Chapter 1

Introduction and
Background

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 CHAPTER 1
Introduction and Background

1.1 Need of pure water

Water is the most important resource for every living organism, as the
existence of life in the world is not possible without water. The availability of pure
and clean water is an essential factor for human beings, birds, animals and aquatic
environment. This valuable resource is getting polluted due to direct or indirect
discharge of industrial, agriculture and domestic waste in the surface or ground water
resources. Polluted water is not suitable for drinking, recreation, agriculture and
industry. It diminishes the quality of water in lakes and rivers and more seriously, it
destroys aquatic life and reduces its reproductive ability. It has affected all the sectors
of the nature. There are two main sources of water pollution viz. point source and
nonpoint source.
Point source pollution comes directly from a known source like an industrial
or sewage outfall pipe. Point sources are typically associated with manufacturing
processes. It includes factories, wastewater treatment facilities, septic systems, and
other sources that are clearly discharging pollutants into water sources. Non-point
sources are more difficult to identify, because they cannot be traced back to a
particular location. It includes runoff of fertilizers, pesticides, chemicals, and animal
wastes from farms, fields, construction sites and mines (Stuart et al., 2012). Landfills
can also be a non-point source of pollution, if substances leach from the landfill into
water supplies.

1.2 Major constituents of water pollutants

Major constituents of water pollutants can be classified as

• Organic pollutants
• Inorganic pollutants
• Nutrients and agriculture runoff
• Suspended solids and sediments
• Pathogens
• Radioactive pollutants

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 The present work focuses on the degradation of organic pollutants using a
combination of advanced oxidation processes. The organic pollutants can be further
divided into two broad categories, biodegradable and non-biodegradable. The
wastewaters such as, domestic and municipal sewage, wastewater from food
processing industries, canning industries, slaughter houses, paper and pulp mills,
tanneries, breweries, distilleries, etc. have considerable concentration of
biodegradable organic compounds either in suspended, colloidal or dissolved form.
Such pollutants which can undergo degradation and decomposition by bacterial
activity are termed as biodegradable organic pollutants. The dissolved oxygen (DO)
available in the water body will be consumed for aerobic oxidation of organic matter
present in the wastewater. Hence, depletion of the DO will be a serious problem
adversely affecting aquatic life.
Organic pollutants also include aromatic solvents (benzene, toluene and
nitrobenzene, etc.), polychlorinated aromatics (PCBs, chlorophenol, etc.), pesticides
and herbicides (imidacloprid, methomyl, alachlor, atrazine etc.), chlorinated non
aromatics (carbon tetrachloride, chloroform, etc.), high molecular weight
hydrocarbons (dyes, gasoline, amines, etc.) and polycyclic aromatic hydrocarbons
(PAHs). Most of these compounds are toxic and biorefractory organics i.e., they are
resistant to microbial degradation. Such pollutants are termed as non-biodegradable
organic pollutants.

1.2.1 Contamination of water resources due to pesticides

Even though pesticides are widely applied in agriculture sector for the sake of
increased cultivation, its residues pose a negative impact on the environment and
human health because of its toxicity and stability. Very less % of pesticides used in
agriculture, actually reach to the crop and remaining major unused portion enter into
the environment and causes the land and water pollution (Kitsiou et al., 2009).
Significant contamination of surface and ground water due to pesticides has become a
particular concern for fresh water, since it can directly impact the health of aquatic
life and humans (Mahamoodi et al., 2007).
Pesticides are introduced into the environment mainly by industrial effluent,
agriculture runoff and chemical spills (Daneshvar et al., 2007). Due to large scale
development of the agrochemical industry and extensive use of pesticides, the amount

3
and variety of pesticides present in the environment have drastically increased in case
of agricultural dominating countries like India (Joshi and Gogate, 2012; Patil et al.,
2014). Many of these pesticides are carcinogenic and may lead to many health
hazards such as chronic liver damage, cirrhosis and chronic hepatitis, endocrine and
reproductive disorders, lung cancer, liver diseases, reproductive disorders, brain
cancer etc. (Tanaka and Reddy, 2002). Pesticides are not only hazardous in nature, but
are chemically stable, non-biodegradable and are having complex chemical structures.
Hence, it is essential to develop the effective treatment process for their complete
mineralization or conversion into less hazardous compounds. Present work deals with
the development of effective hybrid processes for the degradation or mineralization of
complex pesticide compounds.

1.3 Conventional methods used for the treatment of wastewater and their
limitations.

The conventional methods used for the treatment of wastewater can be classified as
1. Physical methods: Include treatment processes such as screening, mixing,
flocculation, sedimentation, flotation, adsorption, filtration, aeration etc.
2. Chemical methods: Include treatment processes such as precipitation, coagulation
disinfection, oxidation using chemicals etc.
3. Biological methods: Include treatment processes such as aerobic, anaerobic,
anoxic, facultative, combined processes etc.
Even though these methods are applied industrially or domestically for
treatment of wastewater, each of these methods has some serious limitations. Physical
methods lands up in new waste disposal problems since the pollutants are only
transferred from one phase to the other, whereas chemical methods lead to the
formation of concentrated sludge or toxic end products (Chhabra et al., 2015).
Complete mineralization by using physico-chemical methods may not be possible,
especially for a complex effluent stream containing a mixture of pollutants in high
concentration (Devipriya and Yesodharan, 2005). Biological treatment is the most
cost effective and environment friendly alternative for the treatment of wastewaters.
However, most of the industrial effluents contain toxic and/or recalcitrant organic
compounds which inhibit the biological processes, making the process very sluggish
(Ioannou et al., 2015). Biological processes are also limited by the requirement of

4
strict temperature, pressure and pH control for effective operation and growth of
microorganisms. The control of such processes is very difficult, as bacterial growth is
influenced by a great number of factors such as nutrient levels, the availability of
substrates, population density, concentration of pollutant etc. (Dos Santos et al.,
2009). The wastewater containing complex organic pollutants is generally nutrient
deficient and does not support microbial growth. Therefore, apart from simple
dilution, some pretreatment to reduce the toxicity of wastewater is essential to
facilitate the degradation using microbial action (Azhbar et al., 2008). Advanced
oxidation processes (AOP) can be used for the pretreatment of bio-recalcitrant
wastewaters transforming it into the less or non-toxic species, making it suitable for
biodegradation. Hence, there is a need to develop advanced oxidation techniques for
effective treatment of organic pollutants which are expected to meet the stringent
environmental regulations.

1.4 Advanced oxidation processes (AOPs)

Advanced oxidation processes (AOPs) are extensively used for wastewater

treatment and are one of the most promising ways for effective degradation of many
organic pollutants such as pesticides. The basic mechanism of AOPs is the generation
highly reactive free hydroxyl radicals having very high oxidative power (E0=2.8 eV)
and their subsequent attack on the pollutant to be treated (Santos et al., 2011). The
relative oxidizing power of the hydroxyl radical along with other common oxidant is
summarized in Table 1.1 (Metcalf & Eddy, 4th Ed.).
Table 1.1
Comparison of oxidation potential of various oxidizing agents

Oxidizing agent Oxidation potential in eV

Fluorine 3.06
Hydroxyl radical 2.80
Oxygen (atomic) 2.42
Ozone 2.08
Hydrogen peroxide 1.78
Hypochlorite 1.49
Chlorine 1.36
Chlorine dioxide 1.27
Oxygen (molecular) 1.23

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 Hydroxyl radical is the second strongest known oxidant after fluorine. The
hydroxyl radicals are nonselective in their mode of attack and able to react at normal
temperature and pressures (Malato et al., 2002). AOPs found various applications in
wastewater treatment due to their capability to convert numerous organic compounds
into carbon dioxide and water. Advanced oxidation processes differ from the other
physicochemical treatment processes because wastewater compounds are degraded
rather than concentrated or transferred into a different phase. In the last two decades
different AOPs are developed and tested for the degradation of different water
pollutants (inorganic and organic compounds). These processes includes cavitation
(generated either by means of ultrasonic irradiation or using constrictions such as
valves, orifice, venturi, etc. in the hydraulic devices), photocatalytic oxidation (using
ultraviolet radiation/near UV light/ Sun light in the presence of semiconductor
catalyst), Fenton chemistry (using reaction between Ferrous ions and hydrogen
peroxide, i.e. Fenton’s reagent), Photo-Fenton method, Ozonation etc. The
mechanisms of important AOPs are discussed below.

1.5 Cavitation

Cavitation is defined as the phenomena of the continuous formation, growth

and subsequent collapse of micro bubbles or cavities at multiple locations in the
reactor, releasing large magnitudes of energy (Gogate and Pandit, 2004a). The effects
of cavitation are responsible for creation of hot spots, releasing highly reactive free
radicals, cleaning of solid surfaces, and enhancement in mass transfer rates (Suslick,
1990; Suslick et al., 1986; Shah et al., 1999; Pandit and Moholkar, 1996; Thompson
and Doraiswamy, 1999; Adewuyi, 2001). The collapse of bubbles generates localized
‘‘hot spots’’ with transient temperature of about 10,000 K and pressures of about
1000 atm (Didenko et al., 1999). This extreme temperature and pressure condition
leads to the cleavage of water molecules and dissolved oxygen molecules. The
reactions of these entities (O•, H•, OH•) with each other and with H2O and O2 during
the rapid cooling phase generate the HO2• radicals and H2O2. These radicals (OH•, O•
and HO2 •) then subsequently react with organic pollutants and oxidize them. The
following are the possible reactions occurring as a result of cavity collapse (Villaroel
et al., 2014).

H2O +))) OH• + H• (1.1)

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O2+))) 2O• (1.2)
O• + H2O 2OH• (1.3)
OH• + H• H2O (1.4)
• •
2OH O + H2O (1.5)
H• +O2 HO2• (1.6)
2OH• H2O2 (1.7)
2 HO2• H2O2 + O2 (1.8)

The two main mechanisms responsible for the destruction of organic

pollutants using cavitation are the thermal decomposition/pyrolysis of the volatile
pollutant molecule entrapped inside the cavity and/or present at the interface and
secondly, the reaction of OH•, O•, HO2• radicals with the pollutant (Pang et al., 2011).
The radicals produced during cavitation are extremely reactive and react
instantaneously after being released into the bulk medium. Hence, they could not
significantly diffuse away from the location of the collapse of the bubble and reach to
the bulk liquid medium in large numbers. Thus, the concentration of the radicals is
higher in the interfacial region between cavitation bubble and the liquid medium as
compared to the total reaction volume. Hence, if the concentration of the organic
compound is low in the vicinity of the bubble, the radicals may merely recombine
without inducing any chemical change. For that reason, the essential requirement for
enhancing the rate of destruction of organic pollutant by cavitation is to increase the
yield of the radicals and increase the interfacial concentration of organic compound
(Sivasankar and Moholkar, 2009).

1.5.1 Types of cavitation

Based on the mode of generation, cavitation can be classified into four type
viz. acoustic, hydrodynamic, optic and particle cavitation (Saharan et al., 2012).
Acoustic and hydrodynamic cavitation have been found to be more efficient in
bringing about the desired chemical changes, whereas optic and particle cavitation are
typically used for single bubble cavitation, which fails to induce chemical change in
the bulk solution (Gogate and Pandit, 2004a).
a. Acoustic cavitation: Acoustic cavitation can be induced by passing the high
frequency sound wave i.e. ultrasound (16 kHz to 2 MHz) through the aqueous
medium (Jyoti and Pandit, 2003).

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b. Hydrodynamic cavitation: Hydrodynamic cavitation can be induced by creating
pressure variation in the flowing liquid by passing it through the mechanical
constrictions or throttling devices such as venturi, orifice plate etc. (Gogate and
Pandit, 2005).
c. Optical cavitation: Optical cavitation can be induced by photons of high intensity
light (laser light), which is capable of rupturing the liquid continuum (Gogate,
2008a).
d. Particle induced cavitation: Here, cavitation can be induced by rupturing the
liquid medium through passage of a beam of elementary particles i.e. protons
(Gogate, 2008a).

1.5.2 Acoustic cavitation

In acoustic cavitation, a high intensity sinusoidal sound wave imposes varying

pressure upon existing cavities in the solution (Young, 1989). During the rarefaction
cycle, the liquid medium is broken and pulled apart at several locations, which are
weak spots in the fluid. The number of bubbles that are generated during this negative
pressure or rarefaction cycle is proportional to the concentration of such weak spots
present in the fluid (Brennen, 1995). Fig. 1.1 illustrates the formation, growth and
collapse of the cavities due to ultrasound cavitation. As indicated in the Fig. 1.1, a
bubble formed, grows during successive cycles of compression and rarefaction until it
reaches a critical size known as its resonance size.
The resonance size of a bubble depends on the applied frequency of the sound
wave (Leong et al., 2011). When bubbles reach their resonance size, two possible
events may occur, either transient or stable cavitation. The bubble may reach to
unstable size and collapse violently, within a single acoustic cycle or over a small
number of cycles. This is known as a transient cavitation. Violent collapse of the
cavities generates transient temperature and pressure conditions resulting in the
formation of free radicals. Such type of cavitation is capable of destructing complex
organic pollutants and hence, it is more useful in wastewater treatment applications.
The other possibility is that the bubble oscillates for many cycles at, or near, the linear
resonance size. This is known as a stable cavitation. It is undesirable, since it leads to
incomplete cavity collapse resulting in milder cavitational effects (Leong et al., 2011;
Yasui, 2011).

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Fig. 1.1 Schematic representation of mechanism of ultrasound cavitation

1.5.3 Hydrodynamic cavitation

In hydrodynamic cavitation, the cavitation is induced by the flow of the liquid

through simple mechanical constrictions such as venturi or an orifice under controlled
conditions (Gogate and Pandit, 2005). As the liquid passes through the mechanical
constriction such as venturi, orifice plate, etc., the pressure at the throat or vena-
contracta of the constriction is reduced below the vapor pressure of the liquid at the
operating temperature and produces millions of micro cavities. The cavities generated
subsequently collapse, as the reduced pressure is recovered in the downstream section
of the constriction (Gogate and Pandit, 2001). The basic principle of hydrodynamic
cavitation can be described by using the Bernoulli’s theorem and fluid flow &
pressure variation in hydrodynamic cavitation set-up (Fig.1.2).

ଵ

௦௧௔௧௜௖ 
ௗ௬௡௔௠௜௖  
 
௦௧௔௧௜௖   ଶ (1.9)
ଶ

Where, Pstatic and P dynamic are static and dynamic pressures, ρ and v are the
density and velocity of the liquid. According to the Bernoulli’s equation, as the fluid
velocity increases, the dynamic pressure also increases and consequently reduces the
static pressure, since sum of dynamic and static pressure is constant. If the static
pressure falls below the cavitation threshold of the solvent (i.e. the vapor pressure of
the solvent) large number of vaporous cavities are formed. The millions of cavities
generated consequently collapse when the static pressure is recovered in the

9
downstream section of the cavitating device (Franke et al., 2011; Gogate and Pandit,
2000).

Fig. 1.2 Fluid flow in hydrodynamic cavitator (circular venturi)

The collapse of generated cavities produces ‘localized hot spots’ with the
transient temperature and pressure conditions and water molecules entrapped in the
cavities get dissociated into highly reactive OH• and H• radicals (Bagal and Gogate,
2014). In the hydrodynamic cavitation, the cavitational condition of the fluid can be
simply altered by changing the operating parameters, such as inlet pressure and
cavitation number and geometrical parameters such as the size and shape of the
cavitating device. A dimensionless number known as cavitation number (Cv) has been
used widely by many researchers to relate the flow conditions with the cavitational
intensity (Gogate and Pandit, 2000; Gogate, 2008a). Cavitation number can be
defined as:
 
P −P 
CV =  2 v 
 ρv 2
1 
 
 2  (1.10)
Where, P2 is the fully recovered downstream pressure, Pv is the vapor pressure of the
liquid and v is the velocity at the throat of the cavitating device. Cavitation inception
number, Cvi is the cavitation number at which the inception of cavitation occurs. In
general, the cavitation inception occurs at Cvi equal to 1 and significant cavitational
effects can be obtained at Cv values of less than 1 (Moholkar et al., 1999). Findings of
Gogate and Pandit (2000) have also confirmed that in case of Cv values greater than 1,
the magnitudes of pressure pulses generated are insignificant to bring about a desired

10
chemical change. However, cavitation may occur at a higher cavitation number also,
possibly due to the presence of dissolved gases or some impurities in the liquid
medium (Harrison and Pandit, 1992). The cavitation inception number does not
change with the liquid velocity and is a constant for a given cavitator (Yan and
Thorpe, 1990). The number of cavities generated and the intensity of cavity collapse
increases with a decrease in cavitation number i.e. with an increase in the liquid
velocity. However, very low cavitation number can lead to super cavitation or choked
cavitation due to formation of vaporous cavity cloud, which eventually reduces the
intensity of cavity collapse (Saharan et al., 2011).

1.6 Fenton process

Fenton’s process utilizes the iron catalyzed decomposition of H2O2 in the

acidic environment for the generation of highly reactive hydroxyl radicals (OH•),
which subsequently oxidizes the organic pollutants (Rozas et al., 2010). Hydroxyl
radicals are having very high oxidation potential (2.8 eV), which can be further
utilized to convert the complex organic compounds into environmentally compatible
forms. In recent years, this process has proved to be a good option for effective
treatment of complex organic pollutants, due to its simple way of generation of OH•
radicals and cost effectiveness. This is due to the fact that chemicals required in the
Fenton process are easily available at moderate cost and it does not require any
additional special equipment (Tamimi et al., 2008). The process has a complex
reaction mechanism which can be simplified by using the following set of equations.
The primary reaction is the generation of hydroxyl (OH•) and peroxide (HO2•) radicals
as given in Eq. 1.11 and 1.12 (Rozas et al., 2010)

Fe2+ + H2O2 Fe3+ + OH¯ + OH• (1.11)

Fe3+ + H2O2 Fe2+ + HO2• + H+ (1.12)

The hydroxyl (OH•) and peroxide (HO2•) radicals subsequently attack on the
organic pollutants (OP) and further may lead to complete mineralization as given in
Eq. 1.13. Other simultaneous reactions given in Eq. 1.14 to 1.16 demonstrates the
generation of Fe2+ ions and this way catalyst is restored in the overall process (Santos
et al., 2011).

OP + OH• + HO2• Oxidation by products CO2 and H2O (1.13)

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Fe3+ + H2O2 Fe-OOH 2+ + H+ (1.14)
Fe-OOH 2+ Fe2+ + HO2• (1.15)
Fe3+ + HO2• Fe2+ + O2 + H+ (1.16)

In addition to these, unfortunately few undesirable reactions also occur

simultaneously, which are termed as recombination or scavenging reactions of OH•
radicals. Hence, OH• radicals are not only utilized for the degradation of organic
pollutants, but also to generate other radicals with less oxidative power and other
species (Santos et al., 2011) as given in Eq. 1.17 to 1.20.

OH• + OH• H2O2 (1.17)

• •
H2O2 + OH HO2 + H2O (1.18)
HO2• + HO2• H2O2 + O2 (1.19)
OH•+ O2 HO2• + O• (1.20)

The efficiency of Fenton process depends primarily on the concentration of

H2O2, a molar ratio of Fe2+ ions and H2O2, pH of the process and time of operation.
An optimal concentration of H2O2 and molar ratio of Fe2+ ions and H2O2 is essential to
avoid the scavenging effect of OH• radicals. Strict pH control is required, since the
form of iron species and their catalytic activity depends on the pH of the solution. An
optimal pH in the range of 2-4 is required for the homogeneous Fenton process (Wang
and Xu, 2012). Many researchers have successfully employed the Fenton and Photo-
Fenton process for the degradation of various organic pollutants such as pesticides,
herbicides (Tamimi et al., 2008; Santos et al., 2011; Segura et al., 2008), organic dyes
(Kusic et al., 2006; Ma et al., 2005) and phenolic and aromatic compounds (Kang et
al., 2002; Sun et al., 2007).

1.7 Photo-Fenton process

In photo-Fenton process, the rate of degradation of organic pollutants that can

be obtained by the application of Fenton's reagent is further strongly accelerated and
improved by irradiation with ultraviolet light or visible light or solar light (Tomasevic
et al., 2010). In this process, the hydroxyl radicals are generated by the iron catalyzed
decomposition of H2O2 in the presence of ultraviolet light (UV) under an acidic
condition. It is well known fact, that under acidic conditions a part of ferrous ions
would exist in the form of Fe(OH)2+, which can easily get converted into OH•

12
radicals and Fe2+ under UV irradiation as indicated in the Eq. 1.21. In addition to this
ferric ions also get converted into OH• radicals and ferrous ions in the presence of UV
light as shown in Eq. 1.22. This can establish a cycle of reactions of generating
additional hydroxyl radicals and regeneration of catalyst since Fe2+ ions are restored
(Segura et al., 2008).

Fe (OH)2+ + hν Fe2+ + OH• (1.21)

3+ 2+ •
Fe + H2O + hν Fe + OH (1.22)

Hence, photo-Fenton process leads to greater generation of hydroxyl radicals

as compared to Fenton process, which leads to the higher rate of degradation of
organic pollutants (Mico et al., 2013). The other advantage of the photo-Fenton
process is light sensitivity up to a wavelength of 600 nm. Light irradiation with
wavelength of λ< 580 nm is capable for photo reduction of ferric ions to ferrous ions
together with the generation of •OH radicals (Tomašević et al., 2010).

1.8 Photocatalytic process

Photocatalytic process utilizes a semiconductor catalyst in presence of UV

light for generation of hydroxyl radicals. It is capable of degrading chemical
pollutants by both oxidative and reductive pathways (McMurray et al., 2006).
Schematic representation of mechanism of heterogeneous photocatalysis is as shown
in the Fig. 1.3. When a photocatalyst is irradiated with UV light, valence band
electrons (e−) are promoted to the conduction band leaving a hole (h+) behind. These
electron–hole pairs either recombine to produce heat or interact separately with other
molecules generating free radicals. Simultaneous oxidation and reduction reactions
are initiated on the surface of photocatalyst. In an aqueous suspension, h+ reacts with
H2O to give OH• radicals, whereas e− reacts with adsorbed molecular O2 to produce
superoxide anion radical •O2− which also contribute to the production of OH• radicals
(Mijin et al., 2009). These OH• radicals subsequently attack on the organic pollutants
which eventually leads to mineralization of these compounds. The series of oxidation
and reduction reactions are summarized in the following equations

Photocatalyst + hν h+ + e− (1.23)
h+ + e− heat (1.24)

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Fig. 1.3 Schematic representation of mechanism of heterogeneous photocatalysis

Oxidative reactions:
h+ + H2O H+ + OH• (1.25)
+ +
2 h + 2 H2O 2 H + H2O2 (1.26)
H2O2 OH• + OH• (1.27)
Reductive reaction:
e− + O2 •
O2– (1.28)
•
O2– + H+ HO2• (1.29)
•
O2– + HO2• + H+ H2O2 + O2 (1.30)
• •
H2O2 OH + OH (1.31)

Ultimately, both oxidative and reductive reactions lead to the generation of the
hydroxyl radicals. These highly oxidative hydroxyl radicals react with organic
pollutant and oxidize them.

Organic molecule + OH• degradation products (1.32)

The important parameters which affect the overall efficiency of photocatalytic

processes includes the amount and type of catalyst, the wavelength of the irradiation,
intensity of the radiation, concentration of the pollutants, medium and pH. For
efficient treatment of wastewater using photocatalytic process, a complete
understanding of the effect of these parameters is required.

14
1.8.1 Photocatalysts

Several photocatalysts such as TiO2, ZnO, ZrO2, CeO2, Fe2O3, CdS, ZnS etc.
having adequate band gaps can be applied for the photocatalytic degradation of
organic pollutants (Devipriya et al., 2005). Apart from possessing adequate band gap,
an ideal photocatalyst should be easy to synthesize, cost effective, photostable, non-
toxic and environment friendly (Carp e al., 2004). However, most of the
photocatalysts have certain limitations. PbS and CdS are not sufficiently stable in
aqueous media since they readily undergo photo corrosion and are also toxic (Mills
and Hunte, 1997). ZnO is unstable because it readily dissolves in water to yield
Zn(OH)2, which inactivates the catalyst over time (Bahnemann et al., 1987).
Titanium dioxide is the most promising photocatalyst for the degradation of
large number of organic pollutants due to its stability, low cost and non-toxicity
(Khalid et al., 2013). The widely used polymorphs of TiO2 in photocatalytic
applications are anatase (tetragonal) and rutile (tetragonal) with band gaps of 3.2 and
3.02 respectively (Wunderlich et al., 2004). Calcination of TiO2 plays important role
in the formation of particular crystallite phase. Anatase phase is formed at high
temperature of 400°C, whereas TiO2 undergoes anatase to rutile transformation in the
range from 600-700°C (Hu et al., 2003). The anatase-form of TiO2 crystallite with
small crystallite size shows the better photocatalytic property as compared to rutile
phase. However, the overall efficiency of TiO2 is seriously limited by the narrow light
response range and low separation probability of the photo induced electron hole pairs
(Gupta and Tripathi, 2011). Therefore, it is essential to develop new methods to
improve the photocatalytic activity of titanium dioxide.
The photocatalytic activity of TiO2 can be enhanced by coupling it with noble
metal (Yu et al., 2005; Arabatzis et al., 2003), transition metal ions (or their oxides)
(Yu et al., 2010a; Yu et al., 2010b) and other semiconductors (Li. et al., 2001; Xu et
al., 2011) or anchoring it on a large-surface-area materials, such as mesoporous
materials, zeolites or carbon-based materials (Mohamed, 2012). The addition of
carbon based material such as graphene has been observed to be one of the effective
methods to improve the photocatalytic activity of TiO2 due to its large surface area
and excellent mobility of charge carriers (Xiang et al., 2012; Wang et al., 2010 and
Wang et al., 2012). In addition to this, graphene is easy to produce by using
inexpensive natural graphite through the formation of graphene oxide (GO)

15
(Hummers and Offeman, 1958; Marcano et al., 2010). The presence of oxygen-
containing functional groups in GO and reduced GO makes them an excellent
supporter to anchor TiO2 nanocrystals. The composite of reduced graphene and TiO2
enhances the photocatalytic activity since the graphene act as the electron sink for the
hindrance of charge carrier recombination or as the photosensitizer to generate a
greater density of electron - hole pairs, leading to higher generation of hydroxyl
radicals and increased degradation rates (Mohamed, 2012).

1.9 Oxidation using various combinations of ozone, H2O2 and UV

In an ozonation process, oxidation of organic pollutant occurs in two possible

ways. The first way of oxidation is due to the direct reaction between the ozone and
the organic compounds, and the other way of oxidation is due to the reaction between
the radicals generated in the decomposition of ozone (hydroxyl radicals) and the
organic compounds (Esplugas et al., 2002). Various combinations of ozone (O3),
H2O2 and UV radiation have been used for the successful degradation of organic
pollutants. They are summarized as below

a. Combination of O3 and H2O2:

In this system, hydroxyl radicals are generated by the interaction between the
ozone and the hydrogen peroxide (Staehelin and Hoigne, 1982; Glaze and Kang,
1989). The reaction (Eq. 1.33) is as follows

H2O2 + 2O3 2 OH• + 3O2 (1.33)

b. Combination of O3 and UV:

In this system, the energy supplied by UV radiation interacts with O3 to
generate the hydroxyl radicals (Guittoneau et al., 1990; Beltran et al., 1998). The
reaction (Eq. 1.34) is as follows

௛ఔ
O3 + H2O  2 OH• + O2 (1.34)

c. Combination of H2O2 and UV:

In this system H2O2 dissociates in presence of UV radiation and cleavage of
hydrogen peroxide molecule results in generation of hydroxyl radicals (Guittoneau et
al., 1990). The reaction (Eq. 1.35) is as follows
௛ఔ
H2O2  2OH• (1.35)

16
d. Combination of O3, H2O2 and UV:

This is a very effective method which leads to faster and complete

mineralization of organic pollutants due to enhanced generation of hydroxyl radicals.
The reactions responsible for generation of hydroxyl radicals (Eq. 1.36 to Eq. 1.38)
are as follows (Glaze et al., 1987; Mokrini et al., 1997)

H2O2 + 2O3 2OH• + 3O2 (1.36)

௛ఔ
O3 + H2O  2OH•• + O2 (1.37)
௛ఔ
H2O2  2OH• (1.38)

1.10 Limitations of individual AOPs

Even though advanced oxidation processes are widely applied for the
degradation of model organic pollutants, their application for the treatment of actual
wastewater has their own limitations when applied individually. These limitations are
discussed below for few important AOPs.

1.10.1 Limitations of Fenton process

Application of Fenton process requires an acidic condition with preferred pH

in the range of 2–4. This makes the acidification of the effluent stream essential
before the Fenton treatment. In addition to this, requirement of hydrogen peroxide and
additional process for the removal of the generated iron sludge makes the Fenton
process uneconomical. The necessity of neutralization of the treated solution before
disposal and the risk related to the storage and transportation of hydrogen peroxide
are some of the additional disadvantages of Fenton process (Brillas et al., 2009).
Degree of oxidation that can be obtained by application of Fenton process is also
restricted since the amount of oxidant cannot be increased beyond a certain limit. This
is because the presence of unreacted H2O2 and iron salts in the treated solution can
make it unsuitable for subsequent biological treatment due to their possible impact on
microbial growth. An increase in the total dissolved solid content of the liquid after
treatment is also another shortcoming of this process since it is not permitted
(Babuponnusami and Muthukumar, 2014).

17
1.10.2 Limitations of ozonation

The application of the conventional ozonation process is seriously limited by

the mass transfer resistances and requirement of ozone (Zhang et al., 2006). Use of
hydrogen peroxide for the dissociation of ozone, needs further treatment to remove
the excess unreacted H2O2 whereas, the use of UV source for the dissociation of ozone
makes this process energy and cost intensive (Esplugas et al., 2002).

1.10.3 Limitations of photocatalytic process

In the case of photocatalytic processes the engineering design and fabrication

consideration for providing uniform distribution of UV radiation throughout the
reactor adds cost to the process. If the photocatalyst is added as slurry, then additional
process is required for the separation of catalyst after treatment. Further the
maintenance cost of catalyst regeneration and UV lamp life makes this process even
more costly. Rigorous study is required for obtaining the optimal dosage of catalyst
since the excess amount of catalyst will further increase the cost and leads to light
scattering effect (Cheng et al., 2012).

1.10.4 Limitations of cavitation processes

Although acoustic cavitation is highly successful at laboratory scale, the high

fabrication cost for the ultrasonic horn and transducers, makes it an expensive
operation to be attempted on a large scale. Industrial scale operation using acoustic
cavitation is difficult due to requirement of higher power dissipation for large scale
treatment (Gogate and Pandit, 2004a). Hydrodynamic cavitation can overcome the
shortcomings of ultrasound cavitation due to its cost effectiveness, easy scale up and
higher energy efficiency (Bagal and Gogate, 2014).
However, the fact cannot be ruled out that hydrodynamic cavitation provides
substantially lower intensity of collapse of the individual cavities in terms of
temperature and pressure than acoustic cavitation (Moholkar et al., 1999). Thus the
rates of degradation of organic pollutant and the rate of mineralization can be
significantly lower in the case of hydrodynamic cavitation. Overall, it can be
concluded that none of the AOPs operating individually are beneficial for the
effective destruction of the complex industrial streams. The combination of these
processes may be used to overcome the disadvantages of the individual technique

18
with an emphasis on the enhancement and proper utilization of the generated hydroxyl
radicals under optimized operating conditions.

1.11 Need of hybrid techniques based on cavitation

When applied individually cavitation often gives lower rates of the

degradation and requires higher cost of treatment, however the efficacy of cavitation
can be significantly enhanced by combining it with other advanced oxidation
processes such as H2O2, Fenton and photo-Fenton, ozone, photocatalytic process
(Gogate, 2008a; Gogate, 2008b; Gogate and Pandit, 2004a; Gogate and Pandit,
2004b; Pang et al., 2011; Bagal and Gogate, 2014). A combination of cavitation with
other AOPs has been found to be more efficient for wastewater treatment as compared
to individual AOPs due to substantial increase in the energy efficiency and generation
of quantum of free radicals. The expected synergism between different hybrid
methods is mainly due to an identical controlling reaction mechanism i.e. the free
radical attack (Gogate, 2008a; Gogate, 2008b). Hybrid techniques i.e. combination of
cavitation with other AOPs often leads to the intensification of degradation of organic
pollutants due to the following advantages.
• High turbulence created due to cavitation leads to effective utilization of hydroxyl
radicals i.e. a better contact of the generated free radicals with the pollutant
molecules during cavitation based hybrid processes, which eventually results in
higher oxidation rates (Saharan et al., 2011).
• The combination of cavitation (HC or US) with process intensifying additives
such as H2O2 or ozone substantially enhances the rate of degradation of organic
pollutants, since both H2O2 and ozone dissociates in the presence of cavitation
resulting in the higher generation of hydroxyl radicals (Gogate and Pandit, 2004b;
Gore et al., 2014). The mass transfer resistance, which is a major limiting factor in
the application of hydrogen peroxide and ozone alone, can be also eliminated due
to the enhanced turbulence generated by the cavitation (Gogate, 2008a). It also
results in a reduction in the requirement of the oxidant dosage leading to cost
benefits as well as reducing the disposal load.
• The combination of cavitation (HC or US) with Fenton or photo-Fenton process
also leads to the enhanced generation of hydroxyl radicals, due to regeneration of
ferrous ion catalyst by conversion of Fe (OH) 2+ into ferrous ion in the presence of

19
 cavitation and reduced mass transfer resistances owing to improved turbulence
created by cavitation (Mishra and Gogate, 2010; Joshi and Gogate, 2012).
Minimum loadings of ferrous ion can be sufficient for application of a
combination of cavitation and Fenton process, which will ultimately restrict the
amount of unutilized ferrous ions contributing to an increase in the total dissolved
solid (TDS) content of the effluent stream (Pang et al., 2011).
• The combination of cavitation with a photocatalytic process can also obtain a
higher rate of degradation of organic pollutants as compared to individual
operations. This may be due to the fact that catalyst surface is kept clean, catalyst
particles are kept well mixed in the suspension and the mass transfer resistances
are reduced due to improved local turbulence by cavitation (Gogate, 2008a;
Ahmedchekkat et al., 2011).

1.12 Aim and objectives

Aim: To conduct the significant research in the field of wastewater treatment for
developing innovative techniques that promotes the easy and effective degradation of
organic pollutants.

Objectives:
• To study the effect of operating parameters such as initial pH, ultrasonic
power density (in case of US) and inlet pressure to the cavitating device or
cavitation number (in case of HC) on the efficacy of individual cavitation
processes.
• To develop the effective hybrid processes by using hydrodynamic or
ultrasound cavitation in combination with other advanced oxidation processes
(AOPs) for the degradation of organic pollutants such as pesticides.
• To obtain the synergistic effect of using cavitation processes, in combination
with other advanced oxidation processes (AOPs).
• To identify the reaction byproducts and develop the reaction mechanism.
• To formulate a scheme, particularly for continuous treatment based on
hydrodynamic cavitation which could be beneficial for industries for treating
organic wastes.
• To study the degradation or treatment of actual effluents from industries to
verify the feasibility of the developed hybrid process.

20
1.13 Scope of the thesis

This thesis is organized in such a way that each chapter has its own
introduction, list of references, and appendices if applicable. The first chapter
provides an introductory background of causes of water pollution, the importance of
various advanced oxidation processes in wastewater treatment and their mechanisms.
It includes the application of ultrasound and hydrodynamic cavitation for the effective
degradation of organic pollutants such as pesticides. It also provides an introduction
to cavitation based hybrid techniques i.e. the combination of cavitation with other
AOPs for obtaining the synergy.
The comprehensive literature review on the application of cavitation based
processes (US/HC) and their combinations with various AOPs for the degradation of
organic pollutants is reported in the second chapter. The extensive literature survey
done mainly focuses on the earlier reports indicating the effect of combination of
cavitation processes with other AOPs on the rate of degradation and mineralization of
various organic pollutants. In addition to this, the possible impact of optimization of
operating, geometric or other parameters on the efficacy of cavitation processes is
also discussed. The reports of the earlier work done for the degradation of selected
organic pollutants viz. imidacloprid, methomyl and actual pesticide industrial effluent
have also examined to set the objectives of the present research.
Third chapter presents the study of degradation of imidacloprid by the
application of hydrodynamic cavitation (HC) and hydrodynamic cavitation based
hybrid techniques such as HC + H2O2, HC + Fenton and HC + Photo-Fenton and HC
+ Photolytic and HC + Photocatalytic process. The focus of this study is to harness
the energy associated with hydrodynamic cavitation for intensification of the
degradation of imidacloprid. Forth chapter demonstrates the study of degradation of
methomyl in aqueous solutions by using hydrodynamic cavitation (HC) and
combination of hydrodynamic cavitation with various advanced oxidation processes
(AOPs) such as, HC + H2O2 , HC + Fenton, HC + Ozone. The main objective of this
work is to study the effect of process intensifying agents such as H2O2, Fenton’s
reagent and ozone on the rate of degradation of methomyl by application of
hydrodynamic cavitation.
Fifth chapter exhibits the study of degradation of methomyl in aqueous
solutions by using ultrasonic cavitation (US) and its combination with various

21
advanced oxidation processes (AOPs) such as US + H2O2, US + Fenton, US + Photo-
Fenton, and US + Photocatalytic process. One of aim of this study is to compare the
efficiency of ultrasound and hydrodynamic cavitation by comparing the rate of
degradation of methomyl, rate of TOC reduction and energy efficiency in terms of
cavitational yield. Sixth chapter deals with the study of pretreatment of pesticide
industry effluent by the application of hydrodynamic cavitation (HC) and
hydrodynamic cavitation based hybrid techniques such as HC + H2O2 and HC +
Ozone. The focus of this study is to maximize the biodegradability index and reduce
the toxicity of the pesticide industry effluent by the application of hydrodynamic
cavitation based hybrid techniques. Finally, seventh and eighth chapter reports
overall conclusions and future perspectives of the current study, respectively.

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