Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-024-32605-6

RESEARCH ARTICLE

Efficient treatment of veterinary pharmaceutical industrial wastewater

by catalytic ozonation process: degradation of enrofloxacin
via molecular ozone reactions
Amir Ikhlaq1 · Zafar Masood1 · Umair Yaqub Qazi2 · Muhammad Raashid3 · Osama Shaheen Rizvi1,4 ·
Hafiz Abdul Aziz5 · Muhammad Saad6 · Fei Qi7 · Rahat Javaid8

Received: 2 November 2023 / Accepted: 19 February 2024

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2024

Abstract
The study focused on the efficacious performance of bimetallic Fe-Zn loaded 3A zeolite in catalytic ozonation for the
degradation of highly toxic veterinary antibiotic enrofloxacin in wastewater of the pharmaceutical industry. Batch experi-
ments were conducted in a glass reactor containing a submerged pump holding catalyst pellets at suction. The submerged
pump provided the agitation and recirculation across the solution for effective contact with the catalyst. The effect of ozone
flow (0.8–1.55 mg/min) and catalyst dose (5–15 g/L) on the enrofloxacin degradation and removal of other conventional
pollutants COD, B ­ OD5, turbidity was studied. In batch experiments, 10 g of Fe-Zn 3A zeolite efficiently removed 92% of
enrofloxacin, 77% of COD, 69% B ­ OD5, and 61% turbidity in 1 L sample of pharmaceutical wastewater in 30 min at 1.1 mg/
min of ­O3 flow. The catalytic performance of Fe-Zn 3A zeolite notably exceeded the removal efficiencies of 52%, 51%, 52%,
and 59% for enrofloxacin, COD, B ­ OD5, and turbidity, respectively, achieved with single ozonation process. Furthermore,
an increase in the biodegradability of treated pharmaceutical industrial wastewater was observed and made biodegradable
easily for subsequent treatment.

Keywords Catalytic ozonation · Enrofloxacin · 3A Zeolite · Bimetallic catalyst · Pharmaceutical wastewater

Responsible Editor: Guilherme Luiz Dotto

1
* Rahat Javaid Institute of Environmental Engineering, University
RQAZI@mailbox.sc.edu of Engineering and Technology, Lahore 54890, Pakistan
2
Amir Ikhlaq Department of Chemistry, College of Science, University
aamirikhlaq@uet.edu.pk of Hafr Al Batin, P.O Box 1803, Hafr Al Batin 39524,
Kingdom of Saudi Arabia
Zafar Masood
3
engineerzafar71@gmail.com Chemical Engineering Department KSK Campus, University
of Engineering and Technology, Punjab, Pakistan
Umair Yaqub Qazi
4
umairqazi@uhb.edu.sa Department of Chemistry and Chemical Engineering, Syed
Babar Ali School of Science & Engineering, (SBASSE),
Muhammad Raashid
Lahore University of Management Sciences (LUMS), Sector
Engr_raashid@uet.edu.pk
U, DHA, Lahore Cantt 54792, Pakistan
Osama Shaheen Rizvi 5
Baariq Pharmaceuticals, Sundar Industrial Estate, Lahore,
osama.rizvi@lums.edu.pk; osr677@gmail.com
Pakistan
Hafiz Abdul Aziz 6
Lahore Waste Management Company, Lahore, Pakistan
Aziz_chemist@hotmail.com
7
Beijing Forestry University, Haidian District, No. 35 Qinghua
Muhammad Saad
East Road, Beijing 100083, People’s Republic of China
muhammadsaad.76@gmail.com
8
University of South Carolina, Columbia, SC 29208, USA
Fei Qi
qifei@bjfu.edu.cn

Vol.:(0123456789)

Introduction
It is need of time to control water contamination and
conserve water quality by introducing green technolo-
gies (Javaid et al. 2016; Rizvi et al. 2022). Pharmaceu-
tical active compounds (PhACs) released in wastewater
by pharmaceutical industries have a wide range of side
effects on the marine environment, even at environmen-
tally permissible concentrations (Klavarioti et al. 2009;
Schwarzenbach et al. 2006; Sirés and Brillas 2012) and
conventional wastewater treatment plants are inept for the
treatment of antibiotics and being released into the envi-
ronment (Michael et al. 2013). An increase in endocrine
disruption of aquatic organisms and resistance in multi-
strains are observed in the release of PhACs compounds
in aquatic environments. PhACs are being emancipated by
different sources; the pharmaceutical industry and munici-
pality are the main sources releasing PhACs continuously
(Christou et al. 2018; Deegan et al. 2011; Khetan and Col-
lins 2007). Antibiotics have become the reason to gain
considerable attention worldwide as they cause the pollu-
tion of the marine environment. and antibiotics containing
wastewater should be processed appropriately before being
released into the environment to protect water reservoirs
and environments. Antibiotics are considered emerg-
ing contaminants due to their enormous consumption in
medicines and agriculture. Among them, enrofloxacin
recognized as a highly ecotoxic veterinary antibiotic has
the potential to pose significant health threats to humans
(Ghatak 2014; Wei et al. 2022).
Pharmaceutical wastewater containing antibiotics can-
not be effectively treated using stand-alone biological
processes due to the highly persistent nature of antibiot-
ics and are non-biodegradable (Masood et al. 2023). Over
the years, various advanced oxidation processes (AOPs)
that lead to the production of reactive oxygen species
have been utilized for the treatment of municipal (Ikhlaq
et al. 2019; Ikhlaqa et al. 2019) and numerous industrial
wastewater including pharmaceutical (Masood et al. 2022,
2023), textile (Bilińska et al. 2016; Rizvi et al. 2022), dyes
(Babar et al. 2022; Ikhlaq et al. 2019; Javaid et al. 2021;
Javaid et al. 2016), pulp and paper (Munir et al. 2019;
Munir et al. 2022).
Although the AOPs are considered complicated and
costly techniques for treating refractory organic contami-
nants in wastewater, their application is still inevitable.
The prominent feature of the ozonation process, among
several other AOPs, is that it operates at ambient pres-
sure and temperature, and it does not produce any sludge
while disintegrating the organic compounds in industrial
effluents (Rizvi et al. 2022). Ozone ­(O3) is proven as the
Environmental Science and Pollution Research
most effective oxidant for the treatment of industrial efflu-
ents (Ikhlaq et al. 2022; Rizvi et al. 2022) and frequently
studied with different metal-coated zeolites Ni-Co Zeo-
lite 5A° and Fe Zeolite A as catalysts for the removal of
toxic antibiotics and may improve the biodegradation of
pharmaceutical wastewater so it could be applied as pre-
biological treatment method (Ikhlaq et al. 2020; Masood
et al. 2023). In recent years, catalytic ozonation process
has gained the attention of researchers as it has the quality
to enhance the efficacy of ozonation treatment process.
Catalysts can stimulate ­O 3 disintegration and produce
free radicals, which can improve the deprivation and min-
eralization of organic contaminants. In catalytic ozona-
tion, the organic compounds are affected by two different
methods: (1) direct impact of ozone molecules, and (2)
highly oxidative hydroxyl radicals (•OH) are being gen-
erated due to the indirect free radical mechanism. Ozone
molecules extinguish aromatic rings to form intermediates
like small-chain carboxylic acids, aldehydes, and ketones
by degrading the aromatic organic contaminants (Masood
et al. 2022).
This study is the continuation of the author’s previous
studies to explore the efficacy of metals-loaded zeolites cata-
lytic ozonation for the degradation of veterinary antibiotic in
pharmaceutical wastewater. However, the authors’ previous
studies applied various types of metals coated zeolites as
catalysts in catalytic ozonation (Masood et al. 2022, 2023).
The objective of the current study was to examine the effi-
cacy of bimetallic-loaded zeolite as catalyst in the catalytic
ozonation for the reduction of highly ecotoxic veterinary
antibiotic enrofloxacin in real pharmaceutical wastewater.
For the first time, iron and zinc were loaded on 3A Zeo-
lite and applied as a catalyst in catalytic ozonation for the
treatment of real pharmaceutical wastewater, degradation of
enrofloxacin and removal of conventional pollutants COD
(chemical oxygen demand), turbidity and B ­ OD5 (biologi-
cal oxygen demand) were studied. We conducted an exten-
sive study and spiked the enrofloxacin in pharmaceutical
wastewater for the optimization of operational parameters.
Moreover, the increase in the biodegradability (BOD/COD
ratios) of real pharmaceutical wastewater was studied. An
innovative approach has been applied in this research work
using a catalyst of multi-metal loaded Fe-Zn 3A zeolite, situ-
ated in the suction of a submersible pump. This pump was
then positioned at the bottom of the reactor for the recircu-
lation of wastewater. The effect of operational factors such
as ozone flow, catalyst dose, and pH were evaluated. This
study may help further to find an efficient catalyst in the
catalytic ozonation of antibiotics degradation in pharmaceu-
tical wastewater.
Environmental Science and Pollution Research

Materials and methods
Sampling
The Institute of Environmental Engineering and Research
(IEER), UET Lahore, has research collaboration with Fizi
Pharmaceuticals. Fizi pharmaceutical industry provided
wastewater samples from its effluent tank. Collected samples
were transported to IEER Laboratory for characterization.
The characterization results are presented in Fig. 1. After
characterization, 100 mg/L of enrofloxacin was spiked in
wastewater samples. The concentration of pollutants before
and after treatment was measured by standard methods of
water and wastewater examination (Rice et al. 2012). The
pH of samples was measured by Hanna HI- 9811, USA, and
turbidity was measured in NTU by HACH 2100 P, USA.
Material
3A zeolite was used as a catalyst in this study and was
obtained from Panreac Quimica (Barcelona). Bimetallic
coating of Fe and Zn was carried out on the surface of 3A
zeolite ­(Al12K12.O48Si12.H2O). Analytical-grade chemicals
and deionized water were utilized to perform experimental
work.
Catalyst preparation
The impregnation technique was applied to coat the surface
of 3A zeolite with a bimetallic layer of Fe and Zn, following
the process outlined in the literature (Ikhlaq et al. 2023). In
Pharmaceutical Wastewater Characterization
1400
1237
1281
1200 1135
1098
Pollutants Concentration
this process, 9.0 g each of Ferric Sulfate hydrated and Zinc
oxide were measured with electronic weighing balance and
then dissolved both salts in 120 mL deionized water. After-
ward, 30 g of 3A zeolite was added to this salt solution of
Fe and Zn and stirred at a speed of 120 rpm at 102 °C tem-
perature to completely evaporate the water. Then, this Fe
and Zn-impregnated zeolite was dried at 105 °C for 2 h and
calcined at 550 °C for 6 h (Ikhlaq et al. 2023). Following the
calcination process, the desiccated catalyst was immersed
in a 0.1 M nitric acid solution for 24 h. Then, the washing
of the catalyst was carried out with distilled water until a
constant pH of the water was obtained. Finally, the catalyst
was dried in an oven at 105 °C for 2 h. Figure 2 presents the
schematic for bimetallic Fe/Zn impregnation on the surface
of 3A zeolite.
Since, one of the parameters to measure the efficacy of
our process was the removal efficiency of COD. The COD
measurement may interfere with the presence of nitrates and
chlorides in water. Hence, the leaching out of nitrates and
chlorides in water may affect the analysis. Therefore, in the
current investigation, we used iron sulfate in the impreg-
nation method. Since, the iron was found to have active
sites on zeolite surfaces (in catalytic ozonation processes)
as reported by previous findings (Ikhlaq et al. 2019; Munir
et al. 2022). Therefore, sulfates may not play a significant
role in the interaction of molecular ozone on the catalyst
surface. Even the sulfates present on the catalyst or leach out
from the catalyst may be in a very minute quantity and may
not exert a notable impact on the overall efficacy of the pro-
cess. In the current investigation, we used a real wastewater
matrix that may have a reasonable amount of sulfate as com-
pared to the sulfate leaching out from the catalyst surface.
The results presented in the current study clearly sug-
gested that the studied catalytic process have significantly
higher removal efficiencies of enrofloxacin in real wastewa-
1277 ter matrix that may contain hydroxyl radical scavengers such
as sulfates, nitrates, chlorides, phosphates, carbonates, bicar-
bonates, etc. Since the removal mechanism of enrofloxacin

1000 dominates molecular ozone-based catalytic reactions, hence

843 837 the presence of hydroxyl radical scavengers may not have a
769
800 714 694
remarkable effect on enrofloxacin removal.

600 Experimental setup and procedure

377 393 376 389 373
400
The wastewater treatment process arrangement is given in
Fig. 3. The reactor was made of Pyrex glass. A pump was
200 150
80
submerged in wastewater, whereas the Fe/Zn loaded zeo-
0
lite catalyst was employed at the suction of pump so that
Week 1 Week 2 Week 3 Week 4 Week 5 PEQs wastewater could only enter the pump after passing through
COD mg/L BOD mg/L Turbidity NTU the catalyst. Ozone generator delivered the ozone via the
ceramic sparger placed at the bottom of the reactor, which
Fig. 1  Characterization results of veterinary pharmaceutical wastewa- generated microbubbles in the reactor. For each batch, 1 L
ter of pharmaceutical wastewater sample poured in the reactor.
 Environmental Science and Pollution Research

3A Zeolite Metal salt

Furnace
Evaporation of Deionized
water at 102ºC
Drying at Calcination at
105ºC 550ºC

105 ºC
Washing of catalyst with dislled water

Oven Drying Dipping in Acidic

Soluon (24 h)

Fig. 2  Schematic presentation for bimetallic Fe/Zn impregnation on 3A zeolite

Fig. 3  Schematic presenta-

tion for catalytic ozonation 2
setup for wastewater treatment

11 7

Treated samples were collected for analysis at various time
intervals.
Results and discussion
Catalyst characterization
A Micromeritics USA ASAP 2020 analyzer was utilized to
analyze the pore size and surface area of Fe-Zn 3A zeo-
lite with the BET BJH method. Initially, the surface area of
the non-coated catalyst was 9.2 ­m2/g, whereas after coat-
ing, surface areas increased up to 37.5 ­m2/g, and the pore
volume of the non-coated catalyst was 3.0 cc/g, whereas
coated catalyst pore volume was 12.4 cc/g. To assess the
isoelectric point which was 6.7 ± 0.4, it was measured with
mass transfer method (Balcıoğlu and Ötker 2003). Table 1
shows the physical characteristics of the bimetallic Fe/Zn-
loaded zeolites.
Figure 4 a and b demonstrates the FTIR spectra for 3A
zeolite before metal loading and after Fe and Zn impreg-
nation respectively. The appearance of new peaks for Fe
Environmental Science and Pollution Research

Table 1  Characteristics of bimetallic Fe/Zn loaded 3A zeolite For the elemental analysis of Fe-Zn 3A Zeolite, INSPECT
Descrip- BET Pore Fe (wt%) Zn Pore Dia.
S50 by FEI was utilized. Figure 5 a and b exhibits the EDX
tion area volume(cc/g) (wt%) (nm) mapping for 3A zeolite before and after bimetallic Fe/Zn
­(m2/g) coating respectively. EDX mapping indicates the presence
of 22.7% Fe and 42.9% of Zn on loaded 3A zeolite surface
Non- 9.2 3.0 – – 5.4
coated (Fig. 5b). Figure 5 a and b shows the SEM images of 3A
cata- zeolite before and after and bimetallic Fe/Zn loading respec-
lyst tively. The SEM images were taken at 500 magnifications.
Coated 37.5 12.4 22.6 42.9 5 According to the SEM images, the crevice-type structure
cata-
on the surface was observed for both (3A zeolite before
lyst
and after bimetallic Fe/Zn coating) at a scale of 300 μm.
No notable change was noticed on the surface or structural
morphology of 3A zeolite bimetallic Fe/Zn coating (Fig. 6).
and Zn in the FTIR spectrum (Fig. 4b) after metal load-
ing indicates the incorporation of metals on 3A zeolite. Effect of ozone flow
At 473 ­cm−1, a new peak assigned to Fe that corresponds
to Fe–O–Fe stretching vibrations as the FTIR region for Figure 7b showed that the reduction in COD up to 52%,
Fe–O–Fe stretching vibration is suggested as 462–560 ­cm−1 59%, and 62% was attained with varying ozone flows 0.88,
(Amir et al. 2018). Likewise, another peak at 660 ­cm−1 was 1.1, and 1.55 mg/min, respectively. Turbidity also declined
assigned to Zn that corresponds to zinc oxide stretching from the initial value of 355 to 197, 171 NTU, and 162 NTU
vibrations (Jayarambabu et al. 2014). with 45%, 52%, and 56% removal with different ozone flows

Fig. 4  FTIR spectra of a) 3A

zeolite, b) Fe/Zn-loaded 3A
zeolite
 Environmental Science and Pollution Research

Fig. 5  EDX analysis of a) 3A zeolite, b) Fe/Zn-loaded 3A zeolite

Fig. 6  SEM micrographs of a

3A zeolite, b Fe/Zn-loaded 3A
zeolite

(a) Ozone Flow Optimization (b) Ozone Flow Optimization

60
62 62
56
60
55 59
52 58
Removal Efficiency %

Removal Efficiency %

50
56 56
55
54

45
52 52 52
51
50

40 48

46
35 45
35 44
43
42
0.8 1.0 1.2 1.4 1.6 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
Ozone Flow (mg/min) Ozone Flow (mg/min)
Enrofloxacin R.E% COD R.E % BOD R.E % Turbidity R.E %

Fig. 7  Effect of ozone flow ­(O3 = 0.88 mg/min, 1.1 mg/min, and 1.55 mg/min; COD = 1277 ± 100 mg/L, ­BOD5,0 = 769 ± 75 mg/L, initial tur-
bidly = 373 ± 20 NTU, volume = 1 L; Enrofloxacin = 100 mg/L; time = 30 min; temperature = 25 ± 2 °C; pH = 7. 1 ± 0.2)
Environmental Science and Pollution Research

(Fig. 7b). ­BOD5 decreased significantly from 61 to 69% on
increasing ozone dosage from 0.88 to 1.1 mg/min. A further
increase in ozone dosage to 1.55 mg/min did not enhance
efficiency effectively, resulting in a 71% BOD removal
(Fig. 7b). Likewise, it is worth mentioning that the removal
efficiency of enrofloxacin increased abruptly from 35 to 52%
on increasing ozone flow from 0.88 to 1.1 mg/min (Fig. 7a).
Whereas a further rise to 1.55 mg/min slightly increased
the removal efficiency to 56%. Therefore, an ozone flow of
1.1 mg/min was chosen as an optimized ozonation rate.
Effect of catalyst dose
Figure 8 presents the influence of Fe-Zn bimetallic 3A zeo-
lite catalyst dose on removal efficiency at optimum ozone
flow of 1.1 mg/min. According to the results (Fig. 8b), an
increase in the dose of Fe-Zn 3A zeolite as a catalyst from 5
to 10 g/L efficiently decreased the COD, B ­ OD5, and turbid-
ity. A further increase in Fe-Zn 3A zeolite dose to 15 g/L
lead to insignificant increase in pollutants removal. For
instance, COD removal efficiency increased from 68 to 77%
on increasing the Fe-Zn 3A zeolite dose from 5 to 10 g/L.
Whereas slightly increased to 80% on 15 g/L. Similarly, the
removal efficiencies for B­ OD5 and turbidity increased sig-
nificantly from 61 to 69% and 52 to 61%, respectively, with
increasing dose from 5 to 10 g/L. Figure 8a shows similar
trends for the degradation of enrofloxacin, where an increase
in catalyst dose from 5 to 10 g/L dramatically enhanced the
removal up to 92%, but a further increase to 15 g/L only 4%
removal increased and maximum removal was 96%. There-
fore, a Fe-Zn 3A zeolite dose of 10 g/L was chosen as the
optimal dosage.
Comparison of treatment processes
Figure 9 depicts a comparison in removal efficacy of single
ozonation and catalytic ozonation. Based on the findings,
the catalytic ozonation process demonstrated greater effi-
ciency compared to the ozonation process. Ozonation could
only achieve maximum removal of 59%, 52%, and 51%, for
turbidity, ­BOD5, and COD, respectively. Whereas relatively
higher removal efficiencies of 61%, 69%, and 77% were
attained for turbidity, BOD, and COD, respectively, with
catalytic ozonation process using Fe/Zn bimetallic loaded
3A zeolite (Fig. 9b). The higher removal efficiency of cata-
lytic ozonation for such pollutants could be attributed to the
efficient production of hydroxyl radicals (•OH). Catalytic
ozonation resulted in higher efficiency for the degradation
of enrofloxacin in pharmaceutical wastewater than the single
ozonation (Fig. 9a). Enrofloxacin maximum removal of 92%
was achieved by catalytic ozonation, which is significantly
higher than 52% removal achieved by ozonation. It could be
attributed due to the molecular ozone reactions which are
dominant in catalytic ozonation on enrofloxacin degrada-
tion (Dodd et al. 2006; Von Sonntag and Von Gunten 2012).
Effect of the treatment process on the pH
of the solution
During pharmaceutical wastewater treatment by ozona-
tion, change in pH was insignificant, while in the presence
of catalytic ozonation, rise in pH was slightly high, but
it still followed national environmental quality standards
(NEQS) (Table 2). Since there was no notable alteration
in pH observed, there was no need for pH adjustments

(a) Catalyst Dose Optimization (b) Catalyst Dose Optimization

100 96
92 80 80
90
77
75
Removal Efficiency %

80
Removal Efficiency %

70
71
70 69
68
60 65
64
50
60
61 61

40
34 55

30 52
50
0 5 10 15 20 0 5 10 15 20
Catalyst Dose (g/l) Catalyst Dose (g/l)
Enrofloxacin R.E% COD R.E % BOD R.E % Turbidity R.E %

Fig. 8  Effect of catalyst dose (catalyst dose = 5 g/L, 10 g/L and 15 g/L; ­O3 = 1.1 mg/min; ­COD0 = 1277 ± 100 mg/L, ­BOD5,0 = 769 ± 75 mg/L,
initial turbidly = 373 ± 20 NTU, volume = 1 L; Enrofloxacin = 100 mg/L; time = 30 min; temperature = 25 ± 2 °C; pH = 7. 1 ± 0.2)
 Environmental Science and Pollution Research

(a) Process Comparison (b) Process Comparison

100
92 80 77

70 69
80
Removal Efficiency %

61
60 59

Removal Efficiency %
51 52
60 50
52
40
40
30

20
20
10

0 0
Ozonation Catalytic Ozonation Ozonation Catalytic Ozonation

Enrofloxacin R.E% COD R.E % BOD R.E % Turbidity R.E %

Fig. 9  Comparison of treatment processes ­(O3 = 1.1 mg/min; catalyst dose = 10 g/L; ­COD0 = 1277 ± 100 mg/L, ­BOD5,0 = 769 ± 75 mg/L, initial
turbidly = 373 ± 20 NTU, volume = 1 L; Enrofloxacin = 100 mg/L; time = 30 min; temperature = 24 ± 2 °C; pH = 7. 1 ± 0.2)

Table 2  Treatment process effect on pH Proposed mechanism

Initial pH After ozonation After catalytic ozonation PEQS
Ozone directly targeted the organic pollutants, breaking
7.1 ± 0.2 7.3 ± 0.2 7.5 ± 0.2 6–9 them down into C­ O2 and H
­ 2O. On the other hand, in radical-
based reactions, hydroxyl radicals (•OH) were generated,
which then attacked COD and organic pollutants (Fig. 10).
during both the ozonation and catalytic ozonation pro- The presence of catalyst Fe-Zn 3A zeolite in catalytic
cesses (Masood et al. 2022). The initial pH of pharmaceu- ozonation allowed its surface to facilitate the interactions
tical wastewater was 7.1, which increased to a maximum between ozone and pollutants. Ozone disintegrated on cata-
observed pH of 7.5 (Table 2). lyst surface and transformed into •OH radicals, and these
radicals attacked organic and inorganic pollutants existing

Fig. 10  Schematic process of

ozonation and catalytic ozona-
tion processes
Environmental Science and Pollution Research
in wastewater (Masood et al. 2022). Hydroxyl radicals act
as effective oxidants to degrade the contaminants in waste-
water treatment because these are non-selective species and
instantly disintegrate organic compounds (Masood et al.
2022).
It is indeed important to mention here that enrofloxacin
due to its structure may have high rates of reaction with
molecular ozone as compared with hydroxyl radicals (Dodd
et al. 2006; Von Sonntag and Von Gunten 2012) which may
suggest molecular ozone reactions may be dominant as com-
pared with hydroxyl radicals for the removal of enrofloxacin
in wastewater. On the other hand, in the current investiga-
tion, catalytic ozonation was found to have higher removal
efficiency of enrofloxacin compared to single ozonation
(catalytic ozonation: 92% and ozonation: 52%). The previ-
ous findings suggested that in the case of zeolite catalytic
ozonation processes, both molecular ozone reactions, as well
as hydroxyl radicals-based reactions, may be involved in pol-
lutant removal (Dong et al. 2008; Ikhlaq et al. 2014; Ikhlaq
and Kasprzyk-Hordern 2017; Ikhlaq et al. 2018; Valdés et al.
2009; Valdés et al. 2012). Some studies indicate that only
molecular ozone-based mechanisms may be dominant for
a particular pollutant when zeolites are used as a catalyst
(Ikhlaq et al. 2014; Ikhlaq and Kasprzyk-Hordern 2017;
Ikhlaq et al. 2018). While others suggested that hydroxyl
radicals-based mechanisms may be important in such pro-
cesses (Dong et al. 2008; Valdés et al. 2009; Valdés et al.
2012). In the current investigation, higher removal in the
case of catalytic ozonation processes may be due to the typi-
cal mechanism of a catalyst, where the catalyst provides its
surface for reactants. Hence, the surface reactions on a cata-
lyst may lower the overall activation energy as compared to a
non-catalytic process. Therefore, it has been hypothesized in
the current investigation that molecular ozone may adsorb on
catalyst surface leading to the reactions of molecular ozone
and enrofloxacin on catalyst surface that leads to the high
Fig. 11  Hydroxyl scavenger effect for a) enrofloxacin degradation and b) COD removal ­(O3 = 1.1 mg/min; Fe/Zn 3A Zeolite dose = 10 g/L;
­ ODo = 1365 ± 100 mg/L; Enrofloxacin = 100 mg/L; TBA = 50 mg/L; volume = 1 L; pH = 7. 1 ± 0.3; time = 30 min; T = 24 ± 2 °C)
C
removal efficiency of enrofloxacin in the catalytic ozonation
process as compared to single ozonation. The TBA effect
results presented in the current study further confirm that
molecular ozone reactions are dominant in catalytic ozona-
tion on enrofloxacin. For example, the percent decrease in
removal efficiencies of enrofloxacin in the case of single
ozonation and catalytic ozonation may not be significantly
different when TBA was introduced (Fig. 11a) (Ikhlaq et al.
2014; Ikhlaq and Kasprzyk-Hordern 2017; Ikhlaq et al.
2018). Moreover, it is also useful that the studied catalyst
may also promote hydroxyl radicals production that helps to
reduce the overall COD in real pharmaceutical wastewater.
Since various byproducts formed and natural organic matter
in wastewater may depend on free radicals mechanism. The
results presented in the current investigation further confirm
our hypothesis as the substantial disparity in COD removal
efficiency with and without TBA for ozonation (9%) and
catalytic ozonation (22%) was observed (Fig. 11b).
Conclusions
The findings of this study demonstrated the high effective-
ness of catalyst Fe-Zn 3A zeolite in catalytic ozonation for
the degradation of enrofloxacin along with the high removal
of other pollutants such as COD, ­BOD5, and turbidity in
pharmaceutical industry wastewater. At optimum conditions,
1.1 mg/min of ozone flow, the ozonation process resulted in
removal efficiencies of COD, ­BOD5, and turbidity as 59%,
51%, and 52%, respectively, which remarkably increased to
77%, 69%, and 61% in the presence of an optimum cata-
lyst dose (10 g/L) in 30 min of reaction duration. Moreo-
ver, biodegradability (­ BOD5/COD ratio) of pharmaceutical
wastewater increased from 0.60 to 0.81. The results indi-
cate that the application of modified heterogeneous catalyst
may be used efficiently in the pharmaceutical industry as

pretreatment before biological treatment to achieve NEQS
within a shorter timeframe and reduce the environmental
footprint as compared to traditional treatment technologies.
Notably, the removal of enrofloxacin significantly enhanced
from 52% (single ozonation) to 92% with Fe/Zn 3A zeolite
as catalyst in catalytic ozonation. According to the results
obtained under this research, the removal efficiency of enro-
floxacin was comparatively higher using Fe-Zn 3A zeolite
catalyst than those reported in the authors’ previous research
work in which a removal efficiency of 76% was attained in
catalytic ozonation (Masood et al. 2023). This proves to be
an effective process and has potential in real-world applica-
tions. In the current investigation, T-butanol, a well-known
hydroxyl scavenger, was employed to investigate the mecha-
nism of enrofloxacin degradation. The efficacy of catalytic
ozonation process may not be significantly decreased, and
it was 92% (without TBA) and reduced to 83% (with TBA).
Interestingly, the comparison of single ozonation and cata-
lytic ozonation with and without TBA suggested that the
decrease in enrofloxacin removal was not significantly
higher case of catalytic ozonation as compared to single ozo-
nation, which confirms the catalytic effect in such processes
via molecular ozone reactions. While the removal of COD
may depend on free radicals mechanism since Fe/Zn 3A
zeolite may also promote hydroxyl radicals (•OH) formation
that assists to reduce the overall COD in real pharmaceutical
wastewater. The notable difference of 22% was observed in
COD removal efficiency with and without TBA in the case
of catalytic ozonation and for single ozonation it was 9%.
Acknowledgements The authors would like to acknowledge/thank the
heads of the collaborating organizations, PSF, IEER UET Lahore, and
BAARIQ Pharmaceutical.
Author contribution All the authors have contributed to making this
study publishable. The authors’ contribution is as follows: conceptu-
alization, A. Ikhlaq, U.Y. Qazi and R. Javaid; methodology, A. Ikhlaq,
O.S. Rizvi, Z. Masood, and F. Qi; validation, M. Raashid,, H.A.
Aziz, M. Saad, and F. Qi; formal analysis, O.S. Rizvi and Z. Masood;
resources, A. Ikhlaq, U.Y. Qazi, and R. Javaid; writing—original draft
preparation, O.S. Rizvi; writing—review and editing, A. Ikhlaq, O.S.
Rizvi, U.Y. Qazi, and R. Javaid; visualization, M. Raashid, O.S. Rizvi,
H.A. Aziz, M. Saad, and F. Qi; supervision, A. Ikhlaq, U.Y. Qazi, and
R. Javaid; project administration, U.Y. Qazi, A. Ikhlaq; funding acqui-
sition, A. Ikhlaq, and U.Y. Qazi. All authors have read and agreed to
the publication of the manuscript.
Funding Pakistan Science Foundation has provided the grant for this
research under the research project number PSF/CRP/18th protocol 12.
Data availability All data generated or analyzed during this study are
included in this article.
Declarations
Ethics approval and consent to participate Not applicable.
Consent for publication Not applicable.
Environmental Science and Pollution Research
Competing interests The authors declare no competing interests.
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