Journal of the Indian Chemical Society 99 (2022) 100353

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Journal of the Indian Chemical Society

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Intensification of degradation of acetamiprid by the combination of

ultrasonic cavitation with other advanced oxidation processes (AOPs)
P.B. Patil, S. Raut-Jadhav *
Department of Chemical Engineering, Bharati Vidyapeeth (Deemed to be University) College of Engineering, Pune, 411043, India

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

Keywords: The degradation of acetamiprid has been studied using ultrasonic cavitation (US) and its combination with H2O2,
Ultrasonic cavitation Fenton's reagents and photo-Fenton process. Initially, the optimization of operational parameters has been carried
Acetamiprid out to enhance the performance of US. Maximum degradation of acetamiprid was obtained at ultrasonic power
Fenton
density of 0.22 W/mL, operating pH of 2.5 and acetamiprid concentration of 10 ppm. Further, the rate of
Synergy
Advanced oxidation processes
degradation of acetamiprid obtained by US (0.807
10-3 min-1) was intensified by combining it with hydrogen
peroxide (4.925
10-3 min-1), Fenton's reagent (5.593
10-3 min-1) and photo-Fenton process (39.907
10-3
min-1) with synergistic coefficients of 5.58, 3.14 and 2.04 respectively. The comparison of US and various US
based combined processes have been carried out on the basis of mineralization study and cavitational yield.
Maximum extent of mineralization of 52.25% and cavitational yield of 5.288
10-12 mol/J were observed for US
þ photo-Fenton process. Further, the cost of electricity of 4.128 USD/L and power consumption of 41.650 kWh/L
obtained in the case of US has significantly reduced to 0.233 USD/L and 2.358 kWh/L respectively for US þ
photo-Fenton process. The study of effect of radical scavenger (sodium bicarbonate) has confirmed that degra-
dation of acetamiprid using US based combined processes is controlled by OH radical attack. Comparison of
cavitational yield, power consumption and cost of electricity of US and US based combined processes has indi-
cated US þ photo-Fenton process to be the most energy efficient and cost effective process for the degradation of
acetamiprid.

1. Introduction
The wide use of variety of pesticides in agricultural sector causes the
contamination of water resources. Pesticides are introduced into the
environment mainly due to the release of wastewater from pesticide in-
dustries and agricultural runoff. It is essential to develop an effective
treatment method to degrade these pesticides because most of the pes-
ticides are hazardous and toxic in nature. Acetamiprid used in the present
study is a neonicotinoid group of insecticide and is widely used for crop
protection from the sucking and chewing type of pests as well as for
treatment of seeds [1,2]. Acetamiprid (C10H11ClN4), a nitromethylene
heterocyclic compound can pose potential threat to the environment due
to its easy accumulation owing to its high stability and low hydropho-
bicity (Solubility-4.25 g/L) [3].
Advanced oxidation processes (AOPs) have been successfully used for
the degradation of various organic pesticide pollutants [4–6]. The basic
mechanism of AOPs includes the formation and subsequent attack of
hydroxyl radicals on the pollutant to be treated [7–10]. Various advanced
oxidation processes have been reported for the degradation of organic
pollutants or treatment of industrial effluents such as Fenton and
photo-Fenton processes [11,12], photo-catalytic processes [13–15],
photolytic processes [16] and cavitation based techniques [17–21].
Cavitation can be referred as the phenomena of formation of tiny gas/-
vapour filled cavities, their expansion and violent collapse of these cav-
ities in exceptionally short time span i.e. milliseconds due to pressure
fluctuations [22,23]. In case of US, the cavitational effect is generated by
low frequency sound waves and the organic pollutants present in
wastewater gets degraded due to attack of hydroxyl radicals generated by
thermal dissociation of H2O and dissolved oxygen molecules [24,25].
However, ultrasonic cavitation gives lower degradation efficiency when
used individually and the combination of US with other AOPs such as
H2O2 [19,22], Fenton [20,26] and photo-Fenton [4] etc can greatly
accelerate the degradation rate of pesticide compounds.
Various AOPs such as solar photo-Fenton treatment [1], photo-Fenton
catalytic degradation [2], ozonation [3], and UV–visible photo-
degradation [27] have been reported for the degradation of acetamiprid.

* Corresponding author.
E-mail address: smjadhav@bvucoep.edu.in (S. Raut-Jadhav).

https://doi.org/10.1016/j.jics.2022.100353
Received 22 October 2021; Received in revised form 14 December 2021; Accepted 8 January 2022
0019-4522/© 2022 Indian Chemical Society. Published by Elsevier B.V. All rights reserved.
P.B. Patil, S. Raut-Jadhav
However, US and US based combined processes have not yet applied by
any researcher for the degradation of acetamiprid. Considering this fact,
the degradation of acetamiprid has been studied by using ultrasonic
cavitation for the optimization of three important operational parameters
viz. amplitude of ultrasonic processor, concentration of acetamiprid and
pH of the acetamiprid solution. An attempt has also been made to
intensify the efficiency of US by combining it with H2O2, Fenton's re-
agents and photo-Fenton processes. Degradation of acetamiprid was
studied in the presence of radical scavenger in order to obtain the con-
trolling mechanism. In addition to this, energy efficacy based on cav-
itational yield, the % mineralization of acetamiprid, cost effectiveness
and power consumption of US and US based combined processes were
studied to obtain the most economical and effective process.
2. Materials and methods
2.1. Materials
Acetamiprid (C10H11ClN4) of purity 99.21% was obtained from Crop
Life Science Ltd., Gujarat, India as a gift sample. Chemical structure of
acetamiprid is depicted in Fig. 1. AR grade hydrogen peroxide (H2O2-
30% w/v), sulphuric acid (H2SO4), ferrous sulfate (FeSO4⋅7H2O), sodium
bicarbonate (NaHCO3) and the quenching agent sodium sulfite (Na2SO3)
were obtained from Merck, India. The desired concentration of acet-
amiprid solution was prepared using distilled water.
2.2. Experimental set-up
A schematic representation of an ultrasonic cavitation experimental
set-up has been illustrated in Fig. 2. The experimental set-up include
ultrasonic processor (Frequency - 20 kHz), a temperature indicator,
quartz reactor, UV source and a wooden shield. Ultrasonic processor was
procured from Johnson Plastosonic Pvt. Ltd., India. Cavitation was pro-
duced by using 20 kHz low frequency ultrasonic processor having
maximum power dissipation of 500W. Ultrasonic probe having tip
diameter of 13 cm was dipped in the acetamiprid solution to a depth of
about 2 cm. The experiments were performed in quartz reactor with a
facility of double walled cooling jacket to keep constant temperature (30
 2 C) during all experiments. In case of photolytic and photo-Fenton
processes two UV tubes of 8 W each (make – Phillips, length- 28.5 cm
and diameter – 1.6 cm) were used as a source of UV light and were kept at
2 cm apart from the quartz reactor. Wooden shield has been used for the
protection from harmful UV irradiations.
2.3. Experimental methodology
All the experiments were carried out using fixed operating volume of
250 mL and constant solution temperature of 30  2 C. H2SO4 (1.0 M)
was used to adjust the desired value of an operating pH of acetamiprid
solution. Experimentation was carried out for maximum treatment time
of 120 min using the pulsed mode ultrasonic horn set at 6 s on and 4 s off.
Pulsed mode has been used to ensure the availability of sufficient time
Fig. 1. Chemical structure of acetamiprid (C10H11ClN4).
2
Journal of the Indian Chemical Society 99 (2022) 100353
Fig. 2. Ultrasonic cavitation set-up.
required for dissipation of heat which can further lead to better tem-
perature control [9]. Initially, the effect of power density of ultrasonic
processor on the degradation rate of acetamiprid was studied at various
amplitudes of ultrasonic processor. The operating pH and initial con-
centration of acetamiprid was 3 and 10 ppm respectively. Further, the
effect of the operating pH on the degradation rate of acetamiprid was
studied at the optimized amplitude of 100% and by changing pH in the
range of 2.5–8.1 (2.5, 3, 4, 6 and 8.1). The concentration of acetamiprid
solution was also optimized by changing the concentration of acet-
amiprid from 10 to 30 ppm (10, 15, 20, 25 and 30 ppm) at the optimized
operating pH of 2.5 and the optimized amplitude of 100%.
In order to intensify the degradation rate of acetamiprid that could be
achieved under optimized operating parameters by using US, the ex-
periments were also carried out by combining US with H2O2 and Fenton's
reagent. The experiments of US þ H2O2 were performed using various
molar ratio of acetamiprid: H2O2 viz. 1:2, 1:5, 1:10, 1:15 and 1:20. These
experiments were intended to determine the optimum concentration of
H2O2.
US þ Fenton's reagent was performed for the degradation of acet-
amiprid using various molar ratio of FeSO4.7H2O: H2O2 viz. 1:50, 1:40,
1:30, 1:20 and 1:10 at obtained optimal concentration of H2O2. For
further improvement in the degradation rate of acetamiprid, the exper-
iment was also performed by combining the US with photo-Fenton pro-
cess at the optimal concentration of H2O2 and Fe2þ ions. Furthermore,
the experiments related to individual H2O2 and Fenton process were
performed using magnetic stirrer at the optimal loading of intensifying
agents to check the synergistic effect. The degradation of acetamiprid
was studied in the presence of radical scavenger using three different
loadings of sodium bicarbonate as 0.5, 1.0 and 1.5 g/L. The extent of
mineralization of acetamiprid based on % total organic carbon (TOC)
reduction, energy efficacy, power consumption and cost effectiveness of
all applied processes were evaluated at the optimized conditions to
obtain the most economical and effective process.
2.4. Analysis
Ultraviolet–Visible Spectrophotometer (Make: UV 3000þ) procured
from LABINDIA was used to obtain decrease in the concentration of
acetamiprid during all the experiments. The spectrophotometer was
adjusted at λmax of 246 nm for the detection of acetamiprid. In the ex-
periments involving the addition of H2O2, 0.5 N Na2SO3 (quenching
agent) was instantly added to the samples before analysis. TOC analyzer,
Shimadzu Corp., Japan was used for measuring reduction in the TOC
content during mineralization study. All the experiments related to the
degradation and mineralization of acetamiprid were performed
P.B. Patil, S. Raut-Jadhav
minimum two times and observed that the errors are well below 3% of
the reported results.
3. Result and discussion
3.1. Degradation kinetics for acetamiprid
Degradation kinetics of acetamiprid was investigated by performing
the sonication using operating pH of 2.5 and acetamiprid concentration
of 10 ppm. The amplitude of ultrasonic processor, volume of solution and
operating temperature were kept constant at 100%, 250 mL and 30  2 C
respectively. Assuming the first order kinetics, the degradation rate of
acetamiprid was calculated using following equation Eq. (1).
 
C0
ln ¼ k
t (1)
C
where, C0 ¼ concentration of acetamiprid in mg/L at time t ¼ 0, C ¼
concentration of acetamiprid in mg/L at any time t, k ¼ rate constant in
min-1 and t ¼ time in minutes. The plot of ln (C0/C) v/s time shown in
Fig. 3 is a straight line passing through origin (R2 ¼ 0.996, k ¼ 0.807

10-3 min-1), which confirms that the degradation rate of acetamiprid
follows the first order kinetics.
3.2. Effect of ultrasonic power density
Ultrasonic power density (W/mL) is an important operating param-
eter essential to enhance the performance of sonochemical reactors [4,
25]. The optimization of ultrasonic power density was done by varying
the amplitudes such as 25% (125 W), 50% (250 W), 75% (375 W) and
100% (500 W). Ultrasonic power dissipated per mL of the solution i.e.
ultrasonic power density was evaluated by using Eq. (2) [4].
Calorimetric efficiency
Electical energy input in W
Power density ¼
Treatment volume in L
(2)
The calorimetric efficiency required for the determination of power
density was evaluated using Eq. (3).
Mass of water in kg
specific heat of water in J=kg C
Temperature rise in
Calorimetric efficiency ¼
Electrical energy supplied in W
Treatment time in h
Volume of solution, operating temperature and initial concentration
of acetamiprid were kept constant at 250 mL, 30  2 C and 10 ppm
respectively. The degradation rate of acetamiprid at various ultrasonic
power density have been depicted in Fig. 4. The extent and rate of
degradation of acetamiprid are tabulated in Table 1. Ultrasonic power
density was obtained as 0.12 W/mL for 25% amplitude, 0.16 W/mL for
50% amplitude, 0.19 W/mL for 75% amplitude and 0.22 W/mL for
100%. It has clearly observed that % degradation of acetamiprid and rate
constant increases from 3.61% to 8.43% and 0.286
10-3 min-1 to 0.753

10-3 min-1 by enhancing the power density from 0.12 to 0.22 W/mL for
120 min of sonication. The results obtained are owing to the fact that the
higher ultrasonic power density results into more intense cavitation
phenomena [4,25,26]. The power dissipation rate can affect the cavity
distribution in terms of size, number and maximum life time of cavities in
the liquid medium. Hence, higher ultrasonic power density will generate
more number of vaporous cavities with higher lifetime leading to more
intense collapse of cavities with higher collapse pressure. It further leads
to the production of higher number of OH radicals under the increased
cavitational activity. Prabhu et al. [28] have studied the effect of in-
tensity of irradiation over the range of 1–50 W/cm2 for triple frequency
3
Journal of the Indian Chemical Society 99 (2022) 100353
Fig. 3. First order degradation of acetamiprid (Important conditions: acet-
amiprid concentration ¼ 10 ppm, amplitude ¼ 100%, pH ¼ 2.5).
operation. It has been reported that the higher intensity of ultrasound
cavitation achieve more cavitationally active volume with higher life
time of cavity. Daware and Gogate [29] have also obtained similar results
during the degradation of 3-methylpyridine (3 MP) using ultrasonic bath
and reported that the % degradation of 3 MP enhances from 50.2% to
56.1% with an increase in the ultrasonic power from 25 W to 100 W.
3.3. Effect of the initial pH of the solution
The determination of an optimal pH of the aqueous solution of target
organic pollutant plays a significant role in the enhancement of its rate of
degradation using ultrasonic cavitation [30,31]. In order to study the
effect of pH on the degradation rate of acetamiprid, experiments were
performed by changing the pH of acetamiprid solution from 2.5 to 8.1
(2.5, 3, 4, 6 and 8.1). During all the experiments, acetamiprid concen-
tration and operating temperature were kept constant at 10 ppm and 30
 2 C respectively. Fig. 5 shows the effect of operating pH on the ul-

C
(3)
trasonic degradation of acetamiprid. The % degradation of acetamiprid
and reaction rate constant at various operating pH have been summa-
rized in Table 2. It has clearly observed that the first order rate constant, k
decreases from 0.807
10-3 min-1 to 0.234
10-3 min-1 by increasing the
operating pH of acetamiprid solution from 2.5 to 8.1 (natural pH). The
maximum % degradation of acetamiprid of 9.44% was observed at acidic
pH of 2.5 indicating that the acidic conditions are beneficial for the
degradation of acetamiprid.
The obtained results of higher extent and rate of degradation of
acetamiprid solution at acidic pH may be due to the ample availability of
OH radicals, owing to the fact that acidic conditions can lower the rate of
recombination of hydroxyl radical [4,8,32]. Shriwas and Gogate [18]
have studied the degradation of an organophosphorous pesticide
pollutant methyl parathion using low frequency (20 kHz) ultrasonic
cavitation and reported that acidic pH favours the extent of degradation
of methyl parathion. The maximum rate of degradation of 1.75
10-3
min-1 was observed at pH of 2.5 and it decreased to 2.35
10-4 min-1 at
pH of 7.0. The maximum % degradation of methyl parathion of 10.2%
was observed at acidic pH of 2.5. Similar favourable results at lower pH
have also been observed in case of ultrasonic degradation of methomyl
P.B. Patil, S. Raut-Jadhav Journal of the Indian Chemical Society 99 (2022) 100353

Fig. 4. Degradation kinetics of acetamiprid at various ultrasonic power density Fig. 5. Degradation kinetics of acetamiprid at various operating pH of solution
(Important conditions: acetamiprid concentration ¼ 10 ppm, pH ¼ 3.0). (Important conditions: acetamiprid concentration ¼ 10 ppm, amplitude
¼ 100%).
[4], dichlorvos [10], alachlor [19] and imidacloprid [20] using ultra-
sonic horn type reactor. Hence, it has established that the extent and rate
Table 2
of degradation of pesticide compounds using US is more profound under
The change in the extent of degradation and first order rate constant at various
acidic medium. operating pH of acetamiprid solution.
Operating Extent of degradation (%) after 120 First order rate constant, k
3.4. Effect of initial concentration of acetamiprid pH min of operation
103 (min-1)

2.5 9.44 0.807

Ultrasonic degradation of acetamiprid was studied using different 3 8.43 0.753
initial concentrations ranging from 10 to 30 ppm at constant solution pH 4 3.99 0.351
6 3.20 0.270
and operating temperature of 2.5 and 30  2 C respectively. The obtained
8.1 2.73 0.234
results are shown in Fig. 6. The % degradation of acetamiprid and corre-
sponding values of k obtained after 120 min of operation are tabulated in
Table 3. It has clearly seen that the % degradation of acetamiprid as well as
the rate constant decreases with an increase in the concentration of acet-
amiprid from 10 to 30 ppm. Maximum rate of degradation of 0.807
10-3
min-1 was observed at 10 ppm whereas minimum rate of degradation of
0.659
10-3 min-1 was obtained at 30 ppm. The results obtained are owing
to the fact that higher concentration of acetamiprid increases the number
of target pollutant molecules whereas available hydroxyl radicals for
degradation remains constant. Hence, the number of hydroxyl radicals
available per molecule of target pollutant will be less at higher concen-
tration of acetamiprid. The obtained results have been well supported by
many researchers in their studies. Daware and Gogate [29] have investi-
gated the degradation of 3-methylpyridine (3 MP) at different concentra-
tion of 3 MP in the range of 25–100 mg/L using ultrasonic bath and
reported that the % degradation of 3 MP reduces from 71.1% to 56.1%
with an enhancement in the concentration from 25 to 100 mg/L in 90 min
of operation. Similar results of higher degradation lower concentration of
pollutant have also been observed for the ultrasonic degradation of
p-nitrophenol [22] and acid black 1 [26]. Fig. 6. Degradation kinetics of acetamiprid at various initial concentration of
acetamiprid solution (Important conditions: pH ¼ 2.5, amplitude ¼ 100%).
3.5. US þ H2O2

It is well reported that individual US process may not be able to

Table 1
Ultrasonic degradation of acetamiprid at various ultrasonic power density.
Amplitude Input Energy Calorimetric efficiency Ultrasonic power density Extent of degradation (%) after 120 min of First order rate constant, k
103
(%) (W) (%) (W/mL) operation (min-1)

25 125 23.64 0.12 3.61 0.286

50 250 15.53 0.16 5.86 0.515
75 375 12.36 0.19 7.24 0.634
100 500 10.89 0.22 8.43 0.753

4
P.B. Patil, S. Raut-Jadhav Journal of the Indian Chemical Society 99 (2022) 100353

Table 3 improved dissociation of hydrogen peroxide into OH radicals under the
The change in the extent of degradation and first order rate constant at various cavitation phenomena. However, beyond an optimal concentration of
initial concentrations of acetamiprid solution. H2O2, the degradation rate of acetamiprid has been reduced due to
Initial Concentration Extent of degradation (%) after First order rate constant scavenging of OH radicals and the generation of other free radicals with
(ppm) 120 min of operation k
103 (min-1) less oxidation potential such as O and OH2 radicals due to excess H2O2
10 9.44 0.807 present [4,7,10,18,20]. Jawale et al. [7] have observed the existence of
15 8.47 0.763 optimal concentration of hydrogen peroxide and reported that beyond
20 8.13 0.705 optimal molar ratio of potassium ferrocyanide to H2O2 (1:5) the degra-
25 8.03 0.674
dation rate of potassium ferrocyanide decreases. The existence of an
30 7.90 0.659
optimal loading of H2O2 during US þ H2O2 process has also been re-
ported by Golash and Gogate [10], Bagal and Gogate [19], Patil et al.
[20] and Daware and Gogate [29] for the degradation of dichlorvos,
alachlor, imidacloprid and 3-methylpyridine respectively using ultra-
sonic cavitation.
The combination of US with H2O2 shows substantial synergistic ef-
fect, since the degradation rate obtained for US þ H2O2 process (k ¼
4.925
10-3 min-1) was higher than the sum of degradation rate of US (k
¼ 0.807
10-3 min-1) and H2O2 (k ¼ 0.075
10-3 min-1). The following
equation (Eq. (4)) was used to calculate the synergistic coefficient (Sc) for
US þ H2O2 process.

kðUSþH2 O2 Þ
Sc ¼ ¼ 5:58 (4)
kðUSÞ þ kðH2 O2 Þ

The synergistic effect of US þ H2O2 process has confirmed the fact

that the combination of US and hydrogen peroxide enhances the rate of
dissociation of hydrogen peroxide into hydroxyl radicals and their better
utilization using ultrasonic cavitation. Similarly, synergistic effect is also
observed during the degradation of methomyl [4], imidacloprid [20] and
2,4-dinitrophenol [33] by using the combination of US and H2O2.

Fig. 7. Degradation kinetics of acetamiprid at various molar ratios of acet- 3.6. US þ Fenton process
amiprid: H2O2 (Important conditions: acetamiprid concentration ¼ 10 ppm,
amplitude ¼ 100%, pH ¼ 2.5). Fenton's process (Fe2þ/H2O2) refers to the reaction between Fenton's
reagent i.e. ferrous ions (Fe2þ) and hydrogen peroxide under the acidic
degrade the complex pesticide compounds completely [4,10]. However, conditions to produce ferric ions (Fe3þ) releasing highly reactive hy-
combination of US with additives such as H2O2 can greatly accelerate the droxyl radicals [4,10,24,33]. The performance of ultrasonic cavitation
degradation rate of pesticide compounds. It is expected that combination can be improved by combining it with Fenton's process. The combination
of US with H2O2 would augment the rate of formation of highly reactive of US with Fenton's reagent can enhance the generation of OH radicals
hydroxyl radicals since the sound waves created by US is capable of due to regeneration of homogeneous catalyst i.e. ferrous ions (Fe2þ) in
dissociating H2O2 into the desired OH radicals. In addition to this, local the presence of cavitation and reduced mass transfer resistances owing to
turbulence produced by cavitation phenomena can further increase the improved turbulence created by cavitation [24]. Also the minimum
effective utilization of hydroxyl radicals [4,10,20]. loadings of Fe2þ can be sufficient for US þ Fenton based processes, which
For maximizing the degradation rate of acetamiprid using US þ H2O2 will ultimately restrict the amount of unutilized ferric ions (Fe3þ)
process, the optimization of concentration of the H2O2 is very essential. contributing to low TDS content. Thus, the combination of US with
Hence, initially the concentration of hydrogen peroxide was optimized
by varying the molar concentrations of H2O2 as 2, 5, 10, 15 and 20 times
that of molar concentration of acetamiprid. Fig. 7 shows the degradation
kinetics of acetamiprid at various molar ratios of acetamiprid: H2O2. The
% degradation of acetamiprid and corresponding values of k are sum-
marized in Table 4. Maximum rate and extent of degradation of 4.925

10-3 min-1 and 43.95% was obtained by keeping the concentration of
hydrogen peroxide as 10 times the concentration of acetamiprid. The
obtained results of enhancement in the degradation rate of acetamiprid
till an optimal concentration of hydrogen peroxide are due to the

Table 4
Degradation kinetics of HC þ H2O2 process at various concentrations of H2O2.
Molar ratio of Extent of degradation (%) First order rate
Acetamiprid:H2O2 after 120 min of operation constant, k
103 (min-
1
)

1:2 29.91 2.818

1:5 32.14 3.153 Fig. 8. Degradation kinetics of acetamiprid at various molar ratios of FeS-
1:10 43.95 4.925 O4⋅7H2O: H2O2 (Important conditions: acetamiprid concentration ¼ 10 ppm,
1:15 39.70 4.112
pH ¼ 2.5, amplitude ¼ 100% and optimal molar ratio of acetamiprid: H2O2
1:20 35.71 3.608
¼ 1:10).

5
P.B. Patil, S. Raut-Jadhav Journal of the Indian Chemical Society 99 (2022) 100353

Table 5 process for the degradation of acetamiprid has its own limitations,
Degradation kinetics of HC þ Fenton process at various concentrations of Fen- which can be reduced by combining it with ultrasound cavitation.
ton's reagent. Conventional photo-Fenton process has shown lower efficacy as
Molar ratio of Extent of degradation (%) after First order rate compared to US þ photo-Fenton process, since the mass transfer re-
FeSO4⋅7H2O: H2O2 120 min of operation constant, k
103 (min- sistances are high in absence of turbulence effect generated by cavitation.
1
) In case of conventional photo-Fenton process, the exposure of acet-
1:50 44.25 4.564 amiprid molecules to UV light would also be limited and further, poor
1:40 46.85 4.998 hydroxyl radical utilization may lead to scavenging effect. In addition to
1:30 50.02 5.593
this, photo-Fenton process requires higher loadings of ferrous ions (Fe2þ)
1:20 50.28 5.757
1:10 51.09 6.037 and H2O2 as compared to US þ photo-Fenton process. It may lead to
generation of large quantity of iron sludge contributing to higher TDS
Fenton's reagent overcome the disadvantages of individual methods and content as compared to combined process. Synergistic effect was also
can effectively enhance the degradation rate of organic pollutants. observed for US þ photo-Fenton process. The following equation (Eq.
However, for enhancing the performance of US þ Fenton process, it is (6)) can be used to obtain the synergistic coefficient (Sc) for US þ photo-
recommended to optimize the loadings of Fe2þ ions since the excess Fenton process.
concentration of remaining Fe3þ ions can increase the TDS content in the kðUSþphotoFentonÞ
wastewater [24,25]. Sc ¼ ¼ 2:04 (6)
kðUSÞ þ kðphotoFentonÞ
In order to investigate the effect of addition of Fenton's reagent in case
of US þ Fenton process, the experiments were conducted at optimized Overall, synergistic effect obtained by the application of HC þ photo-
molar ratio of acetamiprid to H2O2 as 1:10 by varying the molar ratio of Fenton process is, may be due to the regeneration of ferrous ions, higher
FeSO4⋅7H2O: H2O2 such as 1:50, 1:40, 1:30, 1:20 and 1:10. The obtained exposure of acetamiprid to UV light, increased rate of formation and
results of degradation kinetics of acetamiprid at various molar ratios of better utilization of hydroxyl radicals by cavitational phenomena. Syn-
FeSO4⋅7H2O: H2O2 have been illustrated in Fig. 8. The % degradation of ergistic effect is also observed during the degradation of pesticide pol-
acetamiprid and corresponding values of k obtained after 120 min of lutants methomyl [4] and imidacloprid [6] using cavitation based
operation are summarized in Table 5. Enhancement in the degradation processes.
rate of acetamiprid was observed by increasing the loading of Fe2þ ions
till an optimal value. However, negligible increase in the rate of degra-
3.8. Degradation of acetamiprid in the presence of radical scavengers
dation of acetamiprid was observed with further increase in the Fe2þ ions
concentration above an optimal value. Very high concentration of Fe2þ
Degradation of acetamiprid in the presence of sodium bicarbonate
ions above an optimum value favours the undesirable scavenging and
(NaHCO3) as OH radical scavenger was studied in order to obtain the
recombination reactions of OH radicals. Maximum degradation rate of
controlling mechanism for the degradation of acetamiprid. The experi-
acetamiprid was found at the molar ratio of FeSO4⋅7H2O to H2O2 as 1:30.
ments were performed using NaHCO3 for US þ H2O2 process at opti-
Similar trend of existence of optimal loadings of Fe2þ ions have been
mized molar ratio of acetamiprid: H2O2 as 1:10. Three different loadings
reported by Shriwas and Gogate [18] and Bagal and Gogate [19] for
of NaHCO3 as 0.5, 1.0 and 1.5 g/L were used at fixed concentration of
degradation of methyl parathion and alachlor. US þ Fenton process has
acetamiprid as 10 ppm. The kinetics of loading of radical scavenger on
also shown synergistic effect since rate constant for individual US (k ¼
the degradation of acetamiprid is shown in Fig. 9 and the results are
0.807
10-3 min-1) and Fenton (k ¼ 0.974
10-3 min-1) processes has
summarized in Table 6. It has been clearly observed that the rate of
increased significantly by augmenting US with Fenton process (k ¼
degradation of acetamiprid decreases in the presence of NaHCO3. The
5.593
10-3 min-1). The following equation (Eq. (5)) was used to obtain
rate of degradation of acetamiprid of 4.925
10-3 min-1 obtained
the synergistic coefficient (Sc) for US þ Fenton process.
without any radical scavenger has drastically reduced to 0.977
10-3
kðUSþFentonÞ min-1, 0.761
10-3 min-1 and 0.416
10-3 min-1 in the presence of
Sc ¼ ¼ 3:14 (5) radical scavenger, NaHCO3 at the loadings of 0.5, 1 and 1.5 g/L respec-
kðUSÞ þ kðFentonÞ
tively. The results obtained are owing to the fact that the availability of
Synergistic effect obtained by the application of US þ Fenton process generated OH radicals for the degradation of acetamiprid reduces due to
is, may be due to the availability of higher density of OH radicals during
the combined process as compared to separate US and Fenton's process
[20]. This is because beneficial cavitational effects are capable of disso-
ciating H2O2 into hydroxyl radicals and can also regenerate the homo-
geneous catalyst (Fe2þ ions) leading to the formation of more number of
OH radicals [20,21]. Similar beneficial synergistic effect for US þ Fen-
ton process has also been observed for degradation of methomyl [4],
triazophos [5] and imidacloprid [6] etc.

3.7. US þ photo-Fenton process

Photo-Fenton process is based on the principle of iron catalysed

decomposition of hydrogen peroxide in the presence of ultraviolet irra-
diation to generate OH radicals. It can be combined with US for further
enhancing the extent and degradation rate of organic pollutants.
Accordingly the degradation of acetamiprid was carried out using US þ
photo-Fenton process at the optimal concentration of H2O2 and Fe2þ
ions. It has been noticed that US þ photo-Fenton process gives very high
rate of degradation of acetamiprid (39.907
10-3 min-1) as compared to
individual US (0.819
10-3 min-1) and photo-Fenton process (18.724
Fig. 9. Kinetics of loading of radical scavenger (NaHCO3) on the degradation of
10-3 min-1) after 60 min of operation. The application of photo-Fenton acetamiprid.

6
P.B. Patil, S. Raut-Jadhav Journal of the Indian Chemical Society 99 (2022) 100353

Table 6
Effect of loading of radical scavenger (NaHCO3) on the degradation of acet-
amiprid using US þ H2O2 process.
NaHCO3 Extent of degradation (%) after First order rate constant, k
loading (g/L) 120 min of operation
103 (min-1)

0 43.95 4.925
0.5 10.31 0.977
1 8.46 0.761
1.5 5.18 0.416

Fig. 11. % TOC reduction during various individual and US based processes
under the optimized conditions (Important conditions: optimal molar ratio of
acetamiprid: H2O2 and FeSO4⋅7H2O: H2O2 ¼ 1:10 and 1:30 respectively, treat-
ment time ¼ 120 min).

cavitational yield of US (2.99
10-13 mol/J) was enhanced by combining

Fig. 10. Energy efficacy of various US based processes under the optimized
conditions (Important conditions: optimal molar ratio of acetamiprid: H2O2 and
FeSO4⋅7H2O: H2O2 ¼ 1:10 and 1:30 respectively, treatment time ¼ 60 min).
the scavenging of these radicals by NaHCO3. Thus, it can be said from the
obtained result that the degradation of acetamiprid is controlled by OH
radical attack. Similar results of the scavenging action of NaHCO3 has
been reported for the degradation of diclofenac sodium [34] and alachlor
[19], Bagal and Gogate [19] have studied the sonochemical degradation
of alachlor and have also reported that the extent of degradation of al-
achlor decreases drastically in the presence of NaHCO3.
3.9. Comparison of extent of degradation, cavitational yield and cost of
electricity for individual and US based combined processes
The efficacy of individual AOPs and US based combined processes
have been compared on the basis of extent of degradation of acetamiprid,
cavitational yield and cost of electricity. The energy efficacy of all applied
processes has been compared on the basis of cavitational yield achieved
at the optimized conditions. The following equation (Eq. (7)) was used to
obtain the cavitational yield.
Moles of acetamiprid degraded
Cavitational yield ¼ ðmol=JÞ
Energy supplied to the system
Cavitational yield of various US based processes under the optimized
conditions has been illustrated in Fig. 10. It has clearly seen that the
it with H2O2 (1.58
10-12 mol/J), Fenton (1.69
10-12 mol/J) and
photo-Fenton processes (5.28
10-12 mol/J). It has also been observed
that US þ photo-Fenton process used for the degradation of acetamiprid
gives 17.66 times higher energy efficacy than ultrasonic cavitation.
Similarly the considerable enhancement in the % degradation of acet-
amiprid has been observed for US þ hydrogen peroxide, US þ Fenton's
reagent and US þ photo-Fenton process than individual processes. The %
degradation of 4.74% obtained using individual US after 60 min of
operation was significantly enhanced to 25.39%, 27.17% and 87.47% by
combining it with H2O2, Fenton's reagent and photo-Fenton processes
respectively.
Even though, the estimation of % degradation of acetamiprid and
energy efficiency based on cavitational yield is important for selecting
the effective process, it is also important to calculate the cost of electricity
and power consumption of all applied processes. The comparison of
extent of degradation, cavitational yield, power consumption and cost of
electricity for individual and combined processes have been tabulated in
Table 7. It has clearly seen that the power consumption (41.650 kWh/L)
and cost of electricity (4.128 USD/L) required in the case of US has
significantly reduced to 2.358 kWh/L and 0.233 USD/L respectively
when ultrasonic cavitation was combined with photo-Fenton process.
The sample calculations of cavitational yield, cost of electricity and
power consumption for US þ photo-Fenton process have been demon-
strated in Appendix A. Raut-Jadhav et al. [4] have investigated the
sonochemical degradation of methomyl and reported that the methomyl
degradation cost of 79892.34 R/m3 obtained in the case of US has
(7) decreased by 98 times for US þ photo-Fenton process (807.58 R/m3).
Similar results have been reported for water disinfection [35] and the
degradation of phenol [36]. US þ photo-Fenton process has observed to
be the most energy efficient and cost effective process.

Table 7
Comparison of extent of degradation, cavitational yield, power consumption and cost of electricity.
Process Extent of degradation (%) after Moles of acetamiprid degraded Cavitational yield after 60 min, Power consumption, Cost of electricity,
60 min after 60 min. (mol/J) (kWh/L) (USD/L)

US 4.74 5.388
10-7 2.993
10-13 41.650 4.128

US þ H2O2 25.39 2.851
10-6 1.584
10-12 7.872 0.780
US þ Fenton 27.17 3.053
10-6 1.696
10-12 7.352 0.728
US þ photo- 87.47 9.823
10-6 5.288
10-12 2.358 0.233
Fenton

7
P.B. Patil, S. Raut-Jadhav Journal of the Indian Chemical Society 99 (2022) 100353

3.10. Mineralization study
Mineralization study of acetamiprid in the case of individual pro-
cesses such as US, H2O2, Fenton, photo-Fenton and US based combined
processes has been performed by calculating the % reduction in TOC. The
obtained results of mineralization study are shown in Fig. 11. It has
clearly seen that the extent of TOC reduction of 5.40% obtained after
treatment time of 120 min by applying individual US has further
enhanced by applying US based combined processes such as US þ H2O2
(24.12%), US þ Fenton (29.12%) and US þ photo-Fenton (52.25%) at
optimal molar ratio of acetamiprid: H2O2 ¼ 1:10 and FeSO4⋅7H2O: H2O2
¼ 1:30. Although, US þ photo-Fenton process lead to highest % degra-
dation of acetamiprid as 87.47% after 60 min of operation, the miner-
alization study using same process has achieved 52.25% of TOC
reduction. The results obtained are credited to the fact that the energy
dissipated by US þ Photo-Fenton process was insufficient for complete
mineralization of acetamiprid since a large amount of acetamiprid might
have got converted into by-products rather than complete mineraliza-
tion. Similar results of insignificant TOC reduction of acetamiprid are
also reported by the application of photo-Fenton catalytic processes [2],
bimetallic Fe/Ni nanoparticles [37] and UV/H2O2 and UV/persulfate
system [38] etc.
4. Conclusions
Degradation of neonicotinoid class of pesticide, acetamiprid has been
carried out by the application of US based AOPs. The important con-
clusions of the present study are:
 Degradation rate of acetamiprid increases with an increase in the
power density of ultrasonic processor (W/mL) due to production of
more number of OH radicals under increased cavitational activity.
Maximum degradation of acetamiprid was observed at ultrasonic
power density of 0.22 W/mL.
 Maximum extent of degradation of 9.44% was observed in case of US
at acidic pH of 2.5 indicating that the lower pH values are beneficial
for the degradation of acetamiprid.
 Rate of degradation of acetamiprid decreases with an increase in the
concentration of acetamiprid from 10 to 30 ppm with maximum rate
of degradation of 0.807
10-3 min-1 observed at 10 ppm.
 Degradation rate of acetamiprid increases with an increase in the
concentration of H2O2 till the optimum molar ratio of acetamiprid:
H2O2 as 1:10, beyond which a reduction in the rate of degradation has
been observed. The rate and extent of degradation of acetamiprid
(4.925
10-3 min-1 and 43.95%) was highest under the optimized
conditions which lead to synergistic coefficient of 5.58.
 Optimization of concentration of Fe2þ ions during US þ Fenton pro-
cess has provided the optimal molar ratio of FeSO4⋅7H2O: H2O2 as
1:30. Under the optimized conditions, maximum rate of degradation
of 5.593
10-3 min-1 and synergistic coefficient of 3.14 were
obtained.
 Combination of US þ photo-Fenton process has significantly
enhanced the degradation rate of acetamiprid and under the opti-
mized conditions, maximum extent of degradation of 87.47% and
synergistic coefficient of 2.04 was obtained.
 Rate of degradation of acetamiprid has drastically reduced by the
addition of sodium bicarbonate as radical scavenger. It indicates that
the sonochemical degradation of acetamiprid is controlled by OH
radical attack.
 Comparison of % degradation, cavitational yield, power consumption
and cost of electricity of all applied processes has indicated that US þ
photo-Fenton process is the most energy efficient and cost effective
process.
Declaration of competing interest
Hence, the authors do not have any conflicts of interest to declare.

Appendix A

Sample calculations of cavitational yield, power consumption and cost of electricity for US þ photo-Fenton process:

a) Cavitational yield (mol/J):

Energy supplied by US þ photo-Fenton process in 60 min of operation

¼ Power
Time ¼ (500 þ 16)
(60
60) ¼ 18,57,600 J

Initial concentration of acetamiprid (C0) ¼ 10 ppm

Acetamiprid concentration at t ¼ 60 min (C) ¼ 1.25 ppm

Moles of acetamiprid degraded ¼ C0 - C ¼ 10–1.25 ¼ 8.75 ppm


8:75
103
¼ 8:75 mg L ¼
0:250 ¼ 9:823
106 mol
222:678

9:823
106
Cavitational yield ¼ ¼ 5:28
1012 mol=J
18; 57; 600

b) Power consumption (kWh/L) and Cost of electricity (USD/L):

10
103
Initial concentration of acetamipridðC0 Þ ¼ 10 ppm ¼ ¼ 4:490
105 mol=L
222:678
Therefore for 100% degradation of acetamiprid, moles of acetamiprid degraded ¼ 4.4907
10-5 mol/L.

8
P.B. Patil, S. Raut-Jadhav Journal of the Indian Chemical Society 99 (2022) 100353


4:490
105 mol=L

Power consumption ¼ ¼ 8:492
106 J L ¼ ð8:492
106Þ
2:777
107 kWh=L ¼ 2:358 kWh=L
5:288
10 12 mol=J

Cost of electricity (considering 1 kWh ¼ Rs. 7.34/- i.e. 0.099 USD) ¼ 2.358
0.099 ¼ 0.233 USD/L

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