of processes, e.g., UV-AOPs. For one log reduction of NDMA
using UV/H2O2, the EEO is approximately 21–265 kWh/m3 using doses of 5–6 mg/L
H2O2 (although this can vary greatly across different waters) [144]. The EEO for
destruction of THMs using TiO2 photocatalysis has been reported at 19–64 kWh/m3
in several surface waters [121]. For perspective, EEO values less than 0.265 kWh/m3
are considered favorable for water treatment [145], which demonstrates that AOPs
are not an efficient means of destroying preformed DBPs.
378 B.K. Mayer and D.R. Ryan

Table 5 Hydroxyl radical (HO•) rate constants with various disinfection byproducts (DBPs)
Chemical kHO• (108/
DBP formula DBP class M s)
Chloroform CHCl3 Trihalomethane 0.11
Dichloromethane CH2Cl2 Halomethane 0.22
Bromoform CHBr3 Trihalomethane 1.5
Dibromomethane CH2Br2 Halomethane 0.99
Bromodichloromethane CHBrCl2 Trihalomethane 0.711
Chlorodibromomethane CHBr2Cl Trihalomethane 0.831
N-Nitrosodimethylamine (NDMA) C2H6N2O Nitrosamines 4.3
Chloronitromethane CH2ClNO2 Halonitromethane 1.94
Dichloronitromethane CHCl2NO2 Halonitromethane 5.12
Trichloronitromethane CCl3NO2 Halonitromethane 0.497
(chloropicrin)
Bromonitromethane CH2BrNO2 Halonitromethane 0.836
Dibromonitromethane CHBr2NO2 Halonitromethane 4.75
Tribromonitromethane CBr3NO2 Halonitromethane 3.25
Bromochloronitromethane CHBrClNO2 Halonitromethane 4.2
Bromodichloronitromethane CBrCl2NO2 Halonitromethane 1.02
Dibromochloronitromethane CBr2ClNO2 Halonitromethane 1.80
Values from [137–140]

6 Summary

Although the premise of disinfection is easily understood, interactions between

disinfectants and the target and nontarget constituents in complex drinking water
matrices are incredibly complex. Accordingly, there is not a one-size-fits-all
approach to minimizing the risks posed by microbial pathogens against those
posed by chemical contaminants, e.g., DBPs. While a given disinfection process
may significantly reduce one DBP, it may lead to substantial increases in another
DBP (e.g., chloramination may reduce THMs and HAAs but increase NDMA).
Likewise, shifts in precursor NOM composition during unit operations prior to
disinfection can have variable impacts on subsequent DBP formation during disin-
fection processes. Overall, removal of this precursor material prior to disinfection
offers the most effective strategy to mitigate DBPs.
The use of AOPs in drinking water treatment trains may impact DBPs via three
different pathways: (1) direct formation during AOP treatment, (2) indirect influ-
ences on DBP formation potential in downstream disinfection, and (3) destruction
of preformed DBPs. High AOP energy and/or chemical inputs are needed to destroy
preformed DBPs, making it much more efficient to avoid DBP production in the
first place.
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 379

The direct generation of DBPs during AOP treatments is generally less of a

concern in comparison to disinfection strategies based on additions of halogenated
oxidants such as chlorine since AOPs do not directly form halogenated DBPs.
However, direct inputs of chemical oxidants, e.g., O3 or H2O2, during AOPs can
generate DBPs such as BrO3 or NDMA. Moreover, as complex organics are
progressively degraded, AOPs can also directly generate their own suite of DBPs
in the event of incomplete oxidation, which produces small molecular weight
organic compounds, e.g., acetaldehyde and formaldehyde. These non-halogenated
organic DBPs can be toxic or can lead to subsequent issues such as enhanced DBP
formation potential, higher biodegradability (AOC or BDOC) in the distribution
system, etc.
In addition to direct DBP formation, AOPs may also strongly influence subse-
quent DBP formation potential as DBP precursor organic material undergoes
dramatic transformations during AOPs. Although AOPs can effectively mitigate
organic precursors to limit downstream formation of DBPs given sufficient energy
and/or chemical inputs to yield complete mineralization, lower inputs lead to
incomplete oxidation, which can exacerbate DBP formation. Thus, AOPs may
either decrease or increase DBP yields during subsequent disinfection processes
depending on the water matrix and process operation.
To simultaneously mitigate concerns related to a wide spectrum of microbial
pathogens, DBPs, and contaminants of emerging concern, drinking water treatment
plants may use dual barriers including an alternative disinfectant such as ozone or
chloramination alongside advanced treatment (e.g., AOP-BAC). The impact of
these processes on DBP formation potential must be evaluated for each individual
source water using selected operational parameters as changes in DBP precursors
during treatment processes can have widely variable impacts on DBP formation,
and care must be taken to avoid increasing DBP formation via incomplete oxidation
during AOP treatments.

References

1. AWWA (2000) Committee report: disinfection at large and medium-size systems. J Am

Water Work Assoc 92:32–43
2. AWWA (2010) Committee report: disinfection survey, part 1 – recent changes, current
practices, and water quality. J Am Water Work Assoc 100:76–90
3. Mayer BK, Yang Y, Gerrity DW, Abbaszadegan M (2015) The impact of capsid proteins on
virus removal and inactivation during water treatment processes. Microbiol Insights 8(Suppl
2):15–28
4. Amy G, Bull R, Craun GF, Siddiqui M (2000) Disinfectants and disinfection by-products.
World Health Organization, Geneva
5. Johnson JD, Jensen JN (1986) THM and TOX formation: routes, rates, and precursors. J Am
Water Work Assoc 78:156–162. doi:10.1111/j.1467-8330.1974.tb00606.x
6. Bull RJ, Gerba C, Trussell RR (1990) Evaluation of health risks associated with disinfection.
Crit Rev Environ Control 20:77–114
380 B.K. Mayer and D.R. Ryan

7. WHO (2016) Chlorine dioxide, chlorate and chlorite in drinking-water: background docu-
ment for development of WHO guidelines for drinking-water quality. World Health
Organization
8. Amy G, Siddiqui M, Ozekin K et al (1998) Empirically based models for predicting
chlorination and ozonation by-products: trihalomethanes, haloacetic acids, chloral hydrate,
and bromate. USEPA, EPA 815-R-98, Cincinnati, OH
9. USEPA (2006) Ultraviolet disinfection guidance manual for the final long term 2 enhanced
surface water treatment rule. Washington, DC
10. Mamane H, Shemer H, Linden KG (2007) Inactivation of E. coli, B. subtilis spores, and MS2,
T4, and T7 phage using UV/H2O2 advanced oxidation. J Hazard Mater 146:479–486. doi:10.
1016/j.jhazmat.2007.04.050
11. Matsunaga T, Tomoda R, Nakajima T et al (1988) Continuous-sterilization system that uses
photosemiconductor powders. Appl Environ Microbiol 54:1330–1333
12. Ryu H, Gerrity D, Crittenden JC, Abbaszadegan M (2008) Photocatalytic inactivation of
Cryptosporidium parvum with TiO2 and low-pressure ultraviolet irradiation. Water Res
42:1523–1530. doi:10.1016/j.watres.2007.10.037
13. Gerrity DW, Ryu H, Crittenden JC, Abbaszadegan M (2008) Photocatalytic inactivation of
viruses using titanium dioxide nanoparticles and low-pressure UV light. J Environ Sci Health
A Tox Hazard Subst Environ Eng 43:1261–1270
14. Cho M, Chung H, Choi W, Yoon J (2005) Different inactivation behaviors of MS-2 phage and
Escherichia coli in TiO2 photocatalytic disinfection. Appl Environ Microbiol 71:270–275
15. Alrousan DMA, Dunlop PSM, McMurray TA, Byrne JA (2009) Photocatalytic inactivation
of E. coli in surface water using immobilised nanoparticle TiO2 films. Water Res 43:47–54.
doi:10.1016/j.watres.2008.10.015
16. Mayer BK, Daugherty E, Abbaszadegan M (2015) Evaluation of the relationship between
bulk organic precursors and disinfection byproduct formation for advanced oxidation pro-
cesses. Chemosphere 121:39–46. doi:10.1016/j.chemosphere.2014.10.070
17. Crittenden JC, Trussell RR, Hand DW et al (2012) Water treatment: principles and design,
3rd edn. Wiley, Hoboken, NJ
18. NHMRC, NRMMC (2011) Australian drinking water guidelines paper 6 national water
quality management strategy. Commonwealth of Australia, Canberra
19. EU (1998) Council Directive. http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri¼OJ:
L:1998:330:0032:0054:EN:PDF
20. Health Canada (2017) Guidelines for Canadian drinking water quality summary table.
Ottawa, ON, Canada
21. USEPA (2009) National Primary Drinking Water Regulations. Washington, DC
22. WHO (2017) Guidelines for drinking-water quality: Fourth edition incorporating the first
addendum
23. Bellar TA, Lichtenberg JJ, Kroner RC (1974) The occurrence of organohalides in chlorinated
drinking water. J Am Water Work Assoc 66:703–706
24. Rook JJ (1974) Formation of halogens during the chlorination of natural water. Water Treat
Exam 23:234–243
25. Richardson SD, Plewa MJ, Wagner ED et al (2007) Occurrence, genotoxicity, and carcino-
genicity of regulated and emerging disinfection by-products in drinking water: a review and
roadmap for research. Mutat Res 636:178–242. doi:10.1016/j.mrrev.2007.09.001
26. Weinberg HS, Krasner SW, Richardson SD, Thruston AD (2002) The occurrence of disin-
fection by-products (DBPs) of health concern in drinking water: results of a nationwide DBP
occurrence study. Athens, GA
27. Mitch WA, Krasner SW, Paul W, Dotson A (2009) Occurrence and formation of nitrogenous
disinfection by-products
28. Clark RM, Boutin BK (2001) Controlling disinfection by-products and microbial contami-
nants in drinking water. Washington, DC
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 381

29. USEPA (2016) Final CCL4 chemical contaminants. In: Contaminant candidate list (CCL)
and regulatory determination. https://www.epa.gov/ccl/chemical-contaminants-ccl-4.
Accessed 11 Jul 2017
30. Khiari D (2017) Water Research Foundation Focus Area: NDMA and other nitrosamines. J
Am Water Work Assoc 109:38–42
31. Russell CG, Brown R, Porter K, Reckhow D (2017) Practical considerations for
implementing nitrosamine control strategies. doi: 10.5942/jawwa.2017.109.0054
32. Krasner SW, Weinberg HS, Richardson SD et al (2006) Occurrence of a new generation of
disinfection byproducts. Environ Sci Technol 40:7175–7185
33. Chowdhury S, Champagne P, McLellan PJ (2009) Models for predicting disinfection
byproduct (DBP) formation in drinking waters: a chronological review. Sci Total Environ
407:4189–4206. doi:10.1016/j.scitotenv.2009.04.006
34. Sohn J, Amy G, Cho J et al (2004) Disinfectant decay and disinfection by-products formation
model development: chlorination and ozonation by-products. Water Res 38:2461–2478.
doi:10.1016/j.watres.2004.03.009
35. Amy GL, Chadik PA, Chowdhury ZK (1987) Developing models for predicting trihalometh-
ane formation potential and kinetics. J Am Water Work Assoc 79:89–97
36. Arora H, LeChevallier MW, Dixon KL (1997) DBP occurrence survey. J Am Water Work
Assoc 89:60–68
37. Richardson SD (1998) Drinking water disinfection byproducts. In: Encyclopedia of environ-
mental analysis and remediation, pp 1398–1421
38. von Gunten U (2003) Ozonation of drinking water: part II. Disinfection and by-product
formation in presence of bromide, iodide or chlorine. Water Res 37:1469–1487
39. von Gunten U, Bruchet A, Costentin E (1996) Bromate formation in advanced oxidation
processes. J Am Water Work Assoc 88:53–65
40. Plewa MJ, Wagner ED, Richardson SD et al (2004) Chemical and biological characterization
of newly discovered lodoacid drinking water disinfection byproducts. Environ Sci Technol
38:4713–4722. doi:10.1021/Es049971v
41. Taurog A, Howells EM, Nachimson HI (1966) Conversion of iodate to iodide in vivo and
in vitro. J Biol Chem 241:4686–4693
42. Bichsel Y, von Gunten U (2000) Formation of iodo-trihalomethanes during disinfection and
oxidation of iodide-containing waters. 34:2784–2791. doi: 10.1021/es9914590
43. Hua G, Reckhow DA, Kim J (2006) Effect of bromide and iodide ions on the formation and
speciation of disinfection byproducts during chlorination. Environ Sci Technol
40:3050–3056. doi:10.1021/es0519278
44. Wright JM, Schwartz J, Vartiainen T et al (2002) 3-Chloro-4-(dichloromethyl)-5-hydroxy-2
(5H)-furanone (MX) and mutagenic activity in massachusetts drinking water. Environ Health
Perspect 110:157–164. doi:10.1289/ehp.02110157
45. Smeds A, Vartiainen T, Mäki-Paakkanen J, Kronberg L (1997) Concentrations of Ames
mutagenic chlorohydroxyfuranones and related compounds in drinking waters. Environ Sci
Technol 31:1033–1039. doi:10.1021/es960504q
46. Kronberg L, Vartiainen T (1988) Ames mutagenicity and concentration of the strong muta-
gen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone and of its geometric isomer E-2-
chloro-3-(dichloromethyl)-4-oxo-butenoic acid in chlorine-treated tap waters. Mutat Res
206:177–182
47. Onstad GD, Weinberg HS, Krasner SW (2008) Occurrence of halogenated furanones in
U.S. drinking waters. Environ Sci Technol 42:3341–3348. doi:10.1021/es071374w
48. Mitch WA, Gerecke AC, Sedlak DL (2003) A N-nitrosodimethylamine (NDMA) precursor
analysis for chlorination of water and wastewater. Water Res 37:3733–3741. doi:10.1016/
S0043-1354(03)00289-6
49. Linge KL, Kristiana I, Liew D et al (2017) Formation of N-nitrosamines in drinking water
sources: case studies from Western Australia. J Am Water Work Assoc 109:E184–E196.
doi:10.5942/jawwa.2017.109.0036
382 B.K. Mayer and D.R. Ryan

50. California Department of Health Services (2005) California drinking water activities related
to NDMA and other nitrosamines. California Department of Health Services, Sacramento.
http://www.waterboards.ca.gov/drinking_water/certlic/drinkingwater/NDMA.shtml
51. Choi J, Valentine RL (2002) Formation of N-nitrosodimethylamine (NDMA) from reaction
of monochloramine: a new disinfection by-product. Water Res 36:817–824. doi:10.1016/
S0043-1354(01)00303-7
52. Marti EJ, Dickenson ERV, Trenholm RA, Batista JR (2017) Treatment of specific NDMA
precursors by biofiltration. J Am Water Work Assoc 109:E273–E286. doi:10.5942/jawwa.
2017.109.0070
53. Park SH, Padhye LP, Wang P et al (2015) N-nitrosodimethylamine (NDMA) formation
potential of amine-based water treatment polymers: effects of in situ chloramination,
breakpoint chlorination, and pre-oxidation. J Hazard Mater 282:133–140. doi:10.1016/j.
jhazmat.2014.07.044
54. Shah AD, Krasner SW, Lee CFT et al (2012) Trade-offs in disinfection byproduct formation
associated with precursor preoxidation for control of N-nitrosodimethylamine formation.
Environ Sci Technol 46:4809–4818. doi:10.1021/es204717j
55. von Gunten U, Salhi E, Schmidt CK, Arnold WA (2010) Kinetics and mechanisms of
N-nitrosodimethylamine formation upon ozonation of N,N-dimethylsulfamide-containing
waters: bromide catalysis. Environ Sci Technol 44(15):5762–5768. doi:10.1021/es1011862
56. Padhye L, Luzinova Y, Cho M et al (2011) PolyDADMAC and dimethylamine as precursors
of N-nitrosodimethylamine during ozonation: reaction kinetics and mechanisms. Environ Sci
Technol 45:4353–4359. doi:10.1021/es104255e
57. Park SH, Wei S, Mizaikoff B et al (2009) Degradation of amine-based water treatment
polymers during chloramination as N-nitrosodimethylamine (NDMA) precursors. Environ
Sci Technol 43:1360–1366. doi:10.1021/es802732z
58. Cornwell DC, Brown RA (2017) Replacement of alum and polyDADMAC with natural
polymers – turbidity removal and residuals reduction impacts. J Am Water Work Assoc 109:
E252–E264
59. Glaze WH, Weinberg HS (1993) Identification and occurrence of ozonation by-products in
drinking water. American Water Works Association Foundation
60. Krasner SW, McGuire MJ, Jacangelo JG et al (1989) The occurrence of disinfection
by-products in U.S. drinking water. J Am Water Work Assoc 81:41–53
61. Leenheer JA, Croue J-P (2003) Characterizing dissolved aquatic matter. Environ Sci Technol
37:18a–26a
62. Jacangelo JG, DeMarco J, Owen DM, Randtke SJ (1995) Selected processes for removing
NOM: an overview. J Am Water Work Assoc. doi:10.2307/41295153
63. Danielsson LG (1982) On the use of filters for distinguishing between dissolved and partic-
ulate fractions in natural waters. Water Res 16:179–182
64. Thurman EM (1985) Organic geochemistry of natural waters1st edn. Nijhoff/Junk, Dor-
drecht, The Nederlands
65. Korshin G, Chow CWK, Fabris R, Drikas M (2009) Absorbance spectroscopy-based exam-
ination of effects of coagulation on the reactivity of fractions of natural organic matter with
varying apparent molecular weights. Water Res 43:1541–1548. doi:10.1016/j.watres.2008.
12.041
66. Edzwald JK, Becker WC, Wattier KL (1985) Surrogate parameters for monitoring organic
matter and THM precursors. J Am Water Work Assoc 77:122–132
67. Kitis M, Karanfil T, Kilduff JE, Wigton A (2001) The reactivity of natural organic matter to
disinfection by-products formation and its relation to specific ultraviolet absorbance. Water
Sci Technol 43:9–16
68. Edzwald J, Tobiason J (1999) Enhanced coagulation: US requirements and a broader view.
Water Sci Technol 40:63–70. doi:10.1016/S0273-1223(99)00641-1
69. Coble PG (1996) Characterization of marine and terrestrial DOM in seawater using
excitation-emission matrix spectroscopy. Mar Chem 51:325–346
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 383

70. Wu FC, Kothawala DN, Evans RD et al (2007) Relationships between DOC concentration,
molecular size and fluorescence properties of DOM in a stream. Appl Geochem
22:1659–1667. doi:10.1016/j.apgeochem.2007.03.024
71. Baghoth SA, Dignum M, Grefte A et al (2009) Characterization of NOM in a drinking water
treatment process train with no disinfectant residual. Water Sci Technol Water Supply
9:379–386. doi:10.2166/ws.2009.569
72. Seredyńska-Sobecka B, Baker A, Lead JR (2007) Characterisation of colloidal and particu-
late organic carbon in freshwaters by thermal fluorescence quenching. Water Res
41:3069–3076. doi:10.1016/j.watres.2007.04.017
73. Baker A, Tipping E, Thacker SA, Gondar D (2008) Relating dissolved organic matter
fluorescence and functional properties. Chemosphere 73:1765–1772. doi:10.1016/j.
chemosphere.2008.09.018
74. Hudson N, Baker A, Ward D et al (2007) Can fluorescence spectrometry be used as a
surrogate for the biochemical oxygen demand (BOD) test in water quality assessment? An
example from South West England. doi: 10.1016/j.scitotenv.2007.10.054
75. Spencer RGM, Bolton L, Baker A (2007) Freeze/thaw and pH effects on freshwater dissolved
organic matter fluorescence and absorbance properties from a number of UK locations. Water
Res 41:2941–2950. doi:10.1016/j.watres.2007.04.012
76. Yang L, Kim D, Uzun H et al (2015) Assessing trihalomethanes (THMs) and
N-nitrosodimethylamine (NDMA) formation potentials in drinking water treatment plants
using fluorescence spectroscopy and parallel factor analysis. Chemosphere 121:84–91.
doi:10.1016/j.chemosphere.2014.11.033
77. Bieroza M, Baker A, Bridgeman J (2009) Relating freshwater organic matter fluorescence to
organic carbon removal efficiency in drinking water treatment. Sci Total Environ
407:1765–1774. doi:10.1016/j.scitotenv.2008.11.013
78. Peiris RH, Hallé C, Budman H et al (2010) Identifying fouling events in a membrane-based
drinking water treatment process using principal component analysis of fluorescence
excitation-emission matrices. Water Res 44:185–194. doi:10.1016/j.watres.2009.09.036
79. Chen W, Westerhoff P, Leenheer JA, Booksh K (2003) Fluorescence excitation-emission
matrix regional integration to quantify spectra for dissolved organic matter. Environ Sci
Technol 37:5701–5710
80. Matilainen A, Gjessing ET, Lahtinen T et al (2011) An overview of the methods used in the
characterisation of natural organic matter (NOM) in relation to drinking water treatment.
Chemosphere 83:1431–1442. doi:10.1016/j.chemosphere.2011.01.018
81. Chow AT, Gao S, Dahlgren RA (2005) Physical and chemical fractionation of dissolved
organic matter and trihalomethane precursors: a review. J Water Supply Res Technol
54:475–507
82. Hwang CJ, Sclimenti MJ, Bruchet A et al (2001) DBP yields of polar NOM fractions from
low humic waters. Proceedings of water quality technology conference AWWA. Denver, CO
83. Liu S, Lim M, Fabris R, et al. (2008) TiO2 photocatalysis of natural organic matter in surface
water: impact on trihalomethane and haloacetic acid formation potential. Environ Sci
Technol 42:6218–6223
84. Mayer BK, Daugherty E, Abbaszadegan M (2014) Disinfection byproduct formation
resulting from settled, filtered, and finished water treated by titanium dioxide photocatalysis.
Chemosphere 117:72–78
85. Pehlivanoglu-Mantas E, Sedlak DL (2008) Measurement of dissolved organic nitrogen forms
in wastewater effluents: concentrations, size distribution and NDMA formation potential.
Water Res 42:3890–3898. doi:10.1016/j.watres.2008.05.017
86. Mitch WA, Sedlak DL (2004) Characterization and fate of N-nitrosodimethylamine pre-
cursors in municipal wastewater treatment plants. Environ Sci Technol 38:1445–1454.
doi:10.1021/es035025n
87. Zhao Z-Y, Gu J-D, Fan X-J, Li H-B (2006) Molecular size distribution of dissolved organic
matter in water of the Pearl River and trihalomethane formation characteristics with chlorine
384 B.K. Mayer and D.R. Ryan

and chlorine dioxide treatments. J Hazard Mater 134:60–66. doi:10.1016/j.jhazmat.2005.10.

032
88. Kitis M, Karanfil T, Wigton A, Kilduff JE (2002) Probing reactivity of dissolved organic
matter for disinfection by-product formation using XAD-8 resin adsorption and ultrafiltration
fractionation. Water Res 36:3834–3848
89. Lin L, Xu B, Lin YL et al (2014) A comparison of carbonaceous, nitrogenous and iodinated
disinfection by-products formation potential in different dissolved organic fractions and their
reduction in drinking water treatment processes. Sep Purif Technol 133:82–90. doi:10.1016/j.
seppur.2014.06.046
90. Her N, Amy G, Foss D et al (2002) Optimization of method for detecting and characterizing
NOM by HPLC-size exclusion chromatography with UV and on-line DOC detection. Envi-
ron Sci Technol 36:1069–1076. doi:10.1021/es015505j
91. Her N, Amy G, Sohn J, Gunten U (2008) UV absorbance ratio index with size exclusion
chromatography (URI-SEC) as an NOM property indicator. J Water Supply Res Technol
57:35. doi:10.2166/aqua.2008.029
92. Her N, Amy G, McKnight D et al (2003) Characterization of DOM as a function of MW by
fluorescence EEM and HPLC-SEC using UVA, DOC, and fluorescence detection. Water Res
37:4295–4303. doi:10.1016/S0043-1354(03)00317-8
93. Sharp EL, Jarvis P, Parsons SA, Jefferson B (2006) Impact of fractional character on the
coagulation of NOM. Colloids Surf A Physicochem Eng Asp 286:104–111. doi: 10.1016/j.
colsurfa.2006.03.009
94. Swietlik J, Dabrowska A, Raczyk-Stanisławiak U, Nawrocki J (2004) Reactivity of natural
organic matter fractions with chlorine dioxide and ozone. Water Res 38:547–558. doi:10.
1016/j.watres.2003.10.034
95. Hua G, Reckhow DA (2007) Characterization of disinfection byproduct precursors based on
hydrophobicity and molecular size. Environ Sci Technol 41:3309–3315
96. Chen C, Zhang X, Zhu L et al (2008) Disinfection by-products and their precursors in a water
treatment plant in North China: seasonal changes and fraction analysis. Sci Total Environ
397:140–147. doi:10.1016/j.scitotenv.2008.02.032
97. Croue J-P, Korshin GV, Benjamin M (2006) Characterization of natural organic matter in
drinking water. Denver, CO
98. Chen Z, Valentine RL (2007) Formation of N-nitrosodimethylamine (NDMA) from humic
substances in natural water. Environ Sci Technol 41:6059–6065. doi:10.1021/es0705386
99. Croue J-P, Debroux FF, Amy GL, Aiken GR, Leenheer JA (1999) Natural organic matter:
structural characteristics and reactive properties. In: Singer PC (ed) Formation and control of
disinfection by-products in drinking water. American Water Works Association, Denver
100. Marhaba TF, Van D (2000) The variation of mass and disinfection by-product formation
potential of dissolved organic matter fractions along a conventional surface water treatment
plant. J Hazard Mater 74:133–147
101. Bond T, Henriet O, Goslan EH et al (2009) Disinfection byproduct formation and fraction-
ation behavior of natural organic matter surrogates. Environ Sci Technol 43:5982–5989
102. Zwiener C, Richardson SD, de Marini DM et al (2007) Drowning in disinfection byproducts?
Assessing swimming pool water. J Environ Sci Technol 41:363–372
103. Westerhoff P, Mezyk SP, Cooper WJ, Minakata D (2007) Electron pulse radiolysis determi-
nation of hydroxyl radical rate constants with Suwannee river fulvic acid and other dissolved
organic matter isolates. Environ Sci Technol 41:4640–4646. doi:10.1021/es062529n
104. Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical review of rate constants
for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals in aqueous
solution. J Phys Chem Ref Data Monogr 17:513–886. doi:10.1063/1.555805
105. Westerhoff P, Aiken G, Amy G, Debroux J (1999) Relationships between the structure of
natural organic matter and its reactivity towards molecular ozone and hydroxyl radicals.
Water Res 33:2265–2276. doi: 10.1016/S0043-1354(98)00447-3
Impact on Disinfection Byproducts Using Advanced Oxidation Processes for. . . 385

106. Richardson SD, Thruston AD, Caughran TV et al (1999) Identification of new ozone
disinfection byproducts in drinking water. Environ Sci Technol 33:3368–3377. doi:10.
1021/es981218c
107. von Gunten U, Hoigne J (1994) Bromate formation during ozonation of bromide-containing
waters: interaction of ozone and hydroxyl radical reactions. Environ Sci Technol
28:1234–1242. doi:10.1021/es00056a009
108. Kishimoto N, Nakamura E (2012) Bromate formation characteristics of UV irradiation,
hydrogen peroxide addition, ozonation, and their combination processes. Int J Photoenergy.
doi:10.1155/2012/107293
109. Symons JM, Zheng MCH (1997) Technical note: does hydroxyl radical oxidize bromide to
bromate? J AWWA 89:106–109
110. von Gunten U, Oliveras Y (1998) Advanced oxidation of bromide-containing waters: bro-
mate formation mechanisms. Environ Sci Technol 32:63–70. doi:10.1021/es970477j
111. Haag WR, Hoigne J (1983) Ozonation of bromide-containing waters: kinetics of formation of
hypobromous acid and bromate. Environ Sci Technol 17:261–267. doi:10.1021/es00111a004
112. Zhao Y-Y, Boyd JM, Woodbeck M et al (2008) Formation of N-nitrosamines from eleven
disinfection treatments of seven different surface waters. Environ Sci Technol 42:4857–4862.
doi:10.1021/es7031423
113. Wert EC, Rosario-Ortiz FL, Drury DD, Snyder SA (2007) Formation of oxidation byproducts
from ozonation of wastewater. Water Res. doi:10.1016/j.watres.2007.01.020
114. Sarathy S, Mohseni M (2010) Effects of UV/H2O2 advanced oxidation on chemical charac-
teristics and chlorine reactivity of surface water natural organic matter. Water Res
44:4087–4096. doi:10.1016/j.watres.2010.05.025
115. Bennani Y, Perez-Rodriguez P, Alani MJ et al (2016) Photoelectrocatalytic oxidation of
phenol for water treatment using a BiVO4 thin-film photoanode. J Mater Res 31:2627–2639.
doi:10.1557/jmr.2016.290
116. Kleiser G, Frimmel FH (2000) Removal of precursors for disinfection by-products (DBPs) –
differences between ozone- and OH-radical-induced oxidation. Sci Total Environ 256:1–9.
doi:10.1016/S0048-9697(00)00377-6
117. Glauner T, Kunz F, Zwiener C, Frimmel FH (2005) Elimination of swimming pool water
disinfection by-products with advanced oxidation processes (AOPs). Acta Hydrochim
Hydrobiol. doi:10.1002/aheh.200400605
118. Chin A, Bérubé PR (2005) Removal of disinfection by-product precursors with ozone-UV
advanced oxidation process. Water Res 39:2136–2144. doi:10.1016/j.watres.2005.03.021
119. Dotson AD, Keen VOS, Metz D, Linden KG (2010) UV/H2O2 treatment of drinking water
increases post-chlorination DBP formation. Water Res 44:3703–3713. doi:10.1016/j.watres.
2010.04.006
120. Toor R, Mohseni M (2007) UV-H2O2 based AOP and its integration with biological
activated carbon treatment for DBP reduction in drinking water. Chemosphere
66:2087–2095. doi:10.1016/j.chemosphere.2006.09.043
121. Gerrity D, Mayer B, Ryu H et al (2009) A comparison of pilot-scale photocatalysis and
enhanced coagulation for disinfection byproduct mitigation. Water Res 43:1597–1610.
doi:10.1016/j.watres.2009.01.010
122. Liu S, Lim M, Fabris R et al (2008) Removal of humic acid using TiO 2 photocatalytic
process – fractionation and molecular weight characterisation studies. doi: 10.1016/j.
chemosphere.2008.01.061
123. Hand DW, Perram DL, Crittenden JC (1995) Destruction of DBP precursors with catalytic
oxidation. J Am Water Work Assoc 87:84–96
124. USEPA (1999) Microbial and disinfection byproduct rules: simultaneous compliance guid-
ance manual. United States Environmental Protection Agency, Washington, EPA 815-R-99-
015
386 B.K. Mayer and D.R. Ryan

125. Prest EI, Hammes F, van Loosdrecht MCM, Vrouwenvelder JS (2016) Biological stability of
drinking water: controlling factors, methods, and challenges. Front Microbiol. doi:10.3389/
fmicb.2016.00045
126. Liao X, Chen C, Yuan B et al (2017) Control of nitrosamines, THMs, and HAAs in heavily
impacted water with O3-BAC. J Am Water Work Assoc 109:E215–E225
127. Kulkarni P, Chellam S (2010) Disinfection by-product formation following chlorination of
drinking water: artificial neural network models and changes in speciation with treatment. Sci
Total Environ 408:4202–4210. doi:10.1016/j.scitotenv.2010.05.040
128. USEPA (2006) National Primary Drinking Water Regulations: stage 2 disinfectants and
disinfection byproducts rule
129. WHO (2000) Environmental health criteria 216: disinfectants and disinfectant by-products,
Geneva
130. Laı̂né J-M, Jacangelo JG, Cummings EW et al (1993) Influence of bromide on low-pressure
membrane filtration for controlling DBPs in surface waters. Am Water Work Assoc 85:87–99
131. Uzun H, Kim D, Karanfil T (2017) The removal of N-nitrosodimethylamine formation
potential in drinking water treatment plants. J Am Water Works Assoc 109:15–28. doi:10.
5942/jawwa.2017.109.0047
132. Fu P, Ruiz H, Thompson K, Spangenberg C (1994) Selecting membranes for removing NOM
and DBP precursors. J Am Water Work Assoc 88:55–72
133. Comninellis C, Kapalka A, Malato S et al (2008) Advanced oxidation processes for water
treatment: advances and trends for R & D. J Chem Technol Biotechnol 83:769–776. doi:10.
1002/jctb
134. Speth TF, Miltner RJ (1990) Technical note: adsorption capacity of GAC for synthetic
organics. JAWWA 82:72–75
135. Crittenden JC, Berrigan JK, Hand DW (1986) Design of rapid small-scale adsorption tests for
a constant diffusivity. J Water Pollut Control Fed 58(4):312–319
136. Marhaba TF (2000) A new look at disinfection by-products in drinking water. Water Eng
Manag 147:30–34
137. Mezyk SP, Cooper WJ, Madden KP, Bartels DM (2004) Free radical destruction of
N-nitrosodimethylamine in water. Environ Sci Technol 38:3161–3167. doi:10.1021/
es0347742
138. Mezyk SP, Helgeson T, Cole SK et al (2006) Free radical chemistry of disinfection-
byproducts. 1. Kinetics of hydrated electron and hydroxyl radical reactions with
halonitromethanes in water. J Phys Chem A 110:2176–2180. doi:10.1021/jp054962+
139. Cole SK, Cooper WJ, Fox RV et al (2007) Free radical chemistry of disinfection byproducts.
2. Rate constants and degradation mechanisms of trichloronitromethane (chloropicrin).
Environ Sci Technol 41:863–869. doi:10.1021/es061410b
140. Haag RW, David Yao CC (1992) Rate constants for reaction of hydroxyl radicals with several
drinking water contaminants. Environ Sci Technol 26:1005–1013
141. Fujioka T, Masaki S, Kodamatani H, Ikehata K (2017) Degradation of
N-nitrosodimethylamine by UV-based advanced oxidation processes for potable reuse: a
short review. Curr Pollut Rep 3:79–87. doi:10.1007/s40726-017-0052-x
142. Lee C, Choi W, Yoon J (2005) UV photolytic mechanism of N-nitrosodimethylamine in
water: roles of dissolved oxygen and solution pH. Environ Sci Technol 39:9702–9709.
doi:10.1021/es051235j
143. Sharpless CM, Linden KG (2003) Experimental and model comparisons of low- and
medium-pressure Hg lamps for the direct and H2O2 assisted UV photodegradation of
N-nitrosodimethylamine in simulated drinking water. Environ Sci Technol 37:1933–1940.
doi:10.1631/jzus.A0820642
144. Tchobanoglous G, Burton FL, Stensel HD (2003) Wastewater engineering: treatment and
reuse. McGraw Hill, New York
145. Bolton JR, Cater SR (1994) Homogeneous photodegradation of pollutants in contaminated
water: an introduction. Aquatic Surf Photochem 467–490
Evolution of Toxicity and Estrogenic
Activity Throughout AOP’s Surface
and Drinking Water Treatment

Tatjana Tišler and Albin Pintar

Abstract Nowadays, increasing pollution of surface and drinking water with

hundreds of chemical compounds, lots of them toxic and persistent, presents a
major problem in access to safe drinking water supply. Although low concentra-
tions of pollutants such as natural and synthetic estrogens have been measured in
surface and drinking water, they could be biologically active even at these concen-
tration levels. Advanced oxidation processes (AOPs) are very powerful tools for
removal of recalcitrant compounds from water streams as they are able to mineral-
ize or degrade organic compounds. In this chapter, development of toxicity and
estrogenic activity of water samples treated by AOPs, which depends on the oxi-
dation process used and experimental conditions, is discussed. Evolution of
species-specific toxicity was particularly evident during the photocatalytic oxida-
tion of herbicide iodosulfuron, as greatly enhanced toxicity of treated samples was
detected in the case of water fleas Daphnia magna. Therefore, it is clearly seen that
the efficiency of applied AOPs for removal of pollutants from surface and drinking
water should be checked by a comprehensive analysis including determination of
remaining parent compounds, identification, and quantification of intermediates as
well as assessment of possible biological adverse effects of treated water samples.

Keywords 17β-Estradiol, Biological activity, Bisphenols, Catalytic wet air

oxidation, Iodosulfuron, Photocatalysis

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2 Treatment Efficiency Evaluations of AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389

T. Tišler (*) and A. Pintar (*)

Department for Environmental Sciences and Engineering, National Institute of Chemistry,
Ljubljana, Slovenia
e-mail: [email protected]; [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 387
Water Treatment, Hdb Env Chem (2019) 67: 387–404, DOI 10.1007/698_2017_127,
© Springer International Publishing AG 2017, Published online: 17 November 2017
388 T. Tišler and A. Pintar

3 Endocrine Disrupting Compounds (EDCs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390

3.1 Evolution of Toxicity and/or Estrogenic Activity of E2- and BPA-Treated Samples
During AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
4 Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
4.1 Evolution of Toxicity and/or Estrogenic Activity of Iodosulfuron Treated Samples
During AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399

Abbreviations

Acetyl-CoA Acetyl coenzyme A

AHAS Acetohydroxyacid synthase enzyme
AOPs Advanced oxidation processes
BPA Bisphenol A
BPAF Bisphenol AF
BPF Bisphenol F
CWAO Catalytic wet air oxidation
D. magna Daphnia magna
D. rerio Danio rerio
D. subspicatus Desmodesmus subspicatus
DAD Diode array detector
DNA Deoxyribonucleic acid
E1 Estrone
E2 17β-Estradiol
E3 Estriol
EDCs Endocrine disrupting compounds
EE2 17α-Ethinylestradiol
ER Calux Estrogen receptor-mediated chemical-activated luciferase gene expression
GFP Green fluorescent protein
HPLC High-performance liquid chromatography
ISO International Organization for Standardization
MQ Ultrapure water
MS Mass spectrometry
MTT 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide
NMR Nuclear magnetic resonance
TOC Total organic carbon
UV Ultraviolet
V. fischeri Vibrio fischeri
WWTPs Wastewater treatment plants
YES Yeast estrogen screen assay

1 Introduction

In recent years, the presence of numerous chemicals such as biocides, pharma-

ceuticals, personal care products, and endocrine disrupting compounds (EDCs) in
effluents, surface water, groundwater, and drinking water has become an issue of
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 389

increasing international attention and concern. It is well known that the presence of
these compounds in environmental samples could have adverse effects on wildlife
[1]. Furthermore, if these compounds occur in drinking water supplies, they may
pose threat to the human population by development or acceleration of different
diseases [2]. Pollution of surface and ground water has contributed significantly to
the lack of drinking water supply, most commonly in poor and water-short coun-
tries, which is mostly linked to faster population growth rate in these countries [3].
A major point source of these compounds in the aquatic environment are
effluents from wastewater treatment plants (WWTPs); for this reason, an efficient
treatment of effluents is necessary to remove these compounds before entering
aquatic environment. Despite removal of a large portion of compounds from
wastewater streams during various treatment processes, WWTPs do not remove
all compounds completely. Microorganisms present in WWTPs are able to degrade
biodegradable compounds, and the level of degradation depends on complexity of
molecule and hydrophilicity. However, toxic and/or persistent pollutants could not
be removed from wastewater streams by means of otherwise very effective con-
ventional biological water treatment processes [4]. In such cases advanced oxi-
dation processes (AOPs), which are based on generation of highly reactive
oxidative radicals such as hydroxyl radicals, have demonstrated high level of
removal efficiency of biocides, EDCs, pharmaceuticals, and personal care products
from water samples [5–7]. Heterogeneous photocatalysis, Fenton-based oxidation,
ultrasound oxidation, electrochemical oxidation, and ozone-based technologies are
most frequently used for these purposes [8].

2 Treatment Efficiency Evaluations of AOPs

An ideal goal of AOPs is a complete mineralization of organic molecules into

carbon dioxide, water, and associated mineral salts. Actually, degradation processes
during AOPs are usually incomplete leading to production of numerous intermedi-
ates or end products. The removal efficiency of a tested (model) compound in the
applied AOP is mostly followed by chemical analyses of parent organic matter and
identification of produced intermediates or end products. For these purposes, liquid
chromatography and gas chromatography methods combined with different tech-
niques such as mass spectrometry are most frequently used [9–13]. However,
intermediates and end products might exhibit adverse effects on aquatic organisms
comparable to or even higher than that observed for the parent compounds. For
these reasons, treated samples should be checked for possible baseline toxicity or
specific toxicity (e.g., estrogenic activity, neurotoxicity, genotoxicity, etc.) induced
by a target mode of toxic action, which is indicative of certain groups of
chemicals [14].
Numerous bioassays, which are based on measuring the degree of response
elicited in the organisms, exposed to a single chemical compound or mixtures of
compounds (e.g., environmental samples), have been developed. Microorganisms,
390 T. Tišler and A. Pintar

algae, invertebrates, and fishes are typically used taxonomic groups of aquatic
organisms involved in bioanalytical testing [15]. Literature review shows that the
efficiency of toxicity removal of aqueous samples after AOPs is mostly determined
by means of the standardized toxicity test procedures using the luminescence
inhibition test with bacteria Vibrio fischeri [16–18], the growth inhibition test
with green algae Desmodesmus subspicatus and Pseudokirchneriella subcapitata
[19, 20], the immobility acute test with water fleas Daphnia magna [19, 21, 22], and
fish early-life stage toxicity test with zebrafish, rainbow trout, and bluegill sunfish
[23, 24].
In addition to the standard procedures with above mentioned organisms, cell
lines are used for toxicological analyses of AOP-treated aqueous samples. Mam-
malian cells (Chinese hamster ovary cells and human ductal breast epithelial tumor
cells) were applied to detect cytotoxic (MTT test), genotoxic (alkaline comet
assay), and mutagenic (Ames test) effects of aqueous samples with selected micro-
pollutants before and after oxidative treatment [25]. Gou et al. [11] reported a novel
approach, based on toxicogenomics toxicity assay with a GFP-fused whole cell
array of Escherichia coli K12, which provides insights into dynamics of the
nature of toxicity mechanisms during the course of electro-Fenton oxidative pro-
cess of three selected contaminants of emerging concern.
The measurement of specific modes of action, i.e., estrogenic activity of
treated samples, is mostly done by in vitro yeast-based estrogenic assays such as
yeast estrogen screen (YES) assay [26–31], E-screen assay using estrogenic
receptor-positive human breast adenocarcinoma cell line MCF-7 [14, 32], and ER
Calux test with human ductal breast epithelial tumor cells [25]. The complexity of
interactions as a consequence of toxicokinetic and toxicodynamic factors is covered
by in vivo bioassays, which are mainly based on the induction of a sensitive bio-
marker, yolk precursor protein vitellogenin, confirming the exposure of fish males
and juveniles to estrogens and xenoestrogens. Fish species like Japanese medaka
fish Oryzias latipes [27], rainbow trout and brown trout [23, 33], and zebrafish
Danio rerio [34] are frequently used for these purposes. Mboula et al. [13] reported
that a genetically modified organism, transgenic medaka line, containing a green
fluorescence protein gene regulated by the regulatory sequence of the choriogenin
H (ChgH) gene was used to assess the estrogenic activity of photocatalytically
treated BPA aqueous samples.

3 Endocrine Disrupting Compounds (EDCs)

The ubiquitous presence of EDCs in wastewater, surface, and drinking water has
become a major concern, since it is evident that they have a potential to elicit
adverse effects on endocrine systems of wildlife and human, including hormone-
dependent cancers [2, 35]. EDCs, a large group of structurally diverse chemicals,
include a variety of natural and synthetic compounds, e.g., estrogenic hormones and
xenoestrogens such as industrial chemicals (surfactants, plasticizers), pesticides,
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 391

heavy metals, and pharmaceuticals. The largest contribution to the estrogenic acti-
vity of water streams belongs to the natural estrogens such as estrone (E1), 17-
β-estradiol (E2), estriol (E3), and synthetic estrogens like 17α-ethinylestradiol
(EE2). These compounds are of a major concern as they induce reproductive and
developmental disturbances in wild fish population at extremely low
concentrations [36].
The main sources of surface water pollution with EDCs are considered to be
municipal wastewater streams [37], mainly contaminated with estrogens (E1,
E2, E3, and EE2) and industrial effluents as well as landfill leachates, where
xenoestrogens (e.g., BPA, alkylphenols, phthalate esters) are frequently present
[38, 39].
Bisphenol A (BPA) is an important industrial high-production-volume chemical,
which is used in the production of epoxy resins and polycarbonate plastics. It is also
present in thermographic papers, coatings, flame retardants, and dental sealants
[40]. Due to its widespread use, it is commonly present in all segments of aquatic
environment. BPA is considered to cause adverse effects on reproduction, devel-
opment, growth, and behavior of wildlife and humans [41–43]. Therefore, stringent
regulations on the production and application of BPA have been accepted in the
European Union [44, 45]. Consequently, the restriction has forced intensive pro-
duction and application of possible alternatives to BPA. Numerous bisphenol
analogues such as bisphenol B, bisphenol E, bisphenol F (BPF), bisphenol S,
bisphenol AF (BPAF), and bisphenol AP have been synthesized. Their presence
has already been confirmed in the aquatic environment [46, 47].

3.1 Evolution of Toxicity and/or Estrogenic Activity of E2-

and BPA-Treated Samples During AOPs

3.1.1 17β-Estradiol (E2)

Most natural and synthetic estrogens as well as xenoestrogens are chemicals with
phenol moiety, which is related to the estrogenic activity of compounds due to
formulation of hydrogen bonds between the OH groups and the estrogenic recep-
tors. The breakage and oxidation of benzene rings occur rapidly due to generation
of hydroxyl radicals during AOPs; therefore, a lack of ability of intermediates to
activate the estrogenic receptors by binding to them is anticipated [26, 48]. Bistan
et al. [49] reported a successful removal of E2 and estrogenic activity during
catalytic wet air oxidation (CWAO) and photolytic/photocatalytic oxidation. The
presence of catalysts in both processes clearly enhanced the degradation of E2,
especially Ru/TiO2 catalyst used in the CWAO process was found to be very
effective as complete E2 removal was noticed. We found that no estrogenically
active intermediates were formed during both oxidation processes, which was
confirmed by removal of estrogenic activity of treated samples. Similar results
with no estrogenic activity of intermediates produced during photocatalytic oxi-
dation of E2 were also obtained in other studies [31, 48].
392 T. Tišler and A. Pintar

However, the presence of some estrogenically active intermediates of E2 gen-

erated during different AOPs was reported. Mboula et al. [13] reported that during
photocatalytic oxidation of E2, the latter was completely removed from the aqueous
solution under UV irradiation using the synthesized catalysts, but the estrogenic
activity of intermediates was not removed probably due to the presence of phenol
moiety in most determined intermediates. It appears that the removal efficiency
depends on the light source and catalyst used. The residual estrogenic activity of
treated aqueous samples was mostly found after oxidation processes of E2 such as
ozonation [28, 32] combined by hydrogen peroxide-assisted oxidation [30] and
chlorination [29, 32, 50, 51]. Estrogenic activity of end product solutions produced
in various AOPs could be attributed to: (1) production of oxidized by-products,
which are equally or even more estrogenically active in comparison to the initial
solution, or (2) the presence of very low concentrations of residual E2, which could
remain in treated samples despite very high removal efficiency. It should be noted
that E2 is estrogenically active at very low concentrations (ng/L) [52].
According to the research findings, it is evident that diverse degradation path-
ways generate different intermediates of E2 during AOPs; a degradation mecha-
nism depends on applied treatment process and operating conditions. This also
applies to removal of estrogenic activity and toxicity of xenoestrogens from
aqueous samples by means of oxidation processes.

3.1.2 Bisphenols

Many studies reported the efficient degradation of BPA. Among the most effective
techniques are the application of O3 and UV/H2O2 with low-pressure Hg UV lamps
that resulted in high level of BPA degradation as well as removal of estrogenic
activity and toxicity of treated aqueous samples [27, 53]. It was found that the
composition of aqueous phase plays an important role in removal efficiency of
BPA, its toxicity, and estrogenic activity. Richard et al. [25] investigated the
efficiency of O3 and UV/H2O2 oxidation of BPA in concentrations detected in
surface water by combining chemical and toxicological analyses. They determined
the formation of cytotoxic by-products after 60 min of UV/H2O2 treatment in pure
water, but no toxic effects of spiked wastewater effluent were observed after
ozonation.
Due to high removal efficiency of BPA from aqueous samples, several studies
deal with photocatalytic oxidation of BPA [9, 18, 54, 55]. In our study [56] removal
of BPA was studied in two oxidation processes, catalytic wet air oxidation (CWAO)
and photolytic/photocatalytic oxidation. CWAO process was found to be most
effective when Ru(3.0 wt. %)/TiO2 catalyst was used at the operating temperature
230
C, as complete degradation of BPA and TOC conversion (>97%) were
determined accompanied with complete removal of estrogenic activity and toxic
effects to algae D. subspicatus and bacteria V. fischeri. On the other hand,
remaining toxicity and estrogenic activity were determined in most photolyti-
cally/photocatalytically treated aqueous samples, even in the sample with complete
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 393

removal of BPA performed in the presence of commercial TiO2-P25 catalyst

illuminated with UV light. Acute toxicity to V. fischeri, D. magna, and D. rerio
as well as estrogenic activity was determined in these samples. However, in some
cases even higher toxicity was detected in comparison to the initial BPA solution,
which could be attributed to the occurrence of intermediates produced during photo
(cata)lysis.
It is well known that production of hydroxyl radicals during oxidation processes
with a TiO2 photocatalyst enhanced the degradation of BPA in aqueous samples. A
mixture of intermediates is produced during BPA oxidation processes before a
complete mineralization is achieved, and some of them are able to elicit adverse
biological effects such as genotoxicity, estrogenic activity, and/or toxicity. Degrad-
ation pathways of BPA are related to the applied oxidation process and operating/
reaction conditions which result in production of various by-products. For example,
Chiang et al. [16] reported that photocatalytic degradation of BPA depended on pH
value of initial BPA aqueous solution, which in turn resulted in the formation of
different intermediates during the oxidation process. At higher pH value (pH ¼ 10)
more stable, but less toxic, intermediates were produced. On the contrary, less
stable and in the early stage of BPA oxidation more toxic intermediates were
generated at lower pH (pH ¼ 3.0). Mboula et al. [55] reported that production of
some by-products suspected to exhibit estrogenic activity depends on catalyst
nature and experimental conditions, i.e., illumination of a photocatalyst. Gou
et al. [11] studied toxicity evolution during electro-Fenton oxidation of BPA by
means of quantitative toxicogenomics assay and found that BPA and its inter-
mediates could cause DNA damage and induce membrane stress.
Degradation of BPA takes place via different pathways generating
various by-products, which involve (1) para-substituted phenols such as p-
hydroxyacetophenone, p-isopropenylphenol, and p-isopropylphenol, (2) hydroxyl-
ated BPA such as monohydroxylated, dihydroxylated BPA and their quinones, and,
finally, (3) aliphatic compounds such as formic, acetic, oxalic, succinic, and
fumaric acids, which are produced after ring opening [9, 11, 12, 17, 55]. Some of
them like p-hydroxyacetophenone exerted slight estrogenic activity detected by
YES assays [57].
Erjavec et al. [58] studied removal of toxicity and estrogenic activity of BPA,
BPF, and BPAF from aqueous solutions in a three-phase batch and continuous
stirred-tank reactor using glass fiber supported TiO2 photocatalyst under UV light.
In the batch reactor, toxic effects of all photocatalytically treated bisphenols were
diminished and completely eliminated after 4 and 6 h of photocatalytic oxidation in
the case of V. fischeri and D. magna, respectively. Furthermore, complete removal
of estrogenic activity of aqueous samples containing BPA and BPF was also
determined after 4 h. BPAF is less prone to photocatalytic oxidation as 57.0,
30.1, 26.4, and 14.7% of the remaining TOC were detected after 2, 4, 6, and 8 h
of degradation process in the batch reactor, respectively. Although various inter-
mediates were produced during the photocatalytic oxidation of BPAF, no acute
toxicity of the aqueous samples after 4 h of treatment was obtained to luminescence
of V. fischeri and mobility of water fleas D. magna. Furthermore, it was confirmed
394 T. Tišler and A. Pintar

by in vitro yeast estrogen screen assay using modified yeast strain Saccharomyces
cerevisiae (John P. Sumpter, Brunel University, UK) that photocatalytic oxidation
of BPAF produced intermediates with no estrogenic activity of treated samples
after 4 h. However, the initial aqueous solutions of BPA, BPF, and BPAF demon-
strated estrogenic activity in a dose-response relationship; the highest estrogenic
potential was obtained in the case of BPAF.

4 Pesticides

Increasing use of pesticides has become a major concern worldwide due to pollu-
tion of surface and ground water through leaching and runoffs. The presence of
herbicides in water poses a potential risk to aquatic organisms as well as humans.
Such example is atrazine, a triazine-based herbicide, which was considered as a
potential carcinogen and endocrine disruptor. In 2004 atrazine was banned from the
EU market due to ubiquitous and persistent groundwater contamination and its
persistence in the environment [59]. New products have appeared on the market,
and one of the recently used has been iodosulfuron-methyl-ester (referred to as
iodosulfuron). It is a systemic sulfonylurea herbicide, widely used to control annual
grasses and broad-leaved weeds mostly in cereal crops [60]. Due to its relatively
high solubility in water (up to 65 g/L, depending on the pH value), iodosulfuron
could be highly mobile in the environment and contaminates surface and drinking
water [61].
A mode of toxic action of iodosulfuron, like other sulfonylureas, involves
inhibition of the enzyme acetohydroxyacid synthase (AHAS), and consequently
synthesis routes of essential amino acids for algal growth are blocked [62].
Branched-chain amino acids such as valine, leucine, and isoleucine are such
examples. AHAS is involved in the first step of biosynthesis process of valine
(from pyruvate alone), leucine (from pyruvate and acetyl-CoA), and isoleucine
(from pyruvate and 2-ketobutyrate). Contrary to microorganisms and plants, which
are able to synthesize fats, amino acids, vitamins, etc., animals are not able to
produce them and are therefore tied to a complex diet [62].

4.1 Evolution of Toxicity and/or Estrogenic Activity

of Iodosulfuron Treated Samples During AOPs

In many cases, mineralization of pollutants during photocatalytic oxidation pro-

cesses is less successful, which could lead to production of more toxic inter-
mediates in comparison to the parent chemicals. Such an example is shown below
in the case of photocatalytic oxidation of iodosulfuron.
Removal of iodosulfuron from aqueous solution was studied in photocatalytic
runs carried out at different experimental conditions. Iodosulfuron-methyl-ester
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 395

was dissolved in tap or ultrapure water (initial concentration was 26.5 mg/L) and
oxidized in a three-phase slurry reactor under UV or visible light irradiation in the
presence of synthesized sol-gel Nd- or nitrogen-doped TiO2 catalysts [63]. After 3 h
of photocatalytic oxidation, toxicity of treated samples was determined by means of
toxicity tests with organisms from different taxonomic groups in order to detect
possible toxic potential of intermediates generated during incomplete degradation
of iodosulfuron. The luminescence of freeze-dried bacteria Vibrio fischeri, the
immobility of water fleas Daphnia magna, and the growth of unicellular green
algae Desmodesmus subspicatus were determined following the exposure to tested
samples. Toxicity tests were performed according to the protocols and ISO stan-
dards, which were described in detail previously [24, 43].
The measured conversions and corresponding residual concentrations of parent
compound obtained during treatment of aqueous solutions of iodosulfuron by
means of photolytic/photocatalytic oxidation carried out at various experimental
conditions are listed in Table 1, while the toxicity of treated samples to bacteria,
algae, and water fleas is plotted in Figs. 1 and 2.

Table 1 Experimental conditions of photolytic/photocatalytic oxidation runs during treatment of

aqueous solutions of iodosulfuron
Residual
Sample Catalyst Light Water Gas Conversion (%) concentration (mg/L)
0 Initial solution / / / / 26.5
1 No catalyst UV Tap Air 47.4 13.9
2 No catalyst UV MQ N2 62.2 10.0
3 No catalyst Visible MQ N2 0.19 26.4
4 No catalyst Visible MQ Air 0.00 26.5
5 TiO2 P-25 UV MQ N2 99.1 0.25
6 TiO2 P-25 Visible MQ N2 87.4 3.32
7 TiO2 P-25 UV MQ Air 98.8 0.32
8 TiO2 P-25 UV Tap Air 99.3 0.20
9 TiO2 P-25 Visible Tap Air 36.0 16.9
10 TiO2P-25 Visible MQ Air 90.1 2.62
11 TiO2-Nd10 UV MQ Air 99.0 0.28
12 TiO2-Nd10 UV Tap Air 56.3 11.6
13 TiO2-Nd10 Visible MQ Air 18.8 21.5
14 TiO2-Nd10 Visible Tap Air 5.79 24.9
15 TiO2-N (1.1) UV MQ Air / /
16 TiO2-N (1.1) UV MQ Air 91.0 2.39
17 TiO2-N (1.1) Visible MQ Air 10.5 23.7
18 TiO2-N (1.2) UV MQ Air 97.2 0.75
19 TiO2-N (1.2) Visible MQ Air 19.9 21.2
20 TiO2-PcN2 UV MQ Air 97.1 0.76
21 TiO2-PcN2 Visible Tap Air 7.10 24.6
22 TiO2-PcN3 Visible MQ Air 10.8 23.6
396 T. Tišler and A. Pintar

Fig. 1 Toxicity of initial 100 0% 0% 87% 36% 90% 19% 6% 11% 20% 7% 11%
aqueous solution of
V. fischeri
iodosulfuron and treated D. magna
samples under visible light 80 D. subspicatus
to bacteria V. fischeri, water

Inhibition (%)
fleas D. magna, and algae
60
D. subspicatus. Numbers
listed above bars represent
the % of iodosulfuron 40
conversion during the
treatment by means of
photolytic/photocatalytic 20
oxidation. See Table 1 for
sample notation
0
0 3 4 6 9 10 13 14 17 19 21 22
Sample

Fig. 2 Toxicity of initial 100 47% 62% 99% 99% 99% 99% 56% 91% 97% 97%
aqueous solution of
V. fischeri
iodosulfuron and treated D. magna
samples under UV light to 80 D. subspicatus
bacteria V. fischeri, water
Inhibition (%)

fleas D. magna, and algae

D. subspicatus. Numbers 60
listed above bars represent
the % of iodosulfuron
40
conversion during the
treatment by means of
photolytic/photocatalytic 20
oxidation. See Table 1 for
sample notation
0
0 1 2 5 7 8 11 12 15 16 18 20
Sample

The results showed that the highest removal of iodosulfuron (>95%) was mostly
determined in photocatalytic experiments using ultrapure (MQ) water under UV
illumination. Contrary, the removal efficiency of iodosulfuron was significantly
lower in the photocatalytic experiments in which visible light illumination was
utilized (Table 1). It is obvious that the degradation level of iodosulfuron dissolved
in tap water is lower than in ultrapure water due to the ionic content such as
hydrogen carbonates, chlorides, nitrates, etc., which can adsorb to the catalyst
surface and consequently decrease the catalyst activity [63].
In the experiments without catalysts (samples 3 and 4) and utilizing visible light,
no photolytic degradation of iodosulfuron was determined, and consequently the
toxicity of both samples to bacteria, algae, and water fleas remained similar to that
of the initial aqueous solution of iodosulfuron (sample 0). The presence of com-
mercial Degussa TiO2 P25 catalyst enhanced the degradation of iodosulfuron
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 397

dissolved in ultrapure water (samples 6 and 10) under visible light, which increased
the toxicity to bacteria (up to 47% of inhibition) and particularly to water fleas. The
presence of Nd- and N-doped TiO2 catalysts in photocatalytic experiments caused
low conversion of iodosulfuron (up to 20%) under visible light; higher degradation
level was achieved using ultrapure water as a solvent of iodosulfuron. These
samples showed slightly higher toxicity to Vibrio fischeri; toxicity threshold
(20% of inhibition) was exceeded. However, toxicity has not changed significantly
in the case of Daphnia magna. Because of high residual iodosulfuron concentration
in photocatalytically treated samples under visible light, 100% of inhibition of
algal growth was determined in all tested samples (Fig. 1).
In the photolytic experiments without catalysts and utilizing UV light illumina-
tion, photolysis exhibited 47% (sample 1) and 62% (sample 2) of degradation of
iodosulfuron; no increased toxicity was observed for luminescence, but immobility
of all exposed water fleas and 100% inhibition of algal growth were determined in
photolytically treated samples. In photocatalytically treated solutions illuminated
with UV light, degradation of iodosulfuron in ultrapure water (samples 5, 7, and 11)
and tap water (sample 8) was almost complete (99%), and the toxicity of these
samples to algae considerably decreased. However, intensive toxic effects (100%
immobility) to water fleas were determined in most of end product solutions in
which very high removal of iodosulfuron from aqueous solutions was achieved. No
clear correlation between the measured conversion levels and toxicity data toward
Vibrio fischeri was obtained (Fig. 2).
To summarize, UV light enhanced the conversion of iodosulfuron as the
acquired percentages of conversion were mostly higher than 90% in the presence
of different catalysts, except in the case of run 12, where tap water was used as a
reaction medium. Consequently, noticeable increase of toxicity to water fleas was
detected in most end product solutions, but diminished toxic effects to algae were
observed in the samples with the highest % of iodosulfuron removal (Table 1). In
the case of Vibrio fischeri, no clear correlation between % of iodosulfuron removal
and inhibition of luminescence was obtained. However, the use of UV light mostly
results in lower toxicity of end product solutions to Vibrio fischeri in comparison to
runs in which visible light irradiation was utilized (Figs. 1 and 2).
It is clearly shown that low degradation level of iodosulfuron in aqueous samples
after photocatalytic oxidation is well correlated with high toxicity obtained to algae
(Fig. 1). We assume that the residual iodosulfuron in treated samples inhibited the
enzyme acetohydroxyacid synthase (AHAS). As these amino acids are crucial for
algal growth and development, the growth of algae was completely inhibited in the
aqueous samples with residual iodosulfuron.
We found a clear correlation between the conversion of iodosulfuron and toxic
effects on water fleas. When high percentage of conversion (equal or higher than
87%) was attained during photocatalytic oxidation (samples 5, 6, 7, 8, 10, 11,
16, 18, and 20), toxicity to Daphnia magna highly increased in comparison to the
initial aqueous solution (sample 0). It was determined that only about 25% of TOC
was removed after 180 min under given operational conditions. We confirmed by
398 T. Tišler and A. Pintar

HPLC analyses that by-products were produced during photocatalytic oxidation of

iodosulfuron (Fig. 3) in significant quantities relating to the TOC data.
Sleiman et al. [10] studied intermediates produced during iodosulfuron degrad-
ation by TiO2 photocatalysts under UV light irradiation. Based on HPLC-MS and
HPLC-NMR analyses, more than 20 intermediates were identified, which were
classified into two groups according to the presence/absence of sulfonylurea bridge.
In our study, these two groups of intermediates were also detected by HPLC ana-
lysis. Immediately after starting the experiment, group A intermediates appeared in
the solution due to iodosulfuron degradation and then progressively disappeared
during the process of photocatalytic oxidation. Simultaneously, group B inter-
mediates that were produced after the cleavage of sulfonylurea bridge appeared and
remained in the aqueous solution until the end of the experiment (Fig. 3).
Sleiman et al. [10] also found that the ultimate organic product of the degradation
process of iodosulfuron was cyanuric acid, which was very resistant to further oxi-
dation. Furthermore, after the aromatic (benzene) ring opening, several short carbo-
xylic acids arose, and they were determined by means of HPLC-DAD. Among them
most important are oxalic, formic, acetic, glycolic, and glyoxylic acids; the major one
was acetic acid, which reached a maximum concentration at 49 μmol/L (3 mg/L)
after 120 min. According to the results obtained in our previous study, acetic and
formic acids were acutely toxic to water fleas [64], and the presence of these

180

150

120
Signal, mV
90
Intermediates 60
Group A
30
Group B
0
0
0'
10
in

20
30
m

45
60
e,

75
tim

90
120
150
180
n

240
tio

300
360
ac

420
Re

0 2 4 6 8 10 12 14 16 18 20
TimeHPLC, min

Fig. 3 3D HPLC chromatograms of aqueous-phase samples withdrawn during photocatalytic

oxidation of aqueous solution of iodosulfuron (c0 ¼ 26.5 mg/L) in a slurry reactor in the presence
of TiO2-N (1.1) catalyst under UV high pressure lamp (Reproduced from Kralchevska et al. [63]
with permission from Elsevier)
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 399

compounds is a probable reason for the significantly increased toxicity of photo-

catalytically treated samples to Daphnia magna with almost complete degradation of
iodosulfuron.
From the obtained results, we conclude that in the process of heterogeneous
photocatalytic oxidation, removal efficiency of iodosulfuron from aqueous solution
and toxicity of treated samples are attributed to the use of different operating and
reaction conditions of the concerned oxidative treatment, i.e., type of water matrix,
source of illumination, gas, and catalyst present in the aqueous suspension.

5 Conclusions

Application of AOPs for water treatment purposes is undoubtedly very perspective

tool for efficient removal of persistent organic pollutants from surface and drinking
water, because in many cases these processes are able to completely mineralize
water dissolved organic pollutants. However, the main concern relates to incom-
plete degradation of compounds, leading to production of intermediates or end
products that can be formed during utilization of AOPs. Furthermore, degradation
products could be even more biologically active in comparison to parent com-
pounds. For instance, production of more toxic intermediates during photocatalytic
oxidation of iodosulfuron was clearly observed as significantly enhanced toxicity to
water fleas D. magna was determined in treated samples exhibiting the highest
iodosulfuron removal efficiency. The toxicity of photocatalytically treated samples
was found to be species-specific as the increased toxicity was not observed to algae
D. subspicatus and bacteria V. fischeri. Therefore, chemical analytical measure-
ments of remaining original compounds in treated water streams and identification
of degradation products should be accompanied with a comprehensive assessment
of potential biological activity, covering non-specific toxicity and different modes
of action (e.g., estrogenic/androgenic activity in the case of EDCs), in order to
determine suitability of the applied advanced oxidation process for surface and
drinking water treatment purposes.

Acknowledgments The authors gratefully acknowledge funding by the Ministry of Education,

Science and Sport of the Republic of Slovenia through Research program No. P2-0150.
The authors thank Mr. Andraž Premru for conducting the experimental work.

References

1. Schwarzenbach RP, Escher BI, Fenner K, Hofstetter TB, Johnson CA, von Gunten U, Wehrli B
(2006) The challenge of micropollutants in aquatic systems. Science 313:1072–1077
2. Woodruff TJ (2011) Bridging epidemiology and model organisms to increase understanding of
endocrine disrupting chemicals and human health effects. J Steroid Biochem Mol Biol 127:
108–117
400 T. Tišler and A. Pintar

3. Jury WA, Vaux HJ (2007) The emerging global water crisis: managing scarcity and conflict
between water users. Adv Agron 95:1–76
4. Alvarez-Corena JR, Bergendahl JA, Hart FL (2016) Advanced oxidation of five contaminants
in water by UV/TiO2: reaction kinetics and byproducts identification. J Environ Manage 181:
544–551
5. Esplugas S, Bila DM, Krause LGT, Dezotti M (2007) Ozonation and advanced oxidation
technologies to remove endocrine disrupting chemicals (EDCs) and pharmaceuticals and
personal care products (PPCPs) in water effluents. J Hazard Mater 149:631–642
6. Silva CP, Otero M, Esteves V (2012) Processes for the elimination of estrogenic steroid hor-
mones from water: a review. Environ Pollut 165:38–58
7. Ribeiro AR, Nunes OC, Pereira MFR, Silva AMT (2016) An overview on the advanced oxi-
dation processes applied for the treatment of water pollutants defined in the recently launched
Directive 2013/39/EU. J Environ Manage 181:544–551
8. Klavarioti M, Mantzavinos D, Kassinos D (2009) Removal of residual pharmaceuticals from
aqueous systems by advanced oxidation processes. Environ Int 35:402–417
9. Ohko Y, Ando I, Niwa C, Tatsuma T, Yamamura T, Nakashima T, Kubota Y, Fujishima A
(2001) Degradation of bisphenol A in water by TiO2 photocatalyst. Environ Sci Technol 35:
2365–2368
10. Sleiman M, Conchon P, Ferronato C, Chovelon J-M (2007) Iodosulfuron degradation by
TiO2 photocatalysis: kinetic and reactional pathway investigations. Appl Catal B Environ
71:279–290
11. Gou N, Yuan S, Lan J, Gao C, Alshawabkeh AN, Gu AZ (2014) A quantitative toxicogenomics
assay reveals the evolution and nature of toxicity during the transformation of environmental
pollutants. Environ Sci Technol 48:8855–8863
12. Kondrakov AO, Ignatev AN, Frimmel FH, Bräse S, Horn H, Revelsky AI (2014) Formation of
genotoxic quinones during bisphenol A degradation by TiO2 photocatalysis and UV photo-
lysis: a comparative study. Appl Catal B Environ 160–161:106–114
13. Mboula VM, Héquet V, Andrès Y, Gru Y, Colin R, Dona-Rodrı́guez JM, Pastrana-Martı́nez
LM, Silva AMT, Leleu M, Tindall AJ, Mateos S, Falaras P (2015) Photocatalytic degradation
of estradiol under simulated solar light and assessment of estrogenic activity. Appl Catal B
Environ 162:437–444
14. Macova M, Escher BI, Reungoat J, Carswell S, Lee Chue K, Keller J, Mueller JF (2010)
Monitoring the biological activity of micropollutants during advanced wastewater treatment with
ozonation and activated carbon filtration. Water Res 44:477–492
15. Rizzo L (2011) Bioassays as a tool for evaluating advanced oxidation processes in water and
wastewater treatment. Water Res 45:4311–4340
16. Chiang K, Lim TM, Tsen L, Lee CC (2004) Photocatalytic degradation and mineralization of
bisphenol A by TiO2 and platinized TiO2. Appl Catal A Gen 261:225–237
17. Rodrı́guez EM, Fernández G, Klamerth N, Maldonado MI, Álvarez PM, Malato S (2010)
Efficiency of different solar advanced oxidation processes on the oxidation of bisphenol A in
water. Appl Catal B Environ 95:228–237
18. Repousia V, Petala A, Frontistisa Z, Antonopoulou M, Konstantinou I, Kondarides DI,
Mantzavinos D (2017) Photocatalytic degradation of bisphenol A over Rh/TiO2 suspensions in
different water matrices. Catal Today 284:59–66
19. Arslan-Alaton I, Aytac E, Kusk KO (2014) Effect of Fenton treatment on the aquatic toxicity
of bisphenol A in different water matrices. Environ Sci Pollut Res 21:12122–12128
20. Brienza M, Mahdi Ahmed M, Escande A, Plantard G, Scrano L, Chiron S, Bufo SA, Goetz V
(2016) Use of solar advanced oxidation processes for wastewater treatment: follow-up on
degradation products, acute toxicity, genotoxicity and estrogenicity. Chemosphere 148: 473–480
21. Lu N, Lu Y, Liu F, Zhao K, Yuan X, Zhao Y, Li Y, Qin H, Zhu J (2013) H3PW12O40/TiO2
catalyst-induced photodegradation of bisphenol A (BPA): kinetics, toxicity and degradation
pathways. Chemosphere 91:1266–1272
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 401

22. Rozas O, Vidal C, Baeza C, Jardim WF, Rossner A, Mansilla HD (2016) Organic micro-
pollutants (OMPs) in natural waters: oxidation by UV/H2O2 treatment and toxicity assessment.
Water Res 98:109–118
23. Stalter D, Magdeburg A, Weil M, Knacker T, Oehlmann J (2010) Toxication or detoxication?
In vivo toxicity assessment of ozonation as advanced wastewater treatment with the rainbow trout.
Water Res 44:439–448
24. Tišler T, Erjavec B, Kaplan R, Şenilă M, Pintar A (2015) Unexpected toxicity to aquatic
organisms of some aqueous bisphenol A samples treated by advanced oxidation processes.
Water Sci Technol 72:29–37
25. Richard J, Boergers A, vom Eyser C, Besterd K, Tuerk J (2014) Toxicity of the micropollutants
bisphenol A, ciprofloxacin, metoprolol and sulfamethoxazole in water samples before and
after the oxidative treatment. Int J Hyg Environ Health 217:506–514
26. Coleman HM, Routledge EJ, Sumpter JP, Eggins BR, Byrne JA (2004) Rapid loss of estro-
genicity of steroid estrogens by UVA photolysis and photocatalysis over an immobilised tita-
nium dioxide catalyst. Water Res 38:3233–3240
27. Chen P-J, Linden KG, Hinton DE, Kashiwada S, Rosenfeldt EJ, Kullman SW (2006) Bio-
logical assessment of bisphenol A degradation in water following direct photolysis and
UV advanced oxidation. Chemosphere 65:1094–1102
28. Bila D, Montalvao AF, Azevedo DA, Dezotti M (2007) Estrogenic activity removal of
17β-estradiol by ozonation and identification of by-products. Chemosphere 69:736–746
29. Rosenfeldt EJ, Chen PJ, Kullman S, Linden KG (2007) Destruction of estrogenic activity in
water using UV advanced oxidation. Sci Total Environ 377:105–113
30. Maniero MG, Bila DM, Dezotti M (2008) Degradation and estrogenic activity removal of
17β-estradiol and 17α-ethinylestradiol by ozonation and O3/H2O2. Sci Total Environ 407:
105–115
31. Benotti MJ, Stanford BD, Wert EC, Snyder SA (2009) Evaluation of a photocatalytic reactor
membrane pilot system for the removal of pharmaceuticals and endocrine disrupting com-
pounds from water. Water Res 43:1513–1522
32. Alum A, Yoon Y, Westerhoff P, Abbaszadegan M (2004) Oxidation of bisphenol A, 17-
β-estradiol, and 17α-ethynyl estradiol and byproduct estrogenicity. Environ Toxicol 19:
257–264
33. Henneberg A, Triebskorn R (2015) Efficiency of advanced wastewater treatment technologies
for the reduction of hormonal activity in effluents and connected surface water bodies by
means of vitellogenin analyses in rainbow trout (Oncorhynchus mykiss) and brown trout
(Salmo trutta f. fario). Environ Sci Eur 27:1–12
34. Wang WJ, Wang W, Tian H, Zhang X, Ru S (2017) A novel enzyme-linked immunosorbent
assay based on anti-lipovitellin monoclonal antibodies for quantification of zebrafish
(Danio rerio) vitellogenin. Ecotoxicol Environ Saf 136:78–83
35. Gross TS, Arnold BS, Sepulveda MS, McDonald K (2003) Endocrine disrupting chemicals and
endocrine active agents. In: Hoffman DJ, Rattner BA, Burton A, Cairns J (eds) Handbook of
ecotoxicology. CRC Press, Boca Raton, pp 1033–1098
36. Jobling S, Nolan M, Tyler CR, Brighty G, Sumpter JP (1998) Widespread sexual disruption in
wild fish. Environ Sci Technol 32:2498–2506
37. K€orner W, Bolz U, Süßmuth W, Hiller G, Schuller W, Hanf V, Hagenmaier H (2000) Input/
output balance of estrogenic active compounds in a major municipal sewage plant in Germany.
Chemosphere 40:1131–1142
38. Yasuhara A, Shiraishi H, Nishikawa M, Yamamoto T, Nakasugi O, Okumura T, Kenmotsu K,
Fukui H, Nagase M, Kawagoshi Y (1999) Organic components in leachates from hazardous
waste disposal sites. Waste Manage Res 17:186–197
39. Zhao J-L, Chen X-W, Yan B, Wei C, Jiang Y-X, Ying G-G (2015) Estrogenic activity and
identification of potential xenoestrogens in a coking wastewater treatment plant. Ecotoxicol
Environ Saf 112:238–246
402 T. Tišler and A. Pintar

40. Staples CA, Dorn PB, Klecka GM, O’Block ST, Harris LR (1998) A review of the environ-
mental fate, effects, and exposures of bisphenol A. Chemosphere 36:2149–2173
41. Chen M-Y, Ike M, Fujita M (2002) Acute toxicity, mutagenicity, and estrogenicity of
bisphenol-A and other bisphenol. Environ Toxicol 17:80–86
42. Mihaich EM, Friederich U, Caspers N, Hall AT, Klecka GM, Dimond SS, Staples CA,
Ortego LS, Hentges SG (2009) Acute and chronic toxicity testing of bisphenol A with
aquatic invertebrates and plants. Ecotoxicol Environ Saf 72:1392–1399
43. Tišler T, Krel A, Gerzelj U, Erjavec B, Sollner Dolenc M, Pintar A (2016) Hazard identifi-
cation and risk characterization of bisphenols A, F and AF to aquatic organisms.
Environ Pollut 212:472–479
44. Directive 2011/8/EU (2011) Amending Directive 2002/72/EC as regards the restriction of
use of bisphenol A in plastic infant feeding bottles. Off J Eur Union L 26/11, Jan 29
45. Directive 2011/10/EU (2011) Regulation on plastic materials and articles intended to come
into contact with food. Off J Eur Union L 12/1, Jan 15
46. Liao C, Liu F, Moon H-B, Yamashita N, Yun S, Kannan K (2012) Bisphenol analogues in
sediments from industrialized areas in the United States, Japan, and Korea: spatial and tem-
poral distributions. Environ Sci Technol 46:11558–11565
47. Song S, Ruan T, Wang T, Liu R, Jiang G (2012) Distribution and preliminary exposure assess-
ment of bisphenol AF (BPAF) in various environmental matrices around a manufacturing plant
in China. Environ Sci Technol 46:13136–13143
48. Ohko Y, Iuchi K-I, Niwa C, Tatsuma T, Nakashima T, Iguchi T, Kubota Y, Fujishima A (2002)
17β-estradiol degradation by TiO2 photocatalysis as a means of reducing estrogenic activity.
Environ Sci Technol 36:4175–4181
49. Bistan M, Tišler T, Pintar A (2012) Conversion and estrogenicity of 17β-estradiol during
photolytic/photocatalytic oxidation and catalytic wet-air oxidation. Acta Chim Slov 59:
389–397
50. Hu J, Cheng S, Aizawa T, Terao J, Kunikane S (2003) Products of aqueous chlorination of
17β-estradiol and their estrogenic activities. Environ Sci Technol 37:5665–5670
51. Li M, Xu B, Liungai Z, Hu H-Y, Chen C, Qiao J, Lu Y (2016) The removal of estrogenic activity
with UV/chlorine technology and identification of novel estrogenic disinfection by-products.
J Hazard Mater 307:119–126
52. Bistan M, Podgorelec M, Marinšek Logar R, Tišler T (2012) Yeast estrogen screen assay as a
tool for detecting estrogenic activity in water bodies. Food Technol Biotechnol 50:427–433
53. Rosenfeldt EJ, Linden KG (2004) Degradation of endocrine disrupting chemicals bisphenol A,
ethinyl estradiol, and estradiol during UV photolysis and advanced oxidation processes.
Environ Sci Technol 38:5476–5483
54. Wang R, Ren D, Xia S, Zhang Y, Zhao J (2009) Photocatalytic degradation of bisphenol A
(BPA) using immobilized TiO2 and UV illumination in a horizontal circulating bed photo-
catalytic reactor (HCBPR). J Hazard Mater 169:926–932
55. Mboula VM, Héquet V, Andrès Y, Pastrana-Martı́nez LM, Dona-Rodrı́guez JM, Silva AMT,
Falaras P (2013) Photocatalytic degradation of endocrine disruptor compounds under simu-
lated solar light. Water Res 47:3997–4005
56. Bistan B, Tišler T, Pintar A (2012) Catalytic and photocatalytic oxidation of aqueous bis-
phenol A solutions: removal, toxicity, and estrogenicity. Ind Eng Chem Res 51:8826–8834
57. Ike M, Chen M-Y, Jin C-S, Fujita M (2002) Acute toxicity, mutagenicity, and estrogenicity of
biodegradation products of bisphenol-A. Environ Toxicol 17:457–461
58. Erjavec B, Hudoklin P, Perc K, Tišler T, Sollner Dolenc M, Pintar A (2016) Glass fiber-
supported TiO2 photocatalyst: efficient mineralization and removal of toxicity/estrogenicity of
bisphenol A and its analogs. Appl Catal B Environ 183:149–158
59. Sass JB, Colangelo A (2006) European Union bans atrazine, while the United States negotiates
continued use. Int J Occup Environ Health 12:260–267
60. Brigante M, Emmelin C, Previtera L, Baudot R, Chovelon JM (2005) Abiotic degradation of
iodosulfuron-methyl-ester in aqueous solution. J Agric Food Chem 53:5347–5352
Evolution of Toxicity and Estrogenic Activity Throughout AOP’s. . . 403

61. European Commission, Health and Consumer Protection Directorate (2003) Review report for
the active substance iodosulfuron. SANCO/10166/2003-Final
62. Duggleby RG, McCourt JA, Guddat LW (2008) Structure and mechanism of inhibition of
plant acetohydroxyacid synthase. Plant Physiol Biochem 46:309–324
63. Kralchevska R, Milanova M, Tišler T, Pintar A, Tyuliev G, Todorovsky D (2012) Photo-
catalytic degradation of the herbicide iodosulfuron by neodymium or nitrogen doped TiO2.
Mater Chem Phys 133:1116–1126
64. Pintar A, Batista J, Tišler T (2008) Catalytic wet-air oxidation of aqueous solutions of
formic acid, acetic acid and phenol in a continuous-flow trickle-bed reactor over Ru/TiO2 catalysts.
Appl Catal B Environ 84:30–41
Chemometric Methods
for the Optimization of the Advanced
Oxidation Processes for the Treatment
of Drinking and Wastewater

Messias Borges Silva, Cristiano Eduardo Rodrigues Reis,

Fabrı́cio Maciel Gomes, Bruno dal Rovere Contesini,
Ana Paula Barbosa Rodrigues de Freitas, Hélcio José Izário Filho,
Leandro Valim de Freitas, and Carla Cristina Almeida Loures

Abstract Advanced Oxidative Processes (AOP) have been successfully employed

as efficient water treatment methods. The utilization of AOP on drinking and
wastewater represents currently an alternative to costly, hazardous, and slow pro-
cesses. In order to further establish the ground basis for AOP in water safety and
security, reliable and consistent methods of analysis are required. As an alternative to
basic statistical methods, which may not successfully describe and forecast the
application of a given treatment methodology of water, the use of chemometrics
has increased significantly over the past decades. Chemometric analyses are an
intersection between analytical chemistry and applied statistical models in order to
predict and extract information from a given condition. This chapter introduces the
concepts of chemometrics in environmental engineering issues and the utilization of
experimental design to efficiently analyze experimental data in environmental sam-
ples. Two case studies are presented to demonstrate the importance of chemometrics

M.B. Silva (*), F.M. Gomes, A.P.B.R. de Freitas, L.V. de Freitas, and C.C.A. Loures
School of Engineering of Lorena - EEL – USP, University of S~ao Paulo, Lorena, Brazil
Faculdade de Engenharia do Campus de Guaratinguetá -UNESP - FEG, Universidade Estadual
Paulista - Julio de Mesquita Filho, Guaratinguetá, Brazil
e-mail: [email protected]; [email protected]; [email protected];
[email protected]; [email protected]
C.E.R. Reis and B.R. Contesini
School of Engineering of Lorena - EEL – USP, University of S~ao Paulo, Lorena, Brazil
e-mail: [email protected]; [email protected]
H.J. Izário Filho
School of Engineering of Lorena – EEL – USP, University of S~ao Paulo, Lorena, Brazil
e-mail: [email protected]

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 405
Water Treatment, Hdb Env Chem (2019) 67: 405–422, DOI 10.1007/698_2017_117,
© Springer International Publishing AG 2017, Published online: 10 November 2017
406 M.B. Silva et al.

in water analyses: (1) considering a Taguchi L16 experimental design, and an

optimization study using Response Surface Methodology, to evaluate photo-Fenton
and ozone AOP-based treatment on an effluent with high concentration of organic
matter; (2) using a Taguchi L9 array to evaluate the combination of photocatalytic
degradation and AOP of an industrial effluent. The results showed in this chapter
demonstrate how a given statistical method can be successfully employed within the
intersection of environmental analyses and water issues.

Keywords Advanced oxidative processes, Chemometric analyses, Chemometric

methods, Taguchi methods

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
2 Chemometrics in Environmental Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
3 AOP for Treating Drinking Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
4 Design of Experiments for the Optimization of AOP for the Treatment of Drinking
Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
5 Case 1: AOP Using RSM and Taguchi Orthogonal Array (Adapted from de Freitas
et al.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
5.1 Characteristics of the Design of Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
5.2 Results of the RSM (Fe2+/H2O2) for Removing the Total Organic Carbon (TOC) 415
5.3 Conclusion Case 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416
6 Case 2: Taguchi Method in AOP (Adapted from de Freitas et al.) . . . . . . . . . . . . . . . . . . . . . . . 417
6.1 Conclusion Case 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421

1 Introduction

Water scarcity is one of the main challenges of the twenty-first century that many
societies around the world are already facing. Throughout the last century, use and
consumption of water grew at twice the rate of population growth and, although
there is not water scarcity globally, the number of regions with chronic levels of
water shortages is increasing. Water scarcity is not only a natural phenomenon, but
is also caused by human action. Nowadays, there is enough freshwater to supply
people who inhabit the planet, however, it is distributed unevenly, wasted, polluted,
and unsustainably managed [1]. Water recycling and remediation of industrial
effluents are key topics of applied research, in order to reduce the environmental
impact of the human activity, and to revert many of the social consequences of
misuse of waterbodies [2]. The growing concern of providing fresh and safe water
systems to the growing society is a concern of all the United Nations Sustainable
development goals (SDG) signatory countries. Among the over 21 SDG, several of
those are directly or indirectly related to water issues, either by the production of
nutritional food systems or by providing freshwater systems to the world as a public
health concern. Water management and water engineering have been intensive
areas of research over the past decades, both of which encompass a few operational
steps. As a rule, the first step for a successful water management program relies on
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 407

water monitoring. Water monitoring is, then, followed by elements of assessment,

restoration, and ultimate protection of stream water quality. As one can imagine,
assessing the aforementioned steps require a strong and robust system of monitoring
of physical, biological, and chemical parameters. As streams and waterbodies are
usually not in a steady state, the monitoring processes usually require a collection of
temporal data points. As one can imagine, the collection of a large number of data
points within monitoring stations can be understood in a larger-scale level would
generate a complicated data matrix aimed at the evaluation of water quality. The
required expertise to extract the most information from such a complex data collec-
tion may not be omnipresent though.
The use of chemometric methods, or multivariate statistical techniques, has
strongly grown over the past years. The urge to pursue the United Nations SDG
has given an additional boost for research and development in water quality and
safety area. The basis for chemometric methods relies on the identification of the
natural clustering pattern and variables in group for the analysis of similarities and
discrepancies among different samples. The most common techniques for classifi-
cation of water quality parameters are known as principal component analysis
(PCA) with factor analysis (FA), and cluster analysis (CA). This chapter reviews
direct applications of such methods, analyzing how the combination of experimen-
tal design optimization techniques with chemometrics can enhance the interpreta-
tion of the most important information one could obtain from a complex matrix.
Chemometrics have been increasingly accepted as standard methods, which
provide several avenues for exploratory assessment of water quality data sets and
classification of water qualities. Chemometric methods identify the natural cluster-
ing pattern and group variables on the basis of similarities between the samples. The
most common chemometric methods for classification are namely, cluster analysis
(CA) and principal component analysis (PCA) with factor analysis (FA). The
discriminant analysis (DA) is used to confirm the groups found by means of the
CA and PCA. These multidimensional data analysis methods are increasingly in use
for environmental studies dealing with measurements and monitoring. The impor-
tance of crosschecking the group analyses between different methods (e.g., CA
and PCA) is also relevant in order to avoid type-II statistical errors. The use of
confirmatory techniques is found, for example, with discriminant analysis (DA),
which will also be further discussed along this chapter. The use of chemometric
methods does not hold as objective to add complexity to datasets. Chemometric
methods aim, on the other hand, to reduce the natural complexity of large datasets,
by offering enhanced interpretation and visualization alternatives. As a general rule,
environmental data do not hold a normal distribution pattern. Since most traditional
statistical design analyses rely on normality of data, the use of FA and DA, for
example, can lead to the accumulation of a significant number of outliers and can
greatly impair the result analysis. Statistical transformation methods, which could
normalize positively skewed data patterns, as Box-Cox, Power, and Logarithmic
transformations. The use of each transformation method depends greatly on the
type of data sets. Particularly in environmental applications, the use of Box-Cox
transformation has been widely used to transform data into linear models.
408 M.B. Silva et al.

2 Chemometrics in Environmental Studies

There has been a significant increase in use of Chemometrics in environmental

studies over the past decades, especially due to the increase in regulation from
governmental agencies and the enhancement of analytical measurement techniques.
Among the different areas of interest in environmental chemometrics, one could
divide them into three major categories: quantitative chemical analytic methods,
prediction of toxicity and toxicological effects, and monitoring and assessment of
environmental quality [3]. Though there are many robust analytical techniques, two
main challenges are still found on the quantitative chemical analysis of organic
compounds classified as pollutants in environmental samples: (1) the natural
complexity of natural components, often not easily identifiable by traditional
methods that are not coupled with mass spectrometry, and (2) the low concentra-
tions of analytes, which are often near or under the detection limit for the
established methods [4]. Though there is lack of selectivity and the presence of
interfering chemicals in complex matrices, the use of advanced statistical analyses
increases the signal response from non-chromatographic methods. The use of
multivariate calibration methods in complex environmental samples focuses on
the application of mathematical models that relate multivariate signals and noises
with analyte concentrations or chemical properties of the interest compound
[5]. The use of univariate calibration relies on a single numerical scalar value per
sample, e.g. intensity of signal, being recorded and analyzed. On the other hand,
multivariate analysis relates complex data arrays on a sample basis and allows
further reading on analytes that lack selectivity. The use of first-order calibration
methods identifies a single response as a vector of values, e.g. time profiles, spectra,
and voltammograms, on a sample basis. As a result of first-order analysis, one could
quantify an analyte in an interfering environment, since the interfering compounds
are also present in the calibration steps and the model development [5]. The use of
second-order calibration methods, however, provides an instrumental response that
can be analyzed as a data matrix on a sample basis, as is the case for an HPLC-
Diode Array Detection chromatogram [6]. The statistical advantage of a second-
order method relies on the power of the sample signal that can be identified in the
presence of interfering compounds, though these may not be present in the calibra-
tion standards. Though there are higher-order data sets, their related calibration
strategies and analysis are often more complex due to the need of higher-order
tensors for calibration, therefore even higher costs are associated.
Multivariate analyses in environmental samples, thus, stand out as an alternative
that provides sufficient analyte concentration in complex matrices. Over the last
30–40 years, the increased use of second and third order instrumental data coupled
with different areas of analytical chemistry has improved and been thoroughly
studied.
Second-order calibration algorithms, such as parallel factor analysis (PARAFAC)
[7], resolution-alternating least squares (MCRALS), and partial least-squares with
residual bilinearization (PLS-RBL), have been applied to different environmental
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 409

analysis, and have been reviewed by Mas et al. [5]. Monitoring of environmental
samples yields large sets of data, e.g. chemical concentrations, physical parameters,
geospatial data, etc. The assumption of chemometric methods is that the variation of
each parameter coming from a single sample can be explained through a reduced
number of different contributions from independent environmental sources, on a
sense that diffuse and point sources can be characterized according to their compo-
sition and attributed to a single factor (e.g., industrial, agricultural, anthropogenic),
which can, then, help to discriminate among the different temporal and geographical
patterns [5].
The use of PCA, as briefly explained in the Introduction, is based on the
extraction of information from the main orthogonal matrix, i.e. from the principal
components, widely used in exploratory analyses. The number of degrees of
freedom in PCA often allows the analyzer to increase interpretability by rotating
the principal components by a number of methods, such as the varimax rotation.
The varimax rotation allows a change of coordinates that maximizes the vector sum
of the factors. Despite being a powerful statistical tool, PCA has some drawbacks
that often do not predict variance in the data matrix, and in environmental complex
samples, the attribution of individual factors to single specific sources is not usually
common [8]. Other alternatives not yet mentioned to PCA include UNMIX and
positive matrix factorization (PMF), as well as MCRALS. Recent use of UNMIX
and PMF includes air quality measurement performed by the United States
Environmental Protection Agency (US-EPA) [9].
The use of chemometrics based on the assessment of toxicity of chemicals often
relies on in vitro and in vivo methods to provide indicators about the reactions of a
given chemical into a biological system. As many other analytical procedures,
measuring with accuracy the toxicological effects of a certain compound can
involve high expenditures, and the cost may be inhibitive. A common alternative
to efficiently estimate the toxicity of a given compound is through the application of
quantitative structure-activity relationships (QSAR), which are data tools relating
indirect toxicity through the structure of a chemical compound [10]. QSAR derives
mathematical models between the backbone of a molecule and its toxicological
effect associated with a library database from previous studies. The use of QSAR
relies, then, on efficient methods to select and predict the most relevant parameters
related with the expected ranges of toxicity levels. Coupling QSAR with other
regression methods, as stepwise and PCA, has been proposed [10], and it has been
known to be a source of robust predictive models of toxicity in water and environ-
mental samples. The use of QSAR modeling techniques can be, then, summarized
according to different groups, according to the statistical method being used to
support the chemical modeling, which are, for example, (1) linear regression,
(2) non-linear regression (e.g., artificial neural networks, and support vector
machines), and (3) methods for classification [10]. The intent of this chapter is
not to provide an extensive literature review on analytical methods, nor statistical
approaches, on chemometrics for environmental approaches. Therefore, further
details regarding these particular methods are not described herein and can be
found in the cited literature.
410 M.B. Silva et al.

3 AOP for Treating Drinking Water

The use of AOP to treat drinking water, i.e., one of the purest types of water, with
extremely low levels of toxic chemicals and organic matter, has been an intensive
subject of study for over half a century now. The use of AOP yields the removal or
the degradation of natural organic matter by a series of chemical reactions. As
mentioned in the previous sections, the very first step one should have when treating
environmental samples, as is the case of drinking water, is the full characterization
of such sample. AOPs can be divided in a series of oxidants, radiation, and different
catalysts (e.g., UV, O3, H2O2, TiO2, Fe2+); AOPs usually operate at temperatures
close to 25
C, and rely on chemical reactions to completely oxidize or mineralize
organic contaminants. The use of OH radical is widespread in AOP, and though
OH-based degradation is not selective, it has high chemical reaction rate. OH
radical reacts with organic matter in three different ways: (1) by an electron
addition to OH from an organic substituent, (2) by H abstraction, yielding carbon
radicals, which react with oxygen to produce peroxyl radicals, and subsequently
ketones/aldehydes and carbon dioxide, and (3) by addition of OH radicals to double
bonds [11]. Among the many constituents of organic matter, the presence of
chromophores, i.e., visible-light absorbing and emitting aromatic rings, is particu-
larly of interest in drinking water. The capacity to degrade chromophoric com-
pounds is, therefore, a desirable trait to technologies of treating drinking water.
AOP methods based on TiO2 and UV, and combinations thereof, are particularly
known to be highly effective in this case. As a natural result of the application of
AOPs in drinking water, if a complete mineralization is not achieved, a wide range
of low-molecular weight compounds may be found in treated drinking water, and
further physical treatment (e.g., filtration) is often required. Nitrous oxide (N2O) is
an important pollutant, which is emitted during the biological nutrient removal
(BNR) processes of wastewater treatment. Since it has a greenhouse effect which is
265 times higher than that of carbon dioxide, even relatively small amounts can
result in a significant carbon footprint [12].

4 Design of Experiments for the Optimization of AOP

for the Treatment of Drinking Water

Aiming at the adequate treatment of water, the use of statistical techniques and the
application of Design of Experiments (DOE) can be determinant for the efficient
understanding of the influence of the factors involved in the process; thus contrib-
uting to the improvement of its results. A DOE method is a test or a series of tests, in
which deliberate changes are made to the input variables of a process or system,
making it possible to observe and identify the reasons for changes in output vari-
ables or responses [13].
A usually complex and costly experimental situation is easily resolved with
DOE. All factors are considered in a minimal number of experiments, and the
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 411

results are verified with recognized statistical methods. The analysis of variance
(ANOVA) is a standard statistical technique that is commonly used in order to
determine the significance of the independent variables on the output responses. It
does not analyze the data directly, but determines the percentage of contribution of
each factor in determining the variability (variance) of data [14].
A direct application of DOE methods is based on orthogonality of arrays, fully
explored by Box-Cox, Placket Burmann, and Taguchi methods. The aim of Taguchi
method is to minimize the variability of the product, identifying the means of giving
it robustness during the process. By reducing the variability, by means of the ideal
adjustment of the input variables, aiming at a certain behavior of the output
variable, the method also allows to reduce the impact of noise sources, reduce
costs, reduce product development time, and achieve robustness [15]. The funda-
mental principle is that to ensure a consistent quality, one must look for processes
that are insensitive to defects from fluctuations, that is, the process must be
designed so that its performance is the least sensitive of all types of noise.
Response surface methodology (RSM) is a collection of statistical and mathe-
matical techniques useful for developing, improving, and optimizing processes. It
has also important applications in the design, development, and formulation of new
products, as well as in the improvement of existing product designs [16]. Experi-
ments for fitting a predictive model involving several continuous variables are
known as response surface experiments. The objectives of RSM include the deter-
mination of variable settings for which the mean response is optimized and the
estimation of the response surface is in the vicinity of this optimum location
[17]. The purpose of mathematical modeling as part of the RSM is described in
three main steps:
1. Establish a relationship, albeit approximate, between y (output variables) and x1,
x2, . . ., xk (input variables) that can be used to predict the response values for
given settings of the control variables.
2. Determine, through hypothesis testing, the significance of the factors whose
levels are represented by x1, x2, . . ., xk.
3. Determine the optimum settings of x1, x2, . . ., xk that result in the optimized
response over a certain region of interest [18].
RSM has several advantages compared to the classical experimental or optimi-
zation methods in which one variable at a time technique is used. Firstly, RSM
offers a large amount of information from a small number of experiments. Indeed,
classical methods are time consuming and a large number of experiments are
needed to explain the behavior of a system. Secondly, it is possible to observe the
interaction effect of the independent parameters on the response using RSM
[19]. Engineering problems usually have more than one output variable, often the
interests of input variable adjustments are divergent for each response. Thus, it is
necessary to define a method that unifies, in the most appropriate way, the statistical
results obtained for all output variables. Multiresponse optimization problems often
involve incommensurate and conflicting responses. In order to overcome the trade-
offs involved in conflicting multivariate optimization, one could explicit the
412 M.B. Silva et al.

preferential parameter to be optimized. In order to illustrate the selection of an

optimization parameter, one could hypothesize a process in which the optimum
temperature and pH levels have been determined experimentally. However, in such
hypothetical case, adjusting pH would potentially damage or be too costly for the
overall process, therefore, the optimization would be done only by adjusting the
temperature factor.
The object of multi-response optimization is to determine the conditions on the
independent variables that lead to optimal or nearly optimal values of the response
variables. Desirability function appears to have been first proposed as a criterion for
response optimization by Harrington, and popularized by Derringer and Suich [20].
The two case studies presented in Sects. 5 and 6 were developed by members of
the research group responsible for this chapter. Though these cases were focused on
the utilization of AOP to treat industrial effluents, the streamline is similar to the
cases in drinking water when it comes to the basic chemometric studies. The results
discussed on Sects. 5 and 6 are analyzed by applications of Taguchi and RSM
methods utilizing different combinations of AOP.

5 Case 1: AOP Using RSM and Taguchi Orthogonal Array

(Adapted from de Freitas et al. [11])

De Freitas et al. employed different sorts of AOP to reduce the chemical load of an
effluent rich in phenolic compounds and with high organic load [8]. Initially, an L16
Taguchi Orthogonal Array was utilized to evaluate the factors of Photo-Fenton and
Ozone AOP methods on the removal of organic matter. Initial results indicated
removal levels of 29.07% of Total Organic Carbon (TOC). The process was then
optimized with a Photo-Fenton RSM. With such optimization, the highest percent-
age of TOC removal was of 54.68%. This condition is associated with a mass ratio
of hydrogen peroxide and ferrous ions equal to 8, which corresponds to 47.8 g of
H2O2 and 5.95 g of Fe2+.

5.1 Characteristics of the Design of Experiments

Table 1 presents each variable with its respective selected levels. The distribution
of factors was made according to symbol in it, with the intention of obtaining
interactions among them, as allowed in Taguchi method.
Table 2 shows the percentage of variation in the TOC for the experiments
conducted in the design of experiments L16. Experiments 13 and 15 had a higher
percentage of TOC removal for the AOP (O3/UV and Photo-Fenton).
The statistical analysis of the L16 Taguchi design (Fig. 1) showed the most
significant parameters for degrading organic matter in the effluent. These corres-
ponded to uncoded factor pH ¼ 3, which was set on a low level, and the adjusted
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 413

Table 1 Control factors and levels for the exploratory study on the phenolic effluent treatment
(reproduced from [11] with permission)
Factor Symbol Level 1 Level 2
a
Hydrogen Peroxide (g) A 38.7 46.5
a
Ferrous ions (g) B 1.26 1.55
pH C 3 5
Ozone (L/h) D 3 5
Temperature E 30 35
Lamp power F 16 28
a
Fenton reagent

Table 2 Taguchi orthogonal array L16 with TOC removal percentage (reproduced from [11] with
permission)
Row A B AB C AC BC E AE F AF D AD AF TOC reduction (%)
1 1 1 1 1 1 1 1 1 1 1 1 1 1 18.28
2 1 1 1 1 1 1 2 2 2 2 2 2 2 23.82
3 1 1 1 1 1 2 2 2 2 2 2 2 2 9.38
4 1 1 1 2 2 2 2 2 2 2 1 1 1 15.74
5 1 2 2 1 1 2 1 1 2 2 1 2 2 23.72
6 1 2 2 1 1 2 2 2 1 1 2 1 1 22.48
7 1 2 2 2 2 1 1 1 2 2 2 1 1 15.89
8 1 2 2 2 2 1 2 2 1 1 1 2 2 15.55
9 2 1 2 1 2 2 1 2 1 2 1 1 2 25.71
10 2 1 2 1 2 2 2 1 2 1 2 2 1 23.74
11 2 1 2 2 1 1 1 2 1 2 2 2 1 22.88
12 2 1 2 2 1 1 2 1 2 1 1 1 2 21.07
13 2 2 1 1 2 1 1 2 2 1 1 2 1 29.07
14 2 2 1 1 2 1 2 1 1 2 2 1 2 26.78
15 2 2 1 2 1 2 1 2 2 1 2 1 2 28.68
16 2 2 1 2 1 2 2 1 1 2 1 2 1 21.82

maximum level factors were: 46.5 g hydrogen peroxide, 1.55 g ferrous ions, and
UV lamp power of 28 W. In the utilized DOE, the interactions among factors were
also evaluated, in which those that were the most significant for the process were
hydrogen peroxide and pH adjusted for level 1, and hydrogen peroxide and tem-
perature for level 2.
The statistical significance of the factors and their interactions towards the TOC
reduction for the treatment of the phenolic effluent was confirmed by ANOVA, as
shown in Table 3. The statistical analysis, at 95% of confidence, showed the most
significant factors for removing the organic load. According to Array F, whose
critical value was 18.51, and for a p-value which was less than 5%, the most
significant factors to the degradation of the organic matter of the phenolic effluent
were H2O2, Fe2+, pH, UV, and interactions H2O2/pH and H2O2/temperature.
414 M.B. Silva et al.

Main Effects Plot for Means

Data Means
A B AB C
25,0

22,5

20,0

1 2 1 2 1 2 1 2
TOC Reduction %

AC E AE F
25,0

22,5

20,0

1 2 1 2 1 2 1 2
AF D AD
25,0

22,5

20,0

1 2 1 2 1 2

Fig. 1 Main effects of percentage variation measures of TOC in the treatment of phenolic effluent
from the L16 design (reproduced from [11] with permission)

Table 3 Analysis of variance of Taguchi’s orthogonal array L16 (reproduced from [11] with
permission)
Source DF SS Adj SS Adj MS F P
A 1 185.232 185.232 185,232 178.97 0.00
B 1 32.833 32.833 32.833 31.72 0.005
AB 1 0.555 0.555 0.555 0.54 0.505
C 1 110.986 110.986 110.986 107.23 0.000
AC 1 26.112 26.112 26.112 25.23 0.007
E 1 0.585 0.585 0.585 0.57 0.494
AE 1 32.490 32.490 32.490 31.39 0.005
F 1 21.160 21.160 21.160 20.44 0.011
AF 1 3.667 3.667 3.667 3.54 0.133
D 1 0.616 0.616 0.616 0.60 0.483
AD 1 1.103 1.103 1.103 1.07 0.360
Residual error 4 4.140 4.140 1.035
Total 15 419.480

Hydrogen peroxide was the most significant factor, with F ¼ 195.6 and a p-value of
0.5%, and the other factors are pH (F ¼ 117.2441 and p-value ¼ 0.84%), ferrous
ions (F ¼ 34.6842 and p-value ¼ 2.76%), lamp power (F ¼ 22.3531 and p-
value ¼ 4.19%) and the interactions H2O2/pH (F ¼ 27.5844 and p-value ¼ 3.44%)
and H2O2/temperature (F ¼ 34.3219 and p-value ¼ 2.79%). The values obtained by
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 415

ANOVA confirmed the significance shown by the main effects chart, displayed as
Fig. 1.
The best experiment for the degradation of the organic load of the phenolic
effluent was experimental condition 13, with 29.07% removal. It has 46.5 g of
hydrogen peroxide, 1.55 g of ferrous ions, pH ¼ 3, ozone flow of 3 L/h, temperature
of 30
C and 28 W ultraviolet lamp power.

5.2 Results of the RSM (Fe2+/H2O2) for Removing the Total

Organic Carbon (TOC)

The percentage of TOC removal for the experiments conducted by the RSM (Fe2+/
H2O2) is reported in Table 4. Experiment 10 presents the greatest percentage of
organic load removal, i.e. 54.68%.
Table 5 presents the ANOVA for the linear and quadratic model proposed to
explain the response of the TOC reduction, based on significant terms of the Pareto
chart and on the variance analysis of the effects. The ANOVA with 95% confi-
dence, F critical equals to 6.61 and a p-value which is less than 5% showed that the

Table 4 Photo-Fenton Experiment Fe2+ H2O2 TOC (%)

response surface
1 1 1 12.14
methodology (reproduced
from [11] with permission) 2 1 1 15.28
3 1 1 33.66
4 1 1 42.35
5 0 0 49.58
6 0 0 51.26
7 0 0 52.69
8 (2)1/2 0 47.6
9 0 (2)1/2 44.53
10 (2)1/2 0 54.68
11 0 (2)1/2 1.44

Table 5 Analysis of variance Factors a

(SS) a
(df) a
(SMQ) F
of RSM Photo-Fenton
A – H2O2 (Q) 1,612.300 1 1,612.300 10.8436
(reproduced from [11] with
permission) B- H2O2 (L) 661.906 1 661.906 4.4517
C – Fe2+ (L) 429.284 1 429.284 2.8872
D – Fe2+ (L) 44.894 1 44.894 0.3019
CB 7.701 1 7.701 0.0518
Error 743.432 5 148.686
Total SS 3,483.202 10
a
SS sum of squares, df degrees of freedom, SMQ average sum of
squares
416 M.B. Silva et al.

60
TOC Removal %

40

20
1
0 0 Fe2+
−1 −1
0
1
H2O2

Fig. 2 Response surface results for TOC removal (%) evaluating the concentrations of ferrous ion
and hydrogen peroxide (reproduced from [11] with permission)

significant factor for the removal of TOC was the addition of hydrogen peroxide to
the quadratic model (F ¼ 10.8436 and p-value ¼ 2.16%).
Figure 2 illustrates how the percentage of TOC removal increases as the mass
amount of H2O2 and Fe2+ increases. It is possible to observe a significant drop in
the quadratic model developed from the RSM when the Fenton reagent is at a low
level (1).
The greatest reduction of TOC (54.68%) was observed for level 0 of hydrogen
peroxide and ferrous ions at a high level (+1.5), which corresponds to experimental
condition number 10 of the response surface chart. In Fig. 2, it is observed that the
majority of experimental data is distributed in the optimal region, which is indicated
in light and dark green color. The parameters used in the optimization of organic
matter degradation of the phenolic effluent for a better experimental condition were
48.3 g of hydrogen peroxide and 5.95 g of ferrous ions. Experimental condition
number 10, with 54.68% removal of the organic load of the effluent, was the most
significant for the process.

5.3 Conclusion Case 1

The case study 1 illustrated how AOP (Photo-Fenton and O3/UV) were evaluated
with Taguchi and RSM designs. Taguchi results demonstrated that Freitas et al. [11]
selected initial factorial levels that were not significant for the removal of organic
load. In this DOE, it was found that the greatest reduction of TOC (%) was related
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 417

to an increase in the concentration of Fe2+ and H2O2, and to the absence of ozone in
the reaction medium. The Photo-Fenton RSM has demonstrated that optimum
conditions of treatment were within the studied region, since the conducted exper-
iment had reached a significant curvature, making it necessary for the accomplish-
ment of the star, i.e. rotational, experiment. The obtained results were significant for
the removal of the TOC (%).
In the process optimization for RSM related to the Photo Fenton method, the
highest percentage of TOC removal 54.68% was achieved, which corresponded
to experimental condition number 10. This condition was associated with the
mass ratio of hydrogen peroxide and ferrous ions being equal to eight, which
corresponded to 47.8 g of H2O2 and 5.95 g of Fe2+. It is concluded that the
Photo-Fenton is the most effective process for the phenolic effluent treatment
used in this work.

6 Case 2: Taguchi Method in AOP (Adapted from de

Freitas et al. [16])

Case study 2 was developed upon the use of a polyester resin effluent, which was
supplied by Valspar industry, located in S~ao Bernardo do Campo, State of S~ao
Paulo, Brazil.
An experimental design Taguchi L9 with AOP and heterogeneous photocatalysis
was used for 1 L of fresh effluent diluted three times. The prepared effluent sample
was previously homogenized and conditioned at room temperature. Semiconductor
titanium dioxide (TiO2) and H2O2 (30% w/v) were added during the initial 50 min
of 1 h of total reaction. The temperature of the reaction medium during the whole
period of the photocatalytic process was controlled at 25
C by using a thermostatic
bath. A centrifugal pump was used for conducting the effluent from the tubular
reactor to the storage tank. Ultraviolet lamps of 15 and 21 W were used. The
statistical planning performed is represented by Taguchi L9 orthogonal array to
which the response variable was TOC and independent variables as factors
proposed for this stage were: pH, titanium dioxide, hydrogen peroxide and UV
radiation power. Table 6 shows the treatment variables with their levels for selected
AOP.

Table 6 Control variables and their levels (reproduced from [16] with permission)
Control variables (factors) Level 1 Level 2 Level 3
A – pH 3.0 5.0 7.0
B – TiO2 (g/L) 0.083 0.167 0.250
C – H2O (g)a 120.0 151.0 182.0
D – UV (W) Not present 15 21
[H2O2] ¼ 30% w/w
a
418 M.B. Silva et al.

Table 7 Results of replica 2 of the percentage reduction obtained in experiments, initial TOC of
7,920 mg/L (reproduced from [16] with permission)
pH TiO2 H2O2 UV Reduction of
Experiment factor A factor B factor C factor D TOC (%)
1 1 1 1 1 31.28
2 1 2 2 2 34.5
3 1 3 3 3 36.4
4 2 1 2 3 35.72
5 2 2 3 1 31.65
6 2 3 1 2 30.02
7 3 1 3 2 30.74
8 3 2 1 3 33.01
9 3 3 2 1 27.48

Initially, the mass of H2O2 (30% w/w) was calculated by a stoichiometric ratio
that depended on the organic load of the effluent. This led a mass of H2O2 of 50 g
per liter of effluent.
The amount of TOC of the effluent in natura had a mean value of 7,920 mg/L
that was subjected to pre-treatment. For each experimental amount of TOC, a
sample in a 60-min reaction was determined. Table 7 shows the arrangement of
orthogonal Taguchi L9 for the treatment of effluent polyester resin using AOP.
Statistical analysis of Taguchi L9, in Fig. 3, showed the most significant param-
eters for the degradation of organic matter in the wastewater, the latter reflecting of
pH ¼ 3, adjusted at a low level and factors set at a maximum level of 182 g
hydrogen peroxide and ultraviolet lamp power of 21 W. According to the plan
performed, the level of titanium dioxide added to the process can be adjusted at low
or medium level, i.e. with values 0.083 g/L and 0.167 g/L.
Statistical analysis at a level of 95% showed the most significant factors for the
removal of organic load. According to the distribution F, which critical value under
these conditions corresponded to 4.26 and a p-value less than 5%, the most
important factors for the degradation of organic matter in the effluent were H2O2,
pH, and UV. The most significant factor was the ultraviolet lamp power with F of
60.65201 and a p-value less than 0.001%, and then the remaining factors were the
pH (F ¼ 30.11586, p-value ¼ 0.10%) and H2O2 (F ¼ 4.67497; p-value ¼ 4.053%).
The values obtained by ANOVA confirmed the significance shown in the graph of
main effects. The ANOVA with F ¼ 2 demonstrated that the factor TiO2 was
significant for TOC removal. An F value greater than 2 was considered as a relevant
effect (factor). The statistical significance factor in TOC reduction in the effluent
treatment was confirmed by ANOVA, as shown in Table 8. Multiple linear regres-
sions provided another statistical approach to evaluate variables in a quantitative
approach. Significant parameters to the regression analysis are shown in Table 9,
where pH, UV, and H2O2 are relevant for the degradation process of the organic
load of the polyester resin effluent.
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 419

pH TiO2
34,8

33,6

32,4

31,2
TOC Removal %

30,0
1 2 3 1 2 3
H2O2 UV
34,8

33,6

32,4

31,2

30,0
1 2 3 1 2 3

Fig. 3 Main effects in TOC percentage variation measurements in the effluent treatment of L9
planning (reproduced from [16] with permission)

Table 8 Analysis of variance Taguchi L16 orthogonal array obtained for TOC (%) removal
(reproduced from [16] with permission)
Source of variation SQ GL SMQ F P-value
pH 53.0700 2.00 26.53499 30.11586 0.00010
TiO2 3.7711 2.00 1.88554 2.13999 0.17366
H2O2 8.2382 2.00 4.11909 4.67497 0.04053
UV 106.8806 2.00 53.44030 60.65201 <0.00001
Error 7.9299 9.00 0.88110

Table 9 Regression parameters

Factor Coefficient t-value Beta coeff. Probability
pH 1.04933 4.573584 0.542040 0.0003
TiO2 5.73042 1.042771 0.123584 0.1580
H2O2 0.0266726 1.627560 0.192891 0.0638
UV 0.245688 5.791488 0.686380 0.0000
Constant 32.2247

Multiple linear regression showed a coefficient of determination (R2) of

0.817404, which demonstrates the efficiency of the degradation of effluent using
the polyester resin of the experimental design. An ANOVA (Table 10) was
performed in order to validate the multiple linear regression equation.
420 M.B. Silva et al.

Table 10 ANOVA of multiple linear regression

Sources of variation df SQ MSQ F P-value
Due to regression 4 147.0425 36.7603 14.55 0.0001
Independent 13 32.84718 2.526706

36
TOC REmoval %

33

3
30

2 UV
27
1
2 1
3
pH

Fig. 4 Graph of the two most influential factors in the process

The most significant factors in the process show how the percentage removal of
TOC is influenced by pH, as seen in Fig. 4. An increasing degradation of the organic
load is observed on the surface. This is achieved by independent variables: pH and
power of the ultraviolet lamp. The percentage of increased removal of organic load
occurs when there is an increase of the power of the lamp and a decrease of pH. The
greatest percentage reduction of the organic load is equal to 39.489%, which
parameters used in this experimental condition were H2O2 ¼ 182 g, pH ¼ 3,
TiO2¼ 0.250 g/L and the lamp power of 21 W. The response variable was
significant for the degradation of organic matter in the effluent.

6.1 Conclusion Case 2

Taguchi planning was applied to the degradation of effluent organic load. The
experimental design showed that further reduction of TOC (%) is related to an
increase in pH and ultraviolet intensity. The results obtained were significant for the
Chemometric Methods for the Optimization of the Advanced Oxidation Processes. . . 421

removal of TOC (%) from polyester resin effluent treated by AOP, and heteroge-
neous photocatalysis.
The Taguchi orthogonal array shows that the optimal removal corresponds to
experimental condition number 3. This condition was inclusive of the weight ratio
of hydrogen peroxide at 183 g, pH ¼ 3, TiO2 ¼ 0.250 g/L and the lamp inten-
sity ¼ 21 W. It can be concluded that the process of heterogeneous photocatalysis is
optimally suitable for the treatment of the effluent studied in this work.

References

1. Ruiz-Aguirre A, Polo-López M, Fernández-Ibá~nez P, Zaragoza G (2017) Integration of

membrane distillation with solar photo-Fenton for purification of water contaminated with
bacillus sp. and clostridium sp. spores. Sci Total Environ 595(1):110–118. https://doi.org/10.
1016/j.scitotenv.2017.03.238
2. Batista LMB, dos Santos AJ, da Silva DR, de Melo Alves AP, Garcia-Segura S, Martinez-
Huitle CA (2017) Solar photocatalytic application of NbO2OH as alternative photocatalyst for
water treatment. Sci Total Environ 596:79–86. https://doi.org/10.1016/j.scitotenv.2017.04.019
3. Slutsky B (1998) Handbook of chemometrics and qualimetrics: part A by D.L. Massart,
B.G.M. Vandeginste, L.M.C. Buydens, S. De Jong, P.J. Lewi, and J. Smeyers-Verbeke. Data
handling in science and technology volume 20a. Elsevier: Amsterdam. J Chem Inf Comput Sci
38(6):1254–1254. https://doi.org/10.1021/ci980427d
4. Hopke PK (2015) Chemometrics applied to environmental systems. Chemometr Intell Lab
Syst 149:205–214. https://doi.org/10.1016/j.chemolab.2015.07.015
5. Mas S, de Juan A, Tauler R, Olivieri AC, Escandar GM (2010) Application of chemometric
methods to environmental analysis of organic pollutants: a review. Talanta 80(3):1052–1067.
https://doi.org/10.1016/j.talanta.2009.09.044
6. Barnard TE, Booksh K, Brereton R, Coomans D, Deming S, Hayashi Y, Mallet Y, Matsuda R,
Nocerino J, Olivero R (2013) Chemometrics in environmental chemistry-statistical methods,
vol 2. Springer, Berlin
7. Murphy KR, Bro R, Stedmon CA (2014) Chemometric analysis of organic matter fluores-
cence. In: Coble P, Baker A, Lead J, Reynolds D, Spencer R (eds) Aquatic organic matter
fluorescence. Cambridge University Press, New York, pp 339–375
8. Pinto VS, Gambarra-Neto FF, Flores IS, Monteiro MR, Li~ao LM (2016) Use of 1H NMR
and chemometrics to detect additives present in the Brazilian commercial gasoline. Fuel
182:27–33
9. Pancras JP, Vedantham R, Landis MS, Norris GA, Ondov JM (2011) Application of epa unmix
and nonparametric wind regression on high time resolution trace elements and speciated
mercury in Tampa, Florida aerosol. Environ Sci Technol 45(8):3511–3518
10. Kar S, Roy K, Leszczynski J (2017) On applications of QSARs in food and agricultural
sciences: history and critical review of recent developments. In: Roy K (ed) Advances in
QSAR modeling. Springer, Cham, pp 203–302
11. de Freitas APBR, de Freitas LV, Loures CCA, da Silva AF, Gonçalves LG, Silva MB (2014)
Taguchi orthogonal array combined with Monte Carlo simulation in the optimization of waste-
water treatment. AJTAS 3(6-1):19–22. http://dx.doi.org/10.11648/j.ajtas.s.2014030601.12
12. Massara TM, Malamis S, Guisasola A, Baeza JA, Noutsopoulos C, Katsou E (2017) A review
on nitrous oxide (N2O) emissions during biological nutrient removal from municipal waste-
water and sludge reject water. Sci Total Environ 596:106–123
13. Montgomery DC (2013) Design and analysis of experiments design and analysis of
experiments8th edn. Wiley, New York
422 M.B. Silva et al.

14. Myers RH, Montgomery DC, Anderson-Cook CM (2016) Response surface methodology:
process and product optimization using designed experiments. Wiley, New York
15. Carbas RJC (2008) Estudo paramétrico de juntas adesivas pelo método de Taguchi.
Ms. Degree Thesis in Mechanical Engineering, Universidade do Porto, Portugal
16. de Freitas APBR, de Freitas LV, Samanamud GL, Marins FAS, Loures CCA, Salman F,
dos Santos TL, Silva MB (2013) Multivariate analysis in advanced oxidation process. In: The
statistical significance of the factors and the sciences. InTech, Rijeka
17. Dean A, Voss D, Draguljic D (2017) Response surface methodology. In: Design and analysis
of experiments. Springer, New York, pp 565–614
18. Bas D, Boyaci H (2007) Modeling and optimization I: usability of response surface method-
ology. J Food Eng 78(3):836–845
19. Chabbi A, Yallese MA, Meddour I, Nouioua M, Mabrouki T, Girardin F (2017) Predictive
modeling and multi-response optimization of technological parameters in turning of
polyoxymethylene polymer (POM C) using RSM and desirability function. Measurement
95:99–115
20. Derringer G, Suich R (1980) Simultaneous optimization of several response variables. J Qual
Technol 12(4):214–219
Index

A Ammonia, 219, 348, 357

Acetaldehyde, 126, 352, 355, 359, 367, 379 Ammonium, 32, 61, 75
Acetaminophen, 119 AMPA, 143
Acetic acid, 74, 224, 238, 393, 398 Ampicillin, 161, 167, 168
Acetohydroxyacid synthase (AHAS), 394 Antibiotic-resistant bacteria (ARB), 161
Acetone, 74, 126, 224 Antibiotics, 28, 139, 143, 161, 270
Acetylaminoantipyrine, 148 Aquifers, 1–12, 17, 31, 159
Acid Orange II, 80, 81, 222, 231, 241, 242 Aromatic acids, 73, 102, 364
Activated carbon (AC), 15, 28, 34, 44, 69, 77, Arsenic, 13, 24, 25, 33, 41
103, 165, 204, 214, 230, 271, 315– Artificial recharge, 1, 17
329 Ascaris lumbricoides, 165, 260, 274
biological (BAC), 90, 202, 372 Ascaris suum, 272
granular activated carbon (GAC), 44, 136, Aspartic acid, 366
181, 374, 375 Assimilable organic carbon (AOC), 29
metal-functionalized, 78, 89 Atrazine, 142, 144, 148, 172, 394
powdered (PAC), 44, 45, 72, 181, 375 Azo dyes, 78, 80, 128, 149, 231, 235, 242, 317
Adsorption, 7, 71–92, 105, 315, 325, 374
Advanced oxidation processes (AOPs), 1, 21,
53, 73, 267 B
disinfection, 267 Bacteria, 10, 42, 55, 159, 257–284, 395
Fenton-like, 69 regrowth, 71, 135
NOMs, 57 removal, 42
Al/Fe-pillared clay, 69 Batch reactors, 211, 215, 271, 393
Akaganeite, 79 Benzene, 140, 367, 398
Alachlor, 142, 144, 148 Benzoic acid, 108, 116
Aldehydes, 28, 59, 74, 116, 125, 180, 348, 352, Benzothiazole, 180
354, 359, 370, 410 Bicarbonates, 142
Algae, 13, 42, 55, 143, 275, 276, 390–399 Biocides, 172, 261, 266, 388
Algal blooms, 6, 8, 358 Biological activity, 387
Alkylphenol ethoxylate, 366 Biologically activated carbon (BAC), 90,
Alkylphenols, 391 202, 372
Amino acids, 28, 46, 56, 73, 102, 105, 107, 135, Bis(2-chloroisopropyl) ether, 202
262, 276, 280, 346, 348, 360, 364, Bisphenols, 387, 392
394, 397 bisphenol A, 366, 391

A. Gil et al. (eds.), Applications of Advanced Oxidation Processes (AOPs) in Drinking 423
Water Treatment, Hdb Env Chem (2019) 67: 423–430, DOI 10.1007/978-3-319-76882-3,
© Springer International Publishing AG, part of Springer Nature 2019
424 Index

Bluegill sunfish, 390 Chromium, 13, 26

Boreholes, 7, 12 Ciprofloxacin, 119, 167, 168
Brachionus calyciflorus, 147 Citric acid, 173, 368
Bromate, 46, 60, 65, 145, 196, 202, 348, 351, Clarification, 35
354, 356, 368, 372 Clarithromycin, 161, 167
Bromine, 57, 214, 264, 359, 364, 371 Clay catalysts, 77, 315, 324
Bromochloromethane, 355 Climate change, 3
Bromodichloromethane, 355 Coagulation, 35, 72
Bromophenols, 180 enhanced, 41, 374
Butanal, 126 Cobalt doped red mud (Co/RM), 321
Butyl butyrate, 193 Colloids, stability, 36
Coloured dissolved organic matter
(CDOM), 119
C Compound parabolic collector, 155
Camphor, 193 Contaminant Candidate List (CCL), 355
Carbadox, 366 Continuous reactors (flow reactors), 211, 217
Carbamazepine, 146, 366 Continuous stirred-tank reactor (CSTR), 221,
Carbapenem, 161 231
Carbohydrates, 28, 56, 102, 126, 361 Copper, 78, 83, 229, 327, 330
Carbonates, 12, 30, 109, 115, 122, 135, 142, Copper oxide, 321
158, 198, 280, 396 Cost, 297
Carbon dioxide, 30, 32, 73, 74, 82, 88, 109, m-Cresol, 81, 229
389, 410 Cryptosporidium sp., 165, 257, 261, 297
Carbon nanotubes, 69, 90, 214, 241, 320, 324, 327 Cyanides, 266
Carbon xerogels, 327 Cyanobacteria, 180, 186, 202
Carboxylic acids, 102 Cyclocitral, 180
Catalase (CAT), 162, 260 Cysteine, 368
Catalysts, 211, 309
clay, 77, 315, 324
cost-effective, 309 D
load, 237 Danio rerio, 390
physicochemical properties, 241 Daphnia magna, 143, 147, 387, 390, 397
sludge-based (SBC), 321 DBP formation potential (DBPFP), 59
Catalytic cracking, 220 Dechlorination, 81
Catalytic supercritical water oxidation Desmodesmus subspicatus, 390
(CSCWO), 328–330 Dichloramine, 348
Catalytic wet peroxide oxidation (CWPO), 69, Dichloroacetic acid, 148
214, 325, 387 2,6-Dichloro-1,4-benzoquinone, 200
Chemical oxidation, 183, 213, 257, 348, 366 Diclofenac, 27, 146
Chemometrics, methods/analyses, 405 Diethyl disulfide, 202
Chloramines, 357 Dimethylamine (DMA), 359
Chlorfenvinphos, 143 Dimethyl-decahydro-naphthalen-1-ol, 195
Chlorination, 14, 72, 86, 155, 257, 264, 281, Dimethyl disulfide, 202
347, 354–357, 372, 392 Diseases, 259
byproducts, 193 Disinfectants, 14, 25, 46, 59, 71, 260, 300,
Chlorine, 46, 264, 300 347, 374
Chlorine dioxide, 183, 264, 300, 346–348, 356, alternative, 372
358, 372 oxidizing, 349, 350, 357, 372
Chlorobenzene, 224 secondary, 300
p-Chloro-m-cresol (PCMC), 81 Disinfection, 21, 34, 46, 257, 259, 297
Chlorodibromomethane, 355 AOP, 349
Chloroform, 62, 74 Disinfection byproducts (DBP), 55, 60, 116,
Chlorophenols, 78, 139, 143, 180, 347, 352 345, 349
Index 425

brominated (B-DBPs), 357, 368 F

iodinated (I-DBPs), 357 Feed flow rate, 238
mitigation, 372 Fenton, 59, 155, 211, 313
nitrogenous (N-DBPs), 358 heterogeneous, 211, 316
precursors, 359 intracellular, 269
Dissolved air flotation, 44 microorganisms, inactivation, 269
Dissolved organic carbon (DOC), 28, 102, oxidation, 222
109, 360 temperature, 232
Dissolved organic matter (DOM), 102 Feroxyhyte, 163
Diuron, 148 Ferric chloride, 39, 43, 73
DNA, damage, 46, 260, 263, 272, 276, 303, Ferric hydroxides, 230
305, 348, 393 Ferric oxyhydroxides, 122, 158
repair, 263 Ferritin, 163
Drinking water, 1, 179, 257 Ferulic acid, 364, 366
disinfection methods, 264 Fe-ZSM-5, 82
sources, 4, 34 Filtration, 13, 27, 33, 42, 47, 72, 103, 181, 197,
treatment, 21, 24, 55, 72, 84, 140, 179, 202, 202, 204
300, 345 Fixed-bed reactors, 217
Dunaliella tertiolecta, 172 Flavoproteins, 163
Dune filtrate, 47 Flocculation, 35, 72
Dyes, 139, 226, 236, 299, 366 Floc removal, 35, 43
Fluidized-bed reactors (FBR), 219
Fluorescence excitation emission matrix
E (FEEM), 29, 110
Electrochemical oxidation, 137, 189, 196, 281, Fluorescent regional integration (FRI), 110
312, 389 Fluorine, 214
Electrocoagulation, 73 Formaldehyde, 116, 126, 347, 352, 355, 359,
Electrospray ionization (ESI), 104, 111 367, 379
Emerging contaminants (ECs), 133, 136, 141, Formic acid, 116, 238, 393, 398
147, 148 Formylaminoantipyrine, 148
Endocrine-disrupting compounds (EDCs), 42, FT-ICR-MS, 111
136, 141, 147, 213, 230, 310, FT-IR spectroscopy, 110
349, 390 Fullerene, 91
Endosulfan, 42 Fulvic acids, 28, 56, 109, 135, 186, 362
Energy efficiency, 133, 147 Fungi, 160, 169, 173, 186, 197, 262,
Entamoeba histolytica, 260, 264, 274 272, 275
Enterococcus faecalis, 169, 274 Furanones, halogenated, 358
Enzymes, 28, 46, 162, 263, 265, 282 Furfuryl alcohol (FFA), 121
ESI-FT-ICRMS, 111 Fusarium solani, 272
Estradiol, 27, 387, 391
Estriol, 391
Estrogenic assays, 147 G
2-Ethyl-cyclohexanone, 195 Geosmin (GSM), 53, 60–65, 179–186
Ethinylestradiol, 27, 391 Giardia sp., 257, 261, 264, 274, 275, 347
Ethylenediamine-N,N0 -disuccinic Glyoxal, 116, 352
acid (EDDS), 173 Glyoxylic acids, 353, 398
Ethylenediaminetetraacetic acid (EDTA), 173 Glyphosate, 143, 145
Ethylenethiourea (ETU), 42 Goethite, 158, 163, 172, 271, 315, 316
2-Ethyl-1-hexanol, 193 Granular activated carbon (GAC), 44, 136, 181,
Eutrophication, 8, 11 374, 375
Evaporation, 2, 3, 5 Graphene oxide (GO), 316, 327
426 Index

Groundwater, 6, 11, 21, 122 I

chlorinated organics, 136 Inactivation, 297
drinking water, 1 Infiltration, 3
Fenton/photo-Fenton, 122, 155 Iodine, 264
microbial contamination, 159 Iodosulfuron, 387, 394
overexploitation, 9 Ion exchange, 13, 15, 29, 55, 75, 87, 88,
pesticides, 394 104, 375
β-Ionone, 180
Iron, 14, 21, 32, 269, 327
H Iron acetate, 242
Haloacetic acid formation potential Iron chelates, 173
(HAAFP), 58 Iron chloride, 90
Haloacetic acids (HAA), 57, 58, 103, 117, 345, Iron molybdate, 315
347, 355, 366 Iron nitrate, 242
Haloacetonitriles, 117 Iron oxides, 32, 41, 78, 158, 163, 242, 317
Heavy metals, 25, 31, 33, 41, 57, 71, 84, Iron sludge, 136, 217, 224, 225, 311, 313
103, 391 Iron sulfate, 242
Helminths, 25, 173, 260, 272, 274 Iron sulfide, 272
Hematite, 83, 158, 172, 225, 242, 271 Isobutyl isobutyrate, 193
Hepatitis, 260, 276 2-Isobutyl-3-methoxypyrazine (IBMP), 179,
Herbicides, 10, 172, 366, 394 180, 200
cis-3-Hexen-1-ol, 180 Isooctyl alcohol, 193
Hormone disruptors, 27 p-Isopropenylphenol, 393
Hospital wastewater, 143, 161 2-Isopropyl-3-methoxypyrazine (IPMP),
Humic acids, 28, 37, 41, 46, 47, 87, 173, 179–182, 184, 185, 200
186, 374 2-Isopropyl-3-methylpyrazine, 200
Humins, 28, 56 p-Isopropylphenol, 393
Hydrodechlorination, 81 Isoproturon, 142, 145
Hydrodynamic cavitation, 74
Hydrogen peroxide, 58, 60, 76, 123, 138, 214,
266, 317, 392, 412 K
ozonation, 312 Ketones, 59, 74, 125, 195, 266, 348, 370, 410
photolysis, 139 cyclic, 195
Hydrogen sulfide, 32, 88, 180
Hydroperoxyl radicals, 104, 111, 184, 214, 223,
234, 266, 267 L
Hydroquinone, 368 Lakes, 5, 11
Hydrotalcite, 241 Lepidocrocite, 79, 163
p-Hydroxyacetophenone, 393 Lipids, 46, 161, 260, 266, 276, 305
Hydroxy-cyclohexadienyl (HCHD•), 123 peroxidation, 162
Hydroxyl radicals, 60, 76, 140, 265, 302, 310, Logarithmic reduction values (LRV), 25
349, 367, 389
2-Hydroxy-3-methylbutyric acid methyl
ester, 200 M
Hydroxy-4a-methyloctahydronaphthalen-2- Magnetite, 83, 163, 225
one, 195 Maleic acid, 74, 123, 138
Hypobromite, 62, 65, 356 Manganese, 14, 21, 32, 33, 48, 316, 317
Hypobromous acid, 369 Mepanipyrim, 148
Hypochlorite, 14, 117, 264, 355 Mercaptans, 180
Hypochlorous acid, 117, 214 Methane, 32
Index 427

Methicillin-resistant Staphylococcus aureus, 161 O

Methylaminoantipyrine, 148 Odor, 179
2-Methyl-2-bornene, 193 Orange II dye, 222
3-Methylbutanoic acid, 200 Oryzias latipes, 390
Methyl glyoxal, 116, 353 Oxalic acid, 74, 148, 173, 224, 238, 321, 368,
2-Methylisoborneol (2-MIB), 60, 62, 179, 393, 398
180, 186 Oxidation, 111, 259, 345
Methyl isobutyrate, 193 chemical, 183, 213, 257, 348, 366
Methyl methacrylate, 193 electrochemical, 137, 189, 196, 281,
Methyl orange, 78, 79 312, 389
3-Methyl-2-oxobutanoic acid, 200 photocatalytic, 59
3-Methyl-2-oxobutanoic acid methyl sonochemical, 136
ester, 200 Oxidative stress, 257
4-Methyl-2-oxovaleric acid, 200 Oxyhalides, 351, 355
2-Methylpropanoic acid, 200 Oxyhydroxides, 122, 158, 163, 321
Methyl propionate, 193 Ozonation, 58, 86, 112, 135, 144–148, 186,
Metolachlor, 53, 60, 62 195, 265, 281, 309, 318, 348, 392
Microbial contamination, 159 photocatalytic, 139
Microbiological standards, 25 Ozone, 14, 28, 46, 53, 58, 60, 112, 135, 139,
Microorganisms, removal, 42 169, 197, 265, 300, 318, 413
Microplastics, 27
Micropollutants, 21, 24, 31, 42, 55, 74, 85, 135,
136, 297, 390 P
Monochloramine, 264, 300, 348, 372 Paracetamol, 317
Montmorillonite, 80, 88, 124, 321, 325 Parasites, 46, 160, 257, 299
MTBE (Methyl tert-butyl ether), 112 Particle size, 243
Municipal water supply, 1 Pathogens, 2, 10, 24, 73, 155, 161, 259, 298,
Myponga Reservoir, Adelaide, 347, 370
Australia, 126 PCR (polymerase chain reaction), 160
Pentachlorophenol, 143
Pentafluorobenzyl hydroxylamine
N hydrochloride (PFBHA), 126
Natural organic matter (NOM), 28, 53, 69, 1-Penten-3-one, 180
133, 345 Peptides, 102, 364
fractionation, 361 Peroxidase, 260, 316
intermediates, 99 Peroxone, 136, 140
oxidation, 99 Peroxyl radicals, 74, 104, 112, 138, 410
separation, 99 Persistent organic pollutants (POPs), 213
structure/reactivity, 364 Personal care products, 24, 388
Nickel, 321 Persulfate, 172, 188–201, 205
Nitrates, 10, 32, 141 Pesticides, 10, 26, 136, 142
Nitrilotriacetic acid, 173 pH, 157, 225
Nitrite, 141 Pharmaceutical and personal care products
Nitrobenzene, 139 (PPCPs), 143, 230, 349
N-Nitrosodiethylamine (NDEA), 355 Pharmaceuticals, 26, 136
N-Nitrosodimethylamine (NDMA), 355, Pharmaceutical wastewater, 226
359, 369 Phenol, 79, 148, 226, 228
N-Nitrosodiphenylamine (NDPhA), 355 Phosphate, 41, 107, 280
N-Nitrosodi-n-propylamine (NDPA), 355 Photocatalysis, 59, 137, 141, 387
N-Nitrosopyrrolidine (NPYR), 355 heterogeneous, 124, 137, 275, 322
Nonanal, 193 homogenous, 116, 138, 271
Nonanoic acid, 193 Photodegradation, 119
Non-purgeable organic carbon (NPOC), 109 Photo-Fenton, 60, 155, 165, 271
428 Index

Photo-Fenton (cont.) River basin management plans (RBMPs), 16

microorganisms, inactivation, 271 Rivers, 6, 11
solar driven, 165
Photolysis, 31, 47, 58, 65, 76, 117, 139, 187,
200, 377, 397 S
Photosensitizing agent, 119 Safe Drinking Water Act (SDWA), 24
Phytophthora capsici, 272, 273 Salicylic acid, 368
Plastics, 27 Saline water, 2, 5
Polarity rapid assessment method (PRAM), 29 Salmonella typhimurium, 268
Poliovirus, 264 Sand filtration, 13, 27, 33, 42, 47, 72, 103, 181,
Pollutants, concentration, 236 197, 202, 204
removal, 21 Saturation index, SI (Langelier saturation index,
Polyoxometalates, 195 LSI), 30
Polysaccharides, 28 Sedimentation, 5, 34, 36, 42, 43, 72, 203, 204
Potassium permanganate, 183 Sepiolite, 241
Powdered activated carbon (PAC), 44, 45, 72, Singlet oxygen, 104, 111, 121, 136, 184, 196,
181, 375 266, 267, 274
Practical calcium carbonate precipitation Size-exclusion chromatography (SEC), 107,
potential (PCCPP), 31 116, 361
Propanal, 126 Sludge-based catalyst (SBC), 321
Protection, 1 Solar disinfection/treatment, 155, 303, 349
Proteins, 28, 73, 102, 105, 107, 161, 260, 276, photo-Fenton, 160, 163, 165
346, 360 Soluble microbiological products (SMPs), 28
Protozoans, 25, 46, 160, 173, 186, 257–279, Specific ultraviolet absorbance (SUVA), 29, 56,
298 85, 104, 108, 117, 360, 367
Pseudokirchneriella subcapitata, 147, 390 Springs, 5–7, 12
Pseudomonas aeruginosa, 265 Streams, 6, 11
Pseudo-nitzschia delicatissima, 172 Sulfamethoxazole, 146, 167
Pyrite, 225 Sulfanilamide, 80
Sulfate radical anion, 117, 193, 198, 349
Sulfates, 158, 172, 196, 242, 268, 281
Q Sulfonylureas, 394, 398
Quality deterioration, 1 Sunscreens, 366
Quantitative microbial risk assessment Superoxide radical, 104, 111, 121, 136, 184,
(QMRA), 25 200, 266, 269, 275, 302, 322
Superoxygen dismutase (SOD), 162, 260
Surface run-off, 34
R Surface water, 2, 11, 21, 34
Rainbow trout, 390 Fenton/photo-Fenton, 155
REACH, 27 microbial contamination, 159
Reactive chlorine species (RCS), 118, 260 Surfactants, 139
Reactive oxygen species (ROS), 104, 111, Sweep coagulation, 41
119, 162, 260, 267, 277, 302,
304, 389
Recharge, artificial 17 T
Removal, 21, 42, 53, 179 Taguchi methods, 406
Resin fractionation, 362 Tannins, 102
Resorcinol, 364 Tartaric acid, 156, 173, 223, 313, 368
Reversed-phase liquid chromatography Taste, 179
(RP-LC), 107 Taste and odor (T&O) compounds, 179–186,
River bank filtrate, 47 197, 202, 205
Index 429

Tetrachloroethylene, 139, 140 UV-Vis, 56, 61, 79, 88, 104, 108, 121, 193
Tetracycline, 167, 168
Textile effluents/wastewater, 219–226,
234–236 V
Theoretical calcium carbonate precipitation Vacuum ultraviolet (VUV), 46, 57, 140, 312
potential at 90 C (TCCPP90), 31 Vanadium, 321
Thioethers, 202 Vancomycin-resistant Enterococcus spp., 161
Titanium dioxide (TiO2), 137, 275, 302 Vibrio fischeri, 143, 147, 148, 390–399
/ UV, 124 Viruses, 10, 25, 42, 46, 160, 166, 173, 260–282,
Toluene, 224 299, 349
Total organic carbon (TOC), 28, 55, 83, 89, Volatile chlorinated organic carbons (VCOCs),
108, 109, 135, 317, 360, 412, 415 139
Total organic halide (TOX), 354, 364
Toxicity tests, 143, 148, 390, 395
Transpiration, 3 W
Treatment, efficiency evaluations, 389 Wastewater treatment, 211
groundwater, 14 plants (WWTPs), 26, 389
surface water, 13 Water, cycle, 3
S-Triazines, 366, 394 disinfection, 155, 259
Triazole, 42 resistance, 260
Trichloramine, 348 microbiology, 257
Trichloroacetic acid, 351, 356 pollutants, 133
2,4,6-Trichloroanisole (TCA), 179–185, 197 quality, chemical, 25
Trichloroethane, 139, 224 conditioning, 30
Trichloroethylene (TCE), 139, 140, 149 NOM, 28
Trichloronitromethane, 117, 378 resource management/protection, 15
2,4,6-Trichlorophenol (TCP), 200, 352 treatment, 1, 69
Triclosan, 366 conventional, 21
Trihalomethane formation potential Wells, 7, 12
(THMFP), 58, 61 Wet hydrogen peroxide catalytic oxidation
Trihalomethanes (THM), 103, 135, 180, 265, (WHPCO), 214, 317
345–355, 375, 378
2,4,6-Trinitrotoluene, 222
Tryptophan, 115, 361, 364, 366 X
Tyrosol, 229 Xenoestrogens, 390

U Y
Ultrasound, 73, 81, 84, 103, 126, 135, 149, 165, Yeast estrogen screen (YES) assay, 390
196, 221, 312, 314, 318, 320
oxidation, 389
Unregulated Contaminant Monitoring Rule Z
(UCMR), 355 Zebrafish, 143, 390
UV/C2, 116 Zeolites, 15, 69, 77, 88, 92, 189, 195, 214,
UV, disinfection, 46, 47, 53, 59, 124, 262, 231–235, 271, 315–325
348, 374 USY, 241
VUV, 46, 57, 140, 312 Zinc, 30, 314, 320, 328
UV/H2O2, 116 ZnO, 36, 59, 137, 277, 312, 320–329