Ultrasonics - Sonochemistry 67 (2020) 105130

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Ultrasonics - Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Review

A review on hybrid techniques for the degradation of organic pollutants in T

aqueous environment
⁎
Sambandam Anandana, , Vinoth Kumar Ponnusamyb, Muthupandian Ashokkumarc
a
Nanomaterials & Solar Energy Conversion Lab, Department of Chemistry, National Institute of Technology, Trichy 620 015, India
b
Department of Medicinal and Applied Chemistry & Research Center for Environmental Medicine, Kaohsiung Medical University, Kaohsiung City 807, Taiwan
c
School of Chemistry, University of Melbourne, Vic 307, Australia

A R T I C LE I N FO A B S T R A C T

Keywords: The creation of the modern world requires many industrial sectors, however, sustainability needs to be con-
Ultrasound sidered while developing industries. In particular, organic pollutants generated by many of these industries
Nanomaterials contaminate the environment leading to health and other issues. Advanced oxidation processes (AOPs) have
Photocatalysis been introduced to remove organic pollutants present in wastewater. Sonolytic degradation of organic pollutants
Ozone
is considered as one of the AOPs, however, this process has its limitations. In order to overcome the limitations,
Organic pollutants
hybrid techniques involving ultrasound and other AOPs have been developed. That is, ultrasound combined with
heterogeneous AOPs (ultrasound/metal ions, ultrasound/metal oxides, and ultrasound/photocatalysis) and
homogeneous AOPs (ultrasound/ozone, ultrasound/H2O2, and ultrasound/persulfate) for the degradation/mi-
neralization of organic pollutants. This review highlights the advantages of using hybrid techniques involving
ultrasound for the degradation of organic pollutants in aqueous solutions.

1. Introduction development. Additional impediment exists in the treatment of dye

Urbanization and industrialization are necessary for the modern
world. The consumption of various forms of energy for industrialization
results in the disposal of a substantial amount of waste into the en-
vironment. This, in turn, leads to greenhouse gas emissions, water
pollution, and other public health problems [1,2]. Of which, water
pollution has become a severe problem due to large amounts of do-
mestic sewage and industrial effluent discharged into the water body.
Wastewater coming from industries like textile, pharmacy, pesticide,
and petrochemical processing contains large amounts of organic com-
pounds such as textile dyes, aromatic compounds, chlorinated hydro-
carbons, and phenolic compounds. These compounds are toxic to the
microorganisms and thus, conventional biochemical processes are not
able to completely degrade them. If these wastewaters are discharged to
the environment without any treatment, these dyes can remain in the
environment for an extended period due to their high stability to light
and temperature. To protect the aqueous environment from such toxic
pollutants, Advanced Oxidation Processes (AOP) [3–5] have been de-
veloped. Various AOP techniques such as Fenton, Fenton-like, photo-
assisted Fenton, photocatalysis, etc. have recently been exploited
(Table 1) for the degradation of the organic pollutants [6–9]. These
processes are cost-prohibitive and complex at the present level of their
wastewater with relatively higher concentration of dyes, as AOPs are
only effective for wastewater with very low concentrations of organic
dyes.
All AOPs are characterized by the utilization of highly reactive
hydroxyl radicals (%OH) with a redox potential of 2.80 eV while in some
cases sulfate free radicals (SO4−%) with a redox potential of 2.5–3.1 eV
as oxidizing agents [10–12]. A rapid evolution of such reactive radicals
need to be increase for efficient pollutant removal. To attain such cri-
terion, researchers utilized ultrasound irradiation because the cavita-
tion effect generated by ultrasound cuases the production of heat,
promotion of mixing or mass transfer, promotion of contact between
materials, dispersion of contaminated layers of chemicals and produc-
tion of free radicals [13–18]. Besides, the physical effects of ultrasound
accelerate the reaction due to the proper mixing of reagents and en-
hanced surface area of the catalyst. However, the limitation is volatile
organics formed during sonication may evaporate and escape into the
atmosphere making it advisable to use a closed reactor for treating
these contaminants. Besides, CO2 produced during the reaction will
redissolve and reduce the pH of the solution.
Many review articles [19–25] are available on the sonochemical
degradation of pollutants in aqueous environment. In this review, at-
tention is given to ultrasound combined with heterogeneous AOPs

⁎
Corresponding author.
E-mail address: sanand@nitt.edu (S. Anandan).

https://doi.org/10.1016/j.ultsonch.2020.105130
Received 2 February 2020; Received in revised form 10 April 2020; Accepted 12 April 2020
Available online 13 April 2020
1350-4177/ © 2020 Elsevier B.V. All rights reserved.
S. Anandan, et al. Ultrasonics - Sonochemistry 67 (2020) 105130

Table 1
Some reactions involved in advanced oxidation processes (Reprinted with
permission from Ref. [6]. Copyright 2009 Elsevier).
Advanced oxidation process Reaction steps

UV-hydrogen peroxide-ozone O3 + OH− → OH.

3O3 + hv → 2OH.
H2O2 + hv → 2OH.
H2O2 + O3 → 2OH.
H2O2 + O3 + hv → OH.
Fenton reactions Fe2+ + H2O2 → Fe3+ + OH. + OH−
Semiconductor photocatalysis TiO2 + hv → TiO2− + OH. (or TiO2+)
(TiO2-semiconductor)
TiO2− + O2 + H+ → TiO2 + HO2
TiO2− + H2O2 + H+ → TiO2 + H2O + OH.
TiO2− + 2H+ → TiO2 + .H2
H+ + H2O → OH. + H+
H+ + OH− → OH.
Fig. 1. Sonolysis of diclofenac in water at different frequencies
Wet oxidation RH + O2 → R. + HO2.
(Co = 50 mg l−1; T = 20 °C). (Reprinted with permission from Ref. [41].
RH + HO2. → R. + H2O2
H2O2 + M → 2OH. Copyright 2008 Elsevier).
RH + OH. → R. + H2O
R. + O2 → ROO.
concentrations. The sonochemical degradation of diclofenac was stu-
ROO. + RH → ROOH + R.
Sonolysis H2O + ))) → OH. + OH− died using three types of ultrasonic bath reactors (216, 617 & 850 kHz)
H2O + ))) → ½H2 + ½H2O2 and the degradation was monitored by HPLC analysis. The concentra-
Sonophotocatalysis (with H2O2) H2O + ))) → OH. + OH− tion vs time plot (Fig. 1) clearly illustrates that the highest degradation
(i) Water sonolysis
of diclofenac was achieved by 617 kHz ultrasonic bath reactor because
H2O + ))) → ½H2 + ½H2O2
(ii) Reaction of H2O2 with H H2O2 + H. → H2O + OH.
it generated the highest hydrogen peroxide formation (9 μM.min−1). A
atoms (formed from water suitable reaction scheme for the degradation of diclofenac based on the
sonolysis) attack of hydroxyl radicals is summarized (Fig. 2).
(iii) Photolytic dissociation of H2O2 + hv → 2OH. Further, Hartmann et al. [41] state that at a fixed ultrasonic fre-
H2O2
quency (617 kHz), the rate of formation of hydrogen peroxide increases
(iv) Reaction of H2O2 with H2O2 + O2.− → OH. + OH− + O2
superoxides (formed in the upon increasing the power from 50 to 150 W (Table 2). Besides,
presence of TiO2 and under Hartmann et al., [41] also noted that upon increasing the power of
UV irradiation) ultrasound, the number of collapsing bubbles get increases which lead
(v) Reaction of H2O2 with H2O2 + e− → OH. + OH−
to enhanced degradation of diclofenac solution.
electrons (conduction band
electrons are generated
Naddeo et al. [42] studied the degradation of diclofenac using
from semiconductor 20 kHz probe sonicator at various operating conditions such as power
photocatalyst under UV density (25–100 W/L), substrate concentration (2.5–80 mg/L), initial
irradiation) solution pH (3.5–11), bulk liquid temperature and the type of sparging
gas (air, oxygen, argon). They measured diclofenac degradation rate
and compared it to the rate of hydrogen peroxide formation (Fig. 3).
(ultrasound/metal ions, ultrasound/metal oxides, and ultrasound/
The degradation rate increased linearly at low concentrations with a
photocatalysis) and homogeneous AOPs (ultrasound/ozone, ultra-
simultaneous decrease in the rate of H2O2 formation. The rates were
sound/H2O2, and ultrasound/persulfate).
found to be independent at high diclofenac concentrations, probably
due to the presence of excess solute.
2. Heterogeneous advanced oxidation processes Madhavan et al. [43] also studied the sonolytic degradation of di-
clofenac (0.01–0.12 mM) and found first-order degradation kinetics at
2.1. Sonolysis an ultrasound frequency of 213 kHz in a continuous wave mode
(Fig. 4). Further, by varying the effect of US power (16–55 mW mL−1)
In a sonochemical process, ultrasound waves are transmitted on the degradation of diclofenac (DF) (0.07 mM), they found that the
through an aqueous solution to generate acoustic cavitation. Highly DF degradation rate increased with an increase in the US power may be
reactive radicals are generated during acoustic cavitation (Reaction 1) attributed to the increased amount of hydroxyl radicals produced due to
[6,8,26–40]. The highly reactive hydrogen (%H) turns into hydro- the formation of a larger number of cavitation bubbles.
peroxyl (HO2%) radicals (Reaction 2) in the presence of oxygen atmo- Another common pollutant, chlorophenol, is detected in industrial
sphere, and later forms hydrogen peroxide (H2O2) (Reactions 3 and 4). wastewaters and effluents from the pharmaceutical, pesticide, paint,
The oxidizing radicals and hydrogen peroxide are used to degrade or- solvent and wood industries. Commonly 2,4,6-trichlorophenol (TCP) is
ganic pollutants by hydroxylation and furthermore by oxidation in the detected in wastewater and effluent streams produced by paper and
presence of air or oxygen. pulp factories due to its strong polarity. Physical treatment methods do
not sufficiently address the removal of TCP; however, chemical treat-
H2O + sonication))))) → %H + %OH (1)
ment methods are quite expensive and the biological treatment process
%H + O2 → HOO% (2) is not a viable option. 2,4,6-trichlorophenol (TCP) was found to un-
dergo degradation due to the oxidation caused by hydroxyl radicals
2 HOO% → H2O2 + O2 (3) generated during the sonication and hence the proposed sonolysis de-
%OH + %OH → H2O2 (4) gradation scheme described in Fig. 5 is the best viable method for the
removal of TCP [44].
Hartmann et al. [41] studied the degradation of diclofenac, a most Sonolysis may help to treat contaminated water containing textile
frequently detected pharmaceutical found in river and surface waters, effluents through hydroxyl radical-mediated chain oxidation processes
which has adverse effects to liver and kidney even at very low

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S. Anandan, et al. Ultrasonics - Sonochemistry 67 (2020) 105130

Fig. 2. Proposed degradation scheme in the sonolysis of diclofenac in water (617 kHz, 90 W). (Reprinted with permission from Ref. [41]. Copyright 2008 Elsevier).

Table 2
Initial formation of H2O2 at different processor power at an ultrasound fre-
quency of 617 kHz (Reprinted with permission from Ref. [41]. Copyright 2008
Elsevier).
Processor power at 617 kHz Initial formation rate of H2O2
(W) (μ M min1)

50 2.8
60 3.8
90 6.1
100 6.7
120 9.0
150 10.1

[45–47]. Eren and Ince [48] studied the sonolytic degradation of two
azo dyes namely Direct Yellow 9 (DY9) and Reactive Red 141 (RR141)
using low and high-frequency ultrasound and the results are tabulated
(presented in Table 3). The results from the low-frequency US alone was
found totally ineffective for bleaching the dyes while high frequency
provided significant color decay in 30 min. The reason for such attri-
butions is due to a larger number of oscillations at a high frequency that
allowed a higher amount of %OH formation.
The effect of Acid Red 88 dye concentration and ultrasound power
on the sonochemical degradation was investigated by Madhavan et al.
[49]. Upon increasing the concentration of dye solution, the rate was
found to increase (Fig. 6) due to an increase in the reaction between
AR88 and %OH radicals. It is noticed that, upon increase the ultrasound
power from 16 to 64 mW mL−1 the degradation rate increased from
Fig. 3. Effect of DCF concentration on H2O2 production and DCF initial de-
gradation rates during ultrasound irradiation at 100 W/L, pH = 3. (Reprinted
with permission from Ref. [42]. Copyright 2010 Elsevier).
0.77 to 47.7 × 10−7 M min−1. This was attributed to an increase in the
number of active bubbles with increasing power which leads to an in-
crease in a number of hydroxyl radicals produced [50].
Many pesticides are currently used for agricultural and non-agri-
cultural activities. Monocrotophos (MCP) is an organophosphate in-
secticide that has been found as a pollutant in an aqueous environment.
Sonolytic degradation of MCP was studied by Madhavan et al. [51]
under the irradiation of 213 kHz US frequency with a 55 mW/mL

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S. Anandan, et al. Ultrasonics - Sonochemistry 67 (2020) 105130

Fig. 6. Effect of AR88 concentration on its sonolytic degradation rate. Acoustic

power = 35mWmL−1. (Reprinted with permission from Ref. [49]. Copyright
Fig. 4. Effect of [DF] on its sonochemical degradation. Inset: ln(C0/C) vs. so-
2010 Elsevier).
nication time plot for different concentrations of DF. (Reprinted with permis-
sion from Ref. [43]. Copyright 2010 Elsevier).
2.2. Sonolysis coupled with metal ions

Fenton's reagent is a combination of an oxidizing reagent (H2O2)

and a catalyst (usually a metal ion). %OH radical is the primary oxi-
dizing chemical species generated by Mn+ initiating the decomposition
of H2O2 in an acidic environment. The amount of %OH radicals could be
increased in the Fenton process upon combination with ultrasound due
to its transient cavitation action. Effective utilization of %OH radicals
could be facilitated through intense micromixing generated during
acoustic cavitation [52]. When the Fenton process was combined with
ultrasound, 99% efficiency was achieved in a very short time for Acid
Black 1 dye in an aqueous environment. Ying-Shih et al. achieved 99%
degradation of carbofuran upon coupling sonolysis with Fenton pro-
cesses [53]. Such effective degradation could be proven that a syner-
getic effect occurred upon coupling ultrasound with Fenton process
(transition metals and oxidants).

Fe2+ + H2O2 + ))) → Fe3+ + %OH + OH− (5)

Different classes of pharmaceuticals such as antibiotics, hormones,

Fig. 5. Degradation scheme of TCP by sonolysis (Reprinted with permission
from Ref. [44]. Copyright 2015 Taylor & Francis).
power. They observed that the sonolytic degradation rate increased
with an increase in the MCP concentration and in addition significant
enhancement in the MCP degradation rate when the acoustic power
was increased from 16 to 55 mW/mL. The reason for such enhancement
in the rate may be due to the increased number of active cavitation
bubbles and hence the generation of more hydroxyl radicals as well as
hydrogen peroxide.
anesthetics, and anti-inflammatories have been encountered in the
aquatic environment in the ngL−1 to mgL−1 concentration range. Of
which, Tetracycline, the second highest antibiotic in production and
use, is used in the treatment of infectious disease in both humans and
animals. Due to its antibacterial nature, it cannot be effectively de-
graded in practice by traditional biological methods [54]. It was de-
graded by sonolysis process effectively at 20 kHz [55]. Coupling so-
nolysis with metal ions such as Fe2+, and Co2+ a slight increase in
tetracycline degradation was noticed. Coupling sonolysis with metal
ions and oxidizing agents (H2O2 or S2O82), called Fenton-like reagents
showed enhanced tetracycline degradation. This may be due to a suf-
ficient supply of %OH radicals by the reaction between metal ions and
H2O2 and metal ions and S2O82− ions (Reactions 5–12).

Table 3
Fractions of color decay after 30 min sonication of the dyes (C0 = 28.75 μM) at the specified frequencies and deposited powers (Pd). The fifth column shows
percentage of decolorization at 861 kHz irradiation with various doses of t-butyl alcohol. (Reprinted with permission from Ref. [48]. Copyright 2010 Elsevier).
Reactor 1 Reactor 2

20 kHz 577 kHz 861 kHz With t-butanol

Pd = 37.3 W Pd = 48.9 W Pd = 48.5 W (m:m dye)
1:10 1:20 1:50 1145 kHz
Pd = 40 W

DY9 6.10% 22.58% 15.78% 20.32 8.67 5.44 21.00%

RR141 0.00% 45.92% 48.73% 0.53 9.26 7.14 49.50%

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S. Anandan, et al. Ultrasonics - Sonochemistry 67 (2020) 105130

%OH + X (organic compounds) → CO2 + H2O (6)

X(g) + ))) → products (7)

H2O2 + metal n+
+H +
→ %OH + H2O + metal (n+1)+
(8)
−
S2O82− + metal n+
→ %SO4 + SO42− (n+1)+
+ metal (9)

S2O82− + ))) → 2%SO4− (10)

%SO4− + H2O → SO42− + %OH + %H (11)

%SO4− + OH− → SO42− + %OH (12)

Thus, ultrasound coupled with a metal ion and an oxidizing agent

significantly decreases the toxicity of tetracycline due to mineraliza-
tion. More than 90% tetracycline degradation efficiency combined with
46% mineralization was achieved after 60 min reaction time for the
initial tetracycline concentration of 50 mg/L and H2O2 and Fe2+ con-
centrations of 2 mM and 0.2 mM, respectively at pH 3.
Babu et al. [56] made an effort to increase the efficiency of ultra-
sonic treatment of degradation of Rhodamine B (RB) dye using Fenton-
like reagent, i.e., coupling Fe2+ ions with H2O2 or S2O82−. They per-
formed experiments with 1 mM Fe2+ ions in combination with
2.64 × 10−2 M of H2O2 or S2O82− and noticed that the color removal
rate increased drastically (Fig. 7), attributed to the synergistic effects of
%OH and SO4%−. Further, sonolysis coupled with Fenton-like oxidation
(FeOOH-H2O2) was performed by Neppolian et al. [57] to facilitate the
degradation of para-chlorobenzoic acid (p-CBA). They performed so-
nolyis, Fenton-like oxidation, and sonolysis coupled with Fenton-like
oxidation in the presence of different initial concentrations of p-CBA at
pH 3 and representative kinetic runs are shown in Fig. 8. The rates of
degradation of p-CBA coupled with FeOOH-H2O2 were found to be
faster (1.54 × 10−2 min−1) compared to sonolysis alone
(4.5 × 10−3 min−1) which may be attributed primarily to the con-
tinuous cleaning and chemical activation of the Iron(III)oxide-hydro-
xide (FeOOH) surfaces by acoustic cavitation and the accelerated mass
transport rates of reactants and products between the solution phase
and the FeOOH surface.
2.3. Sonolysis coupled with metal oxides
Sonolysis alone is not generally deemed to be attractive for appli-
cation in the large-scale process because it is a high energy process. In
addition, not all of the cavitational energy can transform into chemical
and physical effects [58–60]. The equipment set-up used for such
Fig. 8. First-order plot for the degradation of p-CBA by ultrasound only,
FeOOH–H2O2 and the combined ultrasound/FeOOH–H2O2 method.
Concentration of H2O2: 20 mM, amount of FeOOH: 0.3 g/150 mL, pH: 3, and
temperature: 20 °C. (Reprinted with permission from Ref. [57]. Copyright 2004
Elsevier).
sonocatalytic degradation was designed by Wang et al. [59]. The op-
erating cost of the sonication process could be partially offset by op-
erating at milder and optimum operating conditions. Many efforts have
been devoted towards improving the degradation efficiency of sono-
lysis. It is generally known that this process can be accelerated by
adding various kinds of catalyst. Generally, the liquid that contains an
appropriate amount of interface (especially heterogeneous catalyst)
that represents weak points in the liquid for nucleation of the cavitation
bubbles to occur. Whereas, the added excessive catalyst could result in
the scattering of ultrasound waves that may decrease the rates of so-
nolysis degradation [61,62].
Wang et al. [62] validated the sonocatalytic degradation of methyl
orange in aqueous solution by coupling with various TiO2 powders
(Fig. 9). It was found that compared with the initial methyl orange
solution, the absorption for sonocatalytic and ultrasonic degradation
declined to about 75% towards transition crystal TiO2, 56% towards
rutile TiO2, 52% towards mixed TiO2 and 40.88% towards pristine
anatase TiO2. Wang et al. [59,63] performed degradation of methyl
parathion in the presence of commercial anatase TiO2 and nanometer-
sized anatase and rutile TiO2 upon coupled with sonolysis. They noticed

Fig. 9. UV–vis spectra of methyl orange solutions under different conditions:

Fig. 7. Effect of Fenton-like reagents (RB: 2.08 × 10−5 mol/L, initial pH 3, (a) original solution; (b) only ultrasound; (c) ultrasound + anatase TiO2; (d)
H2O2/PDS/PMS: 2.64 × 10−2 mol/L, Fe2+: 1 mmol/L, and temperature ultrasound + mixed TiO2; (e) ultrasound + rutile TiO2 and (f) ultra-
25 °C). (Reprinted with permission from Ref. [56]. Copyright 2015 Mary Ann sound + transition crystal TiO2. (Reprinted with permission from Ref. [62].
Liebert Inc). Copyright 2007 Elsevier).

5
S. Anandan, et al.
Fig. 10. HPLC chromatogram of methyl parathion: (1) methyl parathion; (2) p-
nitrophenol; (3) methyl paraoxon and (4) phosphate derivatives. (Reprinted
with permission from Ref. [63]. Copyright 2006 Elsevier).
degradation of methyl parathion surpassed 90% within 120 min of ul-
trasound irradiation. To explore the primary degradation process and
the total mineralization, the determinations of HPLC chromatogram at
different irradiation moment were conducted and it is shown in Fig. 10.
From the results, it can be understood that the intermediate p-ni-
trophenol appears under 30 min ultrasound irradiation in the presence
of nanometer anatase TiO2 catalysts whereas such intermediate com-
pound was not formed in the case of ordinary anatase TiO2 catalysts.
Similar intermediate p-nitrophenol appears in the case of nanometer
rutile TiO2 catalysts experiment.
Hartmann et al [41] performed sonolytic degradation of diclofenac
(DCF) at different ultrasound frequencies (24, 216, 617 and 850 kHz)
and in the presence of various catalysts (TiO2, SiO2, SnO2, and titano-
silicate). From the results, they concluded that irradiation at 617 kHz
leads to the highest degradation rate of DCF in the presence of various
catalysts. This is due to the presence of micropores in these catalysts can
act as a cavitation nuclei which is attributed for higher degradation
rate.
2.4. Sonolysis coupled with photocatalysis
Sonolysis coupled with photocatalysis (sonophotocatalysis) has
gained more attention in recent years [64–67] The advantages of such
processes results in sonolysis of reactants in the presence of catalyst to
produce more %OH, photocatalysis leads to absorption of photons by the
catalyst generating electron-hole pairs [68,69] This may trigger the
synergistic effects of the sonophotocatalytic process by making use of
the radicals, electron-hole pairs which are formed during the process.
Overall, the mechanism of sonophotocatalysis consists of the following
processes: activation of the photocatalyst surface, enhancement of the
mass transport of organic compounds and breakage of aggregation
[70–72].
Naruke et al. [73] performed the decomposition of malonic acid by
coupling photocatalysis and sonolysis. They noticed that the decom-
position rate of malonic acid was higher for the combined system than
the sum of the rates of photocatalysis (Rutile TiO2) and sonolysis. In
addition, they noticed during such processes production of (COOH)2 is
considered to arise from the coupling of carboxyl radicals (%COOH).
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Ultrasonics - Sonochemistry 67 (2020) 105130
Fig. 11. Decoloration–time profiles during combined sonochemical and pho-
tocatalytic (sonophotocatalytic) degradation at 0.25 g L−1 catalyst loading and
-●- 40 mg/L RB 5; -■- 60 mg/L RB 5. Open symbols show the cumulative effect
of the respective individual sonochemical and photocatalytic runs. (Reprinted
with permission from Ref. [75]. Copyright 2007 Elsevier).
However, it is found a small amount of succinic acid formation during
combined sonophotocatalysis processes due to possible dimerization of
%CH2COOH radicals. The coupling between alkyl and carboxyl radicals
leads to %CH2COOH radicals because the alkyl group is more active
than the carboxylic group on the surface of cavitation bubbles because
of its hydrophobicity [74]. Such an increase in molecular weight and
carbon number (malonic to succinic acid) may be responsible for di-
merization or alkyl carbon chain elongation.
Kritikos [75] tried sonophotocatalytic degradation of reactive black
5 (RB5) by means of ultraviolet irradiation (9 W UVA) over various
TiO2 suspensions and ultrasound irradiation (80 kHz, 135 W). Fig. 11
shows that nearly complete decoloration could be achieved after 25 and
40 min of sonophotocatalytic degradation of 40 and 60 mgL−1 of RB5,
respectively. They concluded that such beneficial effect of coupling
photocatalysis with sonolysis may be attributed to (i) increased pro-
duction of hydroxyl radicals in the reaction mixture arising from the
sonolytic cleavage of water, (ii) enhanced mass transfer of organics
between the liquid phase and the catalyst surface due to the facilitated
transport by shock wave propagation; (iii) catalyst excitation by ul-
trasound-induced luminescence which has a wide wavelength range
below 375 nm (iv) increased catalytic activity due to ultrasound de-
aggregating catalyst particles, thus increasing surface area and (v)
cleaning and sweeping of the catalyst surface due to acoustic micro-
steaming which allows more active catalyst sites to be available for
reaction.
Berberidou et al. [76] studied the degradation of malachite green
(MG) by means of sonophotocatalysis approach with homogeneous and
heterogeneous catalysts under selected experimental conditions: mala-
chite green concentration (2.5–12.5 mg L−1), photocatalyst loading
(TiO2 & Fe3+ + H2O2), UVA lamp intensity (9 W) and ultrasound
power intensity (75–135 W). They noticed photocatalytic degradation
alone was considerably faster than sonolytic degradation however
achieved enhanced efficiency by coupling the two processes. The ben-
eficial synergy of process integration may be attributed to the increased
production of reactive free radicals as well as enhanced catalytic ac-
tivity. In addition, they found with the help of GC/MS analysis, de-
gradation proceeds through the radical attack on the central carbon
atom. They noticed demethylation/oxidation reactions of the di-
methylamino group of malachite green yields smaller molecules and
nitrates (proposed reaction pathway is illustrated in Fig. 12).
Torres et al. [77] coupled sonolysis (300 kHz, 80 W) and solar
photocatalysis (solar simulator + TiO2) for the removal of organic
pollutant, bisphenol A (BPA). The apparatus used for their experiments
are shown in Fig. 13. At a low TiO2 loading, a detrimental effect on the
cavitation activity was observed. Further, they found both the advanced
oxidation processes produced the same by-products by analyzing the
S. Anandan, et al.
Fig. 12. Proposed reaction pathways for MG degradation. (Reprinted with permission from Ref. [76]. Copyright 2007 Elsevier).
intermediates through HPLC-MS in positive electrospray mode. In ad-
dition, they suggested that the degradation pathway may be primarily
caused by hydroxyl radical attack.
A similar detrimental effect was observed by Madhavan et al. [51]
while studying the sonophotocatalytic degradation of MCP in the pre-
sence of TiO2 and Fe3+. They mentioned synergy indices of about 0.62
and 0.87 were noticed, which may be due to the interference of phos-
phate ions formed as an intermediate during the sonophotocatalytic
degradation of MCP. Stock [78] studied the degradation of an azo dye
(Naphthol Blue Black (NBB)) by coupling a high-frequency ultrasonic
generator and UV-photolysis. The absorbance of NBB dye was mon-
itored at 618 nm for the experiments carried out in a simultaneous or
sequential manner. The degradation rate for sonolysis is about 2-times
faster than that of the photocatalysis experiment (Fig. 14).
Reddy et al. [79] synthesized TiO2 and Fe-doped TiO2 as catalysts
for the sonophotocatalytic degradation of the Naphthol Blue Black
(NBB) dye. They quoted that the combined sonolysis and photolysis
process was more beneficial towards colour removal compared to
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Ultrasonics - Sonochemistry 67 (2020) 105130
individual sonolysis and photolysis due to higher %OH radical produc-
tion in the bubble-bulk interface and higher %OH radical production in
the bulk liquid medium for the effective interaction with dye molecules.
In addition, they studied the practical applicability of the sonophoto-
catalytic technique for the real textile wastewater containing NBB dye
extract (Fig. 15). They mentioned that the total organic carbon (TOC)
removal is ~92% with 3 gL−1 of FeTiO2.
Kavitha and Palanisamy [80] observed accelerated sonophotocata-
lytic degradation of Reactive Red (RR) 120 dye by coupling visible light
and ultrasound in the presence of catalysts such as TiO2, Hombikat UV
100 and ZnO. They quoted that ultrasound contributes through cavi-
tation to the scission of H2O2 produced by photocatalysis and sonolysis
which increases the number of reactive radical species inducing oxi-
dation of the substrates and intermediates leading to the observed sy-
nergy.
Likewise, several research groups work towards the complete re-
moval of various pollutants adopting the ultrasound technologies which
summarizes reported findings available on the sonochemical
S. Anandan, et al.
Fig. 14. Kinetics of the degradation of an aqueous solutions of NBB following
6 h of (a, Δ) simultaneous photocatalysis and sonolysis, (b, x) sequential pho-
tocatalysis and sonolysis, (c, □) sonolysis, and (d, ●) photocatalysis. Control
experiments using aqueous solutions of NBB under different conditions: (e, ■)
photolysis (UV and O2 only) and (f, +) O2 only are also shown. Absorbance
values at 618 nm (E) 2.32 × 104 M−1 cm−1) were measured at various times to
determine the concentration of NBB. Inset shows the absorption spectra of an
aqueous solution of NBB recorded following simultaneous photocatalysis and
sonolysis. (Reprinted with permission from Ref. [78]. Copyright 2000 ACS).
Fig. 15. Sonophotocatalytic treatment of textile wastewater with Fe, TiO2 and
Fe doped TiO2 catalyst (pH: 8.05, reaction time: 60 min). (Reprinted with
permission from Ref. [79]. Copyright 2016 Elsevier).
8
Ultrasonics - Sonochemistry 67 (2020) 105130
Fig. 13. Sonochemical/photocatalysis reactor used
for the BPA treatment. Numbers in circles define the
following: (1) Gas container; (2) gas flow control;
(3) temperature control; (4) ultrasound generator;
(5) sampling; (6) thermostatic bath; (7) sonochem-
ical reactor; (8) piezo-electric disc; (9) peristaltic
pump; (10) Pyrex vessels; (11) solar simulator.
(Reprinted with permission from Ref. [77]. Copy-
right 2008 Elsevier).
degradation of various pollutants in the presence of different chemical
additives [58].
3. Homogeneous advanced oxidation processes
3.1. Sonolysis coupled with ozonation
Sonolysis combined with ozonation has been investigated for the
removal of under ground water treatment plant (UWTPs) sewages
[81–84]. The combined sonication with ozonation experiments was
performed using the schematic experimental setup by Naddeo et al.
[85] (Fig. 16). Naddeo et al [85] performed sonolysis coupled ozona-
tion experiments for the degradation of DCF. The removal rate in-
creased significantly upon compared to ozonation alone and such sy-
nergic enhancement is accredited to the improved O3 decomposition in
collapsing bubbles producing further free radicals
By following sonolytic ozonation approach, He et al. [86] examined
the mineralization of Reactive Yellow 84 (RY84) at pH 10 using ozone
flow rate (4.5 g h−1), the energy density of ultrasound (176 Wl−1) and
the initial amount of RY84 (100 mg l−1). Sonolytic ozonation had a
positive effect attributed to a higher mass transfer effect. In addition,
they also proposed a reaction mechanism for the degradation of Re-
active Yellow 84 (RY84) (Fig. 17) based on pyrolysis, free radical at-
tack, and/or ozone oxidation.
In addition, He et al. [87] inspected the mineralization of p-ami-
nophenol (PAP) by coupling sonolysis with ozonation. They noticed
mineralization rate of PAP was enhanced in the coupled experiments
(88% and 99% at 10 and 30 min, respectively) than that observed using
individual techniques (i.e., 72% and 90% efficiency in the presence of
O3 alone; and 3% and 4% in the presence of US alone at 10 and 30 min).
Using GC/MS, they detected intermediates such as 4-iminocyclo-hexa-
2-5-dien-1-one, phenol, but-2-enedioic acid and acetic acid (Fig. 18)
Fig. 16. Experimental set-up: (1) ozone generator; (2) absorption column; (3)
three-way valve; (4) to input ozone gas detection; (5) temperature-controlled
bath; (6) reactor; (7) ultrasonic generator; (8) absorption bottle. (Reprinted
with permission from Ref. [85]. Copyright 2009 Elsevier).
S. Anandan, et al. Ultrasonics - Sonochemistry 67 (2020) 105130

Fig. 17. The probable degradation pathway of RY84.Co 500 mg; pH 10.0; Ozone dose 4.5 gh−1; US energy density 44 Wl−1; temperature 25 °C. (Reprinted with
permission from Ref. [86]. Copyright 2007 Elsevier).

Destaillats et al. [88] performed reduction of the total organic carbon
(TOC) with the coupled accomplishment of ultrasound and ozone
quantities to elucidate the chemical synergism. They choose two rather
persistent by-products namely nitrobenzene and benzoquinone which
are formed upon sonolysis of azobenzene and methyl orange by the
combined effect of sonolysis with ozone.
The decomposition was slow in the presence of ozone alone. A
further advantage of coupling sonolysis with ozonolysis may exclude
the formation of poisonous intermediates by the active species that
provided an additional mineralization route (Fig. 19) [88]. Many re-
searchers [85,89] show that ozonation coupled with ultrasonic irra-
diation is more efficient for the destruction of various pollutants
(Table 4) [85]. For example, Martins et al. [90] studied the combination
and individual techniques (ozonation and/or sonolysis) for the de-
gradation of pararosaniline colorant. They illustrated that the reaction
follows second-order rate for the mineralization of pararosaniline

Fig. 18. The probable degradation pathway of PAP. (Reprinted with permission from Ref. [87]. Copyright 2007 Elsevier).

9
S. Anandan, et al. Ultrasonics - Sonochemistry 67 (2020) 105130

Fig. 19. Initiation, promotion, and inhibition of the decomposition of O3 (aq) under ultrasonic irradiation. (Reprinted with permission from Ref. [88]. Copyright
2000 ACS).

Table 4
Reported Rate Constants for Reactions of the Substrates and Some of the Main
Degradation Byproducts with ¥OH(aq), O3(aq), and ¥ HO2(aq)/¥O2 -(aq) in
Water at Room Temperature (Reprinted with permission from Ref. [85].
Copyright 2009 Elsevier).
*OH O3 *HO2/*O2−
KfOH/M−1s−1 Kf O
3 /M
−1 −1
s Kf HO
2 /M
−1 −1
s

Azobenzene 2 × 1010 220

Methyl orange 2 × 1010
Nitrobenzene 3.9 × 109 0.09
Benzene sulfonate 4.7 × 109 0.23
Phenol 1.8 × 1010 1300
Catechol 1.1 × 1010 2.86 × 105 4.7 × 104/2.7 × 105
Nitrophenol 3.8 × 109 < 50 Fig. 20. Second-order reactions of pararosaniline and/or degradation by-pro-
Hydroquinone 2.1 × 1010 1.43 × 106 8.5 × 103/1.7 × 107 ducts due to ozonation (OZ) and sonolytic ozonation (US + OZ) measured by
Benzoquinone 1.2 × 109 /1.0 × 109 absorbance (206 nm) at 293 K. (Reprinted with permission from Ref. [90].
Oxalate 7.7 × 106 < 0.04 / < 0.20 Copyright 2006 Elsevier).
Hydrogen oxalate 4.7 × 107
Maleic acid 6 × 109 1000 / < 0.06
Formic acid 1.3 × 108 5 H2O2 + ))) → 2 %OH (13)
Formate 3.5 × 109 100 / < 0.01
Formaldehyde 1 × 109 0.1 H2O2 + %OH → %O2H + H2O (14)

H2O2 + %O2H → %OH + H2O + O2 (15)

(Fig. 20). In addition, they also mentioned that sonolytic ozonation
produces various intermediates compared to the individual ozonation
process which illustrates that mineralization by ozonation is a complex
process.
3.2. Sonolysis coupled with H2O2
It is well known that sonolysis of water produced hydrogen peroxide
which can dissociate to give hydroxyl radical readily (Eq. (13)). This
formed hydroxyl radical also react with hydrogen peroxide and form
different oxidizing species that are efficient to degrade the organic
pollutant in water (Eqs. (14)–(17)).
2 %OH → H2O2 (16)
2 %O2H → H2O2 + O2 (17)
The externally added hydrogen peroxide is an added advantage to
the sonolytic degradation systems. The dissociation of externally added
hydrogen peroxide by the acoustic cavitation process along that pro-
duced during sonolysis of water generate reactive hydroxyl radicals in
abundance which in turn improve the degradation process. Upadhyay
et al. published a review article and highlighted the role of external
H2O2 addition during the sonolysis of organic pollutants in an aqueous
environment [91]. The reactors were designed which consisted of the
hydrogen peroxide injection port in some the ultrasound/H2O2 systems.

10
S. Anandan, et al. Ultrasonics - Sonochemistry 67 (2020) 105130

wastewater treatment [96]. Furthermore, in general, it is a well-known

fact that sonolytic cleavage of persulfate anion produces free radicals
which are highly reactive towards the oxidative degradation of organic
compounds (Eqs. (18) and (19)). There are other few side-reactions
occurred during this ultrasound/persulfate-mediated degradation re-
action (Eqs. (20)–(23)) [97,98].

S2O82− + ))) → 2SO4−% (18)

H2O + ))) → %OH + %H (19)

H2O + SO4−% →H −
+ SO4 2−
+ %OH (20)
−
S2O8 2−
+ %OH → HO + S2O8−% (21)

S2O82− + SO4−% → SO42− + S2O8−% (22)

SO4−% + 2SO4−% → S2O82− (23)

Fig. 21. Effect of hydrogen peroxide dosage on the dye decay ratio at pH 11 Songlin et al. tested the degradation of humic acid under ultra-
(Reprinted with permission from Ref. [93]. Copyright 2000 Wiley online). sonication operated at the frequency of 40 kHz in the presence of
persulfate anions [99]. They optimize the amount of persulfate anion
addition, the power density of ultrasound and initial concentration of
Maleki et al. studied the effect of external hydrogen peroxide in sono-
humic acid, contact time, initial pH and temperature to achieve the
lysis of phenol and its degraded by-products [92]. The authors found
highest degradation rate. It was found that nearly 90% of humic acid
that the ultrasound treated effluent possessed 1.65 times less toxic than
degradation at 2 h of contact time under ultrasound/persulfate condi-
the wastewater stream from an industrial plant which contains phenol
tion at an initial pH of 3.0 and the temperature of 40 °C. They also
at 48 h. Hence, it was very clear that ultrasound/H2O2 systems can
concluded that the ultrasonic power 200 W and frequency 40 kHz is
eliminate the toxicity associated with the by-products during the for-
optimum for the oxidative removal of humic acid under this operational
mation of phenol degradation.
condition.
Likewise, Fung et al. examined the decolorization of reactive dyes
Wang et al. investigated systematically the ultrasound/persulfate
under ultrasonic irradiation in the presence of hydrogen peroxide and
system for the degradation of carbamazepine (CBZ) in solution to
the results were compared with the degradation under ultraviolet ra-
identify the factors affecting the kinetics of the process [100]. The in-
diation in a batch operation system [93]. They also studied the kinetics
dividual reaction parameters were optimized, and the degradation
of the system that is operated at different initial pH values. Further-
process was carried out under ultrasound alone, persulfate alone or
more, the dosage of hydrogen peroxide was also optimized under the
ultrasound/persulfate conditions in the optimized condition.
ultrasonic irradiation. The degradation system followed a pseudo-first-
From Fig. 22, it is very clear that the combinational AOPs is sy-
order kinetics with respect to the pH and to the hydrogen peroxide
nergistically favourable for the removal of carbamazepine. The in-
dosage.
dividual AOP such as ultrasound alone and persulfate alone showed a
The dosage of hydrogen peroxide is very vital in this type of ultra-
degradation of mere 1.2% and 25.7%, respectively. Whereas the com-
sound/H2O2 systems and hence it was optimized for the degradation of
bined AOPs (ultrasound/persulfate system) gave a degradation effi-
reactive dye under ultrasonic irradiation at the optimized pH value of
ciency of 89.4% after 2 h reaction. This synergistic effect probably due
11. The results are depicted in Fig. 21. As the dosage of hydrogen
to the combination of numerous factors (1) ultrasound caused a strong
peroxide increases from 0 to 0.2 mL/L the degradation rate also in-
mechanical effect in a homogeneous system and enhance the mass
creases. Nevertheless, further increase of hydrogen peroxide addition
transfer in solution [101]; (2) ultrasound accelerated the persulfate
over 0.5 mL/L, relatively slowed down the rate of degradation and
decomposition and produced reactive free-radical [102]. Hence, the
hence the color removal efficacy was reduced.
A very similar observation was reported by Legrini et al. [94]. Ac-
cording to their explanations, when the optimum dosage of peroxide
exceeded a competitive reaction occurred between the hydroxyl radical
and peroxide. One of the competitive reaction is the formation of hy-
droperoxyl radicals that are less reactive and hence not actively in-
volved in the degradation process. Based on the experimental results,
the authors concluded that the decolorization of synthetic reactive dye
in wastewater by this hybrid ultrasound/H2O2 system followed a
pseudo-first-order kinetics and higher levels of pH enhanced the de-
gradation process by producing more amount of hydroxyl radicals.
Furthermore, the excessive addition of hydrogen peroxide retards the
oxidative degradation of reactive dye as the competitive reaction of
hydroperoxyl radicals with hydroxyl radicals. The coupled system (ul-
trasound/H2O2) drastically improved the degradation rate.

3.3. Sonolysis coupled with persulfate

The free-radicals generated from persulfate anion possesses high

redox potential and hence very powerfully and non-selectively oxidize
the organic species. This highly reactive free-radical can be easily Fig. 22. The time dependence of carbamazepine removal efficiency of different
generated by the sonochemical treatment of persulfate anion [95]. As a combinations (Reprinted with permission from Ref. [100]. Copyright 2016
result, the ultrasound/persulfate system was extensively studied for Elsevier).

11
S. Anandan, et al.
Fig. 23. (a) Time-dependent patterns of removal efficiency of TOC by means of ultrasound, persulfate, sono-activated persulfate, electro-activated persulfate and
sonoelectro-activated persulfate oxidation (b) Hydrogen peroxide concentrations generated in deionized water (pH 3.0) by electrolysis, electroactivated persulfate
and sonoelectro-activated persulfate anions (Reprinted with permission from Ref. [103]. Copyright 2015 Elsevier).
authors concluded that ultrasound irradiation is beneficial to this type
of radical reactions in the binary system.
Persulfate anion dissociation is very effective under ultrasonication
to produce reactive free-radicals. However, the electrolytic dissociation
is also a powerful technique to decompose the persulfate anion. Hence,
Chen et al. used the combined sonoelectrolytic technique for the mi-
neralization of aniline in wastewater in the presence of persulfate anion
[103]. The comparative study results are given in Fig. 23. The de-
gradation process was monitored by gas chromatography-mass spec-
trometer (GC–MS) and showed the formation of iminobenzene radicals
initially by the preliminary oxidation of aniline. This was followed to
convert into azobenzene, nitrobenzene and nitrosobenzene, respec-
tively before mineralized completely. A smaller amount of hydro-
quinone and p-benzoquinone were also detected as by-products. In
conclusion, the sonoelectro-activated persulfate opened an effective
pathway for the mineralization of aromatic compounds in the waste-
water medium.
4. Summary
From the observed results, it is clear that the ultrasonic-assisted
procedure gained interest in the removal of pollutants found in was-
tewater. Several publications available in the literature show that ca-
vitation induced by ultrasound accelerates the destruction of various
contaminants significantly present in the wastewater. Nevertheless, the
ultrasound alone is not a sufficient tool for the faster mineralization as
all the cavitation energy cannot be converting into physical/chemical
effects. However, combining ultrasound with other AOPs (such as
ozonation system or Fenton process) and/or oxidizing agents (such as
H2O2 or persulfate) enhances the reaction rate, decreases the processing
conditions, and reduce the overall energy consumption. Thus, the po-
tential of sonochemistry in environmental remediation is significant,
which, with the help of industries, could be used in large scale opera-
tions as a green technology. It is also reported that the sonolysis could
be easy to couple with the other advanced oxidation processes as well
as conventional treatment techniques. A combination of sonolysis with
other processes such as metal, metaloxides, photocatalysis, ozonation,
H2O2 and persulphate has shown significant synergetic effects on the
degradation of various organic pollutants in the aqueous solution.
Hence, it is necessary to optimize those parameters through the theo-
retical and experimental studies before putting into practice any new
12
Ultrasonics - Sonochemistry 67 (2020) 105130
technology related to wastewater treatment.
5. Future scope
In the past few decades, ultrasound treatment of wastewater has
become a very popular technique as it converts the pollutant to the end
products i.e., carbon dioxide and water. Nevertheless, ultrasound alone
is not a sufficient tool for faster mineralization as all the cavitation
energy cannot be transferred into physical and chemical effects. The
combination of ultrasound with other advanced oxidation processes
(such as ozonation system) and/or oxidizing agents (such as H2O2 or
persulfate) that may overcome the disadvantages of ultrasonic process
on its own. Retrofitting of sonolysis to any other existing effluent
treatment plant can reduce the pretreatment time and costs, as well as
the reduction in the usage of chemicals in an environmentally friendly
way. These hybrid treatment schemes based on sonolysis and it's ret-
rofitting into existing methods of wastewater treatment will be a great
option in the future.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The research described herein was supported by the Department of
Science and Technology (DST), India, under the Water Technology
Initiative scheme (DST/TM/WTI/2k16/258(G)). The authors SA & MA
thank MHRD, New Delhi for sanctioning them a joint Scheme for
Promotion of Academic and Research Collaboration project (SPARC/
2018-2019/P236/SL). The authors are also thankful to the Research
Center for Environmental Medicine, Kaohsiung Medical University,
Kaohsiung City, Taiwan for “The Featured Areas Research Center
Program within the framework of the Higher Education Sprout Project”
by the Ministry of Education (MOE) in Taiwan.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
S. Anandan, et al.
doi.org/10.1016/j.ultsonch.2020.105130.
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