Journal of Environmental Management 208 (2018) 56e76

Contents lists available at ScienceDirect

Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Review

Advanced oxidation processes for the removal of natural organic

matter from drinking water sources: A comprehensive review
€a
Mika Sillanpa € a, b, Mohamed Chaker Ncibi a, *, Anu Matilainen c
a
Laboratory of Green Chemistry, School of Engineering Science, Lappeenranta University of Technology, Sammonkatu 12, 50130, Mikkeli, Finland
b
Department of Civil and Environmental Engineering, Florida International University, Miami, FL, 33174, USA
c
Finnish Safety and Chemicals Agency (Tukes), Kalevantie 2, 33100, Tampere, Finland

a r t i c l e i n f o a b s t r a c t

Article history: Natural organic matter (NOM), a key component in aquatic environments, is a complex matrix of organic
Received 3 August 2017 substances characterized by its fluctuating amounts in water and variable molecular and chemical
Received in revised form properties, leading to various interaction schemes with the biogeosphere and hydrologic cycle. These
10 November 2017
factors, along with the increasing amounts of NOM in surface and ground waters, make the effort of
Accepted 5 December 2017
Available online 14 December 2017
removing naturally-occurring organics from drinking water supplies, and also from municipal waste-
water effluents, a challenging task requiring the development of highly efficient and versatile water
treatment technologies.
Keywords:
AOPs
Advanced oxidation processes (AOPs) received an increasing amount of attention from researchers
NOM around the world, especially during the last decade. The related processes were frequently reported to be
Drinking water among the most suitable water treatment technologies to remove NOM from drinking water supplies
Removal efficiency and mitigate the formation of disinfection by products (DBPs). Thus, the present work overviews recent
Integrated processes research and development studies conducted on the application of AOPs to degrade NOM including UV
and/or ozone-based applications, different Fenton processes and various heterogeneous catalytic and
photocatalytic oxidative processes. Other non-conventional AOPs such as ultrasonication, ionizing ra-
diation and plasma technologies were also reported. Furthermore, since AOPs are unlikely to achieve
complete oxidation of NOM, integration schemes with other water treatment technologies were pre-
sented including membrane filtration, adsorption and others processes.
© 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2. NOM in drinking water supplies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3. AOPs for NOM removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.1. Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.2. Ozone-based processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.3. UV light-based processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.4. Fenton and photo/electro-Fenton processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.5. Heterogeneous catalytic and photocatalytic oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.5.1. Heterogeneous catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.5.2. Heterogeneous photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.6. Non-conventional AOPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

Abbreviations: AC, Activated carbon; AMW, Apparent molecular weight; AOPs, Advanced oxidation processes; BAC, Biological activated carbon; DBPFP, Disinfection by-
product formation potential; DBPs, Disinfection by-products; DOC, Dissolved organic carbon; EfOM, Effluent organic matter; FA, Fulvic acid; HA, Humic acids; HAA, Haloacetic
Acids; HAN, Haloacetonitrile; LEDs, Light emitting diodes; LP, Low pressure; NOM, Natural organic matter; PEC, Photoelectrocatalysis; PMR, Photocatalytic membrane reactor;
SUVA, Specific ultraviolet absorbance; THM, Trihalomethanes; TOC, Total organic carbon; US, Ultrasonication; WWTP, Wastewater treatment plant.
* Corresponding author.
E-mail address: chaker.necibi@lut.fi (M.C. Ncibi).

https://doi.org/10.1016/j.jenvman.2017.12.009
0301-4797/© 2017 Elsevier Ltd. All rights reserved.
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M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76 57

3.7. AOPs integrated with other water treatment technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

3.7.1. AOPs-membranes integrated process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.7.2. AOPs-adsorbents integrated process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.7.3. Other AOPs-based integrated processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4. Summary and future research directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

1. Introduction Thus, as far as NOM is concerned, enhancing the removal effi-

ciencies of those water treatment processes implies a better un-
Natural organic matter (NOM), commonly found in surface and derstanding of its characteristics and the variability patterns of its
ground waters, is a complex matrix of organic compounds resulting composition and amounts in drinking water sources. Such com-
from various interactions between the hydrologic cycle, biosphere bined data, along with the chemistry and hydrology of the water
and geosphere (Matilainen et al., 2010; Sillanpa €a
€, 2015). In general, body itself, will enable a more reliable assessment of the reactivity
NOM originates either from outside the water body including the of NOM or its surrogates, and thus design and apply a reliable
breakdown of terrestrial organisms (allochthonous NOM) or treatment process. In this regard, considering the high variability of
generated in situ via microbial and/or algal activities (autochtho- NOM (quantity and quality wise), no single technology is able to
nous NOM) (Fabris et al., 2008). The former type of NOM reaches remediate the NOM issue in drinking water supplies, hence the
the water sources via drainage within watersheds. Therefore, its need to design and develop more advanced or integrated processes
composition, mainly of humic character, is highly influenced by the able to perform better than the current process based on coagula-
geology, hydrology and potential land-use changes in the original tion and flocculation, followed by sedimentation/flotation and
location (Hudson et al., 2007). On the other hand, autochthonous filtration (Sa€rkka€ et al., 2015; Bhatnagar and Sillanpa
€a€, 2017).
NOM, formed in the water body through microbial and algal ac- The present review is an overview of the recent research studies
tivities, is mainly consisting of soluble organic matter such as car- dealing with AOPs for the removal of NOM and derived organics
bohydrates, amino acids, peptides, enzymes and toxins (Her et al., from drinking water supplies. It is an updated and more elaborate
2004). version of our previous review paper (Matilainen and Sillanpa €a
€,
In addition to the impacts of the sources of organic matter and 2010). In this study, new R&D finding in the field of NOM
the originating, the composition of NOM also depends on the water removal using AOPs, reported in the scientific literature between
chemistry, temperature, pH and biological processes in the water 2010 and 2016, are detailed and discussed. First, NOM behavior in
body (Sillanpa €€
a, 2015). Thus, even for the same location, the water sources and the related problematic issues before, during and
amount and composition of NOM tend to substantiality vary with after conventional water treatment processes are highlighted.
respect to seasonal changes affecting factors such as floods, Then, the efficiencies of various AOPs applied for NOM removal
droughts, rainfalls, snowmelt runoffs (Sharp et al., 2006; Nkambule from drinking water supplies are presented and analyzed along
et al., 2012a). The first two factors, frequently associated with with various interesting integrated schemes with other water
climate change, have a highly visible impacts on the availability of treatment technologies. In the final section, insights on future
water resources and their quality (Hirabayashi et al., 2008; challenges to the field of water treatment are presented and
Kundzewicz et al., 2014). The combination of these climatic commented.
changes were reported to be one of the main reasons for the
increased total amount of NOM in water sources observed world-
wide during the past couple of decades (Eikebrokk et al., 2004; 2. NOM in drinking water supplies
Delpla et al., 2009; Metsa €muuronen et al., 2014).
In this context, the frequent changes in NOM amounts and Drinking water supplies contain NOM at variable compositions
composition have a direct impact on the overall efficiencies of and amounts depending on to the origin of the water sources, the
water treatment processes applied to remediate the issues posed by biological activities and geochemical cycles of the surrounding
NOM in drinking water supplies. Thus, selecting the proper water watershed (Teixeira and Nunes, 2011; Ritson et al., 2014). It was
treatment technology or, most of the time, a combination of reported that dissolved NOM is one of the most ubiquitous com-
selected technologies, is a prerequisite to design and operate pounds on earth and its average concentration in natural waters is
treatment facilities able to face high seasonal variability of NOM. As ranging between few mg/L to hundreds of mg/L (Wall and Choppin,
well, the increasing concentration levels of NOM is posing a serious 2003).
challenge to water treatment processes not only the move the The first endeavor to understand the reactivity of NOM in
natural organic matter from water but also their efficiencies to aquatic environment is to determine its composition and the
remove other organic and inorganic pollutants. Indeed, for the encompassed functional groups. Such task is both essential and
membrane-based technologies, NOM is frequently reported to be very challenging mainly due to the heterogeneity of NOM, its
one of the most problematic fouling agents inducing pore nar- spatiotemporal variations and the structural complexity of its
rowing and even blocking, and the formation of loose cake layer components (Mao et al., 2017). In general, NOM found in drinking
(Cheng et al., 2017). For chemicals-based processes such as oxida- water sources could be arranged into two main groups: hydro-
tion and coagulation, the increasing amounts of NOM in leading to phobic and hydrophilic components. The differentiation between
the utilization of more chemicals and the formation of more sludge the hydrophobic and hydrophilic character of NOM is one of the
(Xu et al., 2016). As well, the efficiency of the adsorption technique characterization tools adopted by researchers, along with further
to remove a wide range of micropollutants from contaminated identification measures such as acidic, alkaline or neutral com-
waters tend to decrease due to the competitive impact of NOM pounds (Papageorgiou et al., 2016).
(Ding et al., 2006; Qi and Schideman, 2008). In this context, it was shown that the main chemical compounds
in NOM are hydrophobic acids of humic character constituting
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M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76
around half of the total organic carbon (TOC) in water (Thurman,
1985). This includes (i) humic acids (HA), soluble in alkali, but
insoluble in acidic waters at pH < 2, (ii) fulvic acids (FA), soluble in
both alkali and acid and (iii) humins, which are insoluble in both
alkali and acid media (Gaffney et al., 1996). Various analytical
studies revealed that while hydrophobic NOM is rich in aromatic
and phenolic compounds, hydrophilic NOM fraction is character-
ized by more aliphatic and nitrogenous compounds including car-
bohydrates and proteins (Goslan et al., 2017). Moreover, the
physicochemical fractionation of NOM in natural waters at specific
pH, as well as the chain length and functional groups, can be used
for additional categorization of the dissolved organic compounds
included within the two main fractions of hydrophobic and hy-
drophilic NOM (Chow et al., 2004; Buchanan et al., 2005; Sharp
et al., 2006). Another method to express NOM hydrophobicity is
the estimation of the specific ultraviolet absorbance (SUVA) which
is defined as the UV absorbance at 254 nm divided by the TOC
concentration (Hua et al., 2015). Such method is based on the
characteristics of aromatic and humic compounds to exhibit higher
absorption at 254 nm than aliphatic and non-humic substances
(Weishaar et al., 2003). Thus, high values of SUVA would revealed
that the NOM contained in the analyzed water sources is mainly
composed of hydrophobic, high molar mass organic compounds,
whereas low SUVA values would designate a NOM fraction mainly
composed of hydrophilic, low molar mass compounds (Ghernaout,
2014).
The following Table 1 shows the variability of NOM hydrophobic
and hydrophilic fractions in various water bodies (natural waters
and the influents of wastewater treatments plants) from around the
world.
As the NOM is produced in, or channeled to, the water body, it
starts to interact with the contained chemical compound. Such
interactions are very variable and thus detrimental to various water
treatment techniques. Indeed, several of these interactions tend to
modify the chemical reactivity of pollutants in surface and ground
waters which could substantially lower the removal efficiency of
chemicals-based water treatment technologies, if those chemicals
changes are not acutely determined beforehand.
For instance, the presence of NOM in natural waters tend to
increase the solubility of hydrophobic anthropogenic compounds,
therefore their bioavailability (Wershaw and Hayes, 2001). As well,
the NOM fraction in water, especially HA and FA, has strong
complexation ability with heavy metals, thus forming organome-
tallic complexes which affects the transportation, bioavailability
and toxicity of those metals (Karlsson et al. 2005; Tang et al., 2014).
Thus, although not inherently toxic, NOM seriously affects the
quality of drinking water supplies either indirectly as a carrier of
toxic metals and hydrophobic organic chemicals or directly by
inducing unpleasant modifications to the organoleptic properties of
water including color, taste and odor (Mohora et al., 2012;
Sillanpa€€
a, 2015). More important is the contribution of NOM in
Table 1
Various NOM fractions in different water bodies.
Water body Location
Millstone River New Jersey, USA
Ulu Pontian River Johor, Malaysia
Drinking water plant intakes Repentigny, Canada
Waco, Texas, USA
Winnipeg, Canada
Luan or Yellow River Tianjin, China
Water source of the Harbin water treatment plant Harbin, China
Water source of the Zahedan drinking Zahedan, Iran
water treatment plant
the formation of disinfection by-products (DBPs) (Bond et al., 2014;
Zheng et al., 2016), which could lead to carcinogenic compounds
such as halogenated trihalomethanes (THMs), haloacetic acids
(HAAs), haloacetonitriles, haloketones and trichloronitromethane
(Bond et al., 2012; Serrano et al., 2015). Therefore, the need to
develop reliable removal processes is an important R&D subject
which will enable the remediation, or at least mitigation, of the
serious direct and indirect problems caused by the presence of
NOM in drinking water sources and its derived toxic compounds
generated by conventional disinfection methods.
In the following section, a comparative assessment of the effi-
ciencies of various AOPs to remove NOM from natural or artificially
contaminated waters and mitigation the formation of DBPs is car-
ried out based on the latest studies in the field (2010e2016).
Furthermore, integrated processes to remove NOM from drinking
water supplies coupling AOPs with other water treatment tech-
niques such as adsorption and membrane separation are also
discussed.
3. AOPs for NOM removal
3.1. Overview
R&D studies on the applicability and efficiency of AOPs for water
and wastewater treatment were conducted during the course of the
last 30 years or so (Parsons and Byrne, 2004). Nevertheless,
monitoring the scientific publications in Elsevier's ScienceDirect
from 2001 to 2016 (Cf. graphical abstract) clearly reveals that the
research investigations on this subject are still gaining momentum
around the world, especially during the last seven years (covered in
the present review), where the number of related papers almost
doubled (2805 articles in 2010e6259 in 2016).
Such increase in the NOM and AOPs-related scientific produc-
tion could be explained by two main reasons, the first is associated
with AOPs in general and the second is specific to NOM.
(i) AOPs have shown promising potentialities to remove pol-
lutants for water media but further R&D are needed to
improve their efficiencies, cope with increasing amounts of
NOM is natural waters, control and limit the formation of
DBPs and develop less expensive installation and operation
schemes.
(ii) Due to its highly heterogonous character, studies on NOM
removal from water bodies using AOPs are basically specific
study cases, hence the still increasing number of scientific
articles.
Basically, the developed AOPs for the removal of NOM and
various organic pollutants are the combination of oxidants, mainly
ozone (O3) and/or hydrogen peroxide (H2O2), with different cata-
lysts and/or radiation (UV, sunlight or artificial light). Thus,
Hydrophobic Hydrophilic References
fraction (mg/L) fraction (mg/L)
0.5 2.3 Marhaba and Lippincott (2000)
2.4 2.6 Zularisam et al. (2006)
4.0 1.4 Hua and Reckhow, 2007
2.1 1.1
3.4 2.1
1.3 1.0 Chen et al. (2008)
43.8 15.6 Lu et al. (2009)
4.5 2.7 Bazrafshan et al. (2012)
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M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76 59

Table 2
Selected research studies on the removal of NOM from waters using ozone-based AOPs, conducted between 2010 and 2016.

Targeted organic Water source O3-AOP features Monitored parameters Main results References
compounds

< O3 combined with H2O2 and/or UV:

Bromate (BrO
3) Natural water from O3 dose: 3.2 and 4.2 mg/L Ozone consumption, - An O3 dose of 4.2 mg/L and a H2O2/O3 ratio Wang et al. (2013a)
the Yellow river (China) Various O3/H2O2 bromate formation above 1 was necessary to maintain the
pretreated with ratios (0e2.5) and THMFP BrO3 concentration below 10 mg/L.
sand filtration The used pilot-scale - Conversely, the addition of H2O2 to the
apparatus ozonation process decreased its efficiency to
is depicted in Fig. 2 reduce THMFP.
- The need to balance BrO 3 reduction and
THMFP control when combining O3 and H2O2.
Bromate and HA Simulated natural O3 dose: 2 mg/L Bromate formation, - The HAs exhibited inhibitory effect towards Zhao et al. (2013)
waters Low pressure (LP) DOC and UV254 bromate formation, in both O3 and UV/O3
UV at 254 nm processes.
- Reducing the ozone dosage in UV/O3 process
reduced the residual O3 concentration and

OH exposure, thus leading to reduction in the
rates of HA removal and bromate formation.
NOM, HAA Raw water from a pond O3 dose: 1e2 mg/mg DOC DOC, UV254, AMW - Compared to simple ozonation, AOPs reacted Black and
and THM (Vancouver, Canada) H2O2: 10 mg/L distribution with all molecular weight NOM fractions rube
Be  (2014)
LP UV at 254 nm of NOM and DBPFP equally.
- Ozonation and AOPs similarly affected both
the biodegradable and non-biodegradable
fractions of DOC.
- Overall, reduction around 45% for both THM
and HAA formation potentials.
NOM Groundwater from a O3 dose: 0.5 mg/L TOC, UV254, SUVA, - THMFP and HAAFP were respectively reduced Agbaba et al. (2016)
100 m deep well H2O2 dose: 10 mg/L THMFP and HAAFP by 43% and 68% during the O3/H2O2/UV
(Vojvodina, Serbia) LP UV at 254 nm process.
UV fluence (dose): - The applied AOPs did not significantly reduce
0.6 and 3 J/cm2 the total NOM content, but changed its
structure and degree of hydrophobicity.
- Bromate formation was observed only in the
O3-based processes (i.e. in O3/UV and O3/
H2O2/UV and not in H2O2/UV)
NOM Natural water from O3 dose: 2.9 and 3.4 mg/L Fluorescence, DOC - The application of H2O2/O3 lead to substantial Peleato et al. (2017)
the Otonabee H2O2/O3 ratios of 0.5 and 1 and UV254 reductions of terrestrial humic-like com-
river (Ontario, Canada) pounds in the water (down to 10e25%,
depending on the initial amount and
composition of NOM in the water samples).
- The results were in contradiction to other
studies reporting the preferential character
of H2O2/O3 and O3 for high molecular weight
organic compounds.

advanced oxidation processes include O3/H2O2 peroxone process
(Allemane et al., 1993), UV/H2O2 (Lin and Wang, 2011), UV/O3 (Zhao
et al., 2013), UV/TiO2 photocatalytic oxidation process (Murray
et al., 2007), Fe2þ/H2O2 Fenton and Fe2þ/H2O2 þ hv photo-Fenton
processes (Murray and Parsons, 2004.), vacuum ultraviolet (VUV)
(Thomson et al., 2004) and ultrasonic (Naddeo et al., 2007)
radiations.
Under near ambient temperature and pressure, the efficiency of
AOPs for the degradative removal of organic compounds from
waters is mainly based on the generation of high amounts of hy-
droxyl radicals (HO) whether by photolysis, ozone, hydrogen
peroxide or irradiation (Glaze et al., 1987; Sillanpa €€
a, 2015). Once
generated, the hydroxyl radicals are highly reactive species and
thus can unselectively react with organic molecules with rate
constants commonly ranging between 106 and 109 L mol1 s1
(Hoigne, 1997; Rosario-Ortiz et al., 2008), which are several orders
of magnitude higher than for chlorine and ozone (Crittenden et al.,
1999). Reaction wise, hydroxyl radicals generated by AOPs tend to
interact with the organic matter through three main mechanisms:
(i) hydrogen abstraction from aliphatic carbon atoms yielding
carbon-centred radicals, (ii) electrophilic addition to double bonds
or aromatic rings, and (iii) electron transfer reactions, where HO
gains an electron from an organic substituent (Legrini et al., 1993;
(Matilainen and Sillanpa €€
a, 2010). The generated organic radicals
continue reacting, prolonging a series of chain reactions.
The high oxidizing capabilities of HO could enable AOPs to
achieve complete oxidation or mineralization of organic contami-
nants at near ambient temperature and pressure. Nonetheless, to
reach this level of degradation, strong oxidation conditions are
needed including higher O3 or H2O2 concentrations and/or long
irradiation times, which will directly affect the prospective large
scale application of AOP mainly for economic reasons related to the
cost of chemicals and the frequent need for maintenance opera-
tions. Thus, for commercial drinking water applications, AOPs are
generally applied under low to moderate oxidation conditions. In
this case, NOM is partially oxidized and higher molecular weight
compounds are transformed into smaller one, such as aldehydes
and carboxylic acids, which are more biodegradable molecules
(Kleiser and Frimmel, 2000; Sarathy and Mohseni, 2009; Liu et al.,
2015). Thus, even under low to mild operating conditions, AOPs are
able to induce chemical modifications to NOM resulting in the
overall decrease of TOC and DBPFP in the treated waters
(Amirsardari et al., 2001; Toor and Mohseni, 2007).
In the following sections, the latest R&D investigations con-
ducted around the world on NOM removal using AOPs are pre-
sented and analyzed in order to comparatively assess the
efficiencies of various AOPs to remove NOM from drinking water
supplies while mitigating the formation of DBPs.
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3.2. Ozone-based processes
Ozone (O3) is strong oxidant frequently used to disinfect waters
and wastewater and for to degradation NOM and organic pollutants
via oxidation (Papageorgiou et al., 2017). Reaction wise, O3 could
interact with NOM through two main mechanisms:
(i) Directly: by electrophilic interactions with specific functional
groups, mostly double bonds and aromatic rings of the
organic compound. This selective method is referred to as
ozonolysis (Carr and Baird, 2000; Dantas et al., 2008).
(ii) Indirectly: the decomposition of O3 in water leads to the
formation of HO and thus the indirect, non-selective, fast
oxidation of the organic matter (Buffle et al., 2006).
Since the generation of hydroxyl radicals via ozonation is
relatively low, additional measures were taken in order to increase
the production of HO which has led to the development of ozone-
based AOPs. This included the addition of H2O2 to the conventional
ozonation process, aka. peroxone process (Duguet et al., 1985;
Irabelli et al., 2008), the combination of ozone with UV irradia-
tion (Chin and Berube, 2005) and the integration of the three
components (Legrini et al., 1993; Camel and Bermond, 1998). As
well, the addition of catalysts to the ozonation process, mainly TiO2
(Allemane et al., 1993) and certain activated carbons (Oh et al.,
2004), were widely reported to promote the decomposition of O3
into highly reactive HO. The combination of O3, TiO2 and UV is
presented in the catalytic oxidation section. It has to be noted that
promoting the decomposition of O3 into HO deceases the disin-
fection capabilities of the process. Thus, if a combined mode of
action (i.e. disinfection and oxidation) is sought, then a well
calculated estimation of the required decomposition rate of O3 is
necessary to ensure the efficiency of the overall ozone-based pro-
cess (von Gunten, 2003).
Among the latest research studies conducted on the application
of ozone-based AOPs for the removal of NOM from natural and
artificially contaminated solutions, Tubi c et al. (2011) carried out a
pilot-scale experiment to study the effect of various O3/H2O2 ratios
on the removal of NOM from groundwater source in Serbia. The
Fig. 1. Schematic representation of the pilot-scale setup used for the treatment of a bromide-containing source water using O3 or O3/H2O2-biological activated carbon (BAC)
processes (Wang et al., 2013a).
main finding was that the higher ratio of O3/H2O2 (2/1) was more
efficient to remove NOM than a lower ratio (1/2). According to
Treguer et al. (2010), an increased dosage of O3 modifies the hy-
drophobic/hydrophilic distribution of the dissolved organic carbon
(DOC) in water by transforming NOM into more hydrophilic and
lower molecular weight compounds. The influence of O3/H2O2 ratio
as well as the dosage of each reagent were also confirmed in other
studies to be highly influential factors on the efficiency of the
peroxone process to mineralize organic compounds (Yoon et al.,
2014; Wu and Englehardt, 2015).
It was reported that the addition of H2O2 to the ozonation
process helps enhancing the degradation rates of organic pollutants
by accelerating O3 decomposition into the highly reactive and
nonselective HO (Antoniou and Andersen, 2012), according to the
following reaction:
H2O2 þ 2 O3 / 3 O2 þ 2 HO (1)
In this regard, an interesting study revised the current mecha-
nistic concepts related to the reaction of O3 with H2O2 in the per-
oxone process based on thermo-kinetic and quantum-chemical
considerations (Merenyi et al., 2010). Other recent studies focused
on assessing and quantifying the NOM fraction in waters treated by
ozone-based processes as well as the properties and weight dis-
tribution of the generated compounds (Lamsal et al., 2011; Bazri
et al., 2012).
The following Table 2 summarizes the operating conditions and
the main findings of selected R&D studies conducted around the
world between 2010 and 2016 on the application of ozone-based
AOPs to remove NOM from natural waters or synthetic aqueous
solutions. For illustration, Fig. 1 depicts a pilot-scale setup used for
the treatment of a bromide-containing source water using O3 or O3/
H2O2-biological activated carbon (BAC) processes (Wang et al.,
2013a).
3.3. UV light-based processes
Water treatment processes based on UV light involve the use of
an artificial light source generally low or medium-pressure
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mercury vapor lamps. In this case, the degradation of the organic
matter occurs directly via photolysis (i.e. photodecomposition),
which depends on the ability of the targeted compounds to absorb
€€
the emitted light (Goslan et al., 2006; Sillanpa a, 2015).
The AOP based on the combination of UV and H2O2 is a well-
established process widely reported by many researchers to
significantly improve the removal efficiency of NOM from natural
waters and synthetic aqueous solutions (Wang et al., 2000;
Gonzalez et al., 2013, The main asset of this AOP is that it com-
bines the photolytic activity of UV and the strong oxidative
mechanism of OH radicals generated by the photocatalytic disso-
ciation of H2O2 (Rosenfeldt et al., 2006).
Commonly, UV-based processes are used in WWTPs (tertiary
treatment) for disinfection purpose either alone (Thompson et al.,
2003) or in combination with chemical disinfectants (Koivunen
and Heinonen-Tanski, 2005). Regarding the application of UV-
based AOPs for the removal or reduction of NOM in waters, an
increasing number of studies were, and are being, conduced
worldwide especially during the last decade or so. Such surge is
mainly due to the increasing amounts of NOM in drinking water
sources and the fact that the commonly applied UV fluence and
H2O2 concentrations for water disinfection were not able to remove
NOM (Sarathy and Mohseni, 2007).
Most of the previous research studies were conducted using
strong advanced oxidation conditions with UV fluences higher than
2.5 J/cm2) and high peroxide concentrations (Kleiser and Frimmel,
2000; Toor and Mohseni, 2007). Although such operating condi-
tions led to substantial removal of NOM and reduction of DBPFP, the
overall process were not economically feasible for large-scale ap-
plications. Usually, the commercial UV/H2O2-based process for the
treatment of drinking water supplies involves the application of
below 2 J/cm2 and initial H2O2 concentrations below 15 mg/L
(Sarathy et al., 2011).
Within this R&D effort, a Canadian study confirmed that
changes in the structural properties of NOM did occur with
economically acceptable UV fluences and H2O2 concentrations
(Sarathy et al., 2011; Lin and Wang, 2011). Thus, it was reported that
the UV/H2O2 process was responsible for:
(i) the decrease of molecular size of the NOM fraction,
(ii) the generation of more biodegradable compounds including
aldehydes, carboxylic acids, amino acids and low molecular
weight alcohols,
(iii) the reduction of NOM aromaticity, and
(iv) the decrease of its hydrophobicity.
In this context, it was started that differences in the spectrum of
medium pressure and low pressure UV lamps tend to modify the
chemical bonds in various ways, which leads to the formation of
different degradation compounds (Metz et al., 2011). Lately, some
drawbacks related to the use of conventional UV lamps were
revealed including instability after long utilization due to over-
heating and low photonic efficiency resulting in high energy con-
sumption, which could justify promoting the application of light
emitting diodes (LEDs) as new sources for UV irradiation source in
photolytic (Umar et al., 2015) and photocatalytic degradation
(Daniel and Gutz, 2007).
Besides, as far as the UV/H2O2 in concerned, other researchers
emphasized upon the need to adequately adjust the amount of
peroxide in this AOP since any excess in H2O2 might act as HO
scavenger, thus reducing the NOM removal efficiency (Song et al.
2012).
In an interesting review paper, Michael-Kordatou et al. (2015)
reported, after studying several papers on the removal of dis-
solved EfOM using UV-based AOPs, that during such processes the
61
structural characteristics of the organic compounds in effluent
waters including aromaticity, carbon bonding and functional, along
with their removal efficiencies are directly related to:
(i) the reactivity with the hydroxyl radicals,
(ii) the molar extinction coefficient and the MW of the
compounds,
(iii) the presence of inorganic chemical species in the water
including carbonates/bicarbonates and chlorides.
(iv) the UV fluence.
Regarding the VUV treatment, highly oxidizing HO are gener-
ated by the photolysis of water at wavelengths lower than 190 nm
(Gonzalez et al. 2004). The application of VUV was reported by
many researchers to have a high efficacy removing NOM from
drinking water supplies (Thomson et al., 2004; Imoberdorf and
Mohseni, 2013) and wastewaters loaded with organic matter,
either alone (Xing et al., 2015) or in combination with peroxide
(Naderi et al., 2017).
The following Table 3 presents the operating conditions and the
main findings of selected R&D studies conducted around the world
between 2010 and 2016 on the application of UV-based AOPs to
remove NOM from natural waters or synthetic aqueous solutions.
3.4. Fenton and photo/electro-Fenton processes
The conventional Fenton process involves the combination of
peroxides, commonly H2O2, and a metal salt or oxide catalyst,
commonly iron. In aqueous solutions, the Fenton's reagent (H2O2
with Fe2þor Fe3þ) generates mainly hydroxyl radical (HO) and to a
lesser extent peroxyl radicals (RO2) (Wardman and Candeias, 1996;
Park and Yoon, 2007). These highly reactive and indiscriminate
radicals produced by the Fenton reaction (Eq. (2)) or the Fenton-
like reaction (Eq. (3)) could, under optimized operating condi-
tions, lead to the complete mineralization of the organic matter in
the treated water (Moncayo-Lasso et al., 2008).
Fe2þ þ H2O2 / Fe3þ þ OH þ HO (2)
Fe3þ þ H2O2 / Fe2þ þ Hþ þ HO2 (3)
The photo-Fenton process is basically a photo-assisted Fenton
reaction involving either natural irradiation from sunlight or an
artificial light source. This photo-assistance promotes the genera-
tion of HO which quickly interact with organic compounds and
thus help increasing the decomposition rate of the targeted organic
matter (Fukushima et al., 2001; Ortega-Go  mez et al., 2014).
The NOM removal efficiencies of the Fenton and photo-Fenton
processes in directly influenced by the concentrations of peroxide
and ferrous ions, pH and reaction time, in the one hand, and the
amount and characteristics of the NOM, on the other hand. Thus, in
order to ensure high mineralization rates, the optimization of those
operating parameters is necessary to develop reliable Fenton-based
processes readily applicable to remove organic matter from
drinking water sources (Ijpelaar et al., 2002; Murray and Parsons,
2004; Kalajd zi
c et al., 2013), treated wastewaters (Zhu et al.,
2011; Hodaifa et al., 2013), as well as landfill leachates (Zhang
et al., 2005; Umar et al., 2010).
Several R&D investigations studied the influence of those key
operating conditions for various Fenton-based oxidative processes,
especially pH which is one of the main influencing parameters. In
this context, many previous and recent studies reported that the
optimum pH for the Fenton and photo-Fenton reactions is generally
between 3 and 4 (Waite, 2002; Park and Yoon, 2007; Moncayo-
Lasso et al., 2008; Saeed et al., 2015).
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Table 3
Selected research studies on the removal of NOM from waters using UV-based AOPs conducted between 2010 and 2016.

Targeted organic Water source UV-based AOP features Monitored parameters Main results References
compounds

< UV/H2O2:
NOM Surface water from the LP UV at 254 nm UV254, TOC, SUVA, - The UV/H2O2 process reduced UV254 by 60% Lamsal et al. (2011)
French river (Nova UV fluence: 1.14 J/cm2 THMFP and HAAFP and TOC by 23%.
Scotia, Canada) H2O2 dose: 23 mg/L - Treatment of the raw water with the UV/H2O2
resulted in the highest reduction of THMFP
(77%) and HAAFP (62%), compared to the
other ozone-based treatments.
Effluent organic Effluent water from a LP UV at 254 nm UV254, DOC and SUVA - The UV/H2O2 process decreased the Audenaert et al.
matter (EfOM) municipal WWTP H2O2 dose: 2 and 4 mM absorbance due to the partial oxidation of (2013)
(Harelbeke, Belgium) chromophoric moieties of EfOM.
- UV/H2O2 modified the polarity of EfOM so
that, at the end of the treatment, most of
the DOC become hydrophilic.
NOM Everglades water LP UV at 254 nm DOC, UV254, and H2O2 - The optimum operating conditions for the Sindelar et al.
(Florida, USA) UV fluence: 2.4 J/cm2 residuals reduction of UV254 and DOC in the tested (2014)
H2O2 dose: 100 mg/L water were UV fluence between 21.8 and
22.3 J/cm2, and the H2O2 dose of 100 mg/L.
- Compared with other oxidants (percarbonate
and perborate), H2O2 was the most efficient
chemical agent in the studied AOPs for the
reduction of DOC.
NOM Groundwater from a LP UV at 254 nm TOC, UV254, SUVA, - Increasing the UV in the combined UV/H2O2 Agbaba et al. (2016)
100 m deep well UV fluences: 0.6 and 3 J/ THMFP and HAAFP process enhanced the formation of
(Vojvodina, Serbia) cm2 aldehydes and carboxylic acids.
H2O2 dose: 10 mg/L - High formations of bromate, THMFP and
HAAFP were observed for the UV/H2O2
HA Synthetic HA solutions LP UV at 254 nm DOC, UV254, SUVA and - The results showed that the UV/H2O2 
Cehovin et al.
UV fluence: 0.3 and the formation of THMs advanced process requires high peroxide (2017)
1.8 J/cm2 and HAAs concentrations and performs better at low
H2O2 dose: 4 and UV254.
12 mg/L - High formation of THMs and HAAs were
reported.
< VUV in combination with UV, O3 or H2O2
NOM Water samples from VUV Hg lamp emitting DOC, UV254, AMW - The combination of VUV and ozone gave the Ratpukdi et al.
the radiation at 254 distribution of NOM best performance with respect to DOC and (2010)
Moorhead water and biodegradability UV254 reduction and biodegradability, when
treatment plant (MN, compared with ozone, UV, VUV and ozone/UV
USA) processes.
- The hydrophilic neutral compounds
constituted the main NOM fraction after
oxidation (39e87%).
NOM Raw surface water from VUV Hg lamp emitting TOC and AMW - VUV and VUV/H2O2 processes were more Imoberdorf and
Trepanier Creek (British radiation at 254 and distribution of NOM effective to decompose NOM than UV and Mohseni (2011)
Columbia, Canada) 185 nm UV/H2O2.
- 99% of the 185 nm radiation was absorbed by
the raw water in the VUV reactor, compared
with 48% for the 254 nm radiation.
- Carbonates and bicarbonates were found to
block the propagation of the 185 nm
radiation.
NOM Two natural and two VUV Hg lamp TOC, AMW distribution - High UV and VUV fluences led to the Ratpukdi et al.
synthetic waters of NOM and the complete mineralization of NOM. (2010)
formation of aldehydes - Faster mineralization rates for waters
and THMs containing NOM with lower AMW.
- The formation of aldehydes and THMs started
to decease when applying fluences above 4 J/
cm2.

Although operating conventional Fenton-based processes in
acidic conditions helps enhancing their efficiencies to decompose
organic matter and prevents the precipitation of the ferrous ions,
several drawbacks are frequently encountered including:
- The need to acidify the raw water and then neutralize the
treated water (Neyens and Baeyens, 2003; Sillanpa €a
€, 2015).
- Usually high concentration ferrous ions (50e80 ppm) are
required to ensure the effective removal of organic contami-
nants, which could substantially increase the iron levels in the
treated effluent water to be discharged into the environment
(threshold around 2 ppm) (Guo et al., 2015).
- The accumulation of iron-loaded sludge requires additional
treatment to lower the iron content before the final discharge of
the sludge.
Several research studies were conducted to find out to potential
valorization schemes of the iron-loaded sludge. A previous study
managed to apply the Fenton-derived sludge as a coagulant for
wastewater pre-treatment prior the Fenton process, which help
reducing the used amount of conventional coagulants by 50% (Yoo
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M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76
Fig. 2. Schematic representation of lab-scale experimental setup for the electro-Fenton process (Yu et al., 2013).
et al., 2001). Recently, many research teams reported the successful
reuse of iron-containing sludge as an iron source for the Fenton-
based process in wastewater treatment (Kishimoto et al., 2013;
Bolobajev et al., 2014).
Regarding the electro-Fenton process, it could be operating via
four different configurations:
(i) In the first one, both Fenton reagents (H2O2 and Fe2þ) are
added (ex-situ) to the reactor and anodic electrodes with
high catalytic activity are used. The electrochemical regen-
eration of Feþ2 from Feþ3 is also included (Qiang et al., 2003).
The lab-scale experimental setup of this configuration is
depicted in the following Fig. 2.
(ii) In the second scenario, only H2O2 is added to the reactor
since the ferrous ions are provided from sacrificial cast iron
anodes (Atmaca, 2009).
(iii) In the third one, only the iron catalyst is added since the H2O2
is continuously produced in situ via electro-generation at a
suitable cathode fed with O2 or air (Brillas et al., 2009; Qiu
et al., 2015)
(iv) In the fourth configuration, both Fenton reagents are pro-
duced in situ (Ventura et al., 2002; Xu et al., 2015).
63
Thus, among the various possible configurations of the electro-
Fenton process, the in situ production and regeneration of the
Fenton reagents (i.e. H2O2 and/or Fe2þ) are the most promising
scenarios for real case applications, in comparison with the con-
ventional Fenton process. Indeed, many R&D studies (Oturan and
Brillas, 2007; Jiang and Zhang, 2007; Olvera-Vargas et al., 2015;
Ren et al., 2016) agreed that the main advantages of this indirect
electro-oxidation process compared with the chemical Fenton
process include:
(i) The continuous on-site production of H2O2 and production/
generation of the iron catalyst, which help avoiding potential
risks related to the transportation, storage and handling of
those chemicals.
(ii) the possibility of controlling degradation kinetics to allow
mechanistic studies,
(iii) the higher degradation rate of organic pollutants because of
the continuous regeneration of Fe2þ at the cathode, which
also minimizes sludge production, and
(iv) the feasibility of overall mineralization at a relatively low
cost if the operation parameters are optimized.
The examination of the literature related to the electro-Fenton-
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Table 4
Selected research studies on the removal of NOM from waters using Fenton-based AOPs conducted between 2010 and 2016.

Targeted organic Water source Fenton-based AOP Monitored parameters Main results References
compounds features

< Fenton and photo-Fenton processes:

HA Synthetic HA Fe2þ: 5e240 mM TOC and absorbance - The oxidation process mostly occurred within the Wu et al. (2011)
solutions H2O2: 80e360 mM first hour.
pH: 4 - Increasing the H2O2 concentration up to 160 mM
enhanced the degradation process.
- The addition of the iron catalyst enhanced the HA
degradation up to a concentration of 60 mM.
HA Synthetic HA Fe2þ: 0e240 mM DOC, TOC and UV254 - Fenton process enabled the mineralization of 27.6% of Wu et al. (2012)
solutions H2O2: 0e360 mM the HA content and around 79% reduction of UV254.
pH: 1-8 - Under optimum reaction conditions (pH 4, 160 mM
H2O2 and 40 mM Fe2þ, at 30  C and for 2 h), UV254
was reduced by 93.3%.
NOM Surface water from Fe3þ: ~1 mg/L TOC, UV254 and THMFP - The studied solar photo-Fenton was effective for the Moncayo-Lasso
the Pance river H2O2: 60 mg/L transformation and partial mineralization of NOM et al. (2012)
(Cali, Colombia) pH: 5e7 under simulated sunlight using low Fe3þ concentra-
Simulated sunlight tion and near neutral pH (6.5).
- The process substantially reduced the THM
concentrations.
HA Synthetic HA Fe2þ: 0e160 mg/L COD and HA - The Fenton process was reported to be fast and Jung et al. (2013)
solutions H2O2: 120 mg/L concentration efficient in a low organic viscous solvent (<5 ppm
pH: 3-8 HA).
- The compared photocatalyst reaction was also fast
and efficient, but within a broader range of pH.
NOM Groundwater Fe2þ: 0.1e0.5 mM DOC, UV254, NOM - Under optimal operating conditions at pH 5.5, around Molnar et al. (2015)
(Vojvodina, Serbia) Fe2þ/H2O2 molar fractionation and 55% DOC was removed.
ratios: 1/5-1/20 DBPFPs - High removals of HAN (98%), THM (80%) and HAA
pH 5.5 and 6 (75%) were achieved.
< Electro-Fenton process
HAs Synthetic HA BDD and Pt as TOC, absorbance and - Around 99% of TOC of initial solution (16.2 ppm) was Trellu et al. (2016)
solutions cathodic electrodes the formation of removed after 7 h of treatment at 1000 mA using BDD
and carbon sponge carboxylic acids as anode and stainless settle as cathode.
and stainless steel - The use of carbon sponge as cathode led to significant
as anodic materials. HAs sorption onto its surface.
Electro-generation - The mineralization of the HAs oxidation by-products
of H2O2 via the to CO2 is more efficient using BDD anode, compared
cathodic material. to the Pt one.
Current intensities:
300e1000 mA
0.1 mM Fe2þ

based processes clearly reveals that most of the published articles
dealt with wastewaters and landfill leachates and very limited
number of papers reported the application of electro-Fenton pro-
cesses for the removal of NOM from drinking water supplies due to
the technical and economic changes related to the delivery O2 for
the electro-generation of peroxide and maintaining optimum
operating conditions (mainly pH) in subsurface aquatic environ-
ments (Liao et al., 2015).
More details about the fundamental chemistry of the Fenton,
photo-Fenton and electro-Fenton reactions could be found in some
interesting review papers (Pignatello et al., 2006; Brillas et al.,
2009; Bokare and Choi, 2014).
The following Table 4 presents the operating conditions and the
main findings of selected R&D studies conducted around the world
between 2010 and 2016 on the application of UV-based AOPs to
remove NOM from natural waters or synthetic aqueous solutions.
3.5. Heterogeneous catalytic and photocatalytic oxidation
3.5.1. Heterogeneous catalysis
Although H2O2 is a relatively strong oxidant, its single applica-
tion for drinking water or wastewater treatment is not efficient to
remove many organic compounds, including NOM, mainly due to
the kinetic limitations at conventionally applied peroxide concen-
trations (Kitis and Kaplan, 2007). Thus, as we have seen in the
previous sections, H2O2 is coupled either with ozone and/or UV or
mixed with iron ions, used as homogeneous catalysts (Fontecha-
Camara et al., 2011).
The other approach is to decompose H2O2 in the aqueous media
over heterogeneous metal catalysts including Fe, Cu, Pt Ti and Ni
and metal oxides such as MnO2, TiO2, Al2O3, FeOOH and CeO2. The
metals and metal oxides could also be immobilized on various
support matrices such as sand, clay, silica and alumina (Pirkanniemi
and Sillanpa €€
a, 2002; Sheldon, 2012).
As for the application of ozonation to remove NOM, specifically
the indirect route of ozone utilization (i.e. decomposition and for-
mation of HO), it is highly depending on the reaction pH and
usually leads to the formation of aldehydes and carboxylic acids,
which do not react with ozone. Such behavior tend to limit the
efficiency of the ozonation process since total mineralization of the
NOM cannot be reached (Nawrocki and Kasprzyk-Hordern, 2010).
In this context, many studies reported that catalytic ozonation
enabled a faster degradation of organic compounds and improved
the mineralization of natural organic matter and other organic
pollutants (Kasprzyk-Hordern et al., 2003).
In addition to the previously mentioned heterogeneous cata-
lysts (i.e. metal and metal oxides), the ozonation reaction could be
catalyzed with other catalysts including raw or modified minerals
such as perovskite (Carbajo et al., 2007), zeolite and volcanic sand
s et al., 2009), alumina (Kasprzyk-Hordern et al., 2006) or
(Valde
organic catalysts such as charcoals (Mortazavi et al., 2010) and
nchez-Polo et al., 2005).
activated carbons (Sa
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M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76 65

Table 5
Selected research studies on the removal of NOM from waters using heterogeneous catalytic oxidation processes, conducted between 2010 and 2016.

Targeted organic Water source Catalytic-AOP features Monitored parameters Main results References
compounds

< Catalytic ozonation

NOM, THM and Groundwater from the O3 dose: 0.4e3 mg/mg UV254, DOC THMFP - Ozonation and O3/TiO2 induced changes in Molnar et al.
haloacetonitrile Central Banat province DOC HANFP NOM structure. HAs were fully oxidized and (2012a)
(HAN) precursors (Vojvodina, Serbia) Catalyst: TiO2 the residual NOM was mainly composed of
Catalyst dose: 1 mg/L hydrophilic compounds (up to 70%).
- Highest removal of NOM's THM precursors
was achieved by O3/TiO2 (up to 80%
reduction of THMFP).
- Direct NOM oxidation by O3 was more
effective for HANFP reduction, compared to
the catalytic route.
NOM Groundwater from the O3 dose: 0.4e3 mg/mg DOC, distribution of - The NOM-rich groundwater (9.85 mg/L) Molnar et al.
Central Banat region DOC NOM and DBPFP included 65% fulvic acid and14% humic acid. (2012b)
(northern Serbia) Catalyst: TiO2 - The oxidation process enabled the complete
Catalyst dose: 1 mg/L removal of humic acid and increased the
content of the hydrophilic fraction.
- Compared to ozonation alone, the application
of TiO2-O3 resulted in a better removal of HAN
precursors, but a lesser removal of THM
precursors.
NOM and Raw surface water from O3 dose: 2.5 mg/L DOC, UV254, SUVA and - Both catalysts promoted the decomposition Chen and Wang
p-chlorobenzoic the Wu-Lo River Catalysts: FeeMn oxide the formation of THMs of aqueous O3 and enhanced the formation (2014)
acid (Pingtung, Taiwan) and TiO2/a-Al2O3 and HAAs of HO
Catalyst dose: 1.25 g/L - The application of FeeMn oxide decreased
UV254 and DOC, and lowered the formation
potential of THMs and HAAs more than TiO2/
a-Al2O3.
HA Synthetic HA solutions O3 dose: 10 mg/L absorbance at 436 nm, - Comparted to simple ozonation, the HA Gümüş and Akbal
Catalysts: iron-coated DOC and UV254 removal substantially increased from 21.4% (2017)
zeolite (ICZ) and to 62% and 48% following the utilization of ICZ
granular activated and GAC, respectively.
carbon (GAC) - Catalytic ozonation yielded better DOC and
Catalyst dose: 0.75 g/L UV254 reduction in both <50 kDa and
<100 kDa fractions of HA, compared to
ozonation.
< H2O2-based catalytic oxidation
NOM Raw surface water from H2O2 dose: 0.047 mol/L COD and true color - The clay catalyst effectively removed NOM Galeano et al.
Pasto river (Colomlia) Catalyst: Al/Fe-pillared (recorded at 455 nm) from the treated drinking water supply. (2012)
clays Indeed, 95% of the COD was removed in 4 h as
Catalyst dose: 0.5 and well as 100% of the true color in around
5 g/L 45 min.
- The composite catalyst exhibited good
chemical stability against iron leaching.

Previous research studies proved that catalytic ozonation
showed better NOM removal efficiency, doubling that of ozonation
alone in some cases (Ernst et al., 2004; Kasprzyk-Hordern et al.,
2005; Alsheyab and Munoz, 2007). It was also reported that cata-
lytic ozonation enabled more formation of aldehydes and increased
the ratio of biodegradable organic compounds, in comparison with
single ozonation (Zhang et al., 2008).
In the following Table 5, the operating conditions and main
results of recent research studies applying heterogeneous catalytic
oxidation to remove NOM are summarized.
3.5.2. Heterogeneous photocatalysis
The heterogeneous photocatalytic oxidation is based on the
utilization of near UV radiation to photoexcite semiconductor cat-
alysts in the presence of oxygen to attack organic compounds in
water or air for purification and disinfection purposes (Zhao and
Yang, 2003; Liqiang et al., 2006; Gaya and Abdullah, 2008).
Various photocatalysts such as ZnO, Fe2O3, CdS, GaP, Cu2O and
ZnS were successfully applied to degrade a wide array of recalci-
trant organic compounds into easily biodegradable ones, and even
reaching a full mineralization under optimum operating conditions
(Chong et al., 2010; Di Paola et al., 2012). Other applications of those
photocatalysts include solar energy conversion (Kamat and
Dimitrijevic, 1990; Horiuchi et al., 2013) and water splitting for
hydrogen production (Kudo and Miseki, 2009; Hisatomi et al.,
2014).
Among those various semiconductors, TiO2 remains the most
widely used benchmark photocatalyst, so far, especially the
Degussa P25 powders, due to their high photocatalytic activity and
nontoxic properties (Hoffmann et al., 1995; Choi et al., 2010a;
Zhang et al., 2010a; Schneider et al., 2014). Other types of TiO2
were also used in many research studies, but mostly for compara-
tive purposes with the Degussa P25. The list includes pure anatase
and rutile forms of TiO2 (Uyguner-Demirel and Bekbolet, 2011).
Basically, the photocatalytic activity of TiO2 consists in the
production of photo-generated electrons in the conduction band of
the catalysts, leading to the formation of highly oxidative holes in
the valence band where a reaction occurs with the adsorbed water
(i.e. surface hydroxyl) to form the highly reactive hydroxyl radicals
(Nosaka et al., 2003; Fujishima et al., 2008). As well, the excited
electrons could be trapped by O2 to form superoxide radical ions
(Xiang et al., 2011). Subsequently, organic compounds are degraded
by holes in the TiO2 surface and by radicals in the bulk solution
(Carp et al., 2004; Matilainen and Sillanpa €a
€, 2010).
In practice, photocatalytic reactions are performed under UV
light due to the band gap energy of bare TiO2 phases (3 or 3.2 eV in
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rutile or anatase phase), thus small amounts of photons can be
absorbed in the visible range (Birben et al., 2017). Other practical
disadvantages include high recombination rate for the photo-
produced electron and holes pairs, and the difficulty to support
powdered TiO2 on some materials (Di Paola et al., 2012).
In order to overcome those limitations and improve the photo-
efficiency of TiO2 and their degradation efficiency of organic com-
pounds, several chemical and structural modifications were carried
out in order to enable light absorption in the visible region
(Usseglio et al., 2007; Macwan et al., 2011). In this regard, various
nanostructured TiO2 materials were developed with enhanced the
visible light photoactivity including nanoparticle and nanofibers
(Choi et al., 2010b), nanotubes (Roy et al., 2011), nanosheets (Guo
et al., 2012), nanowires (Wu et al., 2012) and powdered TiO2
nanoparticles made into films via spray deposition (Gondal et al.,
2014) or atomic layer deposition (Pan et al., 2015).
Alongside the structural changes, several chemical modification
schemes were also reported as promising options to improve the
photocatalytic activity. This mainly consists of doping TiO2 with
non-metals (such as C, N, S or F), metals (such as Fe, Cr or V) or
metal oxides (such as V2O5, ZrO2 or WO3) (Zhang et al., 2010b;
Birben et al., 2017).
Hybrid materials combining TiO2 with carbon materials such as
carbon nanotubes (Woan et al., 2009), activated carbons
(Andriantsiferana et al., 2014) or TiO2-carbon microspheres (Filho
and Zarbin, 2006) were also investigated for the same propose,
along with hybrid membranes combining TiO2 with various poly-
meric compounds such as cellulose (Zeng et al., 2010), polyvinyl
alcohol (Linh et al., 2011), polyurethane (Liu et al., 2012) and pol-
yvinylidene fluoride (Shi et al., 2013).
Similar approach (i.e. structural and/or chemical modifications)
to improve the overall photoactivity and efficiency under visible
light was applied for other heterogeneous catalysts such as
manganese-doped ZnO nanoparticles (Ullah and Dutta, 2008),
silver-doped Cu2O core-shell nanoparticles (Li et al., 2012), Au-
BiVO4 (Cao et al., 2011) or the hybridization of ZnWO4 by graphene
(Bai et al., 2012).
The following Table 6 illustrates the main operating conditions
and the experimental results of selected R&D studies conducted
around the world between 2010 and 2017 on the application of
heterogeneous photocatalysts (pure, structurally-modified or
chemically-doped) to remove NOM from natural waters or syn-
thetic aqueous solutions.
Basically, the application of photocatalysts in water treatment
could be carried out either as a slurry of suspended photocatalyst or
in reactors with the photocatalyst immobilized onto a supporting
solid matrix. The first configuration, although enabling a larger
photocatalyst surface to be effectively illuminated, remains only
efficient in small-scaled photocatalytic reactor (Chen et al., 2001),
since any downstream separation for large slurry volumes would
impose substantial economic constraints. Mass transfer limitations
within slurry reactors could also pose a problem for such configu-
ration. In this regard, a study investigated the mass transfer limi-
tations in slurry photocatalytic reactors employing titanium
dioxide suspensions. The influence of several operating parameters
including photocatalyst loadings, irradiation and total suspension
volume were assessed, and the experimental results proved the
mass transport limitations and the intrinsic non-uniformity of the
radiation field (Ballari et al., 2008).
As for the other configuration (immobilized catalysts), it was
developed to avoid the previously mentioned issues with the slurry
photocatalytic reactors. The reactor designs involving immobilized
films of catalysts were more prone to commercial applications
(Abdel-Maksoud et al., 2016), since they discard the need for a
separation process to recover the catalysts, and enable a large
surface area in the immobilized porous film formed by the
agglomeration of the catalyst particles (Ballari et al., 2008).
Nevertheless, the immobilization of photocatalysts (mostly TiO2)
on inert supports also presents a set of issues mainly related to the
accessibility of the catalytic surface to the photons and the targeted
molecules, and the significant influence of external mass transfer
(i.e. interfacial external diffusion) due to the increasing diffusional
length of the reacting molecules from the solution to the catalyst
surface (Chen et al., 2001). Other studies highlighted the role of
internal mass transfer related to the thickness catalyst film. In this
case, increasing the thickness of the film would limit the reactivity
of the catalysts close to the surface of the support material (Chen
et al., 2000). Further insights on the various types of photo-
catalytic reactors for environmental remediation could be found in
McCullagh et al. (2011).
3.6. Non-conventional AOPs
Recently, a limited number of studies investigated the applica-
bility of non-conventional AOPs to remove NOM from drinking
water supplies and wastewaters. These technologies include the
application of ultrasound (Naddeo et al., 2007), microwaves (Remya
and Lin, 2011), electron-beam irradiation (Roshani and Leitner,
2011), gamma radiation (Basfar et al., 2009; Jime nez-Becerril
et al., 2016) and plasma technologies (Panorel et al., 2011). The
consultation of the related literature reveals that ultrasonication
(US) was, relatively, the mostly applied technology for NOM
removal purposes, followed by microwaves. Application wise, US
could be operated alone due to its ability to generate reactive free
radicals and degrade organic compounds, but this could be ach-
ieved only via high power US (Matilainen and Sillanpa €€
a, 2010).
In most cases, US is associated with other oxidation processes
involving UV (Mahvi et al., 2009), O3 (Ste˛ pniak et al., 2012) and
H2O2 (Pourzamani et al., 2015). The main applications of ultrasound
are the homogenization of the colloidal dispersion of the catalysts
(Reddy et al., 2014), the regeneration of spent absorbents (Chakma
and Moholkar, 2011) and the mitigation of membrane fouling in
integrated AOPs-based technologies were also reported (Kan et al.,
2016).
As for the microwaves, the main application scheme is assisting
conventional AOPs, primarily catalytic and photocatalytic oxidative
degradation (Serpone et al., 2010; Nascimento and Azevedo, 2013)
and also the synthesis of catalysts (Lazau et al., 2011; Yang et al.,
2012). Regarding the applicability of non-conventional processes
to remove (or assist in removing) NOM, more studies need to be
carried out to develop and optimize possible integrated processes,
in term of efficiency, cost-effectiveness (essentially energy re-
quirements), eco-friendliness and safety (processes involving
radiolytic degradation).
3.7. AOPs integrated with other water treatment technologies
Several AOPs are being applied in real case scenarios to treat
drinking water supplies, especially UV, Fenton and O3-based pro-
cesses. Nonetheless, the main issues for a wider application of those
efficient water treatment methods remain the technological com-
plications and economic viability. In general, the widely-used
processes for the treatment of potable water sources are separa-
tion and purification technologies including (micro, ultra and nano)
membrane filtration (Guo et al., 2010; Pendergast and Hoek, 2011;
Metsa €muuronen et al., 2014), reverse or forward osmosis (Malaeb
and Ayoub, 2011; Chun et al., 2015), adsorption technique
(Bhatnagar and Sillanpa €€a, 2017) and/or coagulation (Matilainen
et al., 2010; Keeley et al., 2016).
In order to improve the overall efficiency of water treatment
Table 6
Selected research studies on the removal of NOM from waters using heterogeneous photocatalytic oxidation processes, conducted between 2010 and 2017.

Targeted organic Water source Photocatalytic-AOP Monitored parameters Main results References
compounds features

< Photocatalysis (TiO2/UV)

NOM Two surface waters: Suspended Degussa DOC, UV254, AMW - Reduction of UV254 by 95% within150 min and DOC by 85%. Liu et al. (2010)
Myponga reservoir TiO2 (0.1 g/L) distribution of NOM, - The AMW distribution shifted towards lower molar mass compounds with a
(South Australia) and UVA with maximum THMFP dominant hydrophilic fraction.
Woronora dam (New centred at 365 nm - The photocatalytic treatment reduced THMFP below guideline levels.
South Wales)
NOM Surface water from lake Suspended Degussa DOC - The presence of Cu2þ, Mn2þ, Zn2þ and Fe3þ inhibited the photocatalytic Espinoza et al. (2011)
Hohloh (Black Forest, TiO2 (0.5 g/L) degradation of NOM.
German UV range (290 - Among those cations, Cu2þ had the largest impact as it delayed the molecular
e400 nm) size changes in NOM and reduced the bioavailability of the partially degraded
NOM.
HA Synthetic HA solutions TiO2Degussa P25 DOC, absorbance at - Several anions at elevated concentrations inhibited photocatalytic removal of Uyguner-Demirel
(0.25 g/L) 436 nm, UV365 and HA, based on several spectroscopic parameters. et al. (2013)

M. Sillanpa
125 W UVA lamp fluorescence intensity - Based on the presence of low or high anion matrix, various kinetic model rates
were reported for the photocatalytic removal of the molecular size fractions of
HA.

€a
FA-like humic Surface water from the Suspended anatase TiO2 Fluorescence intensity - The main result is that ZnO showed a better efficiency to degrade humic and Nerger et al. (2015)

€ et al. / Journal of Environmental Management 208 (2018) 56e76

substances, HA-like Grand river (Kitchener, (0.05e0.5 g/L) and liquid protein substances than TiO2, for all tested catalyst concentrations.
humic substances ON, Canada) ZnO photocatalyst (0.05 chromatography - The surface water treated by ZnO-based photocatalysis lead to a reduction in
and protein-like e0.5 g/L) was used for eorganic carbon the irreversible membrane fouling more than the TiO2-based photocatalysis.
substances comparison detection analysis
9 W UVA lamp
< Photocatalysis (modified catalysts/(near)visible light)
HA Synthetic HA solutions Ag-doped TiO2 TOC, UV254, and - Ag-doping of TiO2 nanocrystals enabled a slight shift of the absorption bands Lazau et al. (2011)
nanocrystals supported absorbance at 436 nm towards the visible range.
on natural zeolite - The hybrid catalyst, Ag-doped TiO2 onto zeolite, enhanced the photocatalytic
matrix (1 g/L) activity and degradation of HA under both UV and visible light irradiations, in
UV and visible comparison with undoped composite.
irradiations provided
by a 300 W medium-
pressure Hg lamp
HA Synthetic HA solutions N-doped ZnO Change in absorbance - Compared with ZnO (onset edge of band-to-band transition around 380 nm), Qin et al. (2011)
supported on glass slide and UV254 the N-doped ZnO photocatalyst exhibited a typical absorption feature in the
500 W Xenon lamp visible-light region at 450 nm.
- After studying various heterostructures (combining glass, ZnO and N-doped
ZnO), it was deduced that the presence of a heterojunction at interface of
two semiconductors does not necessarily lead to an improved photoactivity.
NOM Samples from the Pd-modified N-doped DOC, SUVA and - Co-doping reduced the band gap of TiO2 and shifted the absorption edge to Nkambule et al. (2012b)
Plettenberg Bay water TiO2 (5 g/L) turbidity the visible light region.
treatment plant 500 W Xenon lamp - The synergistic effects of N and Pd co-doping of TiO2 enhanced the
(Southern Cape, South photoactivity.
Africa) - The highest photodegradation efficiency (96%) occurred on the hydrophobic
fraction of NOM.
HA Synthetic HA solutions ZnO coupled TiO2/ TOC and UV254 - The hybrid photocatalyst ZnO-TiO2 supported to bamboo charcoal was Wang et al. (2013b)
bamboo charcoal (2 g/L) successfully synthesized the solegel method combined with microwave
500 W Xenon lamp irradiation.
with a UV cut off filter - The interfacial coupling effect between ZnO and TiO2 particles induced the
transformation of TiO2 from the anatase to rutile phase, leading to a
significant red shift of absorption edge.
FA Synthetic FA solutions N-doped TiO2/ UV256 - N-doping and graphene addition induced an increase in the light absorption Yan et al. (2016)
graphene intensity in the visible light region.
nanocomposite (0.5 g/ - The synthesized nanocomposite showed the highest photocatalytic activity of
L) FA (90% of removal within 3 h).
300 W Xenon lamp
(continued on next page)

67
Table 6 (continued )

68
Targeted organic Water source Photocatalytic-AOP Monitored parameters Main results References
compounds features

- The photodegradation performance remained high up to the 3rd utilization

cycle.
< Simulated solar photocatalysis
HA Synthetic HA solutions Anion-doped and co- DOC, absorbance at - N-doped, S-doped and SeN co-doped TiO2 photocatalysts were synthesized. Birben et al. (2015)
doped Degussa P25 and 436 nm, UV254 and - Doping the Degussa P25 did not improve the degradation efficiency.
Hombikat UV-100 TiO2 fluorescence intensity - SeN co-doping of Hombikat UV-100 enabled a higher removal of DOC,
(0.25 g/L) compared with the Degussa P25.
Solar simulator - Overall, Hombikat UV-100 (100% anatase) exhibited better solar photo-
equipped with an air catalytic performance than Degussa P25 (80% anatase and 20% rutile).
cooled Xenon lamp
(wavelength 300
e800 nm and light
intensity 250 W/m2)
HA Synthetic HA solutions Fe-doped TiO2 (0.25 g/ DOC, absorbance at - Fe-doping induced a shift in absorption wavelength values from UV to visible, Birben et al. (2017)

M. Sillanpa
L) 436 nm, UV365, UV280 thus indicating possible activity under solar light.
Solar simulator and UV254 - Undoped TiO2 led to faster removal rates of HA, more than the doped catalyst.
equipped with an air The authors assessed this tendency as substrate specific rather than being

€a
cooled Xenon lamp related to the inefficiency of the visible light to activate the catalytic

€ et al. / Journal of Environmental Management 208 (2018) 56e76

(wavelength 300 performance.
e800 nm and light
intensity 250 W/m2)
and quartz and UV
special glass filters to
simulate outdoor
sunlight irradiation
< Photoelectrocatalysis (PEC)
HA Synthetic HA solutions TiO2/Ti film electrode as DOC, UV254, HA - The PEC process reduced the concentration of DOC by 75% and UV254 by 92%. Li et al. (2011)
anode and RuO2/Ti fractionation and - After 3 h of treatment, around 90% of the HAAs and THMs formation potentials
electrode as cathode. DBPFP were reduced.
10 W pressure mercury - The application of PEC transformed the largely hydrophobic content of HA
lamp (253.7 nm) with a into smaller and hydrophilic compounds.
light intensity around
1.3 mW/cm2
FA Synthetic FA solutions TiO2 nanotube arrays Degradation degree - The degradation degree of FA alone was around 40% for initial concentrations Dong et al. (2016)
used as photoanode of FA between 25 and 100 mg/L.
365 nm UV LED with a - The addition of low-molecular hydroxyl compounds (methanol, ethanediol
37.4 mW/cm2 light and glycerol) contributed to a substantial increase of hydroxyl radicals in the
intensity and a 2 V bias solution, leading to higher degradation rates of FA.
voltage.
 €a
M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76 69

Table 7
Selected research studies on the removal of NOM from waters using photocatalytic membrane reactor, conducted between 2010 and 2016.

Targeted organic Water source PMR features Monitored Main results References
compounds parameters

HA Synthetic HA solutions Ultrafiltration submerged module
made of Polyvinylidenefluoride
(nominal pore size of 0.04 mm)
TiO2 (0.75 g/L)
30 W UVA lamps, primarily
emitting at 365 nm
HA Synthetic HA solutions Microfiltration membrane made of TOC and UV254
hydrophobic
polyvinylidenedifluroride hollow
fiber (nominal pore size of 0.1 mm)
TiO2-ZrO2 binary oxide (150 mg/L)
4 W UV lamp
NOM Natural surface water sampled Two immersed, capillary,
at Upper Silesia water systems ultrafiltration membrane modules: formation potential and
company (Poland) one made of polyvinylidene
fluoride and the other
polyethersulphone
TiO2 (0.1 g/L)
15 W UV lamp, primarily emitting
at 254 nm
TOC and UV254 - The process integrating the Patsios
application of suspended TiO2 et al. (2013)
particles and membrane
ultrafiltration was successfully
operated in a continuous mode
for the removal of HA, with no
reject stream.
- The synergistic effects of
photocatalytic oxidation and
membrane filtration enabled
higher HA removal and lower
DBPFP.
- The application of binary oxide Khan et al. (2015)
TiO2-ZrO2 results in better
reduction of HA fouling in
photocatalytic membrane
reactor, compared with single
TiO2.
- The removal efficiency of the
composite catalyst was further
improved by the addition of
divalent cations such as calcium.
DOC, UV254, THM - The PMR with immersed Rajca (2016)
membrane module was reported
AMW distribution of to be the best configuration to
NOM minimize photocatalyst loss.
- The direct application of the
tested PMR process to treat raw
water (i.e. no pretreatment) was
recommended since pretreating
the water via coagulation did not
improve the NOM removal
efficiency.
- NOM of aromatic structure and
hydrophobic character are
mostly decomposed into aliphatic
and hydrophilic compounds.

facilities, combing two or more of those technologies was proven to
be a viable option. These integrated water treatment processes
include the combination of AOPs with membrane filtration and
adsorption, as well as coagulation and biodegradation (Ang et al.,
2015).
3.7.1. AOPs-membranes integrated process
In membrane-based technologies, the drinking water supply is
generally pretreated with micro or ultrafiltration membranes
before applying nanofiltration or reverse osmosis. Such approach is
necessary because membrane fouling by humic substances signif-
icantly lower the efficiency of ultrafiltration to remove NOM from
water (Sutzkover-Gutman et al., 2010), hence the need to reduce
the fraction of NOM before applying the more sensitive nano-
filtration membranes (fouling wise). In membrane-based integra-
tion scenarios, the application of AOPs, prior or after the membrane
filtration helped improving the quality of the treated water in the
on hand, and reduced the occurrence of the fouling phenomenon
on the other hand (Gao et al., 2011; Jeong et al., 2014).
In this context, a research study investigated and compared the
influence of O3 and UV/H2O2 to pre-treatment a drinking water
supply before its purification using ultrafiltration membrane. The
evolution of organic fouling was also monitored. The main related
results showed that high molecular weight organic compounds
(e.g. proteins and polysaccharides) contributed to 90% of total
fouling phenomenon. The application of both oxidation-based
pretreatments enabled the reduction of the foulants content (i.e.
degradation of high MW organics), which helped improving the
flux of the membrane (61% for UV/H2O2 and 43% for O3) (Pramanik
et al., 2016).
On the other hand, although oxidation-based processes, ozon-
ation and UV/H2O2, were proven to be efficient in reducing mem-
brane fouling, this is valid only for high MW compounds. Indeed,
low efficiencies to reduce the fouling caused by low MW organics
was reported for both processes, mainly due the difficulty to oxide
those low MW fraction in organic matter (Winter et al., 2016). For
the simultaneous application of AOPs and membrane, another
shortcoming of such integrated process was revealed. In this
context, the utilization of strong oxidants such as O3 tend to
degrade the membrane and affects its overall performance (Stark,
2005). In a previous study combining microfiltration on ozona-
tion, O3 was responsible for the degradation of high MW organics.
The generated compounds promoted the growth of microorgan-
isms which led to accelerating the formation of biofilms (Oh et al.,
2007). The addition of UV to this integrated process could mitigate
the issue of biofouling, but the technological feasibility and eco-
nomic viability have to be assessed for large scale application.
Another option to combine AOPs and membranes is increasingly
gaining interests among researchers around the world which is the
development of photocatalytic membrane reactors (PMR) (Huang
et al., 2007; Song et al., 2012; Mozia et al., 2015; Molinari et al.,
2017). In water treatment applications (drinking water supplies
and also treated wastewater effluents), this integrated process is
based on the combination of photocatalytic oxidation and sub-
merged membranes, where the former helps mitigation the fouling
phenomenon by degrading organic compounds present in the
70 €a
M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76
drinking water supply and the latter helps separating the sus-
pended photocatalysts via filtration. The following Table 7 sum-
marizes key operating conditions and experimental findings of
selected research studies applying PMR to treat NOM-containing
natural waters or synthetic solutions.
3.7.2. AOPs-adsorbents integrated process
The other possible integration scenario involves the combina-
tion of AOPs with the adsorption technique.
In this regard, several AOPs were combined with various
adsorbing materials to tackle the issue of removing organic matter
(and organic pollutants from water sources. Such intergraded
processes include the combination of catalytic ozonation and
charcoals. In a related study, the applicability of heterogeneous
catalytic ozonation with bone charcoal to remove humic substances
was assessed, in comparison with other oxidation and advanced
oxidation processes including H2O2, O3, O3/H2O2 and O3/H2O2/bone
charcoal (Mortazavi et al., 2010). The results showed that, under
various pH conditions, adding the charcoal catalyst in the ozonation
process helped increasing the HA degradation rates 1.5 times more
that the single ozonation. Under various temperatures, the reaction
of the catalytic ozonation of HA was also efficient, which makes the
studied process applicable for the degradative removal of humic
substances from water.
Another study combined ozonation with biological granular
activated carbon to remove NOM and THMs precursor from surface
water (Yan et al., 2010). It was revealed that the integrated process
of ozonation and adsorption on AC was more efficient to remove
THMs precursor that the single process. This is mainly due to the
synergetic effect occurring between the ozonation and the bio-
logical granular AC, where the former degrade NOM into more
hydrophilic and lower MW compounds which are effectively
adsorbed by the AC (i.e. easier to diffuse into the porous structure of
AC than the larger MW DOC).
In order to remove NOM and reduce DBPs formation in drinking
water supplies, a research group developed a pilot-scale plant
combining Ozone, UV and biological activated carbon filter (Trang
et al., 2014). The main results showed that the integrated process
was more efficient to remove TOC (19.1%), DOC (17.6%), UV254
(30.7%) and SUVA (16.4%). The removal efficiency of the combined
process was higher than the sum of NOM removal efficiencies of
each process (i.e. O3/UV or AC). It was also reported that DBPFP was
reduced after the integrated process by 39.3% for THMs and 46.1%
for HAAs.
It has to be noted that, in many water treatment studies, the use
of AOPs to regenerate (and reuse) spent adsorbents used for the
removal of NOM from drinking water supplies was successfully
applied (Naghizadeh et al., 2015; Naghizadeh, 2016; Omorogie
et al., 2016).
As for the specific case of photocatalytic degradation, adsorption
takes another dimension as it occurs alongside the photocatalytic
activity of semiconductors such as TiO2 (Reddy et al., 2015) and ZnO
(Oskoei et al., 2016). Those single or hybrid photocatalyst adsor-
bents generally combine high adsorption capabilities and high
photocatalytic activities (Yoneyama and Torimoto, 2000; Upadhyay
et al., 2014). In related research studies, and based of the correlation
between the efficiency of photocatalysts and their adsorptive sur-
faces, two main approaches could be followed to expand the
adsorption surface and promote the photocatalytic activity: (i)
modifying the morphology of the catalyst or (ii) elaborating hybrid
catalysts.
For the first method, a research team synthesized Cu2O nano-
crystals (size ~4 nm) via a synproportionation reaction of Cu2þ with
metal copper powder at room temperature, with a surface area 4
times larger than commercial Cu2O. The produced photocatalyst
showed high adsorption capacity (405 mg/g), combined with high
photocatalytic activity for the degradation of HA (99.5% within 2 h),
which remain almost stable after five cycles of utilization (Jing et al.,
2014). As for the second method, several combinations were
reported:
- Between photocatalysts such as the synthesized TiO2-ZrO2
particles which were proven to be effective in adsorbing and
degrading (under UV light) HA, thus mitigating the fouling Phe-
nomenon of the jointly applied membrane. The same study also
indicated that the larger size of the binary catalyst (~1 mm) helped
avoiding the risk of membrane fouling by the single catalyst (Khan
et al., 2015).
- Improved and combined adsorption and photocatalytic activ-
ities for the removal of NOM (specifically HA) were reported for
different hybrid photocatalysts such as the TiO2/AC (Lim et al., 2011;
Xue et al., 2011), TiO2/coconut shell powder (Kim et al., 2016), TiO2/
zeolite (Liu et al., 2014) and ZnO-TiO2/bamboo charcoal (Wang
et al., 2013a,b).
3.7.3. Other AOPs-based integrated processes
Other integrated technologies include the combination of AOPs
with coagulation or biodegradation. For both integrated processes,
AOPs are generally applied as a pretreatment step (Uyguner et al.,
2007). In this configuration, the oxidative degradation of NOM is
the key factor conditioning the efficiency of the subsequent coag-
ulation or biodegradation stages. Thus, based on the characteristics
of the initial NOM content and the specifically applied AOP, various
intermediates compounds with modified features are then avail-
able for further treatments. At this point, the structural, molecular
and chemical modifications will have a substantial impact on the
choice of coagulants, the doses to be applied and other operating
conditions, mainly pH (Rodríguez et al., 2012; Ayekoe et al., 2017).
The application of coagulation after AOPs was also reported to be an
advantageous additional stage to remove DBPs formed during the
oxidation process (Selcuk et al., 2007; Sillanp€ € and Matilainen,
aa
2014).
For the biodegradation, the issue is less complicated because
most studies are reporting the transformation of formation of high
MW hydrophobic compounds including humic-, fulvic- and
protein-like substances into more biodegradable low MW hydro-
philic compounds (Sallanko and Va €isa
€nen, 2013; Liao et al., 2017).
4. Summary and future research directions
Removing NOM from drinking water supplies, and also from
effluents of municipal WWTP, is a challenging task requiring the
application of highly efficient and versatile water treatment tech-
nology or a combination of purposely-selected technologies. The
first action to be undertaken is the proper characterization of NOM
and its various fractions in order to predict their reactivity with
respect to the to-be-applied technology(ies). This action is very
crucial to select and apply the most suitable treatment process by
achieving the highest decontamination capabilities (efficiency),
mitigate the formation of toxic byproducts (eco-friendliness) and
control the overall cost (cost-effectiveness).
In this regard, AOPs are among the most suitable water treat-
ment processes to remove NOM based on the rapid and non-
selective character of its key active element, the hydroxyl radicals.
Thus, in theory the variability of NOM in water does not pose a
problem to AOPs. Nonetheless, many studies reported that AOPs
tend to have more impact on NOM's hydrophobic (i.e. from hy-
drophobic to hydrophilic character) and high MW compounds (Lin
and Wang, 2011). As well, the highly reactive HO can also interact
with ions and other dissolved organics, frequently found in water
supplies, which could diminish the overall efficiency of AOPs. This
 €a
M. Sillanpa € et al. / Journal of Environmental Management 208 (2018) 56e76
was the case for the removal of NOM (mainly HA) in the presence of
bicarbonate (HCO  
3 ) and halide (Cl and Br ) ions (Ibrahim and
Aziz, 2014; Lou et al., 2016).
In real case applications, AOPs are unlikely to achieve complete
oxidation of the organic matter, but enables the transformation of
NOM into smaller organic compounds and more aliphatic and hy-
drophilic moieties. Those low MW and hydrophilic organics could
be either easily biodegradable molecules or toxic and recalcitrant
DBPs, posing an additional challenge to the large scale application
of AOPs for NOM removal (Mayer et al., 2015), along with bromate
formation in bromide-containing waters (Arvai et al., 2012).
Consequently, integration schemes coupling AOPs with other
water treatment technologies are being extensively investigated as
viable options to mutually overcome the shortcomings of both the
AOPs and associated techniques. Indeed, after decades of R&D
studies, no single water treatment technique is able to tackle the
issue of NOM on its own, at least efficiently and cost-effectively.
Various integrated processes for the removal of NOM were
detailed in this review, and in order to echo the research studies
conducted on this matter, more attention was given to the combi-
nation of AOPs with membrane filtration and adsorption, and to a
lesser extent with coagulation and biodegradation. In this regard,
an important aspect seemed to be neglected in most papers dealing
with integrated processes, which is assessing the synergetic effect
in such multicomponent technologies.
Among the various AOPs (UV and/or O3-based applications,
Fenton and catalytic oxidation), heterogeneous photocatalysis has
received an increasing amount of attention from researchers
around the world during the last decade. The main objectives of the
related research effort are: (i) to optimize the photocatalytic ac-
tivity of the benchmark catalyst in the field, TiO2, via structural
modifications (nanocrystals, nanotubes, nanosheets, etc.) and/or
the combination with other catalysts (ZnO, CuO, ZrO2, etc.) or
materials (polymers, activate carbons, clays, etc.), and (ii) to syn-
thesize novel photocatalysts (single or hybrid) able to compete with
TiO2 through promoted photocatalytic activities under near visible
or solar light.
Application wise and on a worldwide scale, integrated tech-
nologies are highly needed in poor countries with very scarce water
resources, seriously threatened by unwise management strategies
and/or various contamination scenarios. Even for wealthy countries
in water-scarce regions, operating expensive water desalination
facilities using fossil fuels to produce potable water from seawater,
is simply not sustainable and could lead to severe problems if other
options are not being implemented to take over within a decade or
two decades. A combined strategy based on solar-powered desali-
nation plants and integrated wastewater treatment plants are the
pillars for a sustainable solution, along with sound water man-
agement strategies and strict regulations.
Regarding the economic factor, there is a serious lack of in-
vestigations focusing on estimating the costs of applying various
AOPs for the removal of NOM and derived organic compounds from
drinking water sources. Such endeavor is of special importance
when AOPs are scaled up to fully operational applications. Indeed,
in this case the level of specific cost (i.e. cost per unit mass of
contaminant removed or unit volume of effluent treated) needs to
be assessed for the applied AOP (Dewil et al., 2017). Thus, as far as
NOM removal is concerned, determining its removal efficiency by
any AOP (or combined AOPs) needs to be carried out together with
a cost estimation analysis. The comparison with “conventional”
treatment techniques should be based on those two key factors
(treatment efficiency and specific cost). In the literature, limited
numbers of articles assessed the cost of applying selected AOPs for
other pollutants such as ozonation and Fenton oxidation for the
treatment of industrial wastewaters (Canizares et al., 2009), various
71
AOPs involving the use of ultrasound for the removal of phenol,
trichloroethylene and reactive azo dyes (Mahamuni and Adewuyi,
2010), and fluidized bed reactors with advanced oxidation pro-
cesses for the treatment of industrial wastewaters (Tisa et al., 2014).
Such papers could be considered as models for economic assess-
ment studies of different AOPs to remove NOM. For a more sus-
tainable approach, a third factor needs to be taken into
consideration which is the environmental impact, via for instance
life cycle assessments (Serra et al., 2011; Gimenez et al., 2015).
Overall, the R&D effort in this vital field of water treatment still
needs to be further promoted and financially-assisted. This will
allow universities, research centers and cleantech companies to
continue developing and optimizing technologies for efficient wa-
ter treatment, and eventually, reclamation. The technological
transfer from developed to developing countries (where the issue
of potable water is more profound) is of special importance because
it will help avoiding, or at least mitigating, serious potent problems
related to drinking water shortage, from mass migration to armed
conflicts to control water resources. Developing and applying effi-
cient AOP-based technologies to remove NOM and mitigate DBP
formations is a very good start, and making them more efficient and
cost-effective for large scale application in integration with other
advanced water treatment theologies, is the real breakthrough.
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