Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx

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Journal of Industrial and Engineering Chemistry

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

Review on integrated advanced oxidation processes for water and

wastewater treatment
Rushikesh S. Dhamorikar a, Vikesh G. Lade a, *, Pratik V. Kewalramani a, Ankush B. Bindwal b
a
Department of Chemical Engineering, Laxminarayan Innovation Technological University, Bharat Nagar, Nagpur 440 033, Maharashtra, India
b
Distillate and Heavy Oil Processing Division, CSIR Indian Institute of Petroleum, Mohkampur, Haridwar Road, Dehradun 248 005, Uttarakhand, India

A R T I C L E I N F O A B S T R A C T

Keywords: There is currently a steadily growing concern on a global scale for the creation of alternative water reuse
Integrated Advance oxidation process (AOP) technologies, primarily geared toward industry and agriculture. Due to their high chemical stability and/or poor
Wet air oxidation (WAO) biodegradability, advanced oxidation processes (AOPs) are viewed in this context as a highly competitive water
Biological process
treatment method for the removal of these organic pollutants. AOPs have an immense amount of potential for
Membrane process
Microreactor and microwave
treating a variety of these contaminants and enhancing wastewater biodegradability. They still have some sig­
nificant drawbacks, such as high costs of operation, energy intensive and use of additional chemicals. Combining
AOPs with other technique enhances the separation efficiency as compared to individual AOP. AOP is an
emerging technology trying to find its place in competition with other large scale industrial processes for
wastewater treatment and to counter a major drawback of AOP i.e. cost considerations Integration of AOP with
conventional treatment techniques have been studied qualitatively and quantitatively along with their advan­
tages and disadvantages. Quantitative parameters like EEO and performance of each process is discussed in detail
with critical comments on each process along with future prospective is discussed in conclusion. This paper
reviews recent research advancement in the field of conventional AOP and integrated AOPs such as integrated
AOP-biological treatment, integrated AOP-membrane processes, AOP in microreactors, microwave enhanced
AOP, and Catalytic wet air oxidation.

Introduction people. 80 % of diseases and 50 % of child deaths worldwide are related

The environment and public health are significantly impacted by
wastewater, which comprises both household and industrial waste [1].
Eighty percent of the wastewater in the world is thought to be returned
to the environment untreated. Numerous contaminants and poisons
found in this untreated wastewater have the potential to contaminate
soil, water, and the air, which could have a negative impact on human
health and the ecosystem. Wastewater pollution affects the environment
by destroying aquatic habitats, contaminating water supplies, and
releasing dangerous chemicals into the atmosphere. Moreover, the
ecosystem is seriously threatened by the presence of organic contami­
nants in wastewater, including phenols, pesticides, fertilizers, de­
tergents, and synthetic colours. Which can lead to the excessive growth
of algae and aquatic plants known as eutrophication, which lowers ox­
ygen levels in water bodies and endangers marine life, can be caused by
these contaminants (source). Wastewater not only has an adverse effect
on the environment, but it also presents serious health hazards to
to poor water quality.
Estimates show that industrial facilities annually release 300–400
million tons of trash, including hazardous sludge, solvents, and heavy
metals, into the world’s seas. This contributes to the serious environ­
mental issues brought on by wastewater pollution. In addition to having
an adverse effect on the environment, the discharge of untreated in­
dustrial wastewater into water bodies also puts the health of the com­
munities that live near these contaminated water sources at grave risk.
Hazardous materials found in industrial waste include heavy metals,
solvents, and toxic sludge. These materials can cause both acute and
long-term health problems in people, such as neurological conditions,
respiratory problems, and different forms of cancer.
Water scarcity is one of the major problems that is being faced by
humans today. Due to the expansion in population, there is an increasing
demand for potable and usable water in the world and it becomes
important to sustainably fulfill this demand by environmentally friendly
means without damaging the environment. Wastewater treatment

* Corresponding author.
E-mail addresses: dr.vikeshglade@gmail.com, vg.lade@litu.edu.in (V.G. Lade).

https://doi.org/10.1016/j.jiec.2024.04.037
Received 29 January 2024; Received in revised form 20 April 2024; Accepted 22 April 2024
Available online 26 April 2024
1226-086X/© 2024 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

Please cite this article as: Rushikesh S. Dhamorikar et al., Journal of Industrial and Engineering Chemistry, https://doi.org/10.1016/j.jiec.2024.04.037
R.S. Dhamorikar et al.
(effluent treatment), water purification methods are the major solutions
that has been practiced industrially.
The wastewater effluent coming from various chemical-producing
industries, including pesticides, pharmaceuticals, petrochemical, and
other process units, contains various hazardous organic and inorganic
contaminants. These contaminants contain hazardous complex mole­
cules that are bio refractory in nature and cannot be treated with con­
ventional biological processes. This wastewater effluent must be treated
and neutralized, so it is no longer a threat to the environment. There are
various physical, chemical, and biological processes existing for the
treatment of this wastewater. These various processes are generally
classified into primary treatment (e.g., screening, mixing, flocculation,
sedimentation, flotation, and filtration), secondary treatment (e.g.,
aerobic, anaerobic, anoxic, and facultative processes), and tertiary/
advanced treatment (e.g., adsorption, ion exchange, membrane filtra­
tion, disinfection, and oxidation using chemicals). Most of these pro­
cesses except for chemical and biological only involves the transfer of
waste from one phase to another and creates secondary loading on the
environment while advanced chemical and biological processes
accompanied by chemical transformation or complete mineralization of
the waste are more environmentally friendly and effective in neutral­
izing the wastewater but are somewhat less economic due to high
fabrication and maintenance cost.
To meet the ever-increasing material needs and demands of the
growing population there is excessive development in all industrial
sectors for manufacturing consumer goods, pharmaceuticals, industrial
chemicals and agriculture. This has led not only the traces of organic
chemical in the aquatic environment which is called as trace organic
compounds (TOC); but also, the persistent contaminants like micro­
plastics in high levels [2]. It has been seen that, to remove these organic
compounds wastewater treatment plant is installed but conventional
physical and biological wastewater treatment may only partially remove
these chemicals, and TOCs remains in the wastewater treatment plant
effluents and are discharged into surface water [3–5]. Most organic
contaminants found in waterways are persistent in the ecosystem and a
danger to both human and animal health. Therefore, there is an urgent
need for effective treatment processes for highly concentrated organic
wastes. In the field of treating organic wastewater, advanced oxidation
processes (AOPs) are becoming increasingly popular [6,7].
AOP is a wastewater treatment process in which complex molecules
or waste in wastewater is neutralized by OH• radicals which act as strong
oxidizing agents [8]. AOPs are often regarded as the most effective
chemical approach for treating organic wastes [9]. The removal of or­
ganics from wastewater have been carried using AOPs which in turn
improves the biodegradability of compounds [10]. AOPs has the high
oxidation efficiency and also does not give any secondary pollutant [6].
Depending on the mechanism through which these OH• are introduced,
there are different AOP processes such as hydrodynamic cavitation
(generated by means of ultrasonic irradiation or using constrictions such
as valves, orifices, and venturi in hydraulic devices), photo catalytic
oxidation/ UV/peroxide process (using ultraviolet radiation/near UV
light/sunlight in the presence of a semiconductor catalyst or Hydrogen
peroxide), and Fenton chemistry (using the reaction between Ferrous
sulfate and hydrogen peroxide (H2O2), Ozonation (in presence of O3),
electrochemical oxidation [11,12]. The basic aim of the advance
oxidation process is to produce highly active oxidising free radicals such
as hydroxyl radicals (OH•) as they are capable of degrading the organic
pollutant present in the wastewater. The hydroxyl radical is one of the
strongest oxidants, reactive and non-selective. It is capable of rapidly
degrading several organic compounds. OH• radical has single electron in
its outer most shell so, it tries to stabilise themselves either by adding to
some organic compound or taking some electron from organic com­
pound [13]. AOP are very effective in complete mineralization of
organic waste present in the wastewater.
Advanced oxidation processes based on sulphate radicals (SR-AOPs)
are also a workable technique that may eliminate organic contaminants
2
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
by producing highly oxidizing species, primarily sulphate radicals (SO•4).
A variety of organic pollutants can be oxidised and stabilised by
absorbing electrons from surrounding compounds by processes
including addition, substitution, oxidation, and bond cleavage [14].
Additionally, SO•4 has a wider pH range, a higher redox potential
(2.5–3.1 V) than HO• (1.8–2.7 V), produces fewer undesirable by-
products, and reacts with a variety of pollutants [15–17]. Oxidation of
organic contaminants occurs primarily through reaction with OH radi­
cals. All AOPs consist of mainly two basic steps i.e., formation of strong
oxidants and later reaction of oxidant with organic contaminants in
water.
One of the most important methods in wastewater treatment is Wet
Air Oxidation (WAO), which is effective in breaking down a variety of
resistant organic contaminants. Zimmermann came up with wet air
oxidation (WAO), which is one of the most technologically and
economically feasible AOPs for wastewater treatment. Depending on the
flow rate and organic content of the effluent that needs to be treated,
each AOP has a varied applicability range [18]. At low flow rates and
low organic loading, ozonation and wet peroxide oxidation (WPO) based
AOPs are preferable. While biological treatments seem ideal for high
flow rates and low organic content, incineration is only viable for highly
concentrated wastewater at low flow rates. In contrast to other AOPs,
WAO can partially cover the application spectrum of biological and
incineration processes and is suitable for a high organic loading at high
flow rates. The flexible nature of WAO is demonstrated by its capacity to
handle a variety of wastewater circumstances, with an initial chemical
oxygen demand (COD) range of 20 to 200 g/L, therefore serving both
concentrated and diluted wastewater streams [19]. Several other
treatment processes have also been employed for the removal of or­
ganics, including filtration, ion exchange, magnetic separation,
coagulation-flocculation, membrane processes, biodegradation, chemi­
cal oxidation, adsorption, Nano-filtration.
AOP and hybrid/ integrated AOP publication trend and economic
considerations
Since emergence of AOP as a possible solution for advanced
oxidation-based wastewater treatment scientific community and engi­
neers have been working hard to make this technology as economical as
possible so that it can be used at an industrial scale. The hope among
various disciplines that AOP represents in the current scenario can be
seen by the trends of research and review paper every year. It has been
seen that the rate at which research paper increases in this field is not as
the same as review papers and hence there is a need to have review
papers on different innovations and proposals that are going in AOP to
be able to generalise and represent a lot of research work collectively
boosting the research in the field which would otherwise be difficult.
The following Fig. 1 shows the trends as discussed in section above.
Mehrvar & Ein-Mozaffari [20] in their work have given some pa­
rameters and procedure to select effective AOP process that can be in­
tegrated. It is found that the choice of method depends on various factors
such as characterization of wastewater, environmental regulations and
cost. As a result, each process should be optimized depending on a va­
riety of factors, including operation time, operating cost, and energy use.
This analysis examines current successes, advancements, and trends
(during 2003–2009) in the integration of advanced oxidation technol­
ogies with other remediation strategies. In their studies they have also
defined a synergic process parameter which is ratio of combined reac­
tion rate constant to the linear sum of individual rate constant, where
rate refers to the rate of reaction of waste degradation. This parameter
can be used for finding quantitatively better AOP combination or inte­
grating. Along with this parameter the other factors that are essential to
be considered are methods, residence time distribution, cost, energy,
kinetics and modelling etc. The integration of different process should
result in a minimization of residence time or cost of the process while
improvement in the efficiency of treatment. The expressions for finding
R.S. Dhamorikar et al. Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
Table 1
Integrated Advanced Oxidation Processes (AOPs) reviewed and studied.
Reference Integrated Advanced Oxidation
Processes (AOPs) reviewed and
studied
[23] Fenton Oxidation, Radiation,
Photolysis, Photocatalysis, Ozone,
Sonolysis along with detailed
aspects of electrooxidation and
electro-Fenton exclusively along
with their design parameters.
Removal of antibiotics and
organic dyes
[24] Covered chemical based,
photocatalytic based,
sonochemical based,
electrochemical based, ozone
based, integration of AOP with
other processes along with the
advantages and disadvantages of
individual and integrated AOP
with economic aspects of
integrated processes and scale-up
for being used in industrial
Fig. 1. Publication in the field of AOP, AOP hybrid or integrated and AOP
applications
review articles published in Elsevier during 2000–2025 (Data collected on 19/
02/2024).
operating and fixed costs of different processes of physical and chemical
processes based on the depreciation period (40 years) for specified [25] Conducted detailed discussion on
volume (V) and residence time (t) are developed [21,22]. various AOP focusing on catalytic
ozonation, electrochemical
(85000 + 40 × 1500) 1m3 oxidation, electrochemical and
Fixedcostforphotoreactor = ×( )
(40 × 24 × 365)(Vt) 1000L sonochemical and photocatalytic
process along with a
comprehensive review on
(58000) 1m3
FixedcostforActivatedcarbon = ×( ) biological processes including
(40 × 24 × 365)(Vt) 1000L aerobic process such as aerated
lagoons, activated sludge process,
(72 × 40 × 24 × 365(Vt) + 368403) biofilm combined with activated
Fixedcostforbiologicalreactor = sludge process, trickling filter
(40 × 24 × 365)(Vt)
aerobic photo-bio reactors and
anaerobic process such as
(2000) 1m3 facultative lagoons, anaerobic
OperatingcostforPhotoreactor = ×( )
(24 × 365)(Vt) 1000L bioreactors and
phytoremediation. They also
studied AOP-biological combined
(85000 + 40 × 1500) 1m3 processes and found AOP as a pre
OperatingcostforActivatedcarbon = ×( )
(40 × 24 × 365)(Vt) 1000L or post treatment to biological
process with respect to different
(4.58 × (24 × 365)(Vt) + 36295) types of effluents such as organic
Operatingcostforbiologicalreactor = compounds, pulp and paper,
(24 × 365)(Vt) pharmaceutical, nitrogen based
1m3 and from dyes and textile industry
×( ) discussing the feasibility, energy
1000L
and economic considerations.
Table 1 gives an overview of the recent articles in the field of Inte­ [26] Conducted critical review on
grated Advanced Oxidation Processes (AOPs). But some of the research advanced oxidation based
integrated processes like
fields like microwave, microreactor, wet air oxidation etc. integration integration of AOP with
have not been studied extensively as much as it is been studied for adsorption, membrane, filtration
biological and other adsorption methods. Some of the examples of ad­ and biological methods and
sorbents for organic dye pollutants removal found in literature are assessed the treatment efficiency,
versatility, sludge production,
[28–39]. This review article looks into more diverse options providing
operational complexity, energy
reader a larger choice to compare and select among the various available consumption and treatment cost
AOPs. Some other reviews like that of Tufail et al. [40] includes critical of different integrated process.
review on AOP for removal of trace organic contaminants. They exten­ Also discussed limitation of each
sively investigated various integrations and individual AOP such as approach.
photolysis, ozonation, Fenton, anodic oxidation and wet air oxidation
3
Conclusions
Electrochemical AOP is a good
alternative for treating
hazardous waste due to its high
oxidation efficiency and lack of
secondary pollutants.
Electro oxidation process is
more suitable for lower
branched organic molecule such
as fertilizers, starch, and
brewery etc. industrial waste.
Electro Fenton process is more
appropriate for higher organic
branched complex molecules
such as paper and pulp, textile
etc. industrial effluents.
There is need of integrated AOP
for enhancing treatment
efficiency and overcoming
drawbacks of individual AOP.
AOP efficiency is a function of
pH, contaminant concentration,
catalyst concentration, reagent
concentration, radiation
intensity etc.
There is a need of
comprehensive optimization for
economic feasibility.AOP has
higher operational costs
compared to conventional
processes. Intermediates from
developing pollutants yet pose a
challenge for AOPs.
Found that combination of AOP
with other biological process
gives sustainable degradation of
toxic pollutant in wastewater.
Presence of bio enzymes
microorganism along with OH
radicals, superoxide and
sulphate radical help in
sustainable degradation of
pollutant in an economical and
environmentally friendly
manner. One of the major
challenges for industrial use of
AOP is the high operating cost
and hence need optimization
considerations and needs to
have more comprehensive study
on economy and kinetics of
AOP. AOP integrated with
biological process not only have
applications in water treatment
but also in production of high
value end products. Use AOP
integration fulfils the
sustainable development goal
(SDG) 3,6,12 and 13.
Integrated processes showed
optimistic results for
pharmaceutical compounds
(PCs) remediation, albeit with
specific advantages and
limitations depending on factors
like PC nature, AOP type, and
physical/biological processes.
Comparative analyses offer
insights into treatment
efficiency, operational
complexity, and cost-
effectiveness, guiding selection
(continued on next page)
R.S. Dhamorikar et al. Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx

Table 1 (continued ) or in integration with other industrial and AOP process. Yet there has
Reference Integrated Advanced Oxidation Conclusions been very less literature which gives a generalised procedure to design
Processes (AOPs) reviewed and wastewater treatment technology which compares the advantages and
studied disadvantages of integration or combinations with other processes. This
of the most suitable approach for paper attempts to bring to light different advantages and disadvantages
efficient pollutant removal. of individual and integrated processes; so that one has more design
[27] Reviewed electro Fenton and Found that Fenton is more options compared to conventional procedures. It is hence very important
photocatalytic oxidation and effective however more energy
to have quantitative parameters which justifies integrating or combining
integrated treatment based on intensive and hence have cost
Fenton oxidation such as Fenton prohibition and have key different process.
oxidation with persulfate, parameter like PH, hydroxide
coupling Fenton with adsorption/ dosing that affects degradation Types of advanced oxidation processes (AOPs)
membrane filtration and efficiency along with cost
combination with other AOP considerations.
The purpose of AOPs is to oxidize organic and occasionally inorganic
compounds in water and wastewater by reacting with in-situ generated
and found that integration of AOP gives better results when compared to extremely reactive hydroxyl radicals (OH). The pollutants in water and
the performance of individual AOP as it produces more OH radicals. For wastewater can be rapidly and effectively fragmented and transformed
example, photocatalytic process combined with ultrasonic can take the into small inorganic molecules by this strongest oxidant OH radical.
advantage of ultrasonic cleaning resulting in overall higher minerali­ AOPs are classified based on method of generation of free OH radical.
zation of contaminants. They have comprehensively covered limitations Fig. 2 shows the classification of AOPs and also the Integrated/ combi­
of individual AOP and classified integrated AOP as UV radiation based nation of the AOPs for increased efficiency of the treatment method.
AOPs, Ozonation and Fenton based AOPs, electrochemical based AOPs
but yet have not covered recent innovations or integration with main­ UV based/ photocatalytic
stream processes such as membrane, microreactor, microwave, etc. It is
seen that under lower concentration (typically 100 mg/L) of organic UV-based AOPs are those that involve UV irradiation (mainly UV-C)
impurity the kinetics of degradation follows first order kinetics and the interaction of UV light with various radical promoters. UV light
approximately and in such cases the energy required to treat water de­ wavelengths less than that of visible light (400 nm) but greater than that
pends on the volume of water to be treated [41]. The cost of AOPs in­ of X-rays (100 nm). For many organic contaminants and wastewater
cludes cost of various processes such as the energy needed to activate systems, UV light functions as a natural disinfectant agent. Ultraviolet
catalyst, run UV lamps, and power anodes in electrochemical processes. (UV) radiation can effectively inactivate various micro-organisms in
The concept of comparison performance of AOP is Electrical Energy per water and has been increasingly used for water disinfection [43]. Low-
Order (EEO) parameter. EEO was introduced in 2001 and is defined as the pressure or medium-pressure mercury lamps with monochromatic or
energy required in kilowatt-hours (KWh) to degrade a contaminant by polychromatic emission spectra are typically used as UV radiation
one order of magnitude in a unit volume of water or air [42]. sources [44]. Recently, UV LED light sources with particular wavelength
distributions have been researched and summarised for disinfection
P.t.1000
EEO = applications [45].
V.60.log(ccfi )
UV/H2O2
where, Ci is the initial concentration and Cf is the final concentration of One of the most popular advanced oxidation processes (AOPs) is the
wastewater. UV/H2O2 process, which has undergone substantial research and is used
To make AOP economic so being able to be used in mainstream in the advanced treatment of wastewater and drinking water. UV direct
wastewater treatment, AOP is often proposed to be used in combination photolysis and hydroxyl radical (HO•)-assisted indirect photolysis

Fig. 2. Classification of AOPs.

4
R.S. Dhamorikar et al.
both are used in the UV/H2O2 process to break down the target
pollutant. Numerous peer-reviewed scientific publications have
explored UV/H2O2 for organic pollutant removal at the lab scale for
water quality ranging from ultrapure water to landfill leachate [46–48].
UV/H2O2 have been used in a wide range of industries, including textile
industry, pharmaceutical sector, organic pollutant removal etc. [49–53].
Organic pollutants can be effectively mineralized using the UV/ H2O2
process. Operating parameters like UV dose, pH, oxidant dose, and water
quality, have an impact on the effectiveness of UV/H2O2 operations
[54,55]. For pharmaceuticals, the combination of UV and H2O2 process
typically offers better removal efficiencies. UV combined with H2O2
process are governed by H2O2 the concentration, rate of OH• radical
formation, UV light intensity, water constituents, chemical structure of
the pharmaceutical and also the solution pH [11]. A recent study looking
at the removal of C.I. Acid Orange 7 (a dye from textile wastewater)
found that the lack of UV radiation or H2O2 reduced dye removal effi­
ciency. Increase in pH at basic levels and H2O2 concentration up to 2
mmol improved the effectiveness of dye removal but increase in bicar­
bonate anion concentration adversely affected its removal [56]. UV/
H2O2 are capable to degrade the phenolic compounds that are detected
in olive mill wastewater [57].
The main reaction occurs in this system is as follows:
H2 O2 + UV→2⋅ OH (1)
Radiation causes the hydrogen peroxide molecules to react and
produce OH radicals [58]. According to a Haber-Weiss mechanism, the
breakage of the O-O bond causes this breakdown to occur. The following
reactions start the process of producing more chemical OH:
H2 O2 +⋅ OH→H2 O + HO⋅2 (2)
H2 O2 + HO⋅2 →H2 O + O2 + ⋅ OH (3)
UV/TiO2
The breakdown of organic pollutants and other organic compounds
has recently attracted attention in photocatalysis experiments employ­
ing TiO2. Due to its simplicity and improved degrading efficiency, the
treatment of wastewater in a titanium dioxide-suspended slurry reactor
has been widely used. TiO2 photocatalysis is widely used in pollution
removal because of its stability, low cost, and non-toxicity [59]. TiO2 is
applied in two different ways in photocatalytic degradation using UV/
TiO2: (1) immobilised on support materials such quartz sand, ceramic
membrane, glass wool matrix, glass etc. and (2) suspended in aqueous
media [60]. Immobilized TiO2 does not need additional post-treatment
for the recovery of catalyst particles after oxidation that’s why it is
preferable as compared to dispersed TiO2 [61]. An immobilized TiO2
system eliminates post-treatment stages; however, studies indicate that
the degradation performance is reduced due to limiting mass transfer
and loss of photocatalytic activity by the fixation procedure [62]. Also
arsenic-contaminated water can be treated with TiO2 photocatalysis by
oxidising As(III) to the less harmful and less mobile form [63]. Dutschke
et al. investigated degradation of various chlorinated, ethene and
methane derivatives commonly found of chlorinated volatile organic
compound polluted regional groundwater samples. The setup consists of
an O3-bubble column reactor with a carrier-bound TiO2/UV. The
degradation rate of at least 98 % for cis-dichloroethene, trichloroethene
and tetrachloroethene and 85 % for trichloromethane was achieved
without formation of any transformation products [64].
Sonolysis
One of the latest AOP methods is sonolysis, which uses ultrasonic
irradiation to cause the degradation of organics present in water to
release OH radicals. As a result, this approach is thought of as a “green”
strategy because it does not involve adding any external chemicals to the
water system or using chemicals. Sonolysis is the process of breaking
5
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
down molecules through the creation, expansion, and collapse of a
bubble in a liquid using sonic cavitation. Acoustic cavitation is gener­
ated when intense ultrasonic waves contact with dissolved gases in a
liquid media [65]. However, energy is required for producing acoustic
cavity of bubbles from ultrasound irradiation. This results in the cavi­
tation phenomenon, which is the rapid formation, explosion, and
collapse of bubbles inside a liquid media, converting large amounts of
energy into chemical energy. By altering the power and frequency of the
ultrasound the acoustic bubble formation can be controlled and the
same can be used as parameter to control the removal rate of pollutants.
In recent years, the mineralization of organic molecules from waste­
water has mostly been performed using ultrasonic technology. Vajn­
handl and Le Marechal [66] mentioned a few of the significant sonolysis
processes for the oxidation of radioactive metals like As (III), the
degradation of textile colours, the mineralization of organic contami­
nants, the degradation of volatile organic substances, and the removal of
heavy metals [66]. Frequencies for ultrasound range from 20 kHz to 1
GHz. The most common uses of high-frequency ultrasonography are in
medicine for detection, diagnosis, and process monitoring, including
fluid flow. Sonochemical procedures and ultrasonic cleaning are carried
out using low-frequency therapy (power ultrasound, up to 100–200
kHz). Three distinct phases or zones have been identified in sonocata­
lytic reactions, to be more precise. The internal conditions of bubbles
consist of an initial zone with rapid heating and cooling, with temper­
atures and pressures of around 5000 ◦ C and 1000 atm, respectively. The
bubble is surrounded by a region of transition between gas and liquid in
the second zone. With a width of 200 nm and a temperature of around
1900 ◦ C, this phase typically contains non-volatile chemicals. The third
phase is the bulk liquid phase, which allows for the normal operation of
shockwaves, jets, shear forces, temperature, and pressure while still
creating free radicals [67].
The chemistry supporting this AOP includes splitting water into ox­
ygen and hydrogen, which are then further atomized. The production of
intermediate radicals is occasionally followed by light emissions [65].
Commercial US reactors have been employed in many waste treatment
situations, such as the purification of wastewater from different phar­
maceutical industry and colour and pigment industry, as a result of the
scientific community’s growing interest in US irradiation. Some re­
searchers have even created cavitation devices and reactors. The two
most typical reaction systems for the production of acoustic cavitation in
water are bath and probe (also known as horn). Direct sonication, which
involves the ultrasonic source coming into direct contact with the liquid
medium, or submerging a vessel containing the treatment solution in
ultrasound (indirect sonication).
US/ozone
Ozone (O3)-based AOPs such as photocatalysis, photolysis, and
ozone can be combined with Fenton reaction, and sonolysis. O3 has been
used extensively for cleaning water and waste since it was discovered
because of its excellent disinfecting effect. The fundamental distinction
between the ozonation and AOP processes is that the former depends
primarily on direct aqueous ozone oxidation, while the latter depends
heavily on hydroxyl radical oxidation. Depending on the pH of the so­
lution, O3 can directly destroy organic contaminants via electrophilic
reaction or indirectly through radical chain reactions. Wu et al. used
ozone to eliminate extremely hazardous pigments and speed up
biodegradation. Ozone alone possesses the ability to oxidise organic
molecules via direct or indirect hydroxyl radicals [68]. Complex organic
substances are not significantly oxidised by ozone, and it is challenging
to entirely destroy organic contaminants. Thus, the technology of ozone
oxidation is frequently combined with other technologies. Due to the
direct and indirect generation of OH radicals, combining ozone with US
leads to a net improvement in the breakdown of hazardous organic
contaminants.
Ultrasound could enhance the decomposition of ozone, hence
increasing the amounts of the hydroxyl radicals and improving the
R.S. Dhamorikar et al.
degradation efficiency. One potential enhanced oxidation method is the
combining of ultrasonic irradiation with ozonation (US/O3) (AOP).
Sonolysis causes the thermolytic decomposition of ozone in the vapors
phase of a cavitation bubble.
O3 (g) + )))→O2 (g) + O(3P)(g) (4)
O(3P)(g) + H2 O(g)→2⋅ OH(g) (5)
“)))” indicates ultrasonic irradiation. These degradation processes
take place in the gaseous phase [69].
It has been shown that ultrasound increases the mass transfer coef­
ficient, which accelerates the mass transfer of ozone from the gas phase
to the aqueous phase [70,71]. One of ultrasound’s mechanical effects is
the destruction of ozone-containing gas bubbles, which increases the
specific surface area. With ultrasonic irradiation present, the volumetric
mass transfer coefficient would therefore increase [72]. Tezcanli-Güyer
et al. studied the degradation of the textile dye C.I. Acid Orange 7 by
using the combined O3/US AOP [73].
Electrochemical advanced oxidation processes
Conventional methods of treating water and wastewater seek to
eliminate organic and inorganic matter, sterilize, and partially remove
heavy metals and nutrients. The advanced oxidation process is an
alternative to conventional effluent treatment methods. The number of
papers on electrochemical advanced oxidation processes (EAOPs), one
of the AOPs used to break down, significantly increased between 2000
and 2020 [74]. These numbers of researchers shows a great interest in
the application of electrochemical techniques such as EAOPs in the
degradation of drugs, cyanotoxins, and personal care products [75].
EAOPs, such as electro-oxidation (EO), photoelectron-oxidation (PEO),
also called photoelectron catalysis (PEC), the electro-Fenton (EF), and
the photoelectro-Fenton (PEF) are the type of EAOPs used. Because of its
adaptability and simplicity in scalability, the anodic oxidation (AO) or
electrochemical oxidation (EO) is the most researched electrochemical
process among the EAOPs [76].
Electrochemical oxidation (EO)
In an electrochemical reaction, the anode undergoes an oxidation
reaction while the cathode undergoes a reduction reaction. The funda­
mental concept of electrochemical processes, which have been widely
applied as a heavy metal remediation method, is taking advantage of the
redox reactions occurring at both the anode (for example, oxidation of
pollutants) and cathode (for example, reduction of heavy metals) to
remove pollutants [77]. There are various approaches to electro­
chemical oxidation (EO) of organics for wastewater treatment.
1) Direct EO, in which electron transport takes place at the electrode
surface in the absence of additional materials.
2) Indirect EO, which oxidises organic pollutants by using electro active
species produced at the anode surface as bridges for electrons mov­
ing between the electrode and the organic pollutants.
Direct charge transfer reactions between the anode surface and the
included organic pollutants take place during direct anodic oxidation or
electrolysis, which takes place directly on the anode. The only active
component of the mechanism is the mediation of electrons, which can
degrade some organic contaminants at specific potentials more negative
than the oxygen evolution reaction (OER) potential [78]. Tin, antimony,
lead oxides, and boron doped diamond (BDD) are the most typical non-
active anodes [79]. Physically adsorbed HO• radical is produced on the
anode surface by water oxidation in inactive anodes. After that, the
pollutants and HO• interact, causing the breakdown of the contaminants
into intermediates or complete mineralization [80]. Some of the litera­
ture on overview for the treatment of saline water and contaminated
water with refractory pollutants with detailed analysis can be found in
6
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
[70,81–85].
Photoelectron-oxidation
Photocatalytic technologies basically are of two types: homogeneous
and heterogeneous processes. In homogeneous process the catalyst is
dissolved and thus faces the separation difficulty and non-recyclability
of the used catalyst, therefore the process is not suitable for contin­
uous operation [86]. In heterogeneous processes, solid catalyst is used,
which are often a semiconductor and that can be supported on a number
of substrates which in electrochemical cell it can be used as an anode. In
actuality, one hybrid process that combines EO, heterogeneous photo­
catalysis, and direct photolysis is called photoelectron oxidation (PEO),
sometimes known as photoelectron catalysis. The most commonly used
semiconductor in photoelectron oxidation is titanium oxide [87].
Electro-Fenton and photoelectro-Fenton
Due to the generation of highly oxidising species, the Fenton process
has been utilised extensively in the treatment of effluents. It is also less
expensive than other AOPs and offers a simple and reliable application
[88,89]. In the Fenton process, the HO• is indirectly catalytically
generated through the reaction between H2O2 and Fe2+ (Eq. (6) in acid
media [80,90]
Fe2+ + H2 O2 + H+ →Fe3+ + HO⋅ + H2 O (6)
H2O2 is not the only reactant in Fenton’s chemistry; HClO can also
react with Fe2+, producing a significant quantity of OH in the bulk [91].
Gholami et al. [92] has experimentally investigated electro-Fenton
(EF) process for the treatment of petrochemical spent caustic effluent.
The effect of operating parameters, such as H2O2 concentration, reaction
time, pH, and current density on the COD and TOC removal rate were
studied.
The photo-Fenton (PF) technique is used to achieve a higher
mineralization of effluent pollutants, which are often complicated mo­
lecular chains and challenging to mineralize. In the PF process, in
addition to the direct reaction with H2O2 and effluent pollutants, the
source of ultraviolet radiation (UV) is responsible for converting Fe3+ to
Fe2+, permitting constant HO• formation (Eq. (7)) [93].
Fe3+ + H2 O + hv→Fe2+ + HO⋅ + H+ (7)
Wet air oxidation (WAO)
WAO can cover a portion of the application range for biological and
incineration techniques and is suitable for a high organic loading at high
flow rates. In particular, WAO offers a lot of promise for treating
wastewater with a high concentration of organic matter (about 20–200
g/L of COD) and/or hazardous pollutants for which direct biological
treatment is impractical. Using WAO, organic pollutants are subjected to
high temperatures (175–320 ◦ C) and pressures (2.17–20.71 MPa) while
being partially oxidized into biodegradable intermediates or mineral­
ized into carbon dioxide, water, and safe end products which remains in
the aqueous phase. Halogens are converted to halides, sulphur to sul­
phate and phosphorus to phosphates. The oxidant used in the process is
either pure oxygen or air [94]. In comparison with other thermal pro­
cess, WAO will not produce NOx, HCl, dioxins, SO2, fly ash, furans etc.
[95]. The process ability to attain thermal self-sufficiency can be eval­
uated based on the capability that is only noticeable when COD levels
above 30 g/L marks a critical turning point in its viability and makes it
economically feasible in situations where organic concentrations are
high. Furthermore, adding catalysts improves the procedure by
improving the circumstances of the reaction and increasing the target
organics’ mineralization [96–98].
Temperature, the amount of organic matter present, and dissolved
oxygen are all crucial to the reaction kinetics, and pH is a key factor in
removal of total organic carbon or COD [99,100].
R.S. Dhamorikar et al.
Catalytic wet air oxidation
By incorporating catalyst in WAO leads to more effective process for
pollutant removal i.e. catalytic wet air oxidation (CWAO). By using
appropriate catalysts for the WAO process, or catalytic wet air oxidation
(CWAO), pollutants, even those that are refractory, can be more easily
broken down, resulting in reduced capital and operating costs [99,101].
As a result of its shorter residence time and softer operating conditions,
CWAO has an operating cost that is about half Sun that of non-catalytic
WAO, however this depends on the specific type of wastewater [98].
European firms have primarily concentrated on homogeneous catalytic
wet air oxidation (CWAO) methods that utilize soluble transition metal
ions. On the other hand, Japanese companies have investigated het­
erogeneous CWAO techniques that utilize precious metals supported on
materials with a high surface area [98]. Recent research in China shows
the feasibility of CWAO, with operating capacities ranging from 10,000
to 30,000 tons/year [98].
Catalytic Wet Air Oxidation (CWAO) is the integration of catalyst in
the Wet Air Oxidation process for the treatment of wastewater. This
novel technique has the potential to address persistent organic con­
taminants in an efficient manner while reducing the high pressure and
temperature demands that are commonly linked to WAO. By utilizing
catalytic mechanisms, CWAO improves oxidation efficiency, reaction
conditions, and pollutant degradation by adding a new dimension.
A fundamental component of CWAO is homogeneous catalysts,
particularly soluble transition metal ions [98]. Significantly, salts of iron
(Fe2+) and copper (Cu2+), among others, function as catalysts by pro­
moting reactions at lower activation energies. Many commercial wet air
oxidation systems are currently using soluble transition metal catalysts
based on iron or copper salts, and these plants are successfully treating
sludge and industrial effluents. However, homogeneous transition metal
catalysts must be removed from the stream of treated wastewater and
then returned to the reactor inlet or disposed of using appropriate
method. Consequently, in order to comply with current discharge laws,
their utilization must be considered from the early stages of process
design, either in the liquid or solid phases. As the separation step is
required for homogeneous catalyst, so to overcome this issue hetero­
geneous catalyst comes into picture, because of this heterogeneous
catalyst has got a great attention.
Heterogeneous catalytic wet-air oxidation processes
For the CWAO of aqueous pollutants, a variety of solid catalysts, such
as noble metals, metal oxides, and mixed oxides, been ready and put
through testing to identify new catalytic materials with high activity and
stability for the CWAO of model chemicals and real wastewaters. The
catalytic diversification toolset consists of metals such as cobalt (Co),
copper (Cu), iron (Fe), ruthenium (Ru), platinum (Pt), and manganese
dioxide (MnO2), as well as metal oxides including titanium dioxide
(TiO2), cerium oxide (CeO2), and manganese dioxide (MnO2) [102,103].
By utilising these heterogeneous catalysts according to their unique
characteristics, methods of treatment can be modified to the particular
contaminants and operating circumstances. A review of earlier research
in the field shows that many studies on the catalytic wet air oxidation
process used model wastewaters made up of just one organic compound.
Results from experiments using wet-air oxidation of high-concentration
chemical wastewater (Chemical Oxygen Demand (COD) up to 42,800
mg/l) containing different organic acids and inorganic compounds
showed that, at temperature of about 473 K and total operating pressure
of 30 bar, it was possible to easily achieve over 50 % reduction of the
COD concentration in about an hour; additionally, a significant rise in
COD removal using CuSO4 over that without a catalyst was observed.
However, when using heterogeneous catalysts like ZnO and Co2O3, the
improvement was less noticeable [104]. Belkacemi et al. used a batch
stirred autoclave over a range of catalysts to examine the removal effi­
ciency of total organic carbon (TOC up to 22,500 mg/l) from raw high-
strength alcohol-distillery waste liquors. TOC conversions were under
60 % in the ranges of 453–523 K temperature and 5–25 bar of oxygen
7
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
partial pressure, respectively. The greatest TOC removal could be ach­
ieved using Cu (II)/NaY and Mn/Ce oxides as catalysts. The catalysts
were found to be highly effective for minimal contact times, but the
prolonged exposure of the catalyst causes catalyst deactivation by foil­
ing carbonaceous material [104].
Regardless its many benefits, CWAO have drawbacks like catalyst
recovery and reactor corrosion. However, in order to ensure the stability
of heterogeneous oxidation catalysts under hydrothermal operating
conditions, a variety of significant issues must be resolved. These
include: The active ingredient material may leach and sinter; the sup­
porting material might reduce surface area; poisoning of the active sites
by the evolution of carbon monoxide; or the catalyst surface may
accumulate organic or inorganic compounds (coking) [98].
Integrated AOP processes (Hybrid AOP)
Different ideas that exist to use AOP and conventional process for
better economic and degradation efficiency includes:
i) Combined AOP Approach: using AOP and other processes (AOP,
conventional wastewater treatment processes) simultaneously such
that the effect or presence of one enhances the performance of the
other (Fig. 3).
ii) Integrated AOP Approach (Fig. 4): In integration i.e. using one pro­
cess at a time in a concentration regime where it performs at its best
so that we can get higher range of concentration degradation at
economic costs.
Integrated AOP-biological treatment
Due to their great chemical stability and/or low biodegradability,
advanced oxidation processes (AOPs) are regarded as a highly compet­
itive water treatment technology for the removal of such organic con­
taminants. Although chemical oxidation for complete mineralization is
often expensive, it has been extensively documented that when com­
bined with a biological treatment, operational expenses are reduced.
Fahmi et al. studied the single and multi-stages advanced oxidation
process (AOP)-biological treatments for drinking water treatment and
also compared AOP-biological treatment with the ozonation-biological
treatment. The outcome shows that, in comparison to single-stage
ozonation-biological treatment, single-stage AOP-biological treatment
could improve dissolved organic carbon (DOC) elimination. The multi-
stage AOP-biological treatment achieved 71 % removal of DOC;
whereas the single-stage AOP-biological treatment can only remove 41
% of DOC for same oxidation time of 15 min with 4 times repetition
[105]. A much polluted liquid called leachate is produced when rain­
water percolates through landfill waste. In fact, one of the most critical
challenges in waste management is the treatment of these leachates. Del
Moro et al [106] studied the comparison of UV/H2O2 based AOP as an
end treatment and integrated AOP-biological degradation for treating
landfill leachates. They reported that the biological treatment like
Sequencing Batch Biofilter Granular Reactor (SBBGR) alone was able to
remove 64.2 % and 61 % of chemical oxygen demand (COD) and dis­
solved organic carbon (DOC), respectively. When UV/H2O2 based AOP
was combined as an end treatment of SBBGR effluent, it enhanced the
overall COD and DOC removals up to 70.6 % and 68.0 %, respectively
[105].
When chlorine is used to disinfect drinking water, halogenated
byproducts are created that are known to have long-term adverse health
effects [107]. These substances, known as disinfection byproducts
(DBPs), are produced when chlorine reacts with the natural organic
matter (NOM) found in raw source waters. Two well-known DBPs that
have been demonstrated to be toxic and possibly carcinogenic to
humans are trihalomethanes (THMs) and haloacetic acids (HAAs). These
substances pose a major concern to human health [107]. Toor et al.
R.S. Dhamorikar et al.
Fig. 3. Combined AOP processes for wastewater treatment.
Fig. 4. Scheme for Integrated AOP conventional processes.
compared biological activated carbon (BAC) with integrated UV-H2O2
AOP-BAC treatment for disinfection byproducts (DBP) reduction in
drinking water. They found that BAC alone can achieve 11 %, 7 % and
28 % reduction in trihalomethanes (THM), trichloroacetic acid (TCAA)
and non-purgeable organic carbon (NPOC) respectively but when BAC
was integrated with UV-H2O2 based AOP the percent reduction was
increased to 42 % for THM, 50 % for TCAA and 52 % for NPOC. At a
moderate UV fluence of around 500 mJ/cm2, the combination of AOP-
BAC is effective at drastically reducing DBPs. It offers significant DBP
reductions and lowers the operating costs related to running the UV-
H2O2 process at high UV fluences, it can be interpreted from the findings
that combining UV-H2O2 AOP with downstream BAC treatment is a
more practical option than the extended standalone UV-H2O2 treatment
[108].
Increasing the biodegradability of organic pollutants by imple­
menting pretreatment of wastewater with AOPs can lead to the creation
of safe byproducts with a significant amount of organic carbon available
for the following biological process. Complete mineralization of the
8
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
effluent can be achieved with coupled treatments at a significant cost
saving. The biological treatability of wastewater, as determined by the
BOD/COD ratio, is improved when AOPs are employed as a pretreat­
ment to biological systems [109]. Either an increase in BOD or a
decrease in COD can improve the biodegradability of wastewater. Prior
to biological oxidation, methods for pretreatment of actual industrial
wastewater include hydrodynamic cavitation (HC) in combination with
H2O2, Fenton reaction, and ozonation. When combined with the Fenton
process, maximum COD reduction was attained. In addition, when
compared to untreated effluent, this method increased biomass gener­
ation during the aerobic biological process [110]. In order to remove
TN, COD, and ammonium from landfill leachate, Wang et al. used an
advanced Fenton’s technique in combination with biological anaerobic
filter (BANF) and biological aerated filter (BAF). The treatment satisfied
the current discharge standards with an overall COD and TN elimination
of 96.1 % and 95.9 %, respectively [111]. Sirtori et al. studied combined
solar photo Fenton/bio-treatment for the detoxification of pharmaceu­
tical wastewater containing nalidixic acid. Over 95 % of the
R.S. Dhamorikar et al.
pharmaceutical wastewater was degraded by the combined process
when it was used in batch mode, of which 62 % corresponds to the
biological treatment [112]. For the treatment of non-biodegradable
landfill leachate, Wang et al. [113] created a combined treatment that
integrates coagulation, Fenton oxidation, and biological aerated
filtering. The COD removal efficiency was 56 % at an optimum pH of 5,
with an optimum dose of 5 mmol/L of H2O2 and a reaction time of 3 h
[113]. Yongrui et al. compared Fenton’s process with combined Fen­
ton’s and the anaerobic baffled reactor (ABR) for degrading hydrolyzed
polyacrylamide (HPAM) containing wastewater used during oil recov­
ery. They found that, at optimized condition, the combined process was
able to achieve 94.61 % and 91.06 % removal of COD and HPAM,
respectively. Fenton process alone was able to remove 72.92 % of COD
and 69.44 % of HPAM [114].
Integrated AOP-membrane processes
Textile wastewater has high colour content, a low BOD/COD ratio,
and a high salt content (TSS and TDS). The majority of textile effluents
(especially those from the cotton, silk, and wool industries) contain
reactive dyes, which are difficult to biodegrade, which makes the situ­
ation worse. Due to these features, various strategies must be utilized to
effectively remove these contaminants. When the ratio of BOD/COD is
equal to or greater than 0.4, biological treatments are typically used to
treat the dissolved matter in textile wastewater. These techniques can be
either aerobic, anaerobic or both [115]. Membranes have the advantage
of simultaneously eliminating both organic and inorganic contaminants
from wastewater, which lowers the effluent’s colour, BOD, and COD.
Membrane bioreactors (MBRs), ultrafiltration (UF), nanofiltration,
reverse osmosis (RO), and membrane distillation are among the
different membrane processes utilized for textile wastewater.
The Fenton procedure (Fe (II)/H2O2) has been effectively used to
textile industry effluents, removing TOC and colour with efficiencies of
up to 50 % and 70 %, respectively. In order to maximize the benefits of
each process while avoiding its downsides, integrated or combined
systems can be more efficient than individual ones [116]. Lebron et al.
studied integrated photo-Fenton and membrane-based techniques for
textile effluent reclamation. They consider that in two separate pro­
cedures, an advanced oxidation process (AOP, photo-Fenton) was
combined with microfiltration (MF) and nanofiltration (NF); the first
MF-NF-AOP and second MF-AOP-NF. Microfiltration (MF) achieved
99.8 % of colour removal, as well as a reduction on 65.4 % COD. When
integrated MF-AOP was implemented the colour degradation was >
92.3 % and COD was 78.5 % removed. The integration of MF-NF-AOP
results in 69.8 % removal of COD and > 98.5 % colour removal.
When the arrangement was altered to MF-AOP-NF then 78.5 % removal
of COD was achieved and colour removal was greater than 92.3 % [117].
Landfill leachate generally has a dark colour, a strong odour, and a
high concentration of both organic and inorganic materials. The
methods for treating leachate that are most frequently used are those
that are based on biological mechanisms. Utilizing these methods for
leachate does provide some tough challenges. This is because accumu­
lated leachate is less efficient because of its refractory characteristics,
requiring large building sites, and because organic loads and flows are
highly variable. Fenton’s reagent (AOP/Fenton) is a procedure that
produces extremely reactive hydroxyl radicals (OH•), which have the
ability to completely eliminate a variety of organic contaminants. The
organic component is attacked by the free radicals (OH•) that are
created, which causes partial or complete oxidation and the production
of CO2 and H2O. Hydrogen peroxide (H2O2) is used as an oxidizing agent
during the AOP/Fenton, but it is also necessary to add activators, like
iron, to develop the necessary radicals at a high rate [118]. There are
several benefits of combining the AOP/Fenton with the membrane
separation process (MSP). Microfiltration (MF) can significantly cut
down the amount of time needed for treatment by replacing the
decantation stage used to separate the mud created during AOP/Fenton.
9
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
Lak et al. optimized the key Fenton procedure parameters to show
the Fenton process’ efficacy in treating leachate from municipal land­
fills. The initial pH of 5.8, [H2O2]/[Fe Fe2+] molar ratio of 8.0, Fe2+
dosage of 22,500 mg/L, and coagulation pH of 8.7 were the ideal con­
ditions for the highest COD removal (51 %) [119]. Reverse osmosis and
submerged membrane bioreactor (SMBR)-related AOP-Fenton were
studied by Zhang et al. The associated processes were able to efficiently
reduce membrane fouling in RO and remove 94 % and 80 % of COD and
ammonia–nitrogen, respectively (compared to RO applied as only
treatment) [120]. For the purpose of treating landfill leachate, Santos
et al. investigated the efficacy of three distinct approaches utilizing the
integration of advanced oxidation processes based on Fenton’s reagents
(AOP-Fenton) with microfiltration (MF) and nanofiltration (NF) mem­
brane processes. The results show that AOP-Fenton + MF stage was able
to remove 72 % of initial COD, whereas MF applied to raw landfill
leachate shows lower removal percentage of COD and apparent color
than the AOP-Fenton + MF process. The efficient treatment of landfill
leachate was found to be the combination of AOP-Fenton, MF, and NF.
All of the three routes presented high COD and color removal. The COD
removal obtained in the AOP-Fenton/MF/NF association (94–96 %) was
higher than the obtained when AOP-Fenton was applied as only treat­
ment (51 %) [121].
In many crucial technological processes, such as those involving
textiles, leather tanning, paper production, food technology, agricul­
tural research, light-harvesting arrays, photo-electrochemical cells, and
hair coloring, synthetic dyes are widely utilized. Fenton and Fenton-like
reactions are found to be efficient for decolorizing and detoxifying of
textile effluents [122]. Banerjee et al. studies the three combinations of
AOP and NF (AOP followed by NF, NF followed by AOP, two-step NF) for
the removal using a synthetic solution of eosin dye. They found that AOP
followed by NF works well for reducing eosin dye at initial concentra­
tions up to 70 mg/l. It is challenging to lower dye concentration below 1
mg/l for higher concentrations (100–200 mg/l). The appropriate
composition of Fenton’s reagent is 1665 mg/l of H2O2 and 347.5 mg/l of
FeSO4⋅7H2O The eosin concentration was not reduced to less than 1 mg/
l even after operating AOP step for 3 hr, thus NF followed by AOP is
found to be not suitable for dye removal. As two-step NF scheme lowers
eosin concentration to less than 1 mg/l for all feed concentrations of
eosin studied (70–200 mg/l), therefore two step NF is the most suitable
for dye removal[123].
Advanced oxidation processes in micro-reactors
The downsizing of reaction processes by micro-reactors offers
numerous important advantages when compared to the usage of larger,
traditional reactors. Relatively higher surface area-to-volume ratios in
the interior designs of microreactors decrease reactant diffusion paths,
facilitate faster and more efficient heat and mass transfer, and enhance
process control. Advanced oxidation processes (AOPs), which are
frequently employed to eliminate water contaminants, can benefit
greatly from these advantages. The microfluidic devices provide unique
hydrodynamic properties, longer range, and flexibility to tune process
parameters make AOPs more successful at degrading aqueous organic
contaminants. Microreactors also have higher energy efficiency.
When developing AOP systems, some of the same materials that are
used to build conventional reactors are used for microreactors con­
struction usually. Cost, transparency to different wavelengths of radia­
tion (such as infrared, visible, and UV), resistance to chemical oxidation,
resistance to varying process conditions of temperature and pressure,
and suitability for reactor fabrication are all significant material prop­
erties [124,125]. Glass is frequently used to build micro-reactors for
photocatalytic, photo-Fenton, and plasma-phase reactions because of its
transparency to visible light, which enables sufficient light exposure to
the reaction media [126]. Quartz, which is more expensive than glass
but has better UV transparency (e.g., 180–400 nm), is occasionally used
to build photocatalytic microreactors [127]. Another common material
R.S. Dhamorikar et al. Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx

for building micro-reactors employed in water and wastewater treat­

ment (W/WWT) AOPs is silicon [128]. Based on capillary and channel
arrangement some of the microreactor configurations are shown in
Figs. 5–7.
AOP-micro-reactors have been employed in an increasing number of
research to degrade contaminants in water and wastewater [126]. The
photocatalytic AOP has drawn a lot of interest as a green and sustainable
method because it is widely applied to landfill, industrial, hospital, and
municipal leachate W/WWT [129]. Efficiency of the photocatalytic
process is primarily influenced by mass transfer, photon transfer, and
dissolved oxygen concentrations [130]. Sometimes the reaction rates are Fig. 6. Multi-channel microreactor.
constrained by mass transfer, which is influenced by the system’s surface
area to volume ratio. In comparison to conventional reactors, emerging
microfluidic reactor systems have many advantages. Because the inner
channels of microreactors are narrower than those of traditional pho­
tocatalytic reactors, they offer volumetric mass transfer coefficients that
are at least two orders of magnitude higher [131].
A single-capillary micro-reactor with TiO2/SiO2 adsorbed to the
inner wall was constructed by Li et al. The amount of coated TiO2 was
enhanced as a result of the addition of hexagonal SiO2 arrays to the
walls, which increased the effective surface area. In this example,
methylene blue was degraded 150 times faster in a microcapillary
reactor than in a bulk reactor due to its greater surface area to volume
ratio [132]. Recently, single-capillary UV/H2O2 microreactors have
been used to effectively remove pollutants such benzoylecgonine, iso­
xazole, and isothiazolinones. The photodegradation products from these
micro-reactors were then examined [133]. The degradation of 4-chloro­
phenol in a W/WWT process was carried out by Gorges et al. using a 19- Fig. 7. Multi-capillary microreactor.
parallel-channel microreactor with 200 × 300 µm channel cross-
sections. Their investigation yielded the finding that this micro-
an electrical discharge, ozone gas is created. One of the challenges for its
structured reactor has an illuminated specific surface area that is
application to AOPs is the mass transfer limitation of gaseous ozone to
4–400 times greater than that of a traditional photocatalytic reactor
the aqueous phase. It can result in low ozone utilization rates and
[134].
expensive operations. Microchannels within micro-reactors provide
Khongthon et al. used an electrochemical microreactor to carry out a
small transport pathways that enable gas/liquid contact to significantly
number of tests to examine the kinetics of diuron degradation. Their
increase mass transfer as compared to conventional gas–liquid con­
results showed that the process’s rate constant was 1–2 orders of
tactors. Several microreactor designs have been proposed for ozonation
magnitude higher than in a conventional reactor. Microfluidic cells were
AOPs. Gao et al. [138] were the first to improve the ozonation of an azo
able to remove a significant amount of total organic carbon (TOC; up to
dye by using a microporous tube-in-tube microchannel reactor. Two
90 %) without the aid of an electrolyte. In the meantime, the energy
coaxial tubes create an annular microchannel in this reactor. The inner
usage per converted unit of TOC was also relatively low [135]. Rahimi
tube is used to transport ozone gas, and the outer tube is used to
et al. introduced a Y-shaped micro-reactor for the continuous-flow
transport wastewater in the same direction. Ozone gas can penetrate
Fenton AOP-based decolorization of azo dye-contaminated solutions.
into the wastewater stream due to micropores in the inner tube.
These authors demonstrated the benefit of a microreactor for the
Experimental results demonstrated that the use of this microreactor
continuous flow decolorization AOP by reporting an azo dye conversion
greatly improves mass transfers of gaseous ozone into the wastewater
efficiency of 86 % over a residence period of only 4.2 sec [136]. Shi­
stream as compared to the use of a traditional reactor. Additionally, it
nozawa et al. carried out the photo-Fenton AOPs in conventional batch
was found that reducing the width of the annular microchannel from
reactor for degradation of carbofuran under visible light and also
150 to 250 µm considerably boosted ozone usage within the micro­
compared it with micro-reactor process. The process executed in the
reactor. The number of schemes available for integration of micro­
micro-reactor was 7.5 times faster than that in the traditional batch
reactor with other AOPs are illustrated schematically in Fig. 8.
reactor, according to the results [137].
Another particularly successful AOP type for W/WWT is ozonation,
in which organic pollutants are removed either directly by ozone or Microwave enhanced AOP
indirectly by the radicals produced by ozone. By introducing oxygen to
Microwave (MW) technology has attracted growing interest in
wastewater treatment. Because of its unique qualities, including quick
and even heating, hot spots effect, and non-thermal effect. When com­
bined with advanced oxidation processes, MW increases the formation
of active radicals (such as OH• and SO4•), which have a stronger inte­
grated treatment effect. AOP has been widely utilised to lower organic
matter content, eliminate certain pollutant structures, enhance biode­
gradability, and reduce the toxicity of wastewater an electromagnetic
wave with a frequency range of 300 MHz to 300 GHz is called a mi­
crowave (MW). 2.45 GHz is the operating frequency that is most
frequently used for microwave heating. MW has been successfully used
to address a variety of environmental concerns, including wastewater
Fig. 5. Single Channel microreactor. treatment, sludge disposal, and soil remediation, thanks to its

10
R.S. Dhamorikar et al.
Fig. 8. Integration schemes available for microreactor − AOP integrated processes.
advantages of quick and uniform heating [139]. As compared to the
inefficiencies of conventional heating (CH), the MW system directly
generates heat inside the material and transfers it to the outside with a
better conversion efficiency (80–85 %) of electrical energy into heat,
shortening processing times and consuming less energy [140]. In addi­
tion to the thermal effect, some researchers think that MW has a non-
thermal effect that could cause hydrogen bonds to break and aid in
the breakdown of complex chemical components into simpler forms
[141]. When MW is combined with AOPs for water and wastewater
treatment, the integrated AOPs react more quickly and have a more
enhanced integrated treatment effect. Microwave-assisted advanced
oxidation processes (MW-AOPs) have been employed as novel treatment
techniques to reduce a variety of pollutants in water. The treatment
effectiveness of photochemical, electrochemical, and sonochemical
AOPs is improved by the presence of MW [142]. MW is made up of
electric and magnetic fields perpendicular to each other and when it
interacts with materials results in magnetic and dielectric losses and the
production of heat [140]. An effective technology for eliminating
environmental pollutants is the MW- H2O2 system. Table 2 shows the
different studies done with microwave enhanced AOP and their opti­
mum reaction conditions.
Milh et al. discovered that the reaction temperature was the most
important parameter for MW-H2O2 system and that the MW-H2O2 sys­
tem efficiently degraded 4-chlorophenol (4-CP). In order to maintain the
system temperature within the appropriate range, the MW reactor in
actually has the relevant cooling equipment installed, such as con­
densers [151]. In the study by Zhang et al. the MW-Fenton process
improved the traditional Fenton process in terms of reaction time was
reduced to 8 min from 3 hr, sludge output was reduced from 8.50 g/L to
6.40 g/L, and biodegradability was increased from 0.51 to 0.62 [144].
For the treatment of low concentration organic wastewater, photo­
chemical AOPs can be applied but in case of turbid wastewater or high
concentration organic wastewater pre-treatment is required. With the
help of MW oxidation system, turbid or highly concentrated organic
wastewater can be treated without pre-treatment [152]. The integration
and combination of the UV and microwave processes is a workable
technique to quickly and completely degrade organic pollutants in water
and wastewater at different concentrations of pollutants. In the most of
MW-photochemical system experiments, the reactor is equipped with a
microwave discharge electrodeless lamp (MDEL) to obtain both MW and
UV concurrently [153]. Good activation of H2O2, sodium percarbonate
11
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
(SPC), persulfate (PS), and peroxymonosulfate (PMS) was provided by
the MW-UV oxidation system. This resulted in the generation of pre­
dominant radicals (OH• for H2O2, SPC, and SO4• for PS and PMS), which
were incredibly effective in the treatment of toxic organic contaminants
and actual industrial wastewater [154]. Shukla and Remya showed that
the removal and mineralization of Congo red was more efficient by using
MW-UV-PS than MW-UV-H2O2. It suggests that the MW-UV system
based on sulphate radicals performs better [124,125]. Compared to
photocatalysis, MW-assisted photocatalysis shown greater effects, which
was explained by the fact that MW inhibits or slows down the recom­
bination of electron-hole pairs on the catalyst, increasing the formation
of OH• [155]. Since the relative concentration of OH• formed in the
MW/UV system was more than the total of that formed in the UV system
and that formed in the MW system separately, it was evident that the
combined system had a strong synergistic effect [156]. By sequentially
coupling MW and EC, Hashim et al. were able to release more iron ions
and cause the thermal breakdown of Fe-EDTA into simple products. The
MW-EC method’s up to 92 % iron removal as opposed to the traditional
EC method’s (69.6 %) iron removal may have been facilitated by the
unique properties of MW heating [142].
In order to degrade phenol, Wu et al. used combine ultrasonic and
microwave system. They discovered that the Microwave radiation
improved the sono-degradation capability [148]. Gole and Gogate
discovered that the MW-US system was more efficient at degrading
bright green (BG) dye than both separate systems and the US-photolysis
system [157].
Integrated AOP-wet air oxidation process
Wet air oxidation (WAO) in combination with other advanced
oxidation processes (AOPs) or other treatment techniques offers a strong
approach to the ongoing problem of impermeable organic pollutants in
wastewater. Complex organic contaminants are broken down by
advanced oxidation processes that use strong oxidizers like sulphate or
hydroxyl radicals to accelerate oxidation kinetics. AOPs and WAO
integration produces a synergistic benefit. For example, combining
WAO with ozonation offers a versatile method for breaking down
stubborn substances that withstand total oxidation during the WAO
stage [158,159]. This combination emphasises on the complementary
advantages of both processes to produce an increased overall efficiency
in the removal of pollutants.
R.S. Dhamorikar et al. Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx

Table 2
Microwave enhanced AOP for wastewater treatment.
Sr. System Pollutants Reaction conditions Removal (%) Results highlights Reference
No.

1 MW-Fenton Methylene t = 1 min 93.0 % (MB) The MW-Fenton process was able to achieve same removal in 1 [143]
Blue MB = 50 mg/L min as achieved by conventional Fenton process in 65 min.
Fe2+ = 20 mg/L
pH = 3
H2O2 = 200 mg/L
V = 50 mL
Each 15 s irradiation was
followed by a 15 sec
interval
2 MW-Fenton Landfill t = 8 min 75.0 % (COD) The stable fulvic-like acid content, molecular weight, [144]
leachate COD = 2494 mg/L condensation degree, and aromaticity were all reduced by
Fe2+ = 0.04 M MW-Fenton.
pH = 5
H2O2 = 0.32 M
V = 100 mL
3 MW-Fenton Phenol t = 7.11 min 93.91 % The reaction time was almost 80 % faster and the amount of [145]
phenol = 200 mg/L (Phenol) Fe2 + inserted was relatively low compared to the
Fe2+ = 0.2 mM conventional Fenton procedure.
pH = 5
H2O2 = 16 mM
COD = 476.6 mg/L
4 MW-UV-Fenton Pesticide t = 120 min 79.9 % (COD) Within 120 min, Dimethoate, Triazophos, and Malathion, [146]
COD = 183.2 mg/L these three primary pesticides in the wastewater, had totally
H2O2 = 100 mM degraded and mineralized.
Fe2+ = 0.8 mM
pH = 5
V = 1000 mL
5 MW-UV-Fenton Landfill t = 60 min 85 % (COD)89 % Most refractory organics were decomposed into small [147]
leachate pH = 5.0 (TOC) compounds, and 97.9 % of the polycyclic aromatic
Fe2+ = 2 mM hydrocarbons were eliminated.
H2O2 = 52 mM
V = 250 mL
COD = 590 mg/L
Air flow rate = 0.6 L/min
6 MW-US (Sequential Phenol US frequency = 850 kHz 76 % (Phenol) Without H2O2 the synergistic effect between MW and US was [148]
combination) t = 120 min observed at 93 ◦C and with H2O2 60 ◦C.
US power = 40 W
Phenol = 1 mM
H2O2 = 20 mM
V = 1250 mL
7 MW- H2O2 Rhodamine B T = 100 ◦C 43 % (COD) The primary causes of RhB’s effective breakdown at very [149]
t = 14 min alkaline pH levels (>11) were oxygen oxidation and the heat-
H2O2 = 24.5 mM induced action of MW.
pH = 12
RhB = 0.084 mM
8 MW-Persulfate Landfill MW T = 85 ◦C 79.4 % (TOC) After generation, malic, lactic, and acetic acids quickly broke [150]
leachate pH = 7.04 88.4 % (Color) down. Oxalic acid was more difficult to degrade.
PS = 20.0 mM
TOC = 57.7 mg/L
t = 30 min
V = 50 mL

Moreover, the combination of WAO and biological treatment mo­
dalities improves the pollutants’ resistance to degradation. Complex
organic compounds are more vulnerable to later biological degradation
when they are first broken down by WAO into smaller, easier-to-manage
intermediates. By treating pollutants one after the other, the overall
efficacy of pollutant removal is increased while the load of resistant
compounds for biological treatment downstream is decreased [160].
A study was conducted for the removal of organic load from the
composting factory leachate using wet air oxidation process. It was
observed that the COD removal efficiency in WAO process is 7.8–33.3 %
at the temperature range of 100 ◦ C to 300 ◦ C respectively. And ammonia
removal efficiency in WAO process is 6–54.6 % at the temperature range
of 100 ◦ C to 300 ◦ C respectively. By adding granular activated charcoal
(GAC) to the reactor before, COD removal efficiency was improved. The
maximum removal efficiency of COD is 56 % at 300 ◦ C temperature and
68 % removal efficiency of ammonia at same temperature range [160].
The results of this operation on a laboratory scale showed that using this
method combined with an aerobic and anaerobic biological treatment
can be a promising option for the leachate treatment of the compost
plant because higher temperatures cause an increased breakdown of
organic compounds to simpler ones.
Advantages and disadvantages of AOP
The Table 3 represents the advantages and disadvantages; providing
insightful comparison between different AOP and Integrated AOPs .
Potential challenges and future perspectives
Potential challenges and limitations
Despite AOPs promising potential, they also face several technical
challenges and limitations discussed below that need to be addressed.
a) Operational Costs: High energy and chemical costs associated with
AOPs hinder large-scale implementation. Efficient utilization of

12
R.S. Dhamorikar et al. Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx

Table 3
The advantages and disadvantages of various AOPs and Integrated AOPs.
Type of AOP Integrated AOP Advantages Disadvantages EEO,
[161]
kWh/m3

UV based/ UV 1. High energy requirements for the UV lamps

Photocatalytic UV/H2O2 1. UV promote •OH formation 1. Turbidity can interfere with UV radiation 0.3-1.2
2. High efficiency Potential bromated by product
3. No formation of bromated compounds4. Full scale 2. UV light penetration can be obstructed by turbidity3.
drinking water treatment system exists Compounds such as nitrate can interfere with absorbance
of UV light
UV/TiO2 1. Can be performed at higher wavelengths than other 1. Developing technology − No industrial scale 150-450
UV based processes application exists
2. Recycling of the catalysts 2. Need for pretreatment
3. Availability of different photocatalysts4. Operation 3. If the catalyst is added as a slurry, separation step is
at ambient condition required
4. Adapted and optimum concentration of catalyst
required a rigorous studies5. Secondary product can be
formed
UV/TiO2/H2O2 1. Low energy requirement than other AOPs. 1. Requirement of pre-treatment
2. No formation of bromate. Loss of catalytic activity with time.Sensitivity to pH.
3. Use of solar irradiation4. No off-gas treatment.
Fenton Based Classical Fenton Process 1. Not as energy intensive as other AOPs 1. Strict pH limitations (Low pH (<2.5) is required to 0.98
(Fe2+/H2O2) 2. Degradation soluble and insoluble dyes in industrial keep iron in solution)
effluents 2. Iron sludge formation due to combined flocculation of
3. No formation of bromate the reagent and the organic pollutant
4. No off-gas treatment.5. Less energy-intensive than 3. pH adjustment will increase operating cost4. High
ozone and UV alone. maintenance costs
Photo Fenton (Fe3+/ 1. Significantly lower operating costs compared to the 1. The process operates in a narrow pH range of 2–4. 1.1-10
H2O2/UV) Fenton process. 2. Loss of catalyst and formation of process sludge.3. The
2. Absence of the filter press, which results in a much cost of energy and lamps (in the case of UV photo-Fenton)
higher degradation rate of the Photo-Fenton oxidation can be high
compared to the Fenton oxidation. 4. Deposition of iron oxides on the reactor walls can
3. Can treat a wide range of pollutants, including those reduce light penetration
that are difficult to degrade.
4. The process is simple and flexible, and operates
without energy input.
Sono-Fenton (Fe2+/ 1. The Fenton process can treat textile effluent at the 1. Requires a higher concentration of reagents for
H2O2/US) lowest possible cost due to the minimal energy input effective mineralization.
and low reagent cost. 2. Strict pH limitations.3. Some disadvantages limit its
2. The Fenton process is based on inexpensive reagents. use; for example, pH control is needed to keep the pH
3. The reactor arrangement is simple. range around 3, approximately 50–80 ppm of ferrous
ions is required, and sludge streams containing chemicals
such as iron salts are continuously produced, with the
process sometimes inhibited because iron ions can be
consumed faster than their generation
Sono photo Fenton (SPF) 1. The regeneration of the consumed Fe2+ ions on Same as Sono-Fenton (Fe2+/H2O2/US)
(Fe2+/H2O2/US) irradiation.
2. Ferrous salt requirement is very low as compared to
Fenton conditions.
US/Sono based Sonolysis 1. High power ultrasonic irradiation has the advantages 1. Requires expensive equipment 800-
of safety, cleanliness, high penetrability in the aqueous 2. Large amounts of energy 8000
medium 3. Hydrophilic compounds generally difficult to degrade
2. High efficiency of degradation 4. Limited industrial scale application 5. Oxidant may be
3. Conservation of energy needed to improve the efficiency of the treatment,
4. No generation of secondary pollutants thereby increasing cost
5. Nonspecific
6. Less heat transfer relative to UV system.
US/H2O2 1. Rapid reaction rates due to high oxidation potentials. 1. Systems utilizing hydrogen peroxide should be
2. Small footprint due to the oxidation power of the carefully controlled for residual H2O2 as it can have
hydroxyl radical.3. Theoretically, does not introduce potential negative effects on later treatment steps.
new hazardous substances into water. 2. This residual hydrogen peroxide may be harmful to
human.
US/O3 1. Safe, clean, high penetrability in the aqueous The high costs of ultrasonic treatment processes are due
medium. to high capital and operating costs.
2. High efficiency of degradation and conservation of
energy
3. No generation of secondary pollutants4. Synergistic
effects of ozonation with sonication
US/UV/TiO2 1. It effectively kills 99.99 % of the organic 1. UV treatment works best when the water is clear.
microorganisms present in water.2. It kills a variety of Muddy water can affect the contact between UV rays and
chlorine-resistant microorganisms that cannot be microorganisms in the water, thus preventing the
removed by traditional chlorination process.3. It acts effective killing of these microorganisms.2. For inorganic
rapidly. Water can be treated while flowing through the pollutants, UV treatment cannot realize an effective
system extermination.
O3/ Ozone Based O3 1. Strong oxidative power 1. The short lifetime of ozone makes this method costly 0.07-0.3
2. Effective for a wide spectrum of pollutants 2. High energy requirements for the ozone generator
(continued on next page)

13
R.S. Dhamorikar et al.
Table 3 (continued )
Type of AOP Integrated AOP Advantages
3. Existing full-scale applications4. Supplementary
disinfectant
O3/H2O2 1. EEO value less than 1 kWh/m3 concluding that the
process is in a realistic range for full-scale application.
2. Formation of strong non-selective hydroxyl radicals
that are able to break down the conjugated double bond
3. Ozone can be used in its gaseous state and
consequently does not raise the volume of wastewater4.
No sludge generation
O3/UV 1. More effective than O3 or UV alone
2. Disinfectant
3. For equal oxidant concentration, more efficient at
generating hydroxyl radical than H2O2/UV
4. Higher production of OH than H2O2/UV5. Higher
Efficiency than the additive removal efficiencies of
ozone and UV alone.6. Low energy efficiency realistic
range
(EE0 < 1 kWh/m3) for full-scale application
O3/UV/TiO2 1. Heterogeneous catalysts enhances the removal of
contaminants
Electrochemical Electrochemical 1. Good mineralization of effluents contaminated by
Oxidation Oxidation different kinds of organic pollutants
2. Operation at ambient conditions3. Ease of operation
Anodic OxidationElectro 1. It can effectively eliminate organic compounds in the
Fenton(Fe2+/H2O2 (e-) aqueous phase, rather than collecting or transferring
) pollutants into another phase 2)Due to the reactivity of
hydroxyl radicals, it reacts with many aqueous
pollutants without discriminating
2. Hydrogen peroxide can be produced in situ and
continuously.
3. Diluted hydrogen peroxide solution increases safety
during process operations.
4. Not as energy intensive as other AOPs.
5. Degradation of soluble and insoluble dyes in
industrial effluents.
6. No formation of bromate.
7. No off-gas treatment.
8. Less energy-intensive than ozone and UV alone
Photo Electro Fenton 1. Effective for the complete degradation 2. Good
(PEF)(UV/Fe3+/H2O2 mineralization of effluents contaminated by different
(e-)) kinds of organic pollutants
Sono Electro Fenton(US/ 1. The Fenton process can treat effluent at a low cost
Fe3+/ H2O2 (e-)) due to the minimal energy input and low reagent cost.
2. The reactor arrangement is simple.
3. The process is not as energy-intensive as other AOPs.
4. It can degrade soluble and insoluble dyes in
industrial effluents.
5. No formation of bromate.6. No off-gas treatment.
Sulphate Radical 1. Higher redox potential of SO4⋅− (2.5–3.1 V ) than
based that of OH⋅ (1.8–2.7 V ).
2. Moderate pH conditions of 2.0–8.0.3. Longer half-life
(t1/2 = 30–40 μs).
4. Higher oxidation capacity in both carbonate and
phosphate buffer solutions.
5. Sulfate radical based processes have been employed
in the treatment of groups of contaminants that are
“difficult to degrade”
Wet Air Oxidation Catalytic Wet Air 1. CWAO is an attractive technique for sewage sludge
(WAO) Oxidation (CWAO) treatment.
2. It can lower operational conditions, making it more
energy-efficient.3. The process is capable of a high
degree of conversion of toxic organics with more than
99% destruction rate
Hydrodynamic 1. Reactions that require moderately rigorous
Cavitation conditions
2. It is the cheapest and most energy-efficient method of
a cavitation generation.
3. Neither reactants nor UV light are used.
4. requires significantly lower operation costs than the
rest of the AOPs
5. By-products are limited to those expected from the
14
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
Disadvantages EEO,
[161]
kWh/m3
3. Risks associated to ozone generation
4. Low solubility of O3 in water, 5. The formation of
hazardous by-products, in particular, bromate formation
1. Low rate of degradation as equated to the AOP <1
processes due to less production of hydroxyl radicals
2. Ozone may form toxic by-products
3. High cost
4. Requires treatment of access H2O2 due to potential for
microbial growth
1. The possibility of formation of mutagenic organic by- 0.025-
products in processes based on medium pressure UV light 0.1
in real or artificial waters containing nitrates
2. Formation of toxic or carcinogenic by-products
4. UV light penetration can be obstructed by turbidity
5. Compounds such as nitrate can interfere with the
absorbance of UV light
6. Energy and cost intensive processes
7. Contamination due to failure of the UV lamp
1. Reduced efficiency over the time
2. The formation of undesirable hazardous by-products
3. High capital and operational cost
4. Difficult construction of the electrode
5. Erosion and short life of electrode
1. The most significant disadvantage of the AOP process
is its cost. The most significant are the operating and
maintenance costs, associated with the system’s required
energy and chemical reagents
2. Elimination of residual peroxide may be necessary.
Slow production of H2O2 due to the low solubility of
oxygen.
3. Low current efficiency at higher pH.
4. Higher operational costs have limited the application
of Electro Fenton.5. Strict pH limitations (Low pH (<2.5)
is required to keep iron in solution).
6. Iron sludge formation due to combined flocculation of
the reagent and the organic pollutant.
7. pH adjustment will increase operating cost.
8. High maintenance costs.
1. The pH must be extremely acidic (pH 2.5–3.8)
1. Requires a higher concentration of reagents for
effective mineralization.
2. Strict pH limitations.
3. High concentration of Fe2+ and large amount of Fe
sludge is formed, so the wastewater treatment is
expensive and it needs large amount chemicals and
manpower.
The main disadvantages are the low solubility of O3 in
water, the formation of hazardous by-products, in
particular, bromate formation, and the elevated energy
costs.
1. Some materials are not oxidized completely to carbon
dioxide and water, instead, some intermediate
compounds are formed, which represent a quarter of the
original mass of organic matter.
3. The requirement of large space and expense.
Many researchers have observed that the degree of
mineralization achieved using hydrodynamic cavitation
alone is insufficient, due to the limited rate of generation
of oxidizing radicals and the combination with other
advanced oxidation processes helps in the intensification
of oxidation capacity.
(continued on next page)
R.S. Dhamorikar et al.
Table 3 (continued )
Type of AOP Integrated AOP Advantages
oxidation of the contaminants, avoiding the presence of
other dangerous oxidants such as chlorine.
resources and investigation of more integration schemes available is
essential to address this challenge.
b) Catalyst Activity and Recyclability: One of the main challenges is
catalyst deactivation. This is a significant challenge as it can lead to
decreased efficiency and increased operational costs. Potential so­
lutions could include the development of more robust catalysts, the
use of protective coatings, or the implementation of regeneration
processes to restore the catalyst’s activity. Ensuring efficient (photo)
catalysts and their recyclability is crucial. Research should focus on
developing robust and cost-effective catalysts. Use of combined AOP
have been noted to enhance catalyst activity in the process (use of
ultrasound assisted AOP can help in cleaning of photocatalysts).
However, integrated process may not come out directly in enhancing
the activity but reduces the deactivation rate of the catalyst, as the
individual processes now work in lower concentration ranges.
c) Plant/Reactor Design: Designing more efficient treatment plants/
reactors is necessary. Factors such as hydraulic retention time,
reactor geometry, and flow patterns impact treatment performance.
Another challenge is reactor corrosion. The harsh conditions within
AOP reactors can lead to corrosion of the reactor materials. This not
only leads to increased maintenance costs but can also result in the
release of harmful substances into the treated water. To overcome
this, research could focus on the development of more corrosion-
resistant materials or the use of protective linings.
d) Energy consumption: It is another significant challenge. AOPs often
require significant amounts of energy, which can be a major draw­
back, especially for large-scale applications. Research in this area
could focus on improving the energy efficiency of these processes,
perhaps through the use of novel catalysts or optimized reactor
designs.
e) Secondary Pollutant: Finally, the use of chemicals in AOPs can lead
to secondary pollution if not properly managed. Therefore, research
could focus on minimizing the use of chemicals or developing
methods to effectively neutralize or remove any residual chemicals
after treatment.
The addressing of the above challenges is necessary for effective
utilization of AOP in mainstream industrial processes.
Future direction
The scientific community working in this field can explore the
following areas to gain a deeper understanding and broader perspec­
tives. Researchers have explored integrating AOPs with adsorption,
membrane, and biological methods for PC removal. However, there is
limited exploration of combining AOPs with low-cost sustainable ma­
terials like clay and agricultural biomass-based adsorbents (e.g., bio­
char). These processes play a crucial role in addressing emerging
contaminants and ensuring water quality. Following considerations are
discussed in regards with the future prospective of integrated AOPs.
a) Emerging Contaminants and their Impact: Emerging contami­
nants (CECs) are diverse and ubiquitous, posing risks to water
quality, human health, and ecosystems. These include pharmaceu­
tical residues, microplastics, and other persistent pollutants. The
spread of antibiotic-resistant bacteria due to low persistent doses of
residual pharmacological principles in human and animal excreta is
15
Journal of Industrial and Engineering Chemistry xxx (xxxx) xxx
Disadvantages EEO,
[161]
kWh/m3
a significant concern. These contaminants challenge conventional
treatment methods and necessitate innovative approaches.
b) Advanced Reduction Processes (ARPs) and Advanced Oxidation-
Reduction Processes (AORPs): These are emerging alternatives to
AOPs. ARPs may remove contaminants not readily treatable by AOPs
or offer better performance. Examples include electrochemical
reduction and biologically mediated reduction processes. AORPs
combine oxidation and reduction steps, potentially enhancing
treatment efficiency. These integrated approaches can synergisti­
cally address complex pollutant mixtures.
c) Interdisciplinary Approaches: Collaborations between chemists,
engineers, and environmental scientists can lead to breakthroughs.
Understanding the fundamental chemistry and engineering princi­
ples behind AOPs is essential. Research should focus on optimizing
existing technologies and developing novel ones. For instance,
exploring nanomaterial-based catalysts and hybrid processes.
d) Economic Considerations: Addressing operational costs and mak­
ing AOPs economically viable is crucial. Life cycle cost analysis,
energy-efficient designs, and process intensification are areas of in­
terest. Public-private partnerships and policy incentives can drive
innovation and adoption of AOPs in water treatment.
e) Scaling Up and Implementation: Bridging the gap between
laboratory-scale experiments and full-scale implementation is vital.
Pilot studies and demonstration projects are necessary to validate
AOPs’ effectiveness under real-world conditions. Considering the
spatial and temporal variability of water quality, AOPs must be
adaptable and robust across different contexts.
f) Resource Recovery and Circular Economy: AOPs can be harnessed
not only for pollutant removal but also for resource recovery. For
instance, recovering valuable metals from wastewater using AOPs.
Integrating AOPs into a circular economy framework ensures sus­
tainable water management.
g) Smart Monitoring and Control: Leveraging sensor networks, arti­
ficial intelligence, and automation can enhance AOPs’ performance.
Real-time monitoring and adaptive control strategies optimize
treatment efficiency. Predictive models can guide decision-making
and prevent system failures.
Conclusion
Integrating Advanced Oxidation Processes (AOPs) with various
treatment methods proves highly effective in enhancing pollutant
degradation for water treatment. While AOPs alone may be costly for
complete mineralization, integrating them with biological treatments
offers a more economical and efficient solution for removing dissolved
organic carbon (DOC), chemical oxygen demand (COD), and treating
landfill leachates.
Pairing AOPs with Biological Activated Carbon (BAC) and UV-H2O2
processes notably enhances the reduction of trihalomethanes (THM),
trichloroacetic acid (TCAA), and non-purgeable organic carbon (NPOC)
in drinking water. Likewise, combining hydrodynamic cavitation (HC)
with Fenton’s process, and integrating microfiltration (MF) and nano­
filtration (NF) with AOPs, leads to increased COD and color removal,
particularly in effluents from the textile industry.
Innovative methods like microcapillary reactors and microwave
heating systems (MW) demonstrate superior pollutant degradation rates
and energy efficiency compared to traditional approaches. The MW-
Fenton process and the integration of Microwave and UV radiation
R.S. Dhamorikar et al.
further expedite organic pollutant degradation, enhancing biodegrad­
ability and sono-degradation capabilities.
Catalytic Wet Air Oxidation (CWAO) emerges as a novel and sus­
tainable wastewater treatment approach, enabling pollutant oxidation
under milder conditions while adhering to sustainability principles.
Ongoing catalyst development is expected to significantly impact the
market positioning of advanced wastewater treatment technologies.
In summary, integrating AOPs with other treatment methods not
only enhances pollutant removal, including recalcitrant contaminants,
but also represents progress towards more sustainable and efficient
water treatment strategies. These integrated systems are poised to play a
crucial role in advancing wastewater treatment technologies, aligning
with environmental sustainability goals and the needs of modern
society.
CRediT authorship contribution statement
Rushikesh S. Dhamorikar: Formal analysis, Writing – original
draft. Vikesh G. Lade: Conceptualization, Investigation, Supervision,
Writing – review & editing. Pratik V. Kewalramani: Formal analysis,
Resources, Data curation, Writing – review & editing. Ankush B.
Bindwal: Data curation, Formal analysis, Methodology.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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