Process Safety and Environmental Protection 137 (2020) 149–157

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

Treatment of real pharmaceutical wastewater using different

processes based on ultrasound in combination with oxidants
Shubham Chandak, Pushpito K. Ghosh, Parag R. Gogate ∗
Department of Chemical Engineering, Institute of Chemical Technology, Matunga, Mumbai 40019, India

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

Article history: The discharge of effluent from the pharmaceutical industries is a major source of environmental pollu-
Received 12 November 2019 tion due to the toxic and at times carcinogenic nature of contaminants. The current work investigates
Received in revised form 18 February 2020 the treatment of pharmaceutical industry effluent (PIE) using ultrasonic horn, operated individually and
Accepted 19 February 2020
in combination with oxidants. Under controlled operating conditions, the effect of addition of hydrogen
Available online 20 February 2020
peroxide (ratio of COD of PIE: H2 O2 varied over the range from 1:1 to 1:10), ozone (flow rate of 400 mg/h)
and Fenton’s reagent (FeSO4 :H2 O2 ratio of 3:5) was investigated as a possible process intensification
Keywords:
strategy. The combined approach of ultrasound, ozone and CuO catalyst (0.3 g/L) as well as US + H2 O2
Pharmaceutical industry effluent
Ultrasound
+ Ozone was also studied. The combined operation of US with H2 O2 and Ozone resulted in a 73 % COD
Fenton reduction, whereas the combination of the US, ozone and CuO catalyst gave maximum COD reduction
Hydrogen peroxide of 92 %. The study also focused on identification of intermediate products formed during the PIE treat-
Process intensification ment. The component analysis of PIE before and after treatment was carried out by high-resolution liquid
chromatography–mass spectroscopy (HR-LCMS). The research work has clearly established that cavita-
tion in combination with other AOPs can be effectively used for the treatment of PIE with a significant
increase in the extent of COD reduction for the combination approach.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction creates additional stress on water availability. The problem is

Contamination of freshwater bodies and increasing demand for
clean water is leading to significant problems for mankind due to
reduced availability of fresh water. The drastic increase in con-
tamination of freshwater bodies and water consumption without
proper treatment has led to the death of thousands of people
all around the world. Due to increased industrialization, a huge
quantity of polluted water is also produced every year based on
processing in various industries like pharmaceutical (Farhadi et al.,
2012) (Boroski et al., 2009), heavy metals (Aziz et al., 2016), food
processing (Pocostales et al., 2012), textile (Zheng et al., 2012),
biotechnological (Gengec et al., 2012), distilleries, pulp and paper,
petrochemical, etc. Typically the effluent from these industries
contain hazardous substances like complex and toxic aromatic
compounds, nitrogen, phosphorous and sulphur containing com-
pounds, heavy metals, pharmaceutical drugs and intermediates
as well as other emerging and harmful substances (Kerc et al.,
2003). The limitations of conventional methods for effective treat-
ment have meant that this wastewater cannot be recycled, which
∗ Corresponding author.
E-mail address: pr.gogate@ictmumbai.edu.in (P.R. Gogate).
severe in the case of pharmaceuticals sector due to development of
new molecules at regular frequency, which also cannot be treated
effectively using conventional approaches. The mutagenic and car-
cinogenic properties of the pharmaceutical effluent has made its
treatment a priority for pollution control (Meili and Soletti, 2019).
In the past, many researchers have tried different conventional
methods for wastewater treatment such as biological oxidation,
carbon bed adsorption, coagulation/flocculation, membrane sepa-
ration, electrochemical treatment and oxidation using chlorination
and ozonation (Sakumoto and Miyata, 1984). But the reduction in
the level of toxicity using these methods were not as per the lim-
its of the environmental regulations and also the time required
was much longer, especially for the complex effluents. In addition,
some methods mainly converted the pollutants from one phase
to another rather than complete removal (Rajoriya et al., 2017).
Advanced oxidation processes (AOPs) have been considered as a
good alternative for efficient removal of organic pollutants from
wastewater (Andreozzi et al., 1999). In AOPs such as photocatalytic
oxidation, cavitation, ozonation combined with hydrogen peroxide
and Fenton’s chemistry, the generation of highly oxidising hydroxyl
•
( OH) radicals takes place at conditions of ambient temperature
•
and pressure. The OH radicals are short lived and highly reac-
tive that attack the random molecular positions in the pollutants,

https://doi.org/10.1016/j.psep.2020.02.025
0957-5820/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
150 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157
efficiently break the bonds and ultimately can oxidise pollutants
into non-toxic products like CO2 , H2 O and inorganic salts (An et al.,
2010).
Cavitational effects such as generation of highly reactive oxidis-
ing species, conditions of high temperature and pressure, intense
turbulence and liquid circulation can be particularly useful for
degradation of organic pollutants both in individual operations and
in combination approaches involving external oxidants/catalysts
(Gogate and Pandit, 2004; Jawale and Gogate, 2018). The chemical
effects of ultrasound typically do not come from direct coupling of
the acoustic field with a chemical component on a molecular level.
Instead, formation, growth and implosive collapse of bubbles in
liquids exposed to high-intensity ultrasound drives different cavi-
tational effects (Dash et al., 2009). The present work focuses on the
application of cavitation generated using ultrasound for effective
treatment of PIE.
Industrial effluents containing higher concentration of pharma-
ceutical compounds should ideally be treated at source. If these
effluents are mixed with other sources of wastewater that con-
tains biodegradable substrates, before being discharged to drain,
the bacteria in a treatment plant will metabolize the latter and
the toxic pharmaceutical pollutants will pass through unchanged
as ‘Hard COD’. Many of the concentrated streams of PIE exhibits
high concentration of salts (up to 20 % w/v) and carried-over cat-
alysts/solid additives which inhibits microbial growth. Thus it is
imperative to study the treatment aspects of PIE in order to estab-
lish effective combination strategies. Majority of the past work has
typically utilised synthetic effluents obtained by dissolving a spe-
cific contaminant in water. For example, Barik and Gogate (2017)
studied the degradation of 2, 4-dichlorophenol using AOPs such as
US, US + O3 and US + O3 + CuO. The maximum extent of degrada-
tion for the combined operation of US + O3 (flow rate of 400 mg/h)
+ CuO (loading of 0.08 g/L) was reported as 97.03 % (Barik and
Gogate, 2017). Another study reported that the treatment of imida-
cloprid containing wastewater can be effectively performed using
the combination of US and Fenton’s reagent, leading to a maxi-
mum degradation of imidacloprid as 96.5 % in treatment time of
120 min at an optimum pH of 5 (Patil et al., 2014). Thanekar et al.
(2018) investigated the degradation of carbamazepine using a com-
bined approach involving hydrodynamic cavitation (HC), UV, H2 O2
and O3 at an optimized pressure and operating pH. The extent of
degradation achieved for the combined approach of HC + UV, HC +
H2 O2 , HC + O3 and HC + H2 O2 + O3 were 52.9 %, 58.3 %, 91.4 % and
100 % respectively. The present work focuses on treatment of real
effluent that is considered very tough to degrade as it contains dif-
ferent types of toxic compounds, solvents and components which
act as radical scavengers (Chakinala et al., 2008) at different levels.
We now present a brief overview of different studies dealing with
treatment of real wastewater using cavitation based approaches so
as to establish the novelty of the current work.
Joshi and Gogate (2019) studied treatment of real industrial
wastewater obtained from petrochemical sector using HC in com-
bination with other AOPs at 70 L capacity. Combined operation
of HC + Fenton + O2 at H2 O2 loading of 15 g/L and Fenton molar
ratio of 1:20 was reported to result in 63 % COD reduction dur-
ing 180 min of treatment (Joshi and Gogate, 2019). Balcioglu and
Ötker (2003) studied ozonation for treatment of wastewater con-
taminated with antibiotics such as b-lactams. It was stated that
although high removal efficiencies were achieved by ozonation
(COD removals > 50 %), the degree of mineralization was very less
(≈ 20 %), even for long treatment time. It was also reported that
degradation rates increased with an increase in pH as a result of
enhanced ozone decomposition rates into free radicals. Sivakumar
and Muthukumar (2011) investigated the ultrasonic treatment of
pharmaceutical wastewater with extent of treatment characterized
in terms of COD. The study dealt with effect of different operat-
Table 1
Characterization of PIE samples obtained from different locations in plant.
Sample No. Processing Stages COD pH
Sample A Equalization tank 6000-7500 6.5 ± 0.5
Sample B Surface aeration 5000-6500 6.5 ± 0.5
Sample C Diffused aeration 2000-3000 6.5 ± 0.5
Sample D Diffuser 300-500 6.5 ± 0.5
ing conditions such as pH, initial COD (based on dilution of the
obtained wastewater) and use of different additives for intensifi-
cation. It was clearly demonstrated that the combined approach
of ultrasound with carbon tetrachloride or activated carbon gave
effective treatment as compared to the only sonication.
Considering that previous work on real wastewater treat-
ment focused on other sectors than pharmaceutical industries, the
present work focuses on the treatment of real PIE applying differ-
ent approaches based on ultrasound. The main novelty of present
work which illustrates the combination of ultrasonic cavitation
with H2 O2 , Fenton’s reagent and CuO for treatment of real PIE is
evidently emphasized. The study also reports the use of effluents
from different sections in the plant with different levels of initial
COD for the first time (the earlier reported study dealt with diluting
original effluent) and hence expected to give important information
in the applicability of distributed treatment schemes, as an alterna-
tive to the more commonly followed practice of central treatment
facility.
2. Materials and methods
2.1. Chemicals
Hydrogen peroxide (30 % w/v), ferrous sulphate (FeSO4 ),
potassium dichromate (K2 Cr2 O7 ), mercuric sulphate (HgSO4 ) and
sulphuric acid (H2 SO4 ) were procured from S.D. Fine Chem. Pvt.
Ltd. Mumbai and used without further purification (all chemi-
cals were of analytical reagent grade). Chemicals were diluted to
required concentrations using distilled water (typical resistivity of
500,000 ) obtained from laboratory unit for experimental studies
as required. H2 SO4 aqueous solution was used for the adjustment
of pH. All the required laboratory glassware were procured from
J.T. Baker Chem. Pvt. Ltd, Mumbai, India.
2.2. Characterization of PIE
Four samples A, B, C and D of PIE with initial COD of 7500, 6500,
3000 and 500 ppm were taken from different processing stages in
the effluent treatment plant with various properties as enlisted in
Table 1. Typically the pH was maintained around neutral condi-
tions (actual observed value of 6.5 ± 0.5) across all the stages as per
the regulations in India. Along with the typical characteristics men-
tioned in the Table 1, it is important to note that the color of PIE
appeared blackish to transparent with solids present in the form
of particulate matter (variable degrees depending on the source of
effluent). The samples contain same set of pollutants albeit to dif-
ferent concentration levels though the exact quantification could
not be done. The concentration of other constituents like salts or
inorganic compounds is likely to change depending on the pro-
cessing stage. As per the regulations in India, the efficacy was only
monitored with respect to COD as the discharge limitations typ-
ically rely on the values of COD rather than individual pollutant
concentration.
2.3. Experimental setup
The experimental setup for treatment comprised of ultrasonic
horn and 250 mL beaker containing the PIE sample. The titanium
 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157
Fig. 1. Schematic representation of experimental setup based on only ultrasound (A) and ultrasonic horn/ozone combination (B).
horn with 2.1 cm tip diameter operates at a frequency of 22 kHz,
maximum power output of 250 W, and was fitted with single PZT
transducer at the tip of the horn. The power used in the study was
200 W and as per the observed calorimetric efficiency, the actual
power transmitted into the solution was 15.3 W. The tip of the
probe was dipped to a certain depth (typically 2 mm) below the
surface level of PIE sample in the beaker. The beaker was kept in
water bath with ice pellet introduction at regular interval so as
to maintain constant temperature of PIE sample throughout the
experimental study. The schematic diagram of the experimental
setup used in the work is shown in Fig. 1A for the case of only
ultrasound and in Fig. 1B for the case of combination of horn and
ozone.
2.4. Methodology
Different approaches were applied for the treatment of wastew-
ater as single approach is typically not effective for wastewater
treatment (Boczkaj et al., 2018). To quantify the basic efficacy, stud-
ies involving individual approaches were also performed initially.
The different combinations studied in the work involved combina-
151
tion of ultrasound with hydrogen peroxide (varioud loadings of 1:1,
1:5, 1:10), ozone (fixed flow rate of 400 mg/h), CuO catalyst (fixed
loading as 0.3 g/L) and Fenton’s reagent (fixed oxidant molar ratio
of 3:5). Dilution of the PIE was implemented for convenience in the
experimental investigation. The PIE sample of volume 100 ml used
for study was prepared by mixing 50 ml of PIE with 50 ml of distilled
water. The prepared PIE sample was treated using an ultrasonic
horn for a period of 120 min, which has been considered as base
time for comparison of different treatment approaches. The initial
pH of the PIE sample was found to be 6.5 ± 0.5 and was adjusted to
2.5 ± 0.5 for the actual study as acidic conditions are better for treat-
ment using ultrasound based approaches (Saharan et al., 2011). The
PIE sample was taken in a beaker used as simple reactor, which was
kept in water bath. Ice pellets were introduced at regular interval
of time to maintain constant temperature throughout experiment.
The PIE sample was also treated with ozonator with and with-
out the combination of ultrasonic horn for 120 min. To maintain
constant dispersion of ozone throughout the reactor, a ceramic
sparger was connected to the supply line. Proper measures were
taken to prevent the leakage of ozone while using ozone generator
and in addition experiments were conducted inside fume hood to
152 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157
Fig. 2. Ultrasound treatment of PIE samples with varying initial COD (ppm).
Experimental conditions: operating volume =100 mL, operation time = 120 min,
pH = 2 ± 0.5, T = 30 ± 2 ◦ C.
prevent inhalation by the people. The ozonator (model: DOZ400)
was procured from Eltech Engineers Mumbai. All the experiments
were carried out at ambient temperature and pressure. During the
experimental runs, samples were collected at regular intervals and
used for COD analysis. All the experiments were also repeated to
check the reproducibility and the observed variation was typically
between ± 2% of the reported average values, confirming the sat-
isfactory trends.
2.5. Analysis
The presence of pollutants in the PIE was quantified in terms
of COD determined using a COD analyser obtained from HANNA
instruments (model: HI83399). The PIE samples were diluted as
per convenience for COD analysis and the exact value of the CODs
were obtained after multiplying the obtained COD values in the
diluted samples with their dilution factor. Characterization of the
components present in the PIE samples was also done using HRLC-
MS (1290 Infinity UHPLC System, 1260 infinity Nano HPLC with
Chipcube, 6550 iFunnel Q-TOFs; Agilent Technologies, USA) avail-
able at the Sophisticated Analytical Instrument Facility of Indian
Institute of Technology - Bombay, Mumbai, India.
3. Results and discussion
3.1. Effect of only ultrasound
The effect of the initial COD of PIE sample on the extent of COD
reduction was evaluated using only ultrasonic horn for a period of
2 h. The COD reduction of PIE obtained for different samples A, B,
C and D with initial COD of 7500 ppm, 6500 ppm, 3000 ppm and
500 ppm were 9%, 11 %, 13 % and 14 % respectively as depicted
in Fig. 2. From the figure it can be concluded that COD reduction
is inversely proportional to the initial concentration, though the
effect is marginal. The COD reduction is expected to be dependent
on the quantity of ˙OH radicals and on the concentration of con-
taminant molecules present at the interface of cavitation bubble.
The lower extent of COD reduction at higher initial COD values can
be attributed to the fact that number of contaminant molecules
increases with an increase in COD values whereas the quantity of
˙OH radicals remains constant based on fixed condition of ultra-
sound (Jawale and Gogate, 2018). Joshi et al. (2019) reported that
50 % dilution resulted in 6.1 % of COD reduction as compared to 4.2
% and 3% in the case of 25 % dilution and no-dilution respectively
(Joshi and Gogate, 2019). Chakinala et al. (2008) also reported that
the extent of COD reduction is inversely proportional to the initial
COD of the effluent as a COD reduction of 73 % was observed for a
dilution ratio of 50 as compared to 42 % for a dilution ratio of only
Fig. 3. Combined ultrasound and hydrogen peroxide treatment of PIE sample A at
various H2 O2 loadings with respect to initial COD. Experimental conditions: oper-
ating volume =100 mL, operation time = 120 min, pH = 2 ± 0.5, T = 30 ± 2 ◦ C.
10. It is important to note here that the dilution plays an impor-
tant role in the COD reduction but it must be optimized as dilution
increases the quantum of the effluent to be treated (Chakinala et al.,
2008). Also the net COD reduction is different compared to the rel-
ative COD reduction usually discussed everywhere. In the present
work as well, the net COD reduction is infact more for the high COD
effluent (715 ppm) compared to the low COD effluent (70 ppm). The
importance of the current work is thus clearly established as it also
illustrates the importance of the net COD reduction in addition to
the more commonly used relative or percentage COD reduction.
3.2. Effect of ultrasound combination with hydrogen peroxide
Hydrogen peroxide dissociates into hydroxyl radicals in the
presence of ultrasonic irradiation and hence can be used to increase
the extent of degradation of pollutants and hence the mineraliza-
tion (Gogate and Patil, 2015). The COD reduction of PIE at different
loadings of H2 O2 with respect to initial COD of the effluent (1:1, 1:5
and 1:10) has been studied using ultrasonic horn. It was noticed that
formation of sticky blackish residue occurs at the end of experiment
for samples A, B, C and D which can be the due to the formation of
inorganic salts. The effect of various loadings of H2 O2 on the extent
of COD reduction for Sample A has been shown in Fig. 3. The max-
imum COD reduction (29 %) was obtained at an optimum loading
of H2 O2 with respect to COD of 1:5, which was later utilised to
investigate the effect of addition of H2 O2 on the extent of COD
reduction in all other samples. Lower extents of COD reduction
were observed at the other ratios of 1:1 (15 %) and 1:10 (27.5 %) used
in the work. Ghodbane and Hamdaoui (2009) also reported that
the rate of degradation increased by 2.4, 1.7 and 1.5 times with the
addition of 386, 1157 and 1928 mg L−1 of H2 O2 , respectively. It was
reported that beyond the loading of 386 mg L−1 of H2 O2 , decrease
in the extent of COD reduction was noticed, attributed to the scav-
•
enging effect of excess H2 O2 on the OH radicals (Ghauch et al.,
2011) as represented by the following equation.
• •
H2 O2 + OH → H2 O+ O2 H (1)
•
The formed O2 H offer lower oxidation potential as compared
to the hydroxyl radicals and hence lower oxidation effects are
observed. It is again important to understand that the optimum
dosage would specifically depend on the type of effluent and
also the subsequent usage (any residual H2 O2 would inhibit the
microorganisms if a downstream biological oxidation is planned),
clearly directing the need for detailed investigation into the effect
of operating loading of hydrogen peroxide.
The obtained results for the effect of hydrogen peroxide addition
in the case of other samples used in the work have been shown in
Fig. 4. It can be seen that a maximum COD reduction of 29 %, 31 %, 33
%, and 36 % was obtained for PIE samples A, B, C and D respectively
 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157
Fig. 4. Combined ultrasound and hydrogen peroxide treatment of PIE samples with
varying initial COD (ppm). Experimental conditions: operating volume =100 mL,
operation time = 120 min, pH = 2 ± 0.5, T = 30 ± 2 ◦ C, H2 O2 loading = 1:5.
Fig. 5. Combined ultrasound and ozone treatment of PIE samples with varying ini-
tial COD (ppm). Experimental conditions: operating volume =100 mL, operation
time = 120 min, pH = 2 ± 0.5, T = 30 ± 2 ◦ C, ozone gas (400 mg/h).
at the optimum loading. Comparing the effect of addition of H2 O2 , it
can be confirmed that using optimum H2 O2 has shown best results
for sample D with the extent of COD reduction as 36 % compared
to only 14 % with the use of only ultrasound.
3.3. Effect of ultrasound combination with ozone
The characteristics possessed by ozone of being non-specific
and having high oxidation potential (E0 = 2.07 eV) makes it highly
effective for treatment of wastewater containing complex organic
pollutants. The combination of ozone (O3 ) with ultrasound can play
•
a significant role in the enhanced formation of OH radicals which
can lead to improved effect in COD reduction of PIE. In the pres-
•
ence of ultrasound, ozone dissociates to form OH radicals as per
the following mechanism (Ternes et al., 2003).
•
O3 +H2 O → 2 OH + O2 (2)
• •
O3 +HO 2 → OH + 2O2 (3)
During the treatment, in the presence of ultrasound, ozone gas
(400 mg/h) was purged into the reaction mixture and the treat-
ment continued for two hours for investigating the efficacy of
combined operation. The combination of ultrasound and ozone
resulted in enhanced COD reduction as 30 %, 33 %, 35 % and 37
% for PIE samples A, B, C and D respectively as shown in Fig. 5.
Olson et al. (1994) oxidised natural organic matter using the com-
bination of ultrasound (55 W, 22 kHz) and ozone leading to a 91 %
of TOC reduction in 60 min of treatment time (Olson and Barbier,
1994). Kidak and Dogan (2018) reported degradation of Amoxi-
cillin using ultrasound simultaneously with ozone leading to 45
153
Fig. 6. Combined ozone and hydrogen peroxide treatment of PIE samples with
varying initial COD (ppm). Experimental conditions: operating volume =100 mL,
operation time = 120 min, pH = 2 ± 0.5, T = 30 ± 2 ◦ C, ozone gas (400 mg/h), H2 O2
loading = 1:5.
% of TOC removal in 90 min. The increase in TOC reduction was
attributed to increase in the mass transfer of ozone by the ultra-
sound (Kıdak and Doğan, 2018). The higher COD reduction obtained
for the combined treatment of ultrasound and ozone as compared
to only ultrasound is also attributed to the enhanced generation of
˙OH radicals and additional oxidants as nascent oxygen by cavita-
tion induced decomposition of ozone (Gogate and Patil, 2015).
3.4. Effect of combination of ozone and hydrogen peroxide
The reaction of ozone and hydrogen peroxide also gives ˙OH rad-
•
icals which can be utilized for the effective COD reduction. The OH
radical generation by reaction of ozone and hydrogen peroxide is
given as follows.
•
H2 O2 +O3 → HO• 2 + OH + O2 (4)
In order to investigate the efficacy of combined operation of
ozone and hydrogen peroxide on COD reduction, hydrogen perox-
ide was added to the PIE sample at optimized loading of 1:5 (COD
to oxidant ratio) and at the same time ozone gas (400 mg/h) was
purged with treatment continued for 2 h. It was observed that the
hybrid treatment method led to COD reduction of 62 %, 64 %, 63 %
and 66 % for the PIE samples A, B, C and D respectively as shown in
Fig. 6. The obtained COD reduction was higher as compared to that
observed with only use of ozone or hydrogen peroxide.
Kepa et al. (2008) studied the efficiency of H2 O2 + O3 process
for removal of cyanide from water. It was reported that the elimi-
nation of cyanides from water to the permissible level of drinking
water could be achieved with the combination involving optimum
loadings of H2 O2 and Ozone (Kepa et al., 2008). Rosal et al. (2009)
studied the effect of O3 + H2 O2 on the effluent from secondary clar-
ifier of an urban sewage treatment plant. It was reported that high
removal efficiencies could be obtained for most of the pharmaceu-
ticals found in wastewater. The elimination of organic compounds
increased by adding periodic pulses of H2 O2 loading and nearly
complete mineralization was obtained in reaction time of 1 h (Rosal
et al., 2009). Hey et al. (2014) also confirmed that combination
of H2 O2 with ozone was beneficial. Comparison with literature
revealed that better efficacy of combined operation is obtained for
most effluents though the quantitative trends in terms of extent of
increase is different for specific cases as also demonstrated in the
present work.
3.5. Effect of combination of Fenton’s reagent and ultrasound
The combination of Fenton with ultrasound (Sono-Fenton or
US/Fenton) was also applied with an objective to increase the
degradation efficiency. Fenton process is based on the production
154 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157

Fig. 7. Combined ultrasound and Fenton’s reagent treatment of PIE samples with
varying initial COD (ppm). Experimental conditions: operating volume =100 mL,
Fig. 8. Combined ultrasound, ozone, and hydrogen peroxide treatment of PIE sam-
operation time = 120 min, pH = 2 ± 0.5, T = 30 ± 2 ◦ C, Ozone gas (400 mg/h), Fenton’s
ples with varying initial COD (ppm). Experimental conditions: operating volume
reagent ratio = 3:5.
=100 mL, operation time = 120 min, pH = 2 ± 0.5, T = 30 ± 2 ◦ C, ozone gas (400 mg/h),
H2 O2 loading = 1:5.
of highly reactive ˙OH radicals using combination of Ferrous sulfate
(FeSO4 ) and H2 O2 which is typically effective under acidic condi-
tions (Zhang et al., 2005). Use of ultrasound in combination can
increase rate constant for the reaction of ferrous ion Fe(II) with
H2 O2 to get oxidized into Fe(III) and result in enhanced generation
of ˙OH radicals as per the following reaction (Cesaro et al., 2013):
•
Fe2+ +H2 O2 → Fe3+ +−OH+ OH (5)

The breakage of complex formed in the Fenton mechanism due

to ultrasound effects also help in regeneration of Fe (II) giving
higher generation of oxidizing species.
In the current work, the ratio of FeSO4 to H2 O2 was kept con-
stant at 3:5 at an acidic pH of 2.5 ± 0.5. The initial color of the PIE
sample was dark blue and it was observed during the treatment
that the color changed to black and at the end of the treatment a
black residue was also formed. The COD reduction was found to
be 67 %, 69 %, 72 % and 73 % for PIE samples A, B, C and D respec-
tively as shown in Fig. 7. It can be clearly noticed here that the
maximum COD reduction obtained using US + H2 O2 + FeSO4 is 73
% as compared to only 37 %, 36 %, 14 % using US + O3 , US+ H2 O2
and US respectively for the specific case of sample D. Jawale and
Gogate (2008) also studied the effect of Fenton’s reagent in combi-
nation with ultrasound at different Triazophos:FeSO4 :H2 O2 ratios
and reported that the extent of degradation increases as the load-
ings of FeSO4 and H2 O2 are increased (generally higher degradation
was reported as compared to individual operations or combina-
tion with only hydrogen peroxide). It was also reported that in
90 min of reaction time, minimum ratio of (1:1:1) and maximum
of (1:2:4) gave 62.7 % and 92.2 % degradation of Triazophos respec-
tively (Jawale and Gogate, 2018).
3.6. Effect of combination of ultrasound, ozone and hydrogen
peroxide
In order to study the efficacy of the combined operation of ultra-
sound, ozone and hydrogen peroxide on the COD removal of PIE,
H2 O2 (at ratio of COD to H2 O2 as 1:5) was added to the PIE sample
and at the same time, ozone gas (400 mg/h) was purged into the
PIE sample in the presence of ultrasound. The treatment was con-
tinued for two hours and it was observed that the hybrid treatment
method gave a COD reduction of 66 %, 68 %, 70 % and 73 % for PIE
samples A, B, C and D respectively as per the data shown in Fig. 8.
The increase in the extent of COD reduction in combined oper-
ation of ultrasound, O3 and H2 O2 as compared to combination of
ultrasound with only O3 /H2 O2 is due to the combined effect of O3
and H2 O2 . The introduction of H2 O2 increases the probability of
•
reaction of O3 with H2 O2 to generate OH radicals. As discussed
in the earlier section, ˙OH radicals are powerful oxidants and have
Fig. 9. Combined ultrasound, Ozone and CuO treatment of PIE samples with varying
initial COD (ppm). Experimental conditions: operating volume =100 mL, operation
time = 120 min, pH = 2 ± 0.5, T = 30 ± 2 ◦ C, ozone gas (400 mg/h), CuO loading =0.3 g/L.
the potential of oxidizing most organic pollutants. The increased
•
rate of generation of OH radicals can also be due to the fact that
ultrasonic irradiations result in turbulence which further increased
the mass transfer rate of O3 and hence its utilization (Von Gunten,
2003). Effective degradation of Reactive red 198 at 200 mg/L ini-
tial concentration at an optimum H2 O2 loading of 0.03 M was also
reported by Karami et al. (2016) with extents of decolorization and
COD reduction as 100 % and 69 % respectively in 40 min of operat-
ing time at 125 W operating power of ultrasound in the presence of
ozone (Karami et al., 2016). The reported illustration confirms the
beneficial contribution of adding hydrogen peroxide and ozone to
give enhanced quantum of hydroxyl radicals.
3.7. Effect of using combination of ultrasound, ozone and cupric
oxide (CuO)
The main objective of this combined approach was to establish
the extent of COD reduction of PIE by using a catalyst in combination
with ultrasound and ozone. CuO provides a catalytic action for the
dissociation of ozone and hence was utilized in the present work.
In order to study the application of combined approach of ultra-
sound, ozone and CuO for the COD removal of PIE, cupric oxide in
quantity of 0.3 g/L was added in the PIE and treated with ozone gas
(fixed flow rate of 400 mg/h) and ultrasound for 2 h. The combined
treatment resulted in the COD reduction of 86 %, 89 %, 90 % and 92
% for PIE samples A, B, C and D respectively as shown in Fig. 9. It can
be noticed that a maximum of 92 % COD reduction was obtained as
compared to only 37 % using US + O3 which can due to the presence
 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157
Fig. 10. Comparison of different approaches for COD reduction of various PIE samples.
of CuO giving enhancement in active sites for the reaction to take
place or increased nucleation sites for cavity generation leading to
enhanced cavitational intensity.
Li et al. (2010) and Jiang et al. (2013) proposed two different
mechanisms for enhanced mineralization based on heterogeneous
catalytic ozonation: 1) The first mechanism explains that the oxi-
•
dation of an organic compound by ozone or OH takes place on the
surface of the catalyst which generates oxidation by-products and
then the by-products desorbed in the solution are further oxidized
by ozone or ˙OH radicals with higher ease. 2) The second mechanism
states that the adsorbed organic pollutant on the oxidized catalyst
is involved in the electron-transfer (metallic catalyst) reaction to
form organic radical species which are desorbed from the catalyst
•
and then get successively oxidized by OH or O3 in the bulk solu-
tion along with the formed intermediates, again with higher ease
(Li et al., 2010) (Jiang et al., 2013).
A similar study of combined treatment of ultrasound, ozone and
catalyst (ZnO and CuO) was reported by Barik and Gogate (2017)
where the treatment was carried out at various ozone loadings of
100, 200, 300 and 400 mg/h. The other fixed conditions applied
were 20 ppm initial concentration of 2, 4-DCP (2, 4- dichlorophe-
nol), pH of 7, temperature of 30 ± 2 ◦ C and continuous US power
dissipation of 150 W. It was reported that US + O3 + ZnO treatment
at an optimum loading of ZnO as 0.1 g/L and US + O3 + CuO treatment
at an optimum loading of CuO as 0.08 g/L gave 95.66 % and 97.03 %
degradation of 2, 4-DCP respectively. The obtained results in their
work also established that the combination treatment approach
of US + O3 (flow rate of 400 mg/h) + CuO (loading of 0.08 g/L) was
the most effective treatment approach, with significantly intensi-
fied extent of degradation when compared to US alone (Barik and
Gogate, 2017). Liu et al. (2009) studied the degradation of phenol
using US/O3 /coal ash and reported that with the increased dosage
of coal ash from 0.2 to 0.6, 1.0, 2.0 and 3.0 g/L, the kinetics constant
(k) increased from 5.5 × 10−3 to 6.6 × 10−3 , 7.9 × 10−3 , 8.6 × 10−3 ,
and 9.5 × 10−3 min−1 , respectively. It is important to note that the
observed intensification depends on the type of catalyst as well
as the pollutant in question directing the importance of detailed
investigation elucidated in the present work.
3.8. Comparison of different approaches
Comparative data presented in Fig. 10 for different approaches
suggests that the hybrid approach for the treatment of PIE resulted
in the higher amount of COD reduction. Ultrasound in combination
with Fenton’s reagent and in combination with ozone and cata-
lyst (CuO) resulted in COD reduction of 73 % and 92 % respectively
155
•
which can be due to the enhancement in generation OH radicals
with a complimentary effect of ozone and CuO catalyst. Ozone in
combination with only ultrasound gives only 37 % COD reduction,
but when ozone and ultrasound are used in combination with a
catalyst which provides more specific surface area for oxidation
of pollutants, much higher extent of COD reduction i.e., 92 % is
obtained. US + O3 + CuO resulted in the maximum COD reduction
of 92 % as compared to only US, US + H2 O2 , US + O3 , O3 + H2 O2 ,
US + O3 + H2 O2 and US + Fenton which resulted in 14 %, 36 %, 37 %,
66 %, 73 % and 73 % respectively as the COD reduction. The above
results give insight into the fact that the effectiveness of differ-
ent combinations of AOPs depends on the type of effluents to be
treated.
Typically the COD reduction of PIE varied with chemical char-
acteristics, especially in terms of initial COD and salt contents.
Moreover, the combination approach also affected the degree of
mineralization. For example, US + O3 resulted in slightly better
treatment efficacy as compared to US + H2 O2 for removal of phar-
maceutical compounds from the PIE in the present work.
3.9. Intermediate analysis
The intermediate analysis was based on HRLC-MS and done
for the best treatment approach of combination of ultrasound
with ozone (400 mg/h) and CuO at an optimum loading of CuO
(0.3 g/L) for which the maximum COD reduction was achieved.
Two samples were analysed, one was without any treatment
and the second sample was after treatment by the combined
approach of ultrasound, ozone and CuO. The compounds detected
in the non- treated PIE sample were Gatifloxacin (molecular mass
of 375.4 g), Meperidine acid (molecular mass of 219.3 g), Barbi-
turic acid (molecular mass of 128.1 g), Normeperidine (molecular
mass of 233.3 g), l-Methamphetamine (molecular mass of 149.2 g),
Atenolol (molecular mass of 266.3 g), Warfarin (molecular mass of
308.3 g), Proglumide (molecular mass of 334.4 g), Cetirizine (molec-
ular mass of 388.9 g), Losartan (molecular mass of 422.9 g) and
Sulfamethazine (molecular mass of 278.3 g). The obtained peaks
for the main pollutants in the untreated PIE sample are depicted
in Fig. 11. The by-products/intermediates detected in treated PIE
sample were 4-(2-hydroxy-3- isopropyl aminopropyl) benzoic acid
(molecular mass of 253 g), 9-amino-nonanoic acid (molecular mass
of 173.2 g), Barbituric acid (molecular mass of 128.1 g) and Phyllo-
quinone (Vitamin K1, molecular mass of 450.7 g) as shown in Fig. 12.
The compounds present in the treated PIE sample were derivatives
of carboxylic acid and mainly lower molecular weight compounds
as compared to the different compounds present initially. The con-
156 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157

Fig. 11. Identification of main pollutants in PIE sample by HR-LCMS before treatment. (a) Gatifloxacin, (b) Meperidinic acid, (c) Barbituric acid, (d) Normeperidine, (e)
l-Methamphetamine and (f) Atenolol.

Fig. 12. Identification of pollutants in PIE sample by HR-LCMS after combined treatment of US+H2 O2 +CuO. (a) 4-(2-hydroxy-3- isopropyl aminopropyl) benzoic acid, (b)
9-amino-nonanoic acid, (c) Barbituric acid and (d) Phylloquinone (Vitamin K1).

version of the initial complex nature of the compounds to simple tant requirement considering the possible application of AOPs as
lower chain compounds also clearly mean that the offered toxicity pretreatment to biological oxidation. It can be thus concluded that
to the microorganism will be considerably reduced, a very impor- the combination of US + O3 + H2 O2 can be effectively utilized for
 S. Chandak et al. / Process Safety and Environmental Protection 137 (2020) 149–157
the treatment of PIE removing the initial complex pharmaceutical
compounds present in the wastewater effectively.
4. Conclusions
The present work demonstrated the effectiveness of ultrasound
in combination with oxidizing agents and/or catalysts for the treat-
ment of PIE samples. Combination of ultrasound with ozone and
H2 O2 as well as combination of ultrasound with Fenton’s reagent
resulted in the enhanced extent of degradation as compared to indi-
vidual approaches. Combination of ultrasound with ozone and CuO
resulted in 92 % as the maximum COD reduction at CuO loading of
0.3 g/L during 120 min of treatment.
The use of different approaches for treatment suggested that
ultrasound alone is not very effective in degrading pharma-
ceutical pollutants. Treatment along with catalyst and chemical
oxidizing agents is indeed more effective. For example, US + O3 +
CuO approach resulted in high COD reduction levels (86–92 %)
for all the four effluent samples spanning a 15-fold difference
(7500−500 ppm) in the initial COD levels.
Observation of the above results proves that the combined
approach of US + O3 + CuO can be utilized for the treatment of indus-
trial effluents and can be an effective treatment scheme. The dual
oxidation mechanism of ozone and hydroxyl radicals plays a vital
role in the treatment of effluents and the CuO acts as a catalyst to
•
provide active sites for the degradation as well as for enhanced OH
radical generation, finally giving best results for treatment.
Declaration of Competing Interest
The authors declare that there are no conflicts of interest.
Acknowledgements
Authors would like to acknowledge the support of IPCA, in par-
ticular Dr. Ashok Kumar and personnel at Ratlam site, for providing
samples and help in understanding the effluent characteristics.
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