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Review

Recent developments in photocatalytic water treatment technology: A


review
a,b a,b,c, c c
Meng Nan Chong , Bo Jin *, Christopher W.K. Chow , Chris Saint
a School of Chemical Engineering, The University of Adelaide, 5005 Adelaide, Australia
b School of Earth and Environmental Sciences, The University of Adelaide, Adelaide, South Australia 5005, Australia
cAustralian Water Quality Centre, SA Water Corporation, 5000 Adelaide, South Australia, Australia
article info abstract

Article history: In recent years, semiconductor photocatalytic process has shown a great potential as a low-cost, environmental
Received 21 September 2009 friendly and sustainable treatment technology to align with the zero waste scheme in the water/wastewater
Received in revised form industry. The ability of this advanced oxidation technology has been widely demonstrated to remove persistent
26 February 2010 Accepted 27 organic compounds and microorganisms in water. At present, the main technical barriers that impede its
February 2010 commercialisation remained on the post-recovery of the catalyst particles after water treatment.
Available online 18 March 2010
This paper reviews the recent R&D progresses of engineered-photocatalysts, photo-reactor systems, and
Keywords: the process optimizations and modellings of the photooxidation processes for water treatment. A number of
TiO2 potential and commercial photocatalytic reactor configurations are discussed, in particular the photocatalytic
Photocatalysis membrane reactors. The effects of key photoreactor operation parameters and water quality on the photo-
Water treatment process performances in terms of the mineralization and disinfection are assessed. For the first time, we
Photocatalytic reactors describe how to utilize a multi-variables optimization approach to determine the optimum operation
Kinetic modelling parameters so as to enhance process performance and photooxidation efficiency. Both photomineralization and
Water qualities photo-disinfection kinetics and their modellings associated with the photocatalytic water treatment process are
Life cycle analysis detailed. A brief discussion on the life cycle assessment for retrofitting the photocatalytic technology as an
Mineralization alternative waste treatment process is presented. This paper will deliver a scientific and technical overview
Disinfection and useful information to scientists and engineers who work in this field.

2010 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2998 2.
Fundamentals and mechanism of TiO2 photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2999 2.1. Heterogeneous
TiO2 photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2999 2.2. Homogeneous photo-Fenton
reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3001

* Corresponding author at: School of Earth and Environmental Sciences, The University of Adelaide, Adelaide, South Australia 5005, Australia. Tel.: 61 8 8303
7056; fax: 61 8 8303 6222.
E-mail address: bo.jin@adelaide.edu.au (B. Jin).
0043-1354/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2010.02.039
2998 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7

3. Advancements in photocatalyst immobilization and supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3002 3.1. Challenges in the


development of photocatalytic water treatment process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3002 3.2. Mesoporous
clays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3002 3.3. Nanofibers, nanowires or
nanorods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3003 3.4. Photocatalytic
membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3003 3.5. Photocatalyst modification
and doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3003
4. Photocatalytic reactor configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3005 5. Operational
parameters of the photocatalytic reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3007 5.1. TiO2
loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3008 5.2. pH . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3008 5.3. Temperature . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3009 5.4. Dissolved
oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3010 5.5. Contaminants and their
loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3010 5.6. Light
wavelength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3011 5.7. Light
intensity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3012 5.8. Response surface
analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3012
6. Kinetics and modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3013 6.1.
Photomineralization kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3013 6.2. Photo-
disinfection kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3014
7. Water quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3017 7.1.
Turbidity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3017 7.2. Inorganic
ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3017 7.3. Heavy and noble
metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3019
8. Life cycle assessment of photocatalytic water treatment processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3019 9. Future challenges
and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3020 Acknowledgement . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3021
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3021
1. Introduction reuse is anticipated to offset more
clean water resource. Recy-cling
Increasing demand and shortage wastewaters are usually
of clean water sources due to the associated with the presence of
rapid development of suspended solids, health-threat
industrialisation, population coliforms and soluble refrac-tory
growth and long-term droughts organic compounds that are both
have become an issue worldwide. tedious and expensive to treat
With this growing demand, (Viessman and Hammer, 1998).
various practical strategies and Currently available water
solutions have been adopted to treatment technologies such as
yield more viable water resources. adsorption or coagulation merely
The storage of rainwater for daily concentrate the pollutants present
activities and increasing the by transferring them to other
catchment capacity for phases, but still remain and not
stormwater are just a few being completely eliminated or
examples that could resolve the destroyed (Padmanabhan et al.,
problems in short-term. Water 2006). Other conventional water
industries and governments in treatment methods such as
some arid areas with abundant of sedimentation, filtration, chemical
sunlight, less rainfall and long- and membrane technologies
term drought have a challenge to involve high operating costs and
seek viable water resources. It is could generate toxic secondary
estimated that around 4 billion pollutants into the ecosystem
people worldwide experience to (Gaya and Abdullah, 2008). These
have no or little access to clean concen-trated toxic contaminants
and sanitised water supply, and are highly redundant and have
millions of people died of severe been concerned worldwide due to
waterborne diseases annually the increasing environmental
(Malato et al., 2009). These awareness and legislations.
statistical figures are expected to Chlorination has been the most
grow in the short future, as commonly and widely used
increasing water contamination disinfection process. The disin-
due to overwhelming discharge of fection by-products generated
micropollutants and contami- from chlorination are mutagenic
nants into the natural water cycle and carcinogenic to human health
(Wintgens et al., 2008; (Yang and Cheng, 2007; Lu et al.,
Richardson, 2008; Suarez et al., 2009; Coleman et al., 2005).
2008). In view to suppress the
worsening of clean water
shortage, development of
advanced with low-cost and high These have lead to the rapid
efficiency water treatment R&D in the field of Advanced
technologies to treat the Oxidation Processes (AOPs) as
wastewater is desirable. the innovative water treatment
technologies. The rationales of
these AOPs are based on the in-
situ generation of highly reactive
transitory species (i.e. H2O2, OH ,
One of a few attractive O2 e, O3) for mineralization of
options is the possible reuse of refractory organic compounds,
onsite rural wastewater or the water pathogens and disinfection
treated municipal wastewater by-products (Esplugas et al.,
from treatment plants for 2002; Pera-Titus et al., 2004).
agricultural and industrial Among these AOPs,
activities (Bradley et al., 2002; heterogeneous photocatalysis
Lapena et al., 1995). Since these employing semi-conductor
wastewa-ters constitute one of the catalysts (TiO2, ZnO, Fe2O3,
largest possible water resources, CdS, GaP and ZnS) has
its
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 2999
demonstrated its efficiency in degrading a wide range of ambiguous semiconductor TiO2 catalyst have been intensively reported in many
refractory organics into readily biodegradable compounds, and eventually literatures (Gaya and Abdullah, 2008; Fujishima et al., 2000). The
mineralized them to innocuous carbon dioxide and water. Among the semiconductor TiO2 has been widely utilised as a photocatalyst for
semiconductor catalysts, titanium dioxide (TiO 2) has received the greatest inducing a series of reductive and oxida-tive reactions on its surface. This
interest in R&D of photocatalysis technology. The TiO 2 is the most active is solely contributed by the distinct lone electron characteristic in its outer
photocatalyst under the photon energy of 300 nm < l < 390 nm and orbital. When photon energy (hv) of greater than or equal to the bandgap
remains stable after the repeated catalytic cycles, whereas Cds or GaP are energy of TiO2 is illuminated onto its surface, usually 3.2 eV (anatase) or
degraded along to produce toxic products (Malato et al., 2009). Other than 3.0 eV (rutile), the lone electron will be photoex-cited to the empty
these, the multi-faceted func-tional properties of TiO2 catalyst, such as conduction band in femtoseconds. Fig. 1 depicts the mechanism of the
their chemical and thermal stability or resistance to chemical breakdown electronehole pair formation when the TiO2 particle is irradiated with
and their strong mechanical properties have promoted its wide application adequate hv. The light wavelength for such photon energy usually
in photocatalytic water treatment. corresponds to l < 400 nm. The photonic excitation leaves behind an
empty unfilled valence band, and thus creating the electron-hole pair (e

eh ). The series of chain oxidativeereductive reactions (Eqs. (2.1)e(2.11))
A number of important features for the heterogeneous photocatalysis that occur at the photon activated surface was widely postulated as
have extended their feasible applications in water treatment, such as; (1) follows:
ambient operating temperature and pressure, (2) complete mineralization
of parents and their intermediate compounds without secondary pollution
and (3) low operating costs. The fact that the highly reactive oxygen
species (ROS) generated as a result of the photo-induced charge
(2.1)
separation on TiO2 surfaces for microbial inactivation and organic Photoexcitation: TiO2 hv / e h
mineralization without creating any secondary pollution is well- (2.2)
Charge-carrier trapping of e : e CB / e TR
documented. So far, the application of such TiO 2 catalysts for water
treatment is still experiencing a series of technical challenges. The post-
(2.3)
separation of the semi-conductor TiO2 catalyst after water treatment Charge-carrier trapping of h: h VB /h TR
remains as the major obstacle towards the practicality as an industrial
process. The fine particle size of the TiO 2, together with their large
surface area-to-volume ratio and surface energy creates a strong tendency Electron-hole recombination: e TR h VB(h TR)

for catalyst agglomeration during the operation. Such particles


agglomeration is highly detrimental in views of particles size (2.4)
/ e CB heat
preservation, surface-area reduction and its reusable lifespan. Other
technical challenges include in the catalysts development with broader Photoexcited e scavenging: (O2)ads e / O2 (2.5)
photoactivity range and its integration with feasible photocatalytic reactor
system. In addition, the understanding of the theory behind the common
(2.6)
reactor operational parameters and their inter-actions is also inadequate Oxidation of hydroxyls: OH h / OH
and presents a difficult task for process optimization. A number of
commonly made mistakes in studying kinetic modelling on either the
photo-mineralization or photo-disinfection have also been seen over the Photodegradation by OH : ReH OH / R0 H2O (2.7)
years.

This review paper aims to give an overview of the under-standing and


development of photocatalytic water treatment technology, from
fundamentals of catalyst and photoreactor development, to process
optimization and kinetics modelling, and eventually the water parameters
that affects the process efficiency. A short outlines of the feasible
application of pho-tocatalytic water technology via life cycle
interpretation and the possible future challenges are also recommended.
2. Fundamentals and mechanism of TiO2 photocatalysis

2.1. Heterogeneous TiO2 photocatalysis


Fig. 1 e Photo-induced formation mechanism of
The fundamentals of photophysics and photochemistry electronehole pair in a semiconductor TiO2 particle with
underlying the heterogeneous photocatalysis employing the the presence of water pollutant (P).
3000 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
formic acid) can be mineralized surface contact with the catalyst
by direct elec-trochemical during the photocatalytic
oxidation where the e TR is degradation. If the mass transfer
Direct photoholes: R h / R / expression. For heterogeneous
scavenged by metals ions in the steps are rate limiting, a change in
Intermediate(s)/Final photocatalysis, the liquid phase
Degradation Products system without water presents the aera-tion or liquid flow
organic compounds are degraded
(Byrne and Eggins, 1998).
Protonation of superoxides: O2 OH to its corresponding intermediates conditions past the TiO2

Although the h TR has been photocatalyst may alter the overall
and further mineralized to carbon
widely regarded for its ability to photocatalytic reaction rate.
dioxide and water, if the
oxidize organic species directly,
Co-scavenging of e : HOO e / HO this possibility is remained irradiation time is extended (Eq.
(2.12)).
inconclusive. The h TR are
powerful oxidants (1.0 to 3.5 V TiO2
=hv Similarly, the surface
Formation of H2O2: HOO H / H2O
against NHE), while e TR are Organic Contaminants interaction of microorganisms
good redundant (0.5 to 1.5 V /Intermediates/CO2 H2O with the catalyst used during the
against NHE), depending on the (2.12) photo-disinfection is essential for

type of catalysts and oxidation
The e TR and h TR in (Eq. conditions. The overall photocatalysis
(2.4)) represent the surface trap- reaction as portrayed by (Eq.
ped valence band electron and (2.12)) can be divided into five
conduction-band hole independent steps, which are
respectively. It was reported that shown in Fig. 2 (Herrmann, 1999;
these trapped carriers are usually Fogler, 1999):
TiO2 surface bounded and do not
recombine imme-diately after 1. Mass transfer of the organic
photon excitation (Furube et al., Many elementary mechanistic contaminant(s) (e.g. A) in the
2001). In the absence of electron studies on different surro-gate liquid phase to the TiO2
scavengers (Eq. (2.4)), the organic compounds (e.g. phenol, surface.
photoexcited electron recombines chlorophenol, oxalic acid) have 2. Adsorption of the organic
with the valence band hole in been extensively investigated in contaminant(s) onto the photon
nanosec-onds with simultaneous
the photo-degradation over TiO2 activated TiO2 surface (i.e.
dissipation of heat energy. Thus,
surface. Aromatic compounds can surface activation by photon
the presence of electron energy occurs simultaneously
be hydroxylated by the reactive
scavengers is vital for prolonging in this step).
OH radical that leads to
the recombination and successful 3. Photocatalysis reaction for the
functioning of photocatalysis. successive oxidation/addition and Fig. 2 e Steps in heterogeneous
eventually ring opening. The adsorbed phase on the TiO2
(Eq. (2.5)) depicts how the catalytic reaction (Fogler,
resulting intermediates, mostly surface (e.g. A / B).
presence of oxygen in prevents 4. Desorption of the 1999).
the recombination of aldehydes and carboxylic acids
intermediate(s) (e.g. B) from
electronehole pair, while allowing will be further carboxylated to
the TiO2 surface.
the formation of superoxides produce innocuous carbon dioxide
radical (O2 ). This O2 radical can and water. Since the
photocatalysis reaction occurs on 5. Mass transfer of the
be further protonated to form the
the photon activated surface of intermediate(s) (e.g. B) from
hydroperoxyl radical (HO2 ) and the interface region to the bulk
TiO2, the under-standing of the
subsequently H2O2 as shown in fluid.
reaction steps that involves
(Eqs. (2.9) and (2.10)),
photodegradation of organics is
respectively. The HO2 radical essential in the formulation of In terms of rate determination,
formed was also reported to have kinetic the overall rate of reac-tion is
scavenging property and thus, the equal to the slowest step. When
co-existence of these radical the mass transfer steps (1 and 5)
species can doubly prolong the are very fast compared with the

recombination time of the h TR in reaction steps (2, 3 and 4), the
the entire photocatalysis reaction. organic concentrations in the
However it should be noted that imme-diate vicinity of the active
all these occurrences in sites are indistinguishable from
photocatalysis were attributed to those in the bulk liquid phase. In
the presence of both dissolved
this scene, the mass transfer steps
oxygen (DO) and water
are not rate limiting and do not
molecules. Without the presence
of water mole-cules, the highly affect the overall rate of
reactive hydroxyl radicals (OH ) photocatalytic reaction.
could not be formed and impede Vinodgopal and Kamat (1992)
the photodegradation of liquid reported the dependence of the
phase organics. This was photo-degradation rate of the
evidenced from a few reports that organic surrogate on surface
the photocatalysis reaction did not coverage of the photocatalysts
proceed in the absence of water used. This outlines the importance
molecules. Some simple organic of molecules adsorption or
compounds (e.g. oxalate and
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3001
compounds in highly saline is owing to the fact that at such
enhancing the inactivation rate. conditions (Neyens and Baeyens, 2 3 low pH 2.8, the precipitation does
Fe (aq) H2O2 / Fe (aq) OH HO
When the generated ROS contacts 2003; Bacardit et al., 2007; not take place and further
2
Machulek et al., 2007). Numerous The Fe can be reverted back to
promotes theFe presence of
closely with the microorganisms,
studies on the photo-Fenton mechanisms: dominant iron species of
the cell wall will be the initial site
degradation of water pollutants 3 2 2
of attacked (Maness et al., 1999). Fe (aq) H2O2 / Fe [Fe(OH)] in water. Such a low
(aq) HO2
such as chlor-ophenol (Pera-Titus optimum pH 2.8, however, is not
The lipo-polysaccharide layer of
et al., 2004), pesticides (Fallmann cost effective for opera-tion as it
the cell external wall is the initial
et al., 1999; Huston and requires high chemical costs for
site attacked by the photo-induced 3 2
Pignatello, 1999) and phenolic or Fe (aq) HO2 / Fe (aq) O2 H pH rectification. The presence of
ROS. This is followed by the site
aromatic compounds with organic different ions such as carbonate
attack on the peptidoglycan layer, 1
loading of up to 25 g L have 2 3
peroxidation of the lipid (CO 3 ), phosphate (PO 4 ),
membrane and the eventual been investigated (Gernjak et al., 2
When a light source is sulphate (SO 4 ) and chlorine
oxidation on the proteins 2004, 2007). A number of litera-
present, the rate of photo-Fenton (Cl ) also affects the iron
tures (Neyens and Baeyens, 2003;
membrane. All these will cause a was reported to be positively equilibrium in water. These ions
Pignatello et al., 2006; Gogate
rapid leakage of potassium ions enhanced compared to the dark have the potential to raise the
and Pandit, 2004) have provided a
from the bacterial cells, resulting condition. This is mainly due to water pH and effectively lowered
comprehensive reviewof the basic 2
in direct reduction of cell the regeneration of Fe (aq) from the photo-Fenton reaction rate.
understanding and clarity of the 2 3
viability. The decrease in cell the photochemical effect of light Both CO 3 and PO 4 have a
principles underlying the Fenton
viability is usually linked to the and the concurrent generation of double detrimental effect on the
reaction.
peroxidation of polyunsaturated the OH radicals in the system. reaction, as they precipitate the
phospholipid compo-nents of the 2
Such a reversion cycle of Fe iron and as well as scav-enges the
cell membrane (i.e. loss of (aq) / Fe
3
(aq) / Fe
2
(aq) OH radicals. A higher pH of
essential cell func-tions) and In the absence of a light continuously generates OH , 4.0e5.0 was determined to be
eventually leads to cell death. The provided that the concentration of sufficient to sustain the photo-
source, hydrogen peroxide (H2O2)
formation of oxidative stress and Fenton reaction with 2e6 mM of
2
will decompose by Fe ions that H2O2 in the system is substantial.
its effects on the cell membrane 2
iron for the initiation of the
present in the aqueous phase, The regeneration of the Fe (aq) treatment (Gernjak et al., 2007).
can be observed using advanced
resulting in the formation of 3
from Fe (aq) is the rate-limiting To date, the maximal iron loading
atomic force microscopy or atten-
hydroxyl radicals. The photo- step in the catalytic iron cycle, if 1
uated total reflection Fourier reported was 450 mg L
Fenton reaction is expedited when small amount of iron is present.
transform infrared spectros-copy. light source present, causing rapid (Oliveros et al., 1997; Torrades et
The rate of adsorption and the This photoassisted reaction is
al., 2003).
H2O2 decomposition by ferrous or termed as photo-Fenton reaction,
eventual photo-inactivation is
ferric ions and resulting in the where such reaction could be
known to positively correlate to
formation of radicals. All these activated by irradiation
the bacteri-cidal effect of TiO2 soluble iron-hydroxy or iron wavelengths of up to 600 nm. It
catalyst. In this instance, the complexes can absorb not only was known that this reaction is Although H2O2 may be
transfer of bacterial cell to the UV radiation but also visible better functional under longer generated via the TiO2 photo-
close vicinity of the surface light. However, the actual wavelengths as they are able to catalysis (Eq. (2.11)), its relative
generated ROS site remains as the oxidizing species responsible for overcome the inner filter effects amount in the system may be
the photo-Fenton reaction is still by photolysing the ferric iron inadequate to drive the Fenton
rate-limiting step in the photo-
under discussion (Pignatello et al., complexes. The inner filter effects reaction. Many researchers have
disinfection reaction.
1999). These Fenton and photo- referred to the competitive reported the addition of H2O2 in
Fenton reaction could occur adsorption if photons by other enhancing both the photo-Fenton
simultaneously with TiO2 light absorbing species in the and TiO2 photocatalysis reactions.
photocatalysis during UVeVis water. The H2O2 can inhibit the
recombination of electronehole
irradiation period, post TiO2
pair, while further provides
photocatalysis period or stand- additional OH radicals through
2.2. Homogeneous alone photo-Fenton process. The the following mechanisms:
photo-Fenton Fenton reaction is seen to strongly Even if the photo-Fenton has
reaction higher photoactivity than the
correlate with the post TiO2
photocatalysis reaction and thus, heterogeneous photocatalysis, its
The Fenton reaction is a process is described in detail here. The feasible operation is largely
that does not involve any light mechanism for the Fenton dependent on several water
irradiation as compared with the reaction is shown in (Eq. (2.13)): quality parameters. In the photo-
heterogeneous TiO2 Fenton reaction, the formation of
photocatalysis reaction, whereas the highly photoactive iron
the photo-Fenton does react up to complexes is highly dependent on
a light wavelength of 600 nm. It the water pH and ions content (De
was first recognised in the 1960s Laat et al., 2004). It was reported
and remains one of the most that the pH 2.8 was the frequent
applied AOPs for its ability to optimum pH for photo-Fenton
degrade high loading of organic reaction (Pignatello, 1992). This
3002 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
immobilizatio 2009). Several important
n and supports operating issues with slurry TiO2
H2O2 e / HO HO 3.1. Challenges in the still remain even with a
Since the discovery of development of membrane integration process.
O2 H2O2 / O2 HO HO photocatalytic effect on water photocatalytic water These include the types of
splitting by Fujishima and Honda treatment process membrane, pore size and
(1972) using TiO2 electrode, blockage, regeneration or back-
This combined TiO2 numerous researches have To date, the most widely applied washing and fouling (Lee et al.,
photocatalysis e photo-dark- evolved to synthesis TiO2 catalyst photocatalyst in the research of 2001; Molinari et al., 2002; Xi
Fenton reaction is particularly of different scale, characterise its water treatment is the Degussa P- and Geissen, 2001). A number of
useful for the disinfection process physical properties and determine studies have utilised microns size
25 TiO2 catalyst. This catalyst is
(Domnguez et al., 1998; Maruga its photooxidation performances immobilizers for catalyst fixation
used as a standard reference for
n et al., 2006, 2007). The to the surface-oriented nature of that enhance surface contact with
comparisons of photoactivity
addition of H2O2 to the photocatalysis reaction (Fujishima contami-nants and prevented the
under different treatment
and Honda, 1972; Kondo et al.,
photocatalysis e and dark-Fenton conditions (Serpone et al., 1996). membrane fouling or pores
2008; Hosono et al., 2004; Joo et
system results in a residual The fine particles of the Degussa blocking with rapid back-washing
al., 2005; Wang et al., 1999). The
disinfection to avoid microbial (Xi and Geissen, 2001; Zhang et
TiO2 catalyst in nano-dimensions P-25 TiO2 have always been
regrowth. Rincon and Pulgarin al., 2009). These immobilisers
allows having a large surface applied in a slurry form. This is
(2006) performed trials with TiO2 usually associ-ated with a high include catalyst fixation onto
area-to-volume ratio and can
photocatalysis and photo-Fenton volumetric generation rate of ROS activated carbon (Lee et al.,
further promote the efficient
reaction for the disinfection of as proportional to the amount of 2004), mesoporous clays (Chong
charge separation and trapping at
water contaminated with the physical surface (Nagaveni et et al., 2009a), fibers (Zhu et al.,
surface active sites when the TiO2
Escherichia coli. They found that al., 2004a,b). The light 2004) or even onto the membrane
catalyst in suspension (Pozzo et
the bacterial inactivation rate was itself (Kwak and Kim, 2001). The
opaqueness of this nanoscale TiO2 al., 1997). On the contrary, the
higher than the photocatalysis following subsections outline a
catalysts was reported to have an fixation of catalysts into a large
alone and the decrease in bacterial few catalyst immobilization
enhanced oxidation capability inert substrate reduces the amount
number continued in the dark
compared to the bulk TiO2 of catalyst active sites and also strategies that are suitable for the
condi-tions without significant
catalysts (Siddiquey et al., 2008). enlarges the mass transfer use of slurry reactor or membrane
regrowth within the following 60
limitations. Immobilization of the reactor or both.
h. However, it was found that Although the nanoscale TiO2
such residual disinfection effect catalysts results in increasing the
catalysts show considerable
was highly dependent on the light operation difficulty as the photon
improvement in terms of their
intensity used during the irradi- penetration might not reach every
physical and chemical properties,
ation period, as well as the their particle size and morphology single surface site for photonic
3 remains the main problem in a activation (Pozzo et al., 1997).
relative concentrations of Fe
large-scale water treatment Thus, the slurry type of TiO 2
and H2O2. Further addition of process (Byrne et al., 1998b; Yu et catalyst application is usually 3.2. Mesoporous clays
H2O2 was found to decrease the al., 2002). In this section, the preferred.
overall reaction rate in several current technical challenges that
prevent the application of slurry Natural clays have been used
studies, owing to the formation of
intensively as the support for TiO 2
less penetrative HO2 radicals, as TiO2 photocatalytic system are With the slurry TiO2 system, owing to their high adsorption
described by (Eq. (2.18)): discussed together with the an additional process step would capacity and cost-effectiveness.
possible engineering solutions to need to be entailed for post- Fig. 3 shows the TiO2 crystal
resolve the problem. We will have
separation of the catalysts. This being deposited on a clay material
a brief discussion on the modified
separation process is crucial to (Chong et al., 2009a). Different
TiO2 catalyst with dopants for avoid the loss of catalyst particles types of clays have been
HO H2O2 / HO2 H2O enhanced photo-activity under and introduction of the new investigated, which includes
solar irradiation. bentonite (Sun et al., 2002),
pollutant of contami-nation of
Other combined process of sepiolite (Xie et al., 2009),
TiO2 in the treated water (Yang
photo-Fenton and oxidative montmorillonite (Kun et al.,
and Li, 2007b). The catalyst 2006), zeolite (Fukahori et al.,
processes have also been
recovery can be achieved through 2003) and kaolinite (Chong et al.,
proposed in the literature, such as
process hybrid-ization with
ozone (Beltran-Heredia et al., 2009a). Although these
conventional sedimentation
2001) and ultrasound (Torres et clays are catalytically
al., 2008). However, their (Fernandez-Ibanez et al.,
significance as compared to the 2003), cross-flow filtration (Doll inactive, their superior
TiO2/photo-Fenton will not be
and Frimmel, 2005) or various adsorption capacity has
membrane filtrations (Choo et al.,
discussed in detail. been
2001; Zhao et al., 2002; Zhang et
al., 2008a). Coupled with the pH
control strategy close to the
isoelectric point for induced
3. coagulation, it was reported the
Advancement microfiltration (MF)
s in hybridization can recover the
photocatalyst remaining 3% of the catalyst
particles for reuse (Malato et al.,
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3003
photocatalytic reactions take place membranes (Bosc et al., 2005;
in a reactor where the 3.3. Nanofibers, Zhang et al., 2006a,b; Choi et al.,
hydrodynamics may be strongly nanowires or 2005, 2007), TiO2 supported on
affected and consequently leading nanorods polymer and metallic membranes
to the loss of photoactivity. Other (Kim et al., 2003; Bellobono et
factors that might need to be taken Glass, optical, carbon, titanate and al., 2005a,b) or doted polymer
into a consideration if pillared woven cloths fibers have also membranes containing TiO2
clays are used as the immobilizer been studied as support materials particles entrapped within the
substrate include the density of membrane structure during the
in the photooxidation of various
the clays, particle size distribution membrane fabri-cation process
organic contaminants for water
range and the complementary (Artale et al., 2001; Kleine et al.,
purification (Pozzo et al., 1997).
photoreactor system used. The use 2002; Molinari et al., 2004). Also,
Most of these fibers have a
of mesoporous clays as the the possible TiO2 organic and
protruded rod-shape or
support for nano-size TiO2 have inorganic ceramic membranes
longitudinal morphology. Using
been successfully demonstrated in have been investigated (Kwak and
the nanofibers, nanowires or Kim, 2001; Kim et al., 2003; Yang
a number of studies, including the
nanorods, mass transfer limitation and Wang, 2006). Fig. 4 shows
slurry or membrane processes
can be resolved by their thin different types of PMs for water
(Chong et al., 2009b; Sun et al.,
longitudinal morphology. The use treatment application (Zhang et
2004).
of less durable immo-bilizer al., 2008b; Albu et al., 2007). In
fibers (e.g. of glass or woven most studies, however, PMs may
cloths) however, may lead to a encounter various technical
problems such as membrane
low durability as the deposited
structure deterioration, low
anatase crystals might wear-off, photocatalytic activity and loss of
resulting in a loss of photoactivity
deposited TiO2 layer over time. To
over reaction time. Such
prevent the problems associated
immobilizer fibers also increase
with the TiO2 membrane coating,
pressure drop in the reactor
an approach of using membranes
system. On the contrary, a good
without any deposited TiO2 layer
benefit of nano-fibers with
can be configured into a slurry-
commercial success is that they
membrane hybrid system, which
can be fabricated into MF, will be outlined in Section 4.
ultrafiltration (UF) and
photocatalytic membranes (PMs).
The MF fibers membrane is of
Fig. 3 e Nanocrystal of TiO2 particular interest as it shows high
deposited on clay materials by
pollutant removal rate at low
SEM imaging. (a) 10 mm
transmembrane pressure (<300 3.5. Photocatalyst
resolution; (b) 3 mm resolution.
kPa). A commercial success of modification and
such fabricated MF and UF doping
membranes has been
attractive for increasing the demonstrated by Zhang and co- As TiO2 photocatalytic reactions
surface contact during photo- workers (Zhang et al., 2008a,b). take place under ambient
catalysis reaction. It was proposed Further details on the fabricated operating conditions,
that the natural clays should not nanofibers or nanowires MF photoactivity is usually
be used directly to immobilise membranes can be obtained in the constrained by the narrow
TiO2. This is owing to the literatures. wavelength spectrum for photonic
presence of different surface or activation of catalysts. The
lattice-bounded impurities that higher-end of UV spectrum
might diffuse and further affects required for cata-lysts activation
is usually accompanied by high
the TiO2 efficiency of the
3.4. Photocatalytic operating costs. One attractive
immobilised layer (Chong et al.,
membrane option is to utilize the vast
2009a). In addition, if these
abundance of outdoor solar
impurities are not removed, the
Recently the use of the PMs has irradiation for catalyst activation
polar molecules in the aqueous
been targeted owing to the in a suitably
environment might initiate an
photocatalytic reaction can take
internal reaction within the clay
place on the membrane surface
structure that result in clay
and the treated water could be
swelling (Chong et al., 2009a).
continuously dis-charged without
The swelling will be profound in the loss of photocatalyst particles.
certain type of clays, where Van The PMs can be prepared from
der Waals forces held the entire different materials and synthesis
clay in a turbostatic array. This is methods. These include the
undesirable, particularly if the TiO2/Al2O3 composite
3004 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7

Fig. 4 e (a) FESEM images of the TiO2 nanowire membrane (Zhang et al., 2008b); (b) SEM images of TiO2 nanotube layer formed free-standing
membrane (Albu et al., 2007).
designed photoreactor system. To recombination of electronehole
broaden the photoresponse of pairs. Recent studies shown that
TiO2 catalyst for solar spectrum, modified TiO2 catalysts have an
various material engi-neering enhanced photoactivity under
solutions have been devised, solar irradiation (Li et al., 2006;
including composite Ishibai et al., 2008; Shaban and
photocatalysts with carbon Khan, 2008). CNTs coupling with
nanotubes (Yu et al., 2005), dyed TiO2 have shown poten-tial
sensitizers (Vinodgopal et al., prolongation of electronehole
1996), noble metals or metal ions pairs by capturing the elec-tron
incorporation (Ni et al., 2007), within their structure (Yu et al.,
transition metals (Litter, 1999) 2005). As for dye sensitized
and non-metals doping (Fujishima coupling, the excited dye
et al., 2008). molecules under solar
illumination can provide
The rationale in utilizing these additional electrons to the CB for
material engineering strat-egies is enhancing the formation of
to balance both the half-reaction electronehole pairs (Fig. 5a)
rates of the photo-catalytic (Vinodgopal et al., 1996). Dyes
reaction by adding electron such as Methylene Blue, Azure,
acceptor, or modifying the Erythosin, Rhoda-min and Crystal
catalyst structure and Violet have been widely
composition. Fig. 5 presents the functionalised under solar
irradiation (Vinodgopal et al.,
use of different mechanisms to
1996).
enhance the photoactivity of the
catalysts. The presence of electron
Similarly, noble metals (e.g.
acceptors could scavenge the Ag, Ni, Cu, Pt, Rh, and Pd) with
excited electrons and altogether Fermi level lower than TiO2
prevent the catalyst have also been
deposited
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3005
dopants (e.g. N, C, F, S and etc.) slurry photocatalytic reactor was
can improve the photoactivity and photocatalyst immobilised onto still the preferred configuration
feasibility of TiO2 catalysts for continuous inert carrier (Pozzo et owing to its high total surface area
industrial application (Fujishima al., 2000). Various types of of photocatalyst per unit volume
et al., 2008). Further research reactors have been used in the and ease of photocatalysts
efforts may be needed to get a reactivation. The photocatalyst
photocatalytic water treatment,
better understanding of the photo- particles can be separated by
including the annular slurry
activity kinetics, so as to improve
photoreactor (Chong et al., settling tanks or external cross-
the photooxidation effi-ciency for
2009b), cascade photo-reactor flow filtration system to enable
water treatment.
(Chan et al., 2003), downflow continuous operation of the slurry
contactor reactor (Ochuma et al., reactor. A techni-cally promising
2007) and, etc. The disparity solution for solving the
between these two main downstream separa-tion of
configurations is that the first one photocatalyst particles after
requires an additional downstream treatment is via the application of
separation unit for the recovery of hybrid photocatalysisemembrane
4. Photocatalytic photocatalyst particles while the processes. Application of such a
reactor latter permits a continuous hybrid system prevents the use of
configuration operation. a coagulation, flocculation or
sedimentation to separate the
Photocatalytic reactors for water catalyst particles from the treated
treatment can generally be Pareek et al. (2008) addressed water stream. Other bene-fits
classified into two main that the most important factors in include further energy saving and
configurations, depending on the configuring a photocatalytic size of process instal-lation and
deployed state of the reactor are the total irradiated site area required.
Fig. 5 e (a) Steps of photocatalysts: (1) reactors with surface area of catalyst per unit
excitation with a sensitizer in sus-pended photocatalyst particles volume and light distribution
the presence of an adsorbed and (2) reactors with within the reactor. Slurry-type
organic electron acceptor
(EA); photocatalytic reactor usually
performs a high total surface area
(b) Scheme of TiO2 band
structures, chemically ion-doped of photo-catalyst per unit volume,
while the fixed-bed configuration The hybrid
TiO2 and physically ion-
is often associated with mass photocatalyticemembrane reactor
implanted TiO2; (c) Electron
transfer limitation over the system is generally known as the
capture by a metal in contact
immobilised layer of photocatalytic membrane
with a semiconductor surface
(Malato et al., 2009). photocatalysts. The light photon reactors (PMRs). This is owing
distri-bution through either direct to the nature of the hybrid system
or diffuse paths within the where the membrane filtration
unit could be configured into
reactors needs to be decided
on the TiO2 surface for enhanced different positioning with the
(Cassano and Alfano, 2000).
charge separation (Fig. 5b) (Ni et photocatalytic reactor. Fu et al.
Direct photon utilization means
al., 2007). These metals were (2006) designed a submerged
that the photocatalysts are directly
reported to enhance elec-tron membrane reactor (Fig. 6) with
transfer, but require good acti-vated with light photon,
two different reaction zones; UV
knowledge on the optimal rather with the assistance of
various parabolic light deflectors slurry TiO2 zone with a movable
deposited amount needed during
the fabrication process. Although to transfer the photons. To achieve baffle that separates the
noble metals coupling could be uniformity in photon flux submerged membrane module.
efficient in pro-longing the These PMRs can be generalised
distribution within the reactor, a
surface charge separation, their by (1) irradiation of the
correct position of light source is
cost-effectiveness for an industrial membrane module and (2)
essential to ensure maximal and
application is usually replaced by irradiation of a feed tank con-
symmetrical light transmission
more economical transition or taining photocatalyst in
and distribu-tion. The use of
non-metals doping. The suspension (Molinari et al., 2001,
mechanism of such transition and photo-reactors with assisted
2002). For the former
non-metals doping, however, is parabolic light deflectors
configuration, the photocatalyst
different from the noble metals nowadays has become could be either deposited onto the
coupling as the TiO2 is unfavourable, owing to the need membrane or suspended in the
of special configuration and high reaction water. The PMRs allow a
incorporated into the TiO2 crystal
operating costs. This type of continuous operation of the
lattice (Asahi et al., 2001; Irie et
al., 2003; Ihara et al., 2003). Such reactor needs to be specifically
incorporation introduces impurity designed to ensure the maximal
illuminated reactor volume with
in the bandgap of TiO 2 and thus,
reduces the photonic energy minimal pressure requirement for
requirements (Fig. 5c). More good catalyst mixing and
recently, the use of non-metal dispersion. Until recently, the
3006 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7

Fig. 6 e Schematic of submerged membrane photocatalytic reactor (Fu et al., 2006).


photocatalysts in suspension is a physical process where
appears to be the more promising usually a selective organophilic
slurry-type reactor without any arrangement. This PMR chlorophenol (Ryu et al., 2005), membrane was used to act as a
loss of photocatalyst particles as configuration has been well grey water (Rivero et al., 2006), selective barrier for the molecules
well as to control the water described in the literature for para-chlorobenzoate (Huang et to be degraded. Augugliaro et al.
residence time independently. water phase degradation of humic al., 2007), river water (Meng et (2006) observed that a
This enables the treated water to (Sun et al., 2004; Ryu et al., 2005; al., 2005) and dyes (Molinari et
Jung et al., 2007; Tsarenko et al.,
synergistic effect occurs
achieve the predefined level al., 2002, 2004; Ryu et al., 2005;
before being filtered through the 2006) and fulvic acids (Fu et al., Sopajaree et al., 1999a,b). when pervaporation was
hybrid membrane system. In the 2006), bisphenol A (Chin et al., With these PMRs, one of the used, where the
PMRs with immobilised PMs, the 2006), phenol (Molinari et al., main operational issues is the intermediates from the
membrane module functionalised 2002), 4-nitrophenol (Molinari et transmembrane pressure, which
al., 2001), 4- determines both the filtra-tion rate degradation of 4-chlor-
as the support for the
photocatalyst particles and barrier and operating costs. It was known ophenol (i.e.
that the PMR treatment costs
against the different organic
increase if the photocatalysts with
hydroquinone,
molecules in the reaction water.
small particle and colloidal size benzoquinone) could be
Similarly, the membrane also acts
are used. With both the MF and
as a phys-ical barrier against the
UF membrane filtration, the fine
photocatalyst particles and photocatalyst particles can cause
organic molecules or intermediate membrane fouling and
compounds to be degraded in the subsequently reducemembrane
slurry PMRs. permeate flux. Fu et al. (2006)
utilised a spherical ball-shaped
TiO2 particles that promotes
In the PMRs with separation, recovery and reused
immobilised photocatalysts, the while prolonging the membrane
photo-catalytic reaction takes lifespan as the particles do not
place on the surface of the cause pore blockage. Besides, the
membrane or within its pores. The surface charge proper-ties of the
PMs used may be of MF (Ryu et photocatalyst particles can also be
al., 2005; Meng et al., 2005; manipulated to prevent membrane
Rivero et al., 2006; Jung et al., pore blockage. Xi and Geissen
(2001) integrated a thermoplastic
2007; Chin et al., 2007; Huang et
membrane module of cross-flow
al., 2007), UF (Molinari et al.,
MF and found that the low
2002; Tsarenko et al., 2006; Sun
permeate flux occurred when the
et al., 2004; Sopajaree et al.,
operating pH varied from the
1999a, b) and nanofiltration (NF)
isoelectric point of the TiO2
(Molinari et al., 2001, 2002, 2004,
particles used. This is owing to
2006; Augugliaro et al., 2005),
the pH induced coagu-
depending on the targeted
lationeflocculation state of TiO2
colloidal size and final water
that declines the rate of permeate
quality requirement. The MF
flux. This was resolved by
membrane is useful when the
maintaining the oper-ating pH
colloidal size is in the range of
close to the isoelectric point of
0.1e5 mm, while both UF and NF
TiO2 by adding certain
target a smaller particle size
ranges. The photooxidation electrolytes to the TiO2 slurry.
efficiency of the contaminants Even with such control strate-
was reported to be higher when an gies, the quality of permeate is
immobilised PM was used, rather low owing to the rapid pene-
tration of small molecules through
than in the case of PMRs with
the membrane used.
suspended catalyst particles
(Molinari et al., 2004). It was,
however, reported that
immobilising the photocatalyst
particles might cause severe
Recently, different
destruction to the membrane
hybridization of PMRs with
structure owing to their close
dialysis (Azrague et al., 2006),
contact with both UV light and
pervaporation (Camera-Roda and
hydroxyl radicals (Chin et al.,
Santarelli, 2007) and direct
2006). In view of this, the
contact membrane distillation
hybridization configuration of the
(MD) (Mozia et al., 2009) have
membrane process using
been used (Fig. 7). Pervaporation
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3007

Fig. 7 e Schematic diagram of the apparatus for hybrid photocatalysiseMD process: (1) membrane module; (2) distillate tank;
3
(3) feed tank (V [ 2.9 dm ); (4) pump; (5) and (6) heat exchangers; (7) manometers; (8) UV lamp; TFin, TDin, TFout, TDout e inlet and outlet temperatures
of feed and distillate, respectively (Mozia et al., 2009).
removal of 32 pharmaceuti-cals,
endocrine disrupting compounds
and estrogenic
selectively permeable without activity from water. They found
competing with 4-chlor-ophenol that 29 targeted compounds and
for photocatalytic reaction. Other estrogenic activity of greater than
70% were removed while only 3
types of organo-philic membrane
compounds were less than 50%
have also been investigated, such removed at the highest number of
as polymeric UF membranes and TM
UV passes. In the Photo-Cat
polyethersulfonate NF system, the water stream passes
membranes (Bae and Tak, 2005; through a pre-filter bag and a
Lee et al., 2008). A stronger cartridge filter before being mixed
rejection impact on the membrane with a nanoparticle TiO2 slurry
is usually associated with the use stream. The mixed stream then
of the UF or NF membranes. The passes through the reactor within
choice of membrane for an the 3 mm annulus of the 32 UV
efficient hybridization depends on lamps aligned in series, which can
be individually controlled for the
the organic molec-ular size, pH or
varying water quality. The overall
electrostatic interaction and hydraulic residence time for the
Donnan exclusion phenomenon 32 UV passes between 1 and 32 s,
(Meares, 1986). depending on the number of UV
lights being turned on. A cross-
The MD is a process where flow ceramic membrane TiO2
the feed volatile components in recovery unit is hybridized
water are evaporated through a downstream of the reactor to
porous hydrophobic membrane to remove the TiO2 from the flow
produce high quality distillate stream, while allowing the treated
products (Mozia et al., 2009). Its water to exit. The retentate TiO 2
main advantage is that there is no stream is recycled and remixed
membrane fouling when TiO2 is with the fresh TiO2 slurry stream
present. During the process, the that enters the reactor stream.
volatile stream is maintained
inside the membrane pores. The
difference in vapour pressure on
both sides of the porous
membrane remains as a driving
force for the process. This force, 5.
however, largely depends on the Operational
temperatures and solution parameters
composition in the layer adjacent of the
to the membrane (Tomaszewska photocatalyt
et al., 1998; Gryta et al., 2001). It ic reactor
was reported that the feeding
temperature in MD can range After the integration of the
from 303 to 363 K. Similar semiconductor catalyst with a
scaling-up operational constraints photoreactor, the oxidation rates
of low permeate flux and high and efficiency of the pho-
energy demand have redundant its tocatalytic system are highly
current full-scale development. dependent on a number of the
However, some efforts to utilize operation parameters that govern
alternative energy source such as the kinetics of photo-
solar energy to enable MD mineralization and photo-
application was found in the disinfection. This section will
literature (Lawson and Lloyd, discuss the significance of each
1997; Bouguecha et al., 2005). operation parameters on the
corresponding kinetics and some
recent methods to optimize the
photocatalytic system via
Among all the hybrid PMR response surface analysis. The
TM followings outline a range of
systems, the pilot Photo-Cat
photoreactor operating param-
system (Fig. 8) (manufactured by eters that affects the
Purifics Inc., Ontario, Lon-don) photocatalytic performance of
has shown the potential
application. Benotti et al. (2009) TiO2 photocatalysts in water
has evaluated its ability in the treatment.
3008 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7

Fig. 8 e General schematic of photocatalytic reactor membrane pilot system (Benotti et al., 2009).
wavelengths used were different. force. When operating pH <
It was reported that the optimum PZC(TiO2), the surface charge for
catalyst loading for the catalyst becomes positively
5.1. TiO2 loading photomineralization and photo- flow region can ensure that a charged and gradually exerted an
steady state residence time is electrostatic attraction force
disinfection are varied, and
towards the negatively charged
Concentration of TiO2 in the mainly depend on the dimension obtained, while turbulence flow
compounds. Such polar attractions
photocatalytic water treatment of the photoreactor. In addition, removes catalyst deposition or
system affects the overall reaction dead zone (Malato et al., between TiO2 and charged
the determination of photoreactor
photocatalysis reaction rate in a diameter is crucial in not only the 2003). Reactor diameters smaller anionic
true heterogeneous catalytic effective photons absorption but than 20e25 mm were not feasible
regime, where the amount of TiO2 also the water flow for turbulent flow while diameter
is directly proportional to the hydrodynamics (Malato et al., larger than 50e60 mm is
overall photocatalytic reaction 2009). Uniform impractical. This is because large
rate (Gaya and Abdullah, 2008). A diameters usually have lower
linear dependency holds until saturated catalyst loading and
certain extent when the reaction efficiency. In this instance, the
rate starts to aggravate and amount of catalyst should be
becomes independent of TiO2 considered. Usually the TiO2
concentration. This is attributed to
catalysts can be mixed uniformly
the geometry and working
with the targeted water prior to
conditions of the photoreactor
the introduction into the reactor
where the surface reaction is
initiated upon light photon system. During the dark
absorption (Bamba et al., 2008). homogenization period of the
catalyst, a lower initial
When the amount of TiO2
concentration of organic
increases above a saturation level
(leading to a high turbidity state), pollutants is observed owing to
the light photon absorption the strict adsorption of organics
coefficient usually decreases onto the catalysts surface (Xu and
radially. However, such a light Langford, 2000). Similarly,
attenuation over the radial catalystsebacteria interaction was
distance could not be well reported in the photo-disinfection
correlated with the BeereLambert treatment of microorganism
Law owing to the strong (Gogniat et al., 2006).
absorption and scat-tering of light
photons by the TiO2 particles
(Chen et al., 2007). The excess
TiO2 particles can create a light
screening effect that reduces the 5.2. pH
surface area of TiO2 being
exposed to light illumination and In heterogeneous photocatalytic
the photocatalytic efficiency. water system, pH is one of the
Therefore, any chosen most important operating
photoreactor should be operated parameters that affect the charge
below the saturation level of TiO 2 on the catalyst particles, size of
catalyst aggregates and the
photocatalyst used to avoid excess
positions of conductance and
catalyst and ensure efficient
valence bands. Due to the nature
photons absorption. In this sense,
of TiO2 catalyst used, any
both cata-lyst loading and light
variation in the operating pH is
scattering effect can be
known to affect the isoelectric
considered as a function of optical
point or the surface charge of the
path length in the reactor.
photocatalyst used. Many reports
have used the point of zero charge
(PZC) of TiO2 to study the pH
impact on the pho-tocatalytic
A large number of studies oxidation performance (Chong et
have reported the effect of TiO 2 al., 2009b,c; Ochuma et al., 2007;
Chin et al., 2006; Toor et al.,
loadings on the process efficiency
2006). The PZC is a condition
(Gaya and Abdullah, 2008; where the surface charge of TiO 2
Herrmann, 1999; Chong et al., is zero or neutral that lies in the
2009b,c; Ochuma et al., 2007; pH range of 4.5e7.0, depending
Chin et al., 2006). These results on the catalysts used. At PZC of
are mostly independent and a TiO2, the interaction between the
direct comparison cannot be photocatalyst particles and water
made, as the working geom-etry, contaminants is minimal due to
radiation fluxes, intensity and the absence of any electrostatic
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3009
where inappropriate control of
increased density of TiOH 2 (at
organic compounds can intensify low pH) can form electrostatic mean particle size. Since the water pH promotes the
the adsorption onto the photon link with the bacteria of relative sizes between the bacteria electrostatic repulsion, the
negatively charged surfaces, and catalysts are significantly Donnan exclusion phenomena and
activated TiO2 surface for
subsequent photocatalytic resulting in increasing rate of thus, the rejection tendency for
different, the charged TiOH 2
reactions (Xu and Langford, photo-disinfection. Herrera Melia the membrane used (Seffaj et al.,
clusters might not come into full
2000; Gogniat et al., 2006). This n et al. (2000) observed that the 2005; Molinari et al., 2008). It
contact with the bacteria. Sichel et
is particularly significant when bacterial inactivation rate was must be stressed that appropriate
the anionic organic compounds al. (2007) found that the TiO2 pH control strategies must be
enhanced at pH 5.0. It should be
present in a low concentration catalyst is actually adsorbed onto implemented at every different
noted that the enhanced
level. At pH > PZC(TiO2), the fungal spores rather than the location of a photocatalytic water
bactericidal activity of TiO2 at a reverse setting. This is owing to
catalyst surface will be negatively treatment process for efficient
charged and repulse the anionic low pH is due solely to the TiO2 the fact that the fungal spores are- photo-catalytic reaction to
compounds in water. Different pH mediated photo-killing and not larger (a few order of magnitudes) proceed.
will affect the surface charge acidification of the cell. Heyde than the catalyst particles. A small
density of the TiO2 catalyst and Portalier (1990) explained decrease in microbial loadings
(Rincon and Pulgarin, 2004), that the negligible E. coli reaction was observed during the initial
according to the following water to acid conditions was from the dark homogenization period with
equilibrium equations (Eqs. (5.1) presence of an acid tolerance catalyst particles. This is owing to
and (5.2)); response to the bacterium itself, the catalyst agglomeration and
5.3. Temperature
which secreted acid-induced subsequent sedimentation of the
proteins for acid-shock protection. agglomerates. The rate of
bacterial adsorption in this Numerous studies have been
However, Rincon and Pulgarin
instance was found to directly conducted on the dependence of
(2006) did not find any
relate to the bactericidal activity photocatalytic reaction on the
At pH < PZC: TiOH H 4 TiOH2 differences in E. coli inactiva-tion
of the catalyst used. It was also reaction temperature (Muradov et
rates when the initial pH varied
At pH > PZC: TiOH OH 4 TiO H between 4.0 and 9.0. To date, reported that the adsorption al., 1996; Fu et al., 1996; Chen
phenomena during the dark and and Ray, 1998; Rincon and
various types of microorganisms
irradi-ated phase will act Pulgarin, 2003; Evgenidou et al.,
have been successfully inactivated
indifferently and thus, a strong 2005). Although heat energy is
The surface charge density using TiO2 photocatalysis, which
conclusion cannot be made. inadequate to activate the TiO2
distribution for these TiO2 include Lactoba-cillus
surface, the understanding on
catalyst clusters is highly acidophilus, E. coli,
such dependency could be
dependent on the operating pH. It Saccharomyces cerevisiae,
extrapolated when operating the
was reported that the distribution Chlorella vulgaris, Streptococcus
Besides, the interaction process under natural sunlight
of TiOH is 80% at 3 < pH < 10; faecalis and aureus, Enterobacter
between the catalyst particles illumination. Most of the previous
TiO 20% at pH > 10 and TiOH 2 cloacae, total coliforms, Candida
itself also exists and is dependent investigations stated that an
20% at pH < 3. The equilibrium albicans, Fusarium solami,
on the operating pH. The particle increase in photo-catalytic
constants for these reactions at Aspergillus niger and others
size of the same catalysts can vary reaction temperature (>80 C)
different pH (Matsunaga et al., 1985; Herrera
from 300 nm to 4 mm depending promotes the recom-bination of
are pKTiOH2 2:4 and pKTiOH Melian et al., 2000; Ibanez et
on the distant from the PZC of charge carriers and disfavour the
8.0 (Kormann et al., 1991). al., 2003; Seven et al., 2004;
adsorption of organic compounds
During photocatalytic reaction, Lonnen et al., 2005). TiO2 (Malato et al., 2009). At pH
the initial operating pH PZC, the neutral surface charge onto the TiO2 surface (Gaya and
usually drops slightly from the of the catalyst particles is unable Abdullah, 2008). At a reaction
formation of multitude inter- to produce the interactive temperature greater than 80 C, the
mediate by-products that may Although the electrostatic link rejection for solideliquid pho-tocatalytic reaction is
pose different chemical func- between the catalyst parti-cles and separation. Thus, this induces interpreted with
catalyst aggregation where the LangmuireHinshel-wood (LeH)
tional groups and affect the water microorganisms were reported to
catalyst becomes larger, leading to mechanism where the adsorption
pH indifferently (Stylidi et al., exist, a subsequent microbial cell
catalyst sedimentation (Blanco of the reactants is disfavoured
2003). adsorption and eventual
and Malato, 2001). This phys-ical resulting in KC becomes 1. This
penetration of the catalysts
property is usually manipulated in will reduce the LeH expression
A similar electrostatic through the cell wall are highly
the hybridized PMR system, (Eq. (6.1)) into the apparent rate
interaction enhancement for dependent on the
where the pH of the treated equation
photo-disinfection of
wastewater is neutralized to pH 7
microorganisms was observed
for the subsequent recovery of
during the photocatalytic process
(Gogniat et al., 2006). During the catalyst particles. The larger TiO 2
photo-disinfection, the initial clusters can settle faster than the
photo-induced damage to the smaller one. It was reported that
micro-organisms takes place on with such neutralisation strategy,
the lipopolysaccharide layer of almost 97% of the catalysts can
the external cell wall and on the be recovered in the settling tank.
peptidoglycan layer. This is The remaining TiO2 catalysts can
followed by lipid membrane be recovered via the down-stream
peroxidation and the subsequent MF system. Similarly, the water
oxidation of the membrane pH will also affect the effective
protein and polysaccharides. An separation in the PMR system
3010 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
TiO2 catalyst is usually conducted absorption characteristics for UV
below ambient temperature of 80 photons at intensities of 185 and
r kapparentC. All these C to prevent high water heating conditions, provided the oxygen 254 nm, respectively. The DO
drastically reduce the costs (high heat capacity) sparging rate and the pho- molecules act as an inner filter in
(Herrmann, 2005). toreactor gas hold-up are known this case and cause a sharp
photocatalytic activity of TiO2
(Chong et al., 2009c). In this attenuation in UV light intensity
when the reaction temperature
rises. The desorption of degraded equilibrium law, it is also mainly at UV-C germicidal
necessary to account for the region. There is no report found to
products from the TiO2 surface is
5.4. Dissolved oxygen decrease in oxygen solubility with determine the DO impact on a
the rate-limiting step when
increasing reaction temperature. photocatalysis process using UV-
temperatures rise. On the
Dissolved oxygen (DO) plays an A or UV-B light sources. To date,
contrary, a low temperature below As discussed, it is preferential to
80 C actually favours adsorption important role in TiO2 pho- operate the photoreactor under the effect of DO on the efficiency
which is a spontaneous tocatalysis reaction to assure ambient conditions to prevent the of photo-disinfection rate has
exothermic phenomenon, sufficient electron scavengers been paid little attention. The
elevate cost of air or oxygen
resulting in getting KC of LeH present to trap the excited formation of various ROS under
sparging for enhanced electron
model 1, enhancing the conduction-band electron from the series of redox reactions on
sink.
adsorption of final reaction recombination (Chong et al., the catalysts surface was assumed
products. A further reaction in 2009b). The oxygen does not to be similar in both
temperature down to 0 C will The presence of dissolved
affect the adsorption on the TiO2 photomineralization and photo-
cause an increase in the apparent oxygen is also suggested to
catalyst surface as the reduction disinfection reaction. If sufficient
activation energy. As a induce the cleavage mechanism
reaction takes place at a different nutrients are available, the
consequence, the optimum for aromatic ringsin organic
location from where oxidation constant sparging of DO will
reaction temperature for pollutants that are present in the
occurs (Malato et al., 2009). generally promote microbial
photomineralization is reported to water matrices. Wang and Hong
Other roles for DO may involve growth and offset the photo-
be in the range of 20e80 C (2000) proposed that during
in the formation of other ROS and
(Malato et al., 2009). aromatic ring cleavage in the disinfection rate. This indirectly
the stabiliza-tion of radical
degradation of a dioxyl prolongs the irradiation time
intermediates, mineralization and
compound, the molecular oxygen necessary to achieve the desired
direct pho-tocatalytic reactions.
For photo-disinfection using will follow the cleaving attack of inactivation level. It is thus
The total amount of DO in a
TiO2 photocatalysis, the increase a second hydroxyl radical. The recommended that the effect of
reactor depends on a few
in the reaction temperature analogous partial pressure of DO on the microbial inactivation
technical considerations. For a
increased the inactiva-tion rate of oxygen applied during the should be investigated thoroughly
photo-reactor, the total delivered
microorganisms (Rincon and reaction for a closed reactor in a particular photoreactor
DO not only acts as an electron
Pulgarin, 2003). This is consistent system is also important. A system before improvising the DO
sink but also provides sufficient
with the Vant HoffeArrhenius significantly higher partial sparging strategy.
buoyant force for complete
equation (Eq. (5.3)), where the pressure of oxygen will result in a
suspension of TiO2 particles. higher initial organics
rate constant k is linearly Photoreactor sparging with pure photomineralization rate than its
proportional to the exponential
oxygen in TiO2 slurry reactor is structural transformation (Chen
( 1/T);
usually a cost-ineffective solution, and Ray, 1998; Wang and Hong,
T2 T1 as the amount of DO being held-
5.5. Contaminants and
ln k2 R 2000). It was reported that at low
their loading
k1 Ea 1 1 up is a function of the oxygen pressure of 0.5 kPa, 75%
photoreactor geometry. The of the original 2-CB compounds
difference between the two were trans-formed, but only 1% Previous investigations have
in which k1 and k2 are the sparging media of air and oxygen reported the dependency of the
of them was mineralized to CO 2
is usually not very drastic as the TiO2 photocatalytic reaction rate
constants for temperatures T1 and after 5 h of UV irradiation (Wang
mass transfer of oxygen to the on the concentration of water
T2, Ea is the energy of activation and Hong, 2000). Though contaminants (Ochuma et al.,
close vicinity of the surface is the
and R is the universal gas elevated partial pressure of 2007; Toor et al., 2006; Chong et
rate dependent step (Habibi et al.,
constant. The viability of a oxygen is imperative, it is difficult al., 2009b,c). Under similar
2005). Generally the Henrys Law
microbe to the catalyst activity to quantify their specific influence
depends on its incubation
can be assumed to give a good operating conditions, a
approximation of the amount of on the surface activity of TiO2,
temperature, type and resistance owing to the polyphasic nature of
variation in the initial
oxygen dissolved under the
to temperature change. The order concentration of the water
experimental the photocatalytic liquid phase
of resistance of microorganisms
to conven-tional disinfection
reaction (Herrmann, 1999). contami-nants will result in
treatment is of: Non-forming different irradiation time
spores bacteria < Viruses < necessary to achieve
Forming spores bacteria <
Helminths < Protozoa (oocysts). The detrimental effect of DO complete mineralization or
To date, there is no on the photocatalysis reaction was disinfection. Owing to the
comprehensive study conducted reported by Shirayama et al.
photonic nature of the
to compare the effect of TiO 2 (2001). They observed an
elevated photodegradation rate of photocatalysis reaction,
photo-disinfection on each
microorganism types under chlorinated hydrocarbons in the excessively high
different operating temperature. absence of DO. This could be
Thus, the photo-disinfection using explained by the strong
concentration of organic
substrates is known to
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3011
organic in the real wastewater, a threshold for the type of rutile
simultaneously saturate the TiO2 slow photomineralization kinetics in resistance are explained by TiO2 used.
surface and reduce the photonic are attained with prolong their cell wall permeability, size
efficiency leading to photocatalyst irradiation times to achieve and complexity of the specific For UV irradiation, its
deactivation (Saquib and Muneer, complete mineralization. Slow microorganisms. Each micro- corresponding electromagnetic
2003). kinetics turnover of the organism might also be of spectrum can be classified as UV-
Not all organic substrates will photocatalytic water treatment as infectious nature, which causes A, UV-B and UV-C, according to
have such profound effect on the a stand-alone process means a epidemic diseases when they its emitting wavelength. The UV-
irradiation time, and this also higher initial cost on the reactor multiply in water. Most bacteria A range has its light wavelength
depends on the corre-sponding volume and site area is required.
can be killed easily with TiO2 spans from 315 to 400 nm
chemical nature of the targeted Recently, this heterogeneous
photocatalysis, but a complete (3.10e3.94 eV), while UV-B has
photocatalytic technology has
compounds for TiO2 inactivation might have to be wavelength range of 280e315 nm
been coupled with biological
photocatalysis reaction. For ensured as they are highly (3.94e4.43 eV) and the germicidal
treatment to increase its indus-
instances, 4-chlorophenol will infectious. Similarly, this UV-C ranges from 100 to 280 nm
trial feasibility (Parra et al.,
undergo a degradation pathway infectious nature can also be (4.43e12.4 eV) (Rincon and
2002). Such coupling allows the
with constant evolution of found in viruses (adenoviruses, Pulgarin, 2005). In most of the
retention time in biological
intermediate(s) product (i.e. enteroviruses, hepatitis A and E previous studies, the UV-A light
treatment stages to be reduced,
hydroquinone and benzoquinone) viruses, noroviruses and provides light photons sufficient
where the non-biodegradable
while oxalic acid will undergo saproviruses, rotaviruses) and the for photonic activation of the
compounds of the wastewater can
direct transformation to carbon most in protozoa (Acanthamoeba catalyst (Bhatkhnade et al., 2004;
be turned into biodegradable
dioxide and water (Bahnemann, spp, Cryptosporidium parvum, Chin et al., 2006; Ochuma et al.,
compounds with the aid of
2004). In the case of 4-chlor- Cyclospora cayetanensis, 2007). As with outdoor solar
photocatalytic treatment.
ophenol, such evolution of Entamoeba histolytica, Giardia irradiation, the UV-C is usually
intermediate(s) will further intestina-lis, Naegleria fowleri, absorbed by the atmosphere and
prolong the irradiation time Toxoplasma gondii (WHO, 2006). not reaching the earth surface.
necessary for total mineralization All these protozoa are highly Only the lamp-driven photo-
owing to the direct competition infectious in low concentration reactor system can utilize UV-C
over unselective TiO2 surfaces. In and the photocatalytic treatment irradiation artificially for photonic
the development of mathematical should be targeted on these micro-
Similarly, the photo- activation of catalyst and
model that represents the kinetics organisms as the surrogate
disinfection efficiency of various reduction of viable
of mineralization while relating to indicators. This is to ensure that
microorganisms has been assessed microorganisms. The mechanism
the TiO2 loading required, adequate photocatalytic treatment
for the possible applica-tion of of UV-C cell destruction involves
to prevent the outbreak of the
commonly used water quality photocatalytic technology to the direct induction on pyrimidine
epidemic diseases in the treated
parameters such as chemical replace the chemical disinfectant and purine and pyrimidine
water, if photocatalytic treatment
oxygen demand (COD), total methods. In general, the adducts on the cell DNA.
organic carbon (TOC) or is chosen.
mechanism involved in the However, not all micro-organisms
dissolved organic carbon (DOC) are susceptible to the UV-C
microbial disinfection includes
could be more appropriate to radiation and some highly
the destruction of the microbial
account for such competitiveness resistant microorganisms can
protein structures and inhibition 5.6. Light wavelength
of intermediate(s) with its
of their enzymatic activities survive through disin-fection
predecessor compounds. Also
(Maness et al., 1999). Compared process. These include Legionella
organic substrates with elec-tron- The photochemical effects of light
to the persistency during organic pneumonphila and
withdrawing nature such as sources with different wavelength
photomineralization, a general emitting ranges will have a Cryptosporidium parvum oocysts
benzoic acid and nitroben-zene
classification in the bacterial profound consequence on the (Malato et al., 2009).
were found to strongly adhere and
resistance to the disinfectant used photocatalytic reaction rate,
more susceptible to direct
has also been proposed. Among depending on the types of
oxidation than those with electron photocatalysts used e crystalline
donating groups (Bhatkhnade et all, the most resistance infectious
phase, anatase-to-rutile
type of microorganisms are The natural UV radiation that
al., 2004). Most of the TiO2 composition and any state of
prions, followed by coccidia photocatalyst modifications. reaches the surface of the earth
studies conducted to date, utilises
(Cryptospo-ridium), bacterial Using commercial Degussa P-25 consists of both UV-A and UV-B
a range of model organic
endospores (Bacillus), TiO2, which has a crystalline ratio spectrums. The photolysis
substrates with different
mycobacteria (M. tuberculosis), of anatase 70/80: 20/30, a light mechanism for both UV
substituent groups but these rarely
viruses (poliovirus), fungi wavelength at l < 380 nm is irradiations on cell inac-tivation is
convey any useful infor-mation
(Aspergillus), Gram-negative sufficient for photonic activation dissimilar to the discussed UV-C
and merely test on the photo-
(Pseudomonas) and eventually (Herrmann, 1999; Bahnemann, mechanism. Both UV-A and UV-
efficiency of a new pho-tocatalyst 2004). The crystalline phase of
Gram-positive bacteria B irradiations can be absorbed by
or an integrated reactor column.
rutile TiO2 has a smaller bandgap cellular
Some field kinetics of the (Enterococcus) (Malato et al.,
2009). Their differences energy of EB w 3.02 eV,
photomineralization of real
wastewater has also been reported compared to the anatase TiO2 of
(Marugan et al., 2007; Radjenov 3.2 eV (Gaya and Abdullah,
c et al., 2009; Vilar et al., 2009; 2008). This dictates that rutile
Malato-Rodrguez et al., 1996). TiO2 can be activated with light
It was observed that owing to the wavelength of up to 400 nm,
persistency of the dissolved depending on the bandgap
3012 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
toactivity of current TiO2 catalysts cause irreversible damage to the
used. E. coli. In the intermittent light
irradiations with constant
components called intracellular Later, it was discovered that
interruptions, the bacteria were
chromophores. L-trytophan is the the dependency of the reac-tion
seen to regrow during the
best known intracellular rate on radiant intensity behaves
subsequent 24 or 48 h. Some
chromophore and is thought to indifferently under different
studies suggested that this
contain unsaturated bonds such as 5.7. Light intensity lighting conditions (Curco et al.,
regrowth is due to the dark-repair
flavins, steroids and quinines 2002; Qamar et al., 2006;
mecha-nism where the partially
(Tyrrell and Keyse, 1990). Among The photonic nature of the Karunakaran and Senthilvelan,
damaged cells recover in the
these UV irradia-tions, the UV-A photocatalysis reaction has out- 2005). The linear dependency of
presence of nutrients (Sun et al.,
irradiation is toxic only in the lined the dependency of the the photocatalytic reaction rate on
2003; Shang et al., 2009). Others
presence of oxygen. The ROS or overall photocatalytic rate on the radiant flux (F) changed to a
0.5
have suggested that the damaged
oxidative stress generated from light source used. Light intensity square-root dependency (F ) but not totally inactivated cells
the chromophore light absorption is one of the few parameters that above certain threshold value. could recover its viability through
can damage cells and cell affect the degree of photocatalytic Such a shift in dependency form photo-repairing under radi-ation
components, leading to lipid reaction on organic substrates. was postu-lated owing to the of 300e500 nm or on the re-
peroxidation, pyrimidine dimer Fujishima et al. (2000) indicated amount of photo-generated holes synthesis and post replication of
formation and eventually DNA the initiation of TiO2 available during the electronehole cells (Rincon and Pulgarin, 2003;
lesions. The contact between the photocatalysis reaction rates is not pair formation. In the TiO2 Sichel et al., 2007). It must be
ROS and DNA results in single highly dependent on light catalyst used, the photo-induced noted in this case that for photo-
strand breaks and nucleic acid intensity, where a few photons of generation of valence band holes disinfection using different light
modifications. Such damages on 1
energy (i.e. as low as 1 mW cm ) are much less than the intensity, a final conclusive point
the DNA are usually lethal or
can sufficiently induce the surface conduction-band electrons cannot be made directly. The
mutagenic irreversible. With the
reaction. To achieve a high available. In this instance, the disinfection results of 400 W/m
2
presence of TiO2 catalyst as the photocatalytic reaction rate, photo-generated holes are the at 2.5 h irradiation might not be
light sensitizers, a high degree of particularly in water treatment, a rate-limiting step and the details the same as the result arose from
cell damages is seen as the relatively high light intensity is derivation of the square-root 2
amount ROS generated increases required to adequately provide 1000 W/m for 1 h. Thus, in order
dependency can be obtained from
accordingly. A few to predict the minimum irradiation
each TiO2 surface active sites with Malato et al. (2009). At high
microorganisms that are resistant required at constant irradiance,
suffi-cient photons energy intensities, the dependency of the
to UV-A photolysis have been preliminary studies into both the
required. However, when using photocatalytic reaction rate on
0
photo-reactor performance and
inactivated successfully by TiO2 the nominal TiO2 particles radiant flux reduced to zero (F ). microbial consortia (different
photocatalysis, namely; E. without modifications, the surface This was explained by the resis-tants) presents is important.
cloacae, E. coli, P.aeruginosa and reaction is restricted to photons saturated surface coverage of the
S. typhimurium with wavelengths shorter than the catalyst, resulting in a mass
absorption edge of approximately transfer limitation in the
400 nm. The organic conversion adsorption and desorption and
(Ibanez et al., 2003). in the presence of UV wavelength thus, pre-venting the effect of
5.8. Response surface
A longer wavelength of solar (l < 400 nm) in many studies light intensity to set in. An
analysis
irradiation (l > 400 nm) has also obeyed the linear proportionality increase in the fluid turbulency in
been used in solar disinfection correlation to the incident radiant this case might help to alleviate
flux. This was evidenced by From the earlier discussions on
(SODIS) study (Sichel et al., the mass transfer problem on the
Glatzmaier et al. (1990) and the effect of the operation
2007; Lonnen et al., 2005; Berney surface of the catalyst. The
Glatzmaier (1991), where they parameters on the photocatalytic
et al., 2006; Kehoe et al., 2004; desorbed final products might
observed that the destruction of reaction rate, it can be seen that
McGuigan et al., 2006. However, also affect the dependency of
dioxin and polychlorinated these parameters would affect the
the photo-killing mechanism is as reaction rate on radiant flux, as
biphenyls was significantly system indifferently. In overall, it
yet unclear as it involves a variety they might scavenge the electron
enhanced in the presence of high can be interpreted that a multi-
of microbial and a larger mixed acceptors and further promote the
intensity photons. A similar variable (MV) optimization
spectrum of UV-A and solar electronehole pair recombination.
finding was reported in Magrini approach is actually required to
irradiation. A similar cell optimize a pho-toreactor system
and Webb (1990) where the
destruction mechanism to the one organic decomposition rate was as parameter interaction might
proposed for UV-A irradiation is reported to increase with the exist. Parameter interactions refer
thought to take place in this radiation intensity. to the relationship between
mixed light spectrum. In the Rincon and Pulgarin (2004) operating parameters such as TiO 2
SODIS, the pathogens in the reported that the residual dis-
loading on pH or pH on
drinking water contained in PET infecting ability of the
bottles were found to be photocatalyst largely depends on
inactivated within 6 h of sunlight the duration of light intensity
exposure. However, significant without any temporal
research and developments on the interruptions. They investigated
disinfection using photocatalytic- the effect of light intensities at
2
mediated process need to be 400 and 1000 W/m on bacterial
conducted to broaden the pho- lethality and regrowth, and found
that the higher intensity without
any temporal interruptions can
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3013
the reac-tion rate dependency on total decomposition achieved.
radiant flux. For the optimization the four different parameters kinetic models for the Numerous assumptions for the
of a photoreactor system, the according to the statistical interpretation of experimental LeH saturation kinetics type exist
conventional one-parameter-at-a- regression as shown in (Eq. (5.4)); data enables the design and and for the applicability in the rate
time approach is mostly used to optimization of photoreactor of photomineralization, any of the
unveil the effects of one system with sufficient capacity four possible situations is valid:
parameter after another. Although and minimal non-illuminated (i) reactions take place between
k k k
two adsorbed components of
X X XX

this conventional optimization Ro b0 biXi bijXi2 reactor volume. In this section,


approach is widely acceptable, the i1 i1 i the different kinetics and rate radicals and organics; (ii) the
i<j

reported outcomes could be of model for both reactions are between the radicals
where Ro is the predicted in water and adsorbed organics;
insig-nificant and have less photomineralization and photo-
response output of the photo- (iii) reactions take place between
predictive power if the condition disinfection will be discussed
mineralization rate, and i, j are the radical on the surface and
for one operating parameter linear, quadratic coefficients, along with the common
changes. misconceptions in kinetic organics in water; (iv) reaction
respectively. The parameters of b
modelling. occurs with both radical and
and k are regression coeffi-cient
organics in water.
This has lead to the and the number of parameters
application of effective design of studied in the experi-ment,
exper-iments (DOE), statistical Some researchers found that
respectively, and Xi, Xj (I 1, 4; 6.1. Photomineralization
analysis and response surface kinetics simpler zero- or first-order
j 1, 4, i s j ) represent the kinetics is sufficient to model the
analysis for photocatalytic studies
number of independent variables photomineralization of organic
(Chong et al., 2009d; Liu and In most of the photocatalytic
in the study. This model (Eq. compounds. This was, however
Chiou, 2005; Lizama et al., 2002; studies, kinetic or mechanistic
(5.4)) is empirical and only applicable for limited
Korbahti and Rauf, 2008; Calza independent for each photoreactor studies over the irradiated TiO2 conditions where the solute
et al., 2006; Fu et al., 2007). system. Subsequent verification surfaces usually only involve a concentration is inade-quately
Using this approach, different works are required to deter-mine single constituent model organic low. In most kinetic studies, a
permuta-tions of experimental the accuracy and applicability of compound. The kinetics of plateau-type of kinetic profile is
design are involved and the such model for the prediction of different organic compounds usually seen where the oxidation
operational parameters and spans photoreaction rate under the ranging from dye molecules, rate increases with irradiation
are defined. As compared to the variation of its parameters. Other pesticides, herbicides and time until the rate becomes zero
conventional one-parameter-at-a- DOE approach to photocatalytic phenolic compounds to simple (Minero, 1999; Cunningham and
time approach, the MV opti- reactor optimization has also been alkanes, haloalkanes, aliphatic Sedlak, 1996). The appearance of
mization approach has pre- applied over the years, such as alcohols and carboxylic acids such kinetics regime usually fits
determined experimental points central composite design (Cho have been investigated the LeH scheme. According to the
that are dispersed uniformly and Zoh, 2007), Bayesian (Herrmann, 1999; Bahnemann, LeH model (Eq. (6.1)), the
throughout the study domain, i.e. (Jaworski et al., 2008) and 2004; Gaya and Abdullah, 2008; photocatalytic reaction rate (r) is
only a small region is covered in PlacketteBurman designs (Wu et Malato et al., 2009). The non- proportional to the fraction of
the domain of conventional study. al., 2006). selective nature of the OH surface coverage by the organic
This allows the optimization radicals means that the disappear-
substrate (qx), kr is the reaction
process to be more time-effective ance rate of the studied compound
rate constant, C is the
and enhances the identification of with irradiation time should not
concentration of organic species
parameter interac-tions, where be referenced as a standard for
and K is the Langmuir adsorption
they can be interpreted using reactor design purpose. This is
6. Kinetics and constant:
commercial statis-tical software because that numerous
modelling
such as Design Expert software. intermediates are formed en-route
to complete mineralization and
Kinetics and mechanistic studies
neglecting this aspectisa common r dC krqx krKC
on the photomineralization or
mistake in portraying the dt 1 KC
Chong et al. (2009d) proposed photo-disinfection rate of the
photomineralization kinetics. In
the use of Taguchi-DOE water contaminants are useful for The applicability of (Eq. (6.1))
this instance, the organic
approach, together with analysis process scale-up. The appropriate depends on several assump-tions,
concentrations can be expressed
of variance, statistical regression utilization of which include (i) the reaction
collectively in COD or TOC to
and response surface analysis to system is in dynamic equilibrium;
yield an in-depth understanding
study the combined effects of four (ii) the reaction is surface
on the photomineralization
key operation parameters that mediated; (3) the
kinetics.
affect the photocatalytic reaction
rate in an annular photoreactor.
They utilised 9 experimental
permutations to analyse the 81 As the LeH model is a
possible parameters combination. surface-area dependent, the
It was reported that the interaction reaction rate is expected to
increase with irradiation times
between the TiO2 loading and
since less organic substrate will
aeration rate had a positive
remain after increased irradiation
synergistic effect on the overall
reaction rate. A response surface times with higher surface
model was developed to correlate availability. A zero rate of
degradation is associated with the
3014 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
Rearranging and integration of of photo-disinfection data,
(Eq. (6.4)) yields the typical because of process complexity
pseudo-first-order model as in and vari-ability. The general
competition for the TiO2 active
(Eqs. (6.5) and (6.6)): expression for the empirical
surface sites by the interme-diates
and other reactive oxygen species 0
k t photo-disinfection models for
is not limiting (Chong et al., C Coe demand-free conditionis
2009c). If these assumptions are ln C0 krKt k0t expressed in (Eq. (6.8)). In this
valid, the reactor scheme only C instance, demand-free conditions
consists of adsorption surface assume that the catalyst
sites, organic molecules and its
concentration is constant with
intermediates, electronehole pairs The apparent rate constant
and the reactive oxygen species. irradiation time.
however, is only served as a
The rate constant (kr) for most of comparison and description for
the photocatalytic reaction in the photocatalytic reaction rate in
water is usually reported to be in
6 9 1
the reactor system. Fig. 9 shows a
the order of 10 e10 (Ms) typical saturation kinetic plot for dN kmNxCnTm 1

(Malato et al., 2009). This kr- Fig. 9 e Typical saturation dt


the degradation of organic dye
value is the proportionality molecules in an annular kinetics plot for the degradation
constant for the intrinsic reactivity of organic dye molecules in an where dN/dt rate of
photoreactor system where the
of photo-activated surface with C. inactivation; N number of
reaction rate increases to a point annular photoreactor system
Others have also related the k r is bacterial survivors at irradiation
where the rate plateaus off. To (Chong et al., 2009b).
proportional to the power law of time t; k experimental reaction
n
interpret the maximal
effective radiant flux (i.e. F e) rate; C concentration of
photomineralization rate, the
during the photomineralization photocatalyst used; m, n and x are
tailing regime of the LeH
reaction (Cunningham and the empirical constants. However,
saturation profile should be r b1TOC&
Sedlak, 1996; Monllor-Satoca et the most commonly employed
al., 2007). The K-param-eter is neglected. Only the slope of the b3TOC& disinfection model in photo-
the dynamic Langmuir adsorption tangent to the inflexion point TOC;O b2
disinfection studies to date is the
1 should be used to obtain the This (Eq. (6.7)) allows the
constant (M ) that represents the simple mechanistic
maximal photomineralization rate. prediction of TOC degradation as
catalysts adsorption capacity. (Eq. ChickeWatson (CeW) model (Eq.
(6.1)) can be solved explicitly for In this instance, the unit for the a function of irradiation time.
Similar reciprocal plots of 1/r (6.9)) (Cho et al., 2004; Cho and
t using discrete change in C from slope has the same chemical
against 1/[TOC] can be used to Yoon, 2008).
initial concentration to a reference reaction order as the zero-order
point: rate constant. determine the empirical
parameters, b1, b2 and b3 as in log N k0T
KC Co krKt (Eq. (6.3)). The irradiation time NO
ln Co taken to achieve the fractional
A lump-sum LeH saturation
C degradation of TOC can also be
kinetics profile has also been used
to simplify the approximation for estimated when (Eq. (6.7)) is
The K-value can be obtained a specific photo-catalytic reactor expressed as in (Eq. (6.2)). Such
using a linearized form of (Eq. system (Minero et al., 1996). In an empirical lump-sum LeH
(6.1)), where 1/r is plotted against such an empirical lump-sum LeH model has greatly summarized the
1/C: approach, the degree of organics needs for precise kinetics
measurement and made a great
1 1 1 mineralization is actually
approximation for any particular
expressed in terms of TOC (Eq.
r0 kr krKC0 photoreactor system, provided
(6.7)):
sufficient data are collected for
It was reported that the real K-
the determination of rate
value obtained from the linearized
parameters.
plot of 1/r against 1/C is
significantly smaller (Malato et
al., 2009). This was explained by
the differences in
6.2. Photo-disinfection
adsorptionedesorption kinetics
phenomena during dark and
illumi-nated period. When the Since the first application of
organics concentration is low (in semiconductor catalysts for
mM), an apparent first-order disinfection by Matsunaga et al.
rate constant (Eq. (6.4)) could be (1985), few studies have been
1
expressed where k0 (min ) found in the literatures which
comprehensively study the kinetic
krK:
modelling of photo-disinfection of
microorganisms in a water
dC krKC k0C treatment process. Empirical
kinetic models have been the
r dt
mostly applied for interpretation
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3015
followed by (ii) a typical log- according to the Rational Model
In this CeW model, the photo- linear inactiva-tion region and with the introduction of both x
disinfection rate is expressed as a ends with (iii) a long deceleration and m s 1 to yield the
linear function of the enumerated process at the end of the HomePower model (Eq. (6.14)):
bacteria and catalyst loading. The disinfection, which is known as
the tailing. The presence of log 1 x 1 1 kCnTm
combined kinetic parameter of CT log NO Nx 1
between the catalyst shoulder was justified by the N

O
x



cumulative damage nature of
concentration and irradiation time
photo-disinfection treatment on Anotai (1996) reported that this
required to ach-ieve complete
the cytoplasmic membrane rather HomePower model may provide a
inactivation is widely used as a
than an instantly lethal (Gyurek better fit than both the Hom and
reference for process design.
and Finch, 1998). However, the Rational models. However, the
Other than this, this CT-values
tailing during the photo- existence of four empirical
concept is usually used to
disinfection is not well parameters in the model may
compare the efficacy of different
understood. Benabbou et al. result in an over-parameterization
disinfectant used in water
(2007) proposed that the tailing with null physical meanings for
treatment (Finch et al., 1993).
region was related to the each parameter within the model.
This CeW model however, may
competition for photocatalysis To
not always be applicable as many
between organic products released
studies may have experienced a
from constant cell lyses and the
curvilinear or non-linear photo-
remaining intact cells. Others
disinfec-tion profile. Hom (1972)
have proposed that the tailing
reproduced a useful empirical
deviations from the log-linear
modi-fication on CeW model
reduction were due to the
after having observed that the
presence of variations in the
disinfection plots of natural bacterial population resistant to
algalebacterial systems were the disin-fectant used (Lambert
curvilinear, rather than typical and Johnston, 2000).
log-linear type (Eq. (6.10)). In the Nevertheless, the use of CT Fig. 10 e Common non-linearity
Hom model, the bacterial in the photo-disinfection
concept or Hom model can lead to
inactivation level is predicted in a an over-design for a photo- kinetics profile using TiO2
non-linear function of C and T, disinfection system (Gyurek and catalyst, along with the
depending on the empirical appropriate disinfection models
Finch, 1998). A further
parameters of n and m used (Marugan et al., 2008).
modification to the Hom model
respectively. Since this Hom was made to account for the
model is a two-parameter model, simultaneous presence of
it should be stressed that the shoulder, log-linear reduction and
model is only applicable to a tailing (Eq. (6.11)) (Marugan et
the different bacterial inactivation
photo-disinfection profile with a al., 2008; Cho et al., 2003);
regions is a power law expression
maximum of two different non-
(Eq. (6.12)), when m 1 for the
linear regions. For m-value
generalised differ-ential equation
greater than unity, the inactivation
(Eq. (6.8)) (Gyurek and Finch,
curve displays an initial
1998);
shoulder while tailing is seen
when the m-value is less than dN kNxCn
unity. log N k11 exp k2t&k3 dt
NO
Integration of (Eq. (6.12))
Eq. (6.11) is known as the yields the Rational model (Eq.
modified Hom model and it (6.13)). If x 1, this Rational
expands the applicability of the model can be reverted back to the
Hom model for the fitting of the CeW model. In this instance, the
log N k0CnTm
initial shoulder, log-linear Rational model assumes that x s
NO
reduction and prolonged tailing 1;
Marugan et al. (2008) have behaviours. Another detailed
outlined the common non- empirical model that can detail
linearity found in the photo- N log 1 NOx 1 x 1 kC
log x 1
disinfection kinetics profile using
NO


Degussa P-25 TiO2 catalyst fitted
The Rational model (Eq.
with common disin-fection
(6.13)) can describe both
models (Fig. 10). In their study,
shoulder and tailing
they found that three different
characteristics for x less than or
inactivation regions in the photo-
greater than unity respectively.
disinfection profile, namely (i) a
Similarly, the Hom model (Eq.
lag or initial smooth decay,
(6.10)) can also be integrated
known as the shoulder,
3016 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
phenomenon and precedes in a account the shoulder and
similar way to a chemical reaction tailing, an intermediate
(Lambert and Johnston, 2000). population stage is usually sug-
reduce the number of null postulated number of lethal steps
The classical CeW model is a gested with different rates of
parameters, the Selleck model are considered to survive the
typical example of the disinfection for each microbial
(Eq. (6.15)) was proposed. This photo-disinfection process. As for
mechanistic photo-disinfection state. Typically, two different
model assumes that the catalyst the tailing region, many have
kinetics model. In the model, the microbial states for the number of
concentration remains constant regarded that it was owing to the
apparent exponential decay curves damaged bacterial and undamaged
during the irradiation period: presence of a microbial
for bacterial survival ratios with bacteria (i.e. Cdam Cundam) were
subpopulation resistant to thermal
dS kCS irradiation times follow a similar introduced to account for such
sterilisation. Najm (2006) also
dt 1 KCT decay mecha-nism of a chemical non-linearity in bacterial survivor
suggested that the tailing is due
where S is the survival ratio reaction, and are thus applicable curves. A similar Lang-
to the intrinsic distribution of
N/No at irradiation time t; k and K under both phenomena. This can muireHinshelwood (LeH) type of
bacterial resistance to the
be visualised when the CeW mechanistic model (Eqs. (6.19)
are the rate constants. In this sterilisation method, making the
model is integrated and (6.20)) can also be applied to
model, the shoulder was bacteria more resistant, adapted
mathematically, with N assuming represent the photo-disinfection
assumed to be a result of and inaccessible to heat treatment.
to be the number of moles of kinetics to yield more meaningful
cumulative effects of the chemical Marugan et al. (2008) reviewed
reactant to yield the log-linear kinetic terms (Marugan et al.,
disinfectant on the microbial that such tailing was not a
curve of a first-order reaction. 2008). Johnston et al. (2000)
target during the contact time. A common phenomenon in water showed that the inoculum size of
gradual decrease in the disinfection treatment. So far, no the bacteria has a large impact on
permeability of the outer cell justifiable explanation has been resistance distribution and thus,
membrane of E. coli as an action To formulate a mechanistic proposed to account for the the errors associated with this
of the catalysts can be idealized model for photo-disinfection occurrence of tailing in the term should be given attention
by a series of first-order reaction kinetics, the occurrence of both water disinfection treatment with during the mechanistic modelling.
steps on a single E. coli cell that shoulder and tailing region well-mixed conditions and
leads to lethality. This model can should be rationalized equally resistant cloned-bacterial
be modified to account for the idealistically. The presence of population. It was sug-gested that dC k1KundamCundamhundam
disinfection of coliform bacteria shoulder can be justified undam
the tailing was a result of
in water/ wastewater effluent (Eq. mechanistically by the single-hit gradual deterioration in the rate of dt 1 KundamCundamhundam KdamCdamhdam
(6.16)) (Gyurek and Finch,
multiple targets or a serial disinfection, and total inactivation dCdam k1KundamCundamhundam
1998): k2KdamCdamhdam
phenomenon event (Gyurek and was achiev-able only after a
Finch, 1998). Under mechanistic sufficient retention time. The
dt 1 K
undam
h
C undam K
dam dam
h
C dam


log N n log 1 CT assumption, the damage to the random colli-sions between the undam

K microbial cell is viewed as catalyst and bacteria can be where ki is the true log-linear
No
cumulative rather than instantly expressed by the Poisson deactivation rate constant for the
Although empirical models reaction between generated ROS
lethal. This dictates that a large probability, as the number of
provide a simple correlation of with bacteria. The pseudo-
number of critical molecules need collisions supersede prior to the
the photo-disinfection data, the adsorption constant, Ki, represents
to be denatured prior to cell number of microbial death
mathematical nature of their the surface inter-action between
inactivation (Gyurek and Finch, (Gyurek and Finch, 1998). If the the catalyst and bacteria. This
relevant terms yields null or
1998). Severin et al. (1984) destruction rate of the constant is similar to the
misinterpret physical meaning.
proposed that the cumulative microorganisms is assumed to be adsorption equilibrium constant in
For instance, the m-value > 1 in
inactivation of a single bacterium the same for the first and l th the conventional LeH model.
the Hom model actually suggests
can be collectively represented by target at the kth bacteria site, thus Due to the significant size
that photocatalytic reactivity
a series of integer steps. These the rate of destruction for the
increases with irradi-ation time in
disinfection steps were thought to microorgan-isms is given by;
the ASP. If the vitalistic
pass on a bacterium from one
assumption of bacterial
level to another in a first-order
population resistance distribution
reaction with respect to the
is valid, this actually indi-cates
catalyst used until a finite number
that the most resistant bacteria are
of lethal (l ) events was reached.
killed first prior to the least
The microorganisms which dNK kCNK 1 kCNK
resistant one (Lambert and dt
accumulate less than the
Johnston, 2000). This shows that
the rationale for the applicability Solving for K 0 to K l 1
of Hom model is contradictory. gives the log fraction of microbial
survival, not exceeding l 1 at the
end of the contact time;
It was proposed that the
" #
mechanistic models could convey ln
N
kCT ln l 1 kCTK
X
a better physical meaning in their
No K0 K!
kinetic terms. It was hypothesized
that the photo-disinfection Lambert and Johnston (2000)
mechanism can be viewed as a stated in the formulation of all
pure physicochemical mechanistic models that take into
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3017
and (6.25)) to the experimental 1
NTU is a 1.0 mg L of specified
differences between E. coli cells measurements of (Cundam Cdam)/ 7.1. Turbidity size of silica suspension and can
and the catalyst agglomerates, Co can be achieved using a non- be prepared for laboratory
these constants do not represent linear regression algorithm Turbidity often refers to the investigation. The turbidity
strict adsorption phenomena but a coupled with a fifth-order insoluble particulates that are standard can be calibrated with a
more general surface interaction RungeeKutta numerical approach. present in the targeted water photoelectric detector or neph-
during photo-disinfection. These Marugan et al. (2008) showed a (Viessman and Hammer, 1998). alometry for the intensity of
adsorption constants allow the good fitting of such mecha-nistic The presence of such insoluble scattered light.
shoulder representation in the LeH model to the photo- particulate matters are highly
photo-disinfection kinetics data. disinfection of E. coli under detrimental to the TiO2
The inhibition coefficient, hi is a different loadings of Degussa P25
photocatalysis based process, as
power coefficient that accounts TiO2 catalyst. they can affect the optical
for the tailing in the bacteria
properties and further impede the
inactivation curve. Marugan et
penetration of UV light by strong
al. (2008) proposed that hi is dCundam kKCundamh scattering and absorption of the 7.2. Inorganic ions
needed to account for the dt 1 KCundamh KCdamh rays (Chin et al., 2004; Tang and
inhibition produced by the dCdam k KCundamh KCdamh Chen, 2004). This will cause a The presence of inorganic ions in
increasing concentrations in the variation in the predicted use of the targeted water for TiO2
medium of cell lysis and
dt 1 KCundamh KCdamh TiO2 loading, UV penetration photocatalytic treatment is
oxidation products competing for
the ROS. This is particularly path and light intensity. Also, expected. To functionalise a TiO2
important towards the end of excessive levels of turbidity can water treatment process, the basic
photo-disinfection, as high reduce both the understanding of these inorganic
concentrations of these
7. Water quality photomineralization and photo- ions on the photocatalytic
compounds and small numbers of disinfection efficiency of the performance is essential.
In a full-scale plant for water pollutants that present in water Crittenden et al. (1996) reported
viable bacteria are present in the
treatment, a number of technical owing to the shielding effects that that when a photocatalyst is
suspension. In this instance, the h i utilised in either slurry or fixed-
issues have to be sorted out. Water attenuate the light pene-tration
in the proposed LeH model bed configuration to treat real
quality of the influents in the causing those pollutants to flee
essentially means that the reaction waters with different inorganic
treatment plant can vary with from the treatment (Rincon and
order with respect to the time. In this section, the ions, photocatalyst deactiva-tion
microbial population is higher Pulgarin, 2005; Chin et al., 2004;
was usually observed. This
implication of TiO2 photocatalytic Tang and Chen, 2004). Suspended
than one. resulted from a strong inhi-bition
processes for treatment of water solids will also shield target from the inorganic ions on the
sources of different qualities will pollutants from oxidation
be discussed. This enables a fuller surface of the TiO2 semiconductor
reactions. In this instance, the
understanding on the effects of used. Thus, the presence of these
suspended solids refer to the non-
Both (Eqs. (6.19) and (6.20)) various key water quality inorganic ions together with their
filterable residue that is retained permissible levels on the photo-
have six independent parame-ters parameters on the suitability of
on the filter medium after
that describe photo-disinfection applying such advanced TiO2 catalytic performance of TiO2 in
filtration. All these factors
rates. This constitutes a high risk photocatalytic processes. water treatment has to be
ultimately decrease the overall
of over-fitting the experimental determined to ensure minimal
photocatalytic efficiency for water
data, where the statistical disturbances on the efficient
treat-ment. To ensure rapid
significance of parameters and the operation of the TiO2 based
photocatalytic reaction rate, the
plausibility of the model are low. treatment process. With such
turbidity of the targeted water
By taking into account the dataa cost-effective fouling
should be kept below 5 neph-
intrinsic kinetics of ROS attack, prevention with inorganic ions
alometric turbidity units (NTU)
the catalystebacteria interaction and photocatalyst regeneration
for optimal UV light utilization
strategies can be customized.
and the inhi-bition by-products and photocatalytic reaction
are similar for both undamaged (Gelover et al., 2006; Ferna
and damaged bacteria, the ndezs-Ibanez et al., 2009).
following are assumed: A number of studies have
Rincon and Pulgarin (2003)
been conducted on the effects of
observed that the water turbidity
different inorganic anions or
higher than 30 NTU will
k1 k2 k cations, on both TiO2 photo-
negatively affect the rate of
mineralization and photo-
Kundam Kdam K photocatalytic disinfection. The disinfection reactions (Rincon
limit of 5 NTU is arbitrary and and
h h h depends on the receiving water
undam dam bodiesand the treatment levels
required. Since TiO2
With these, (Eqs. (6.19) and photocatalytic processes are
(6.20)) are reduced to (Eqs. (6.24) retrofitted to advanced water
and (6.25)). The three treatment stage, prior reduction in
independent parameters allow a turbidity could be achieved via
simul-taneous fitting of three conventional treatment processes
different inactivation regimes of such as screening, filtration,
shoulder, log-linear and sedimenta-tion, coagulation and
tailing. Fitting of (Eqs. (6.24) flocculation. The standard for 1
3018 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
have negligible effects. This is
2 2 2
because the Ca , Mg and Zn
Pulgarin, 2004; Habibi et al., are at their maximum oxidation
colloidal stability as screening
states resulting in their inability to
2005; Ozkan et al., 2004; effects become more profound.
inhibit the photocatalysis reaction.
Schmelling et al., 1997; Leng et 2 This was followed the double
The presence of Fe can catalyse
al., 2000; Wong and Chu, 2003; layer compression and surface Cl OH / Cl OH
both the Fenton and photo-Fenton
Wang et al., 2004; Chen et al., charge neutralisation, which
reactions. However Choi et al.
Cl h / Cl
1997; Riga et al., 2007; Guillard 2 increases the mass transfer
(1994) observed that Fe fouled
et al., 2003). It must be limitations and reduces surface
the photocatalysts surface by
emphasized, however, that most contacts between the pollut-ants
introducing an rusty orange
of these studies have concentrated colour change via the formation and catalysts. Other inorganic
The Cl accounted for its
on how different inorganic ions 3 ions also affect photo-degradation
of Fe(OH)3, while the PO 4 in the inhibitory effect on TiO2 photo-
2
affect the rates of photocatalytic nominal pH range remains rates, where the presence of SO 4 catalysis through a preferential
reactions with a model surrogate strongly adsorbed onto the TiO2 in a TiO2 coated glass spiral adsorption displacement
organic compound. The surrogate surface and further inhibits its reactor could double the mechanism over the surface
model organic compound can be photoactivity (Kerzhentsev et al., disappearance rate of the pesticide bound OH ions. This reduces the
biased towards its photocatalytic 1996; Abdullah et al., 1990). monocrotophos (Zhu et al., 1995). number of OH ions available on
performance owing to its Some research groups observed
2 The Mn
2
improved the the TiO2 surface, and the
underlying chemical properties that NO3 , SO 4 , ClO4 and HCO3 substituted Cl further increases
inhibit the surface activity of the photoactivity by simultaneously
and the main constituent groups increases the electronehole pairs the recombination of elec-
photo-catalysts, while others tronehole pairs. Among other
that form the compound. For and preventing their
instance, the model compounds suggest no such impact. Both NO3 chlorinated molecules, Cl ions are
2 recombination (Mu et al., 2004).
with either electron-withdrawing and SO 4 have detrimental effect readily released in the solution.
or donating groups will contribute on the photo-disinfection rate This effect could be of benefit in a
2 process where photocatalysis is
a different degree of interaction to (Habibi et al., 2005). The Cu
can enhance the photocatalytic Several mechanisms for associated with a biological
degradation pathways (Herrmann, fouling effects of inorganic ions
activity at its concentration up to depuration system, which is
1999). Due to the zwitterionic generally not efficient for
0.1 mM, while further increases in on TiO2 photoactivity have been
nature of the TiO2 particles used, its concentration reduce the proposed (Burns et al., 1999; chlorinated compounds
it is also possible that the reaction rate (Okonomoto et al., Rizzo et al., 2007). These include (Herrmann, 1999). Other ions
operating pH might have a 1985). Nitrogen-containing UV screening, competitive 3
such as PO 4 are known to avert
molecules are mineralized into adsorption to surface active sites,
profound effect on the selective
adsorption of amino acids over
inhibition of inorganic ions on the NH 4 and mostly NO3 . competition for photons, surface 2
the TiO2 catalysts, while CO 3
Ammonium ions are relatively deposition of precipitates and
surface of the TiO2 particles and other ionic species react with
stable and their proportion elemental metals, radical and hole
(Guillard et al., 2003). However, depends mainly on the initial OH radicals to compete with
scavenging and direct reaction
oxidation degree of nitrogen on microorganisms and further
few discussions have been centred
with the photocatalyst. The NO3 reduce the efficiency. Thus, the
on considering how the chemical the irradiation time. Pollutants
containing sulfur atoms are ion was reported to UV screening presence of inorganic ions in
nature of the model organic used the photocatalyst than inhibiting
mineralized into sulphate ions. water subjected to TiO2
and the operating pH in the
While Cl has no inhibition on the the TiO2 surface (Burns et al., photocatalytic treatment is an
photocatalytic reactor on the photo-catalytic degradation of 1999). The competition for impor-tant factor in determining
inhibition of different inorganic trichloroethylene at a surface active sites involves the its successful implementation.
ions in photocatalytic water concentration up to 3.0 mM. On constant displacement of
treatment. contrary, the addition of oxyanion
hydroxide ions from TiO2 surface
oxidants such as ClO2 , ClO3 ,
and thus, further reduces the To resolve TiO2
IO4 , S2O8 and BrO3 increased generation of radicals. Quantum
photo-reactivity by scavenging
photocatalyst fouling issue,
yield is reduced as a result of the
To date, the effects of both conduction-band electrons and direct competition of inor-ganic preventative or
reducing the charge-carrier

inorganic cations (i.e. Na , K , ions for light photons (lowered regenerative strategies can
recombination (Martin et al., number of photons entering the
2 2 2 2 2
Ca , Cu , Mn , Mg , Ni , 1995). The presence of salts is
reactor). A similar decrease in
be adopted, depending on
2 2 3 also known to diminish the
Fe , Zn , Al ) and inorganic photonic efficiency was observed the nature of the
anions (i.e. Cl , NO3 , HCO3 , when precipitates were formed
2 2 3
photocatalysts
ClO4 , SO 4 , HPO 4 , PO 4 ) on and deposited onto the TiO2
the photocatalytic water treatment
deactivation in the water
surface, blocking the accessibility
have been investigated (Rincon of both photons and organic matrix.
and Pulgarin, 2004; Habibi et al., compounds. The ultimate
inorganic anions that were
2005; O zkan et al., 2004;
determined to scavenge both the
Schmelling et al., 1997; Leng et ,
al., 2000; Wong and Chu, 2003; hole and radicals include Cl
Wang et al., 2004; Chen et al., 2 3
HCO3 , SO 4and PO 4 (Diebold,
1997; Riga et al., 2007; Guillard 2003). A mechanism for Cl and
et al., 2003). A general consensus
from these studies concludes that HCO3 in inhibiting photocatalysis
2 2 3 3 via hydroxyl radical and holes
Cu , Fe , Al , Cl , PO 4 at
scavenging was proposed by
certain levels may decrease
Matthews and McEnvoy, 1992;
photo-mineralization reaction
2 2 2 Lindner et al., 1995, respectively:
rates while Ca , Mg , Zn may
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3019
7.3. Heavy and noble pump and connecting tubing and
Fouling preventative strategies by metals agglomerate (few hundreds of are operated in batch mode
means of water pre-treatment, nm) when the conversion (Munoz et al., 2006). Further
complexation and photocatalyst Heavy metals that might be increased. Since the technical details of these plants
surface modifi-cations can be present in trace amount in the photosensitive surface was not can be found in the literature
wastewater stream are highly masked, a relatively large amount (Gernjak et al., 2006; Lapertot et
addressed, while rinsing the TiO 2
toxic in some of their valence of silver was recovered, leaving al., 2006).
surface with different chemical states (Kabra et al., 2004). Due to behind concentration of lower
solutions constitutes the the pliable nature of biological than the detection limits of atomic
regenerative strategies. Water pre- treatment, these intoxicant metals absorption spectroscopy ( 0.01
treatment with ion exchange can remain and permeate through ppm) in the solution. The effect of In order to assess these
resins is one of a few methods the treatment process. To treat various factors on the
that can be employed to ensure photocatalytic processes as
such metals, TiO2 photocatalytic photoreduction of silver on TiO2
minimal disturbances by emerging technologies for large-
process has been reported to surface were further investigated
inorganic ions. Burns et al. (1999) simultaneously convert these scale water/wastewater treatment,
(Huang et al., 1996). Angelidis et a life cycle assessment (LCA)
discussed that the operational cost metals into non-toxic ionic states
al. (1998) also reported that even
of water pre-treatment with ion and further reduced them into should be evaluated based on the
at low concen-tration of metal
exchange resins can be minimised their corresponding elemental currently available data. LCA is
ions, the photodeposition of
if the fouling ions were identified form on the TiO2 surface for one of the most widely accepted
and selectively removed. Other metals on the TiO2 surface from
metal recovery. Prairie et al. tools that not only consider the
preventative strat-egies such as solution was still effectively
(1994) reported that metals of environ-mental impact of the
complexation of fouling agents performed. However, they noted
Ag(I), Cr(IV), Hg(II) and Pt(II) emergent photocatalytic water
afterescorting the ions through that the rate of photodeposition
were easily treated with TiO 2 of treat-ment, but also its technical
the reactor can be utilised, was enhanced when Pt-loaded
0.1 wt% whereas Cd(II), Cu(II) was used instead of unloaded feasibility and costs. Andreozzi et
provided that the strong fouling and Ni(II) could not be removed. al. (1999) also pointed out that the
ions are hard to remove from the TiO2 particles. This metal
The extent of such metals potential application of ROS-
feed water stream. Modifications conversion and recovery process photodeposition property on TiO2 based oxidation processes entails
of the TiO2 surface to increase the are highly dependent on the surface is particularly useful when high costs for energy and
hydrophobicity and adsorption standard reduction potential of the the water legislation limit on the
reactants consumption. Thus, to
capacity is an upstream metals for the reduction reactions. metal contents becomes more
It was reported that for an consider the feasibility of
preventative way to enhance the stringent.
efficient removal of the metals, a photocatalytic water treatment on
rate of photodegradation in the
positive potential of greater than the whole, a compre-hensive LCA
presence of fouling ions.
0.4 V or the flat band potential of based on viable technical data
However, this method is unstable
TiO2 was required (Herrmann, should be carried out. Munoz et
and impractical compared to the
1999; Kabra et al., 2004). Since al. (2005) carried out a simplified
others, where the modifica-tions 8. Life cycle
are reported to be displaced away the rates of both oxidation LCA based on small-scale
assessment of
with time. As for the regenerative (organics) and reduction (metals) laboratory data of heterogeneous
photocatalytic water
strategies, different types of on the TiO2 surface are photocatalysis and other AOPs.
treatment processes
chemical rinsing were reported to intrinsically interrelated, the However, they found that small-
potentially resolubilize surface present of suffi-cient organics in scale labo-ratory data
In the current development of
deposits, precipitates and reduced the water matrices were found to interpretation in their LCA study
facilitate the metal recovery. The photocatalytic water/waste-water
metals. The fouled ions usually do can lead to inconclusive results.
redox process for the metal treatment processes, their possible
not form strong surface
application for the industry is still
complexes and can be easily reduction on the TiO2 surface is
being investigated at pilot plant
displaced by an ion exchange given below:
scale. A few pilot plants have
rinse. Abdullah et al. (1990) Using LCA, the
been established to obtain
reported that TiO2 fouling with feasibility data, such as the environmental burdens from a
SO
2
4 and PO
3
4 can be displaced treatment efficiency, site area product, process or activity via
TiO2 hv o
requirements for targeted volume, materials and energy balances can
by NaOH, KOH and NaHCO3,
Mn H2O /M nH electrical energy consumption, be defined and reduced as well as
while Cl can be easily regenerated
process emissions and chemical the waste discharges, its impacts
with water. More complex Herrmann et al. (1988) reported
costs. The heterogeneous photo- on the environment and the
mixtures of inorganic ions need to that small crystallites of silver (3
catalysis and photo-Fenton plants environmental improvement
be investigated to better mimic and 8 nm) were initially deposited
located at the INETI (Insti-tuto opportunities over the whole life
real water matrices in photo- and began to
Nacional de Engenharia, cycle (Consoli
catalytic water treatment or after
investigation of water matrices Technologia Industrial e
with one known inorganic ion Inovacao, Portugal) and PSA
composition at a time. (Plataforma Solar de Almeria,
Spain) are two renowned pilot
plants that have delivered most of
these data for technical analysis.
Both plants consist of compound
2
parabolic collectors (4.16 m
aperture area) exposed to sunlight,
a reservoir tank, a recirculation
3020 w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7
et al., 1993). This holistic LCA approach in decision making over other collector infrastructure and high power needed to pump the wastewater
environmental assessment approaches includes all the burdens and through the system. However, the results from the impact categories
impacts, and focuses on the emissions and wastes generated (Azapagic cannot be compared directly to each other as they were expressed in
and Clift, 1999). different measurement units. From the engineering point of view, these
Munoz et al. (2006) carried out a LCA based on the two pilot plants constraints mainly arise from the low photoactivity of the catalyst used
3 under solar irradiation. Further materials engineering solutions and studies
of INETI and PSA, which treated 1 m of methy-phenylglycerine (MPG)
to destroy non-biodegradable and toxic compounds to a level that met the should be carried out to resolve such technical issues to permit the scale-
quality of aquatic ecosystems with both homogeneous photo-Fenton and up of the technology to a commercially viable process.
heterogeneous photocatalysis. Other technically rationale assumptions
were also made to facilitate the estimation of energy and materials
consumed and produced. Nine impact categories of the possible large-
scale photocatalytic water treatment process were included in the analysis,
namely; global warming potential, ozone depletion potential, human 9. Future challenges and prospects
toxicity potential, fresh-water aquatic toxicity potential, photochemical
oxidant formation potential, acidification potential, eutrophication Semiconductor photocatalytic technology using either UV light or solar
potential, non-renewable energy consumption and land use. has become more prominent owing to its advantages of the use of vast
additive chemicals or disinfec-tants and its mineralization aspects. These
are particularly important, as recalcitrant organics are mineralized rather
than being transformed to another phase. Coupled with the ambient
Fig. 11 shows the LCA results for possible large-scale water operation of the process, all these make photo-catalytic water treatment
application using photocatalytic technology. The LCA results showed that technology a viable alternative for commercialisation in the near future.
the retrofitting of heterogeneous photocatalysis process to the existing Different water contaminants, ranging from hazardous contaminants of
biological wastewater treatment can lower eutrophication potential, but pesticides, herbicides and detergents to pathogens, viruses, coliforms and
require higher site area requirement and electricity consumption. These sporesare effectively removedby this photo-catalytic process.
technical constraints are a direct result from the requirement for a large
land area and the raw materials to build the parabolic
Fig. 11 e Life cycle impact assessment results for the alternatives under study (Munoz et al., 2006).
w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 2 9 9 7 e3 0 2 7 3021
photo-disinfection kinetics and (v) with chemical and physical
effective design of photocatalytic operations: a tool for
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