VIETNAM NATIONAL UNIVERSITY, HANOI

VIETNAM JAPAN UNIVERSITY

OLADELE HONOUR ADEDAYO

TREATMENT OF PHARMACEUTICAL
ANTIBIOTIC WASTEWATER USING
PHOTOCATALYTIC PROCESSES WITH
COMMERCIAL TiO2 POWDER

MASTER’S THESIS
 VIETNAM NATIONAL UNIVERSITY, HANOI
VIETNAM JAPAN UNIVERSITY

OLADELE HONOUR ADEDAYO

TREATMENT OF PHARMACEUTICAL
ANTIBIOTIC WASTEWATER USING
PHOTOCATALYTIC PROCESSES WITH
COMMERCIAL TiO2 POWDER

MAJOR: ENVIRONMENTAL ENGINEERING

CODE: 8520320.01

RESEARCH SUPERVISORS:
Dr. TRAN THI VIET HA
Associate Prof. Dr. NGUYEN MINH PHUONG

Hanoi, 2020
 ACKNOWLEDGMENT
I would like to express my deepest gratitude to my principal supervisor, Dr. Tran Thi
Viet Ha for her immense support, good recommendations, essential criticisms, great
feedbacks, and invaluable advice all through the period of this research. She has shaped
my learning experience and made me better. So also to my second supervisor, Associate
Prof. Nguyen Minh Phuong, Deputy Head, Lab of Environmental Chemistry, Faculty
of Chemistry, Hanoi University of Science, Vietnam, thank you for her timely
suggestion, her help, and necessary guidance in relation to this research.
Furthermore, I would like to specially appreciate Dr. Babatunde Koiki, Department of
Chemical Sciences, University of Johannesburg, DFC, South Africa for his constant
encouragement and immense absolute support throughout my study. Thank you so
much, I am deeply indebted.
In addition, I am grateful to VNU Vietnam Japan University, Ritsumeikan University,
both MEE teaching and non-teaching staff including Prof. Jun Nakajima, Prof. Cao The
Ha, Assoc. Prof Ikuro Kasuga, Assoc. Prof Sato Keisuke, Dr. Nguyen Thi An Hang for
the valuable teachings, opportunities, and devoted support throughout my Master’s
degree program at VJU.
Finally, I would like to express my heartfelt gratitude to my family and friends for their
prayers, massive loving support and relentless faith in me all through the period of my
study. You’re one in a million, this study would not have been accomplished without
them.

Thank you for making this dream a reality.

Oladele Honour Adedayo
Hanoi, August 2020.

i
 TABLE OF CONTENTS
ACKNOWLEDGMENT .................................................................................................. i
LIST OF TABLES .......................................................................................................... iv
LIST OF FIGURES ......................................................................................................... v
LIST OF ABBREVIATIONS......................................................................................... vi
INTRODUCTION ........................................................................................................... 1
Research Objectives ......................................................................................................... 4
Structure of thesis ............................................................................................................ 5
CHAPTER 1 LITERATURE REVIEW ..................................................................... 7
1.1. Antibiotics pollution in the environment. ................................................................. 7
1.2. Recent methods of water and wastewater treatment. ............................................... 7
1.2.1.Treatment by activated sludge ................................................................................ 9
1.2.2. Membrane Filtration .............................................................................................. 9
1.2.3. Chlorination ........................................................................................................... 9
1.2.4. Adsorption method .............................................................................................. 10
1.2.5. Photolysis ............................................................................................................. 11
1.2.6. Electrochemical oxidation ................................................................................... 11
1.3. Advanced oxidation processes ............................................................................... 14
1.3.1. UV/O3 method ..................................................................................................... 14
1.3.2. UV/O3 /H2O2 method ........................................................................................... 15
1.3.3. Fenton method ..................................................................................................... 15
1.3.4. Heterogeneous Photocatalysis process ................................................................ 15
1.4. Mechanism of photocatalysis .................................................................................. 17
CHAPTER 2 MATERIALS AND METHODS ........................................................ 20
2.1. Materials.................................................................................................................. 20
2.1.1. Preparation of glassware and apparatus .............................................................. 21
2.1.2. Preparation of sample solution ............................................................................ 21
2.1.3. Equipments Used ................................................................................................. 22
2.2. Methodologies......................................................................................................... 23
2.2.1. Survey Methodology ........................................................................................... 23
2.2.2. Characterization of the TiO2 material ................................................................. 23
2.2.3. Experimental design and set-up........................................................................... 24
2.2.4. Experimental procedure ....................................................................................... 25
2.3. Analytical methods ................................................................................................. 27
CHAPTER 3 RESULTS AND DISCUSSION .......................................................... 28
3.1 The analysis of the survey carried out during the study ......................................... 28
3.2. The characterization result of the photocatalyst ..................................................... 31
3.2.1. Morphology analysis using Scanning Electron Microscope (SEM) .................. 31
3.2.2. Fourier Transform Infrared Spectroscopy (FTIR) analysis ................................ 33
3.3. Photodegradation of Antibiotic pollutant ............................................................... 34

ii
3.3.1. Effect of initial concentration on the removal of TC with TiO 2 ......................... 34
3.3.2. Effect of catalyst dose on the degradation efficiency of TC with TiO2 ............. 35
3.3.3. Effect of pH value on the degradation efficiency of TC with TiO 2.................... 37
3.3.4. Effect of temperature on the degradation efficiency of TC with TiO 2 ............... 39
3.3.5. The removal of TC with the optimized conditions ............................................. 40
CHAPTER 4 CONCLUSION..................................................................................... 41
REFERENCES............................................................................................................... 42
APPENDICE .................................................................................................................. 49

iii
 LIST OF TABLES
Table 1.1. The advantages and limitations of various methods utilized for the treatment
of wastewater ................................................................................................................. 13
Table 1.2. The removal efficiencies of various target pollutants using different kinds of
photocatalyst .................................................................................................................. 16
Table 2.1. Chemical Structure and the properties of Tetracycline (TC) ...................... 13
Table 3.1. Questions and responses of the survey participants, total number of
participants =123 ........................................................................................................... 21

iv
 LIST OF FIGURES
Figure 1.1. Schematic diagram of detailed mechanism of photocatalytic reaction ..... 18
Figure 2.1. Images of some chemicals and apparatus used during the experiments, a)
Tetracycline crystalline powder b) Titanium (IV) oxide, anatase powder c) the 500mL
volumetric glass handmade dark beaker ....................................................................... 21
Figure 2.2. The equipments used during this research ................................................. 22
Figure 2.3. Schematic illustration of the set-up of the photocatalytic experiment ...... 24
Figure 2.4. Overview of the experimental procedure .................................................. 26
Figure 2.5. Showing the standard calibration curve of TC .......................................... 27
Figure 3.1. Distribution based on age groups ............................................................... 28
Figure 3.2. distribution based on educational qualifications ....................................... 28
Figure 3.3. The SEM images and EDX spectra of TiO2 particle ................................. 32
Figure 3.4. The mapping images of a) TiO2 material consisting of b) titanium and c)
oxygen elemental particles ............................................................................................ 33
Figure 3.5. The Fourier transform infrared spectra of TiO2 material using the FT/IR-
4600typeA machine ....................................................................................................... 34
Figure 3.6. The effect of initial concentration on TC removal efficiency, Volume of the
sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm,
temperature= 25℃, Total reaction time = 180 min, absorbance wavelength for
tetracycline = 357 nm .................................................................................................... 35
Figure 3.7. The effect of catalyst dose on Tc removal efficiency, Volume of the sample
solution= 200 mL; TC concentration= 40 ppm, temperature= 25℃, Total reaction time
= 180 min, absorbance wavelength for tetracycline = 357 nm ..................................... 36
Figure 3.8. a) Effect of pH on the removal efficiency of Tc, Volume of the sample
solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm, temperature=
25℃, Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm
b) the pH0 vs 𝒑𝑯∆ using the salt addition method ....................................................... 38
Figure 3.9. Effect of temperature on the removal efficiency of Tc, Volume of the
sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm,
temperature= 25℃, 35℃, 45℃ Total reaction time = 180 min, absorbance wavelength
for tetracycline = 357 nm ............................................................................................... 39
Figure 3.10. the optimized condition on the removal efficiency of Tc, Volume of the
sample solution= 200 mL; TC concentration= 40 ppm, TiO2 dosage = 0.1g/L, pH = 7,
Temperature= 45℃, Total reaction time = 180 min, absorbance wavelength for
tetracycline = 357 nm .................................................................................................... 40

v
 LIST OF ABBREVIATIONS
AOPs Advanced Oxidation Processes

APIs Active pharmaceutical ingredients

AS Activated sludge

BDD Boron-doped diamond electrode

CD Conduction band

EDX Energy dispersive x-ray spectroscopy

FTIR Fourier-transform infrared spectroscopy

MF Membrane filtration

PPCPs Pharmacological and personal care products

SEM Scanning Electron Microscope

STPs Sewage treatment plants

TC Tetracycline

TiO2 Titanium dioxide

TOC Total organic carbon

UV Ultraviolet

VB Valence band

vi
 INTRODUCTION
Antibiotics were developed to restrain and destroy certain microorganisms, nonetheless,
based on the chemical structures, antibiotics are commonly categorized into macrolides,
quinolone, sulfonamides, aminoglycosides, and tetracycline (TC) (Binh et al., 2018).
Antibiotics have long been widely used for the prevention of human and animal
diseases. Although most antibiotics cannot be fully absorbed, approximately 90%
(Halling-Sorensen et al., 1998) were discharged into the environment with the fecal
matter of patients and livestock in an unaltered form and as metabolites when utilized
as manure, results in certain levels of contaminants, thereby infiltrating the aquatic
ecosystem even at low concentration. As shown in the Figure below, antibiotics exist in
the environment primarily from pharmaceutical intake by human and through animal
breeding. The pathway for both animal and human antibiotic deposits existence in the
environment comprises of expired antibiotics discarded from hospitals; antibiotic
remains in medical appliances and vials utilized in the hospital; prescribed antibiotic
drugs discharged through the patient’s feces and urine. Likewise, the route of antibiotic
existence in the environment through animal/ livestock breeding may involve low doses
of antibiotic residues which have accumulated over a relatively long term ingestion

The route of the existence of pharmaceutical deposits in the water environment

(Haller et al., 2002). Several studies in recent years have implied that the pervasiveness

1
of pharmacological and personal care products (PPCPs) and their metabolites are
typically found in the sewage treatment plants (STPs) effluent, also in water
environment owing to the heavy load from pharmaceutical companies which are
discharged into rivers, lakes and other superficial waters. The occurrence of these
pollutants in water could be largely attributed to the incapability of most STPs to
achieve complete degradation with only the biological oxidation process, which is a
contributory factor to the prevalence of Eco toxicological implications for the aquatic
microorganisms (Richards & Cole, 2006).

Presently, in several developed countries such as the United States and the European
Union, the challenges from antibiotic pollution have become an important
environmental issue and related researches are evolving rapidly. Every human life
activity generates wastes, more directly related to the country or citizen’s standard of
living and the quantity of wastes produced over time. Around 23% of the global
population lives in developed nations and expend 78% of the available resources;
however, 82% of waste materials are yielded (Halling-Sorensen et al., 1998).
Furthermore, it should also be noted that the amount of accumulated waste tends to
increase remarkably in direct contrast to the level of industrialization of a country.
Presently, approximately 5,000,000 identified substances have been reported, with
roughly 70,000 usages worldwide, and a recent estimate of 1,000 new chemicals are
reportedly incorporated in the list each year (Kumar & Vyas, 2013). The problems
associated with appropriate water treatment and resources cannot be handled
objectively but have to be managed by a wide range of procedures. Issues associated
with toxic effects of organic compounds that are very active in water even at trace levels
must be eradicated through the disinfection of water utilized by the general populace
especially in the rural communities.

In order to tackle this wider range of issues, advanced processes that vary due to
complexity levels of these problems and their scales for application are required.
Formerly, waste products have been disposed of and eliminated by discharging them
directly into the environment without treatment, not until the depleting self- purifying
efficacy of the environment has been exhausted and the permissible standards were

2
significantly exceeded, thereby resulting in environmental contamination.

Subsequently, Advanced Oxidation Processes (AOPs) which are currently used as an

alternative treatment for a wide variety of recalcitrant micro pollutants includes UV/O3
process, UV-H2O2, heterogeneous photocatalysis, Fenton and photo-Fenton reaction,
sonolysis, non-thermal plasma, electrolysis, etc. (Goslan et al., 2006). Photocatalysis, a
branch of advanced oxidation processes(AOPs) is a promising technique for the
removal of these organics from water/wastewater, due to the in-situ generation of strong
oxidants which possess the ability to degrade these pollutants. In this study, the
photocatalytic activity of Titanium dioxide (TiO2) powder was investigated by checking
the degradation efficiency of tetracycline. The characteristics of TiO2 powder were
characterized by Scanning Electron Microscopy (SEM), and Fourier-transform infrared
spectroscopy (FTIR). Different dosage of the photo-catalyst as well as different
concentrations of pollutants, were varied in the degradation processes under UV light
conditions.

3
 Research Objectives
This work was carried out with the following objectives;

1. Survey on the behavior and awareness of residents concerning pharmaceutical

products and wastewater pollutants in Hanoi which was achieved by
questionnaires about pharmaceutical wastewater concerning the use of
antibiotics for their wellbeing

2. Treat model pharmaceutical wastewater using the photocatalytic treatment

method.

3. Characterization of the TiO2 photocatalyst

4. Study on the effects of some experimental variables on the photodegradation

ability of the TiO2 photocatalyst to obtain the optimal condition.

4
 Structure of thesis
The thesis includes 4 chapters which is categorized into literature review, materials and
methodology, results and discussions, and finally conclusions.

Chapter 1: Literature Review

The literature review discusses the conventional methods of wastewater treatment, the
challenges and disadvantages involved with the conventional treatment methods,
advanced oxidation processes focusing on the application of photocatalysis to the
treatment of wastewater, mechanism of photocatalysis and photocatalytic degradation
of pharmaceutical effluent.

Chapter 2: Materials and methodology

This section focuses on the materials, equipment, experimental design and methods
used for this research. The characterization of the photocatalyst, survey process, and
analytical method are also stated.

Chapter 3: Results and discussions

The results of the calibration process, adsorption capacity, photocatalytic activity of

TiO2, and optimization of experimental conditions are presented in this section. The
effects of various experimental conditions such as temperature, pH, and catalyst load,
etc. on the optimized condition of tetracycline treatment by TiO2 are discussed. Analysis
of the data obtained from survey activities is also included.

Chapter 4: Conclusions sums up the key findings from the study.

Appendices comprise some photos of the study’s research activities.

5
 CHAPTER 1. LITERATURE REVIEW
1.1. Antibiotics pollution in the environment.

The consistent use of antibiotics in humans and veterinarians has become so widespread
that their existence is now very prevalent in the environment and virtually, the entire
world recognizes their emergence in the biotic and abiotic environment such as surface
water, soils, wastewater, aquatic life, groundwater, etc. (Gothwal & Shashidhar, 2015).
Antibiotics are detectable globally at different concentrations. According to other
reports in USA, 6 classes of antibiotics were discovered in raw effluent. Amongst which
the concentration of sulfamethazine in the influent was detected to decrease from 0.21
𝜇𝑔/𝐿 to a negligible value below the detection limit in the effluent, the others include
sulfamethoxazole with its influent concentrations of 1.25 𝜇𝑔/𝐿 which was decreased to
0.37 𝜇𝑔/𝐿, the other antibiotics including tetracycline, trimethozin, ciprofloxacin and
erythromycin has influent concentration ranging between 0. 25 𝜇𝑔/𝐿 -1.25 𝜇𝑔/𝐿, which
reduces to 0. 21 𝜇𝑔/𝐿 -1.30 𝜇𝑔/𝐿 25 𝜇𝑔/𝐿 in the effluent concentration respectively
(Karthikeyan & Meyer, 2006). Furthermore, in a wastewater treatment plant in china,
20 antibiotics were found in the raw influent while 17 were detected in the effluent
wastewater. The total concentration of antibiotics per capita was approximately 500 –
900 𝜇𝑔 𝑝𝑒𝑟 person in the samples of influents obtained and mean value of 175 𝜇𝑔 𝑝𝑒𝑟
person in the effluent (Zhou et al., 2013). Non-detectable range – 7.3 𝜇𝑔/𝐿 was reported
for macrolides, sulfonamides and trimethoprim from 37 rivers in Japan (Alidina et al.,
2014). Other studies have also reported on the adverse impacts of the existence of
antibiotics in aquatic life, for example, distortion of the fish’s immune system has been
reported to be one of the implication of Tetracycline prevalence (0.1 – 50 𝜇𝑔/𝐿) in the
aquatic environment (Grondel et al., 1985), harmful effects on the population growth
rate and breeding rate of zebra fish due to the 200 𝜇𝑔/𝐿 concentration of
sulfamethoxazole and norfloxacin was reported (Yan et al., 2016). Thus, the emergence
and perseverance of antibiotics in the environment has to be controlled and managed.

1.2. Recent methods of water and wastewater treatment.

The increasing demand for clean water alongside its decreasing resources caused by the
expansion of industries, human population swelling, and long-term droughts have

7
become an intense problem everywhere on the planet. It leads to the demand for
development of the newly, practically and economically attractive technologies
enabling reasonable water use. It is estimated that over 4 billion individuals have really
limited access to clean water and millions of people die per annum due to diseases
caused by bacteriologically damaged water (Malato et al., 2009). It should be expected
that in future those numbers will increase consistent with rising environmental pollution
caused by the deposition of hazardous substances to the natural water cycle (Chong et
al., 2010). Improvement of cheap and efficient water and wastewater treatment
technologies is necessary, due to the low quality of remaining natural water and lack of
clean water.

The conventional methods of water treatment, which include membrane filtration,

sedimentation, coagulation, activated carbon adsorption, flocculation, chlorination and
either used in single or combined processes, cannot eradicate from drinking water, the
microorganisms, organic and inorganic toxic compounds. Hence, the emergence of
modern water and wastewater treatment processes such as membrane processing, UV
disinfection and the advanced phase of the oxidation process are therefore studied
(Bodzek & Rajca, 2012). Moreover, these methods only facilitate the reformation of
pollutants transport or concentration from one stage to the other; meanwhile, achieving
complete removal or degradation is unlikely. Although, chlorination is widely used to
disinfect but this process is a vast contributory to the development of mutagenic toxins,
immunotoxin and carcinogenic byproduct (Matilainen & Sillanpää, 2010). Chemical
and membrane applications, which include Nano filtration, microfiltration, reverse
osmosis, and ultrafiltration, distinguished by high operational and maintenance costs,
which may further influence the effects of secondary environmental toxic pollutants.
Although membranes have become an ideal replacement for conventional technologies,
their treatment approaches are considerably restricted partly because these techniques
only ensure the complete isolation of microbes, inorganic and organic substances. So,
the highly concentrated stream (10% volume of effluent) containing active harmful
microbes poses a significant threat to the receiving aquatic environment where these
effluents are deposited (Bodzek & Rajca, 2012).

8
1.2.1. Treatment by activated sludge

Activated sludge is a process that enhances the production of bacteria and microbes by
feeding on the organic component yielded by the wastewater aeration process (El-
Gohary et al., 1995). Activated sludge process is typically more ecofriendly than other
chemical processes including chlorination, this treatment requires minimal operational
procedures and cheaper cost of initial startup, which are some of the benefits of
activated sludge treatment (New et al., 2000). Despite its advantages, the challenges of
utilizing activated sludge methods of treatment include the excessive production of
sludge, pigmented colors, froth formation in the secondary clarifiers and a huge demand
for energy usage and output (Oz et al., 2004).

1.2.2. Membrane Filtration

The efficacy of membrane filtration in the removal of pharmaceuticals and APIs is

intrinsically linked to the features of the membrane including the pore depth, solubility
ability, specific surface area/structure, molecular mass of the pollutant and surface
loading (Bellona et al., 2004). A selection of prototypes and full-scale membrane
models such as sequence membrane, reverse electro dialysis, microfiltration, membrane
bioreactors, Nano filtration, reverse osmosis, and ultrafiltration have been investigated
and tested (Snyder et al., 2007). The elimination of the substantial proportion of toxic
organic pollutants by the microfiltration and ultrafiltration has no relative influence
because the pores range from 100-1,000 times the size of the micro contaminants such
that there is no apparent physical retention. They demonstrated some removal ability
when run as MBRs and retention are vastly greater than secondary clarifier levels. MF/
UF can yield economic solution and sustainability when vulnerable surface waters
warranted the advanced mode of treatment with the use of limited space. However, the
enormous energy demand and expensive cost are some of the constraints in the
utilization of micro and ultra-filtration (Larsen et al., 2004).

1.2.3. Chlorination

The degradation of some pharmaceutical products, such as sulfonamides (Qiang et al.,

2006), 17 α-ethinylestradiol, and 17 β-estradiol (Alum et al., 2004) through the

9
chlorination process has been detected to be efficient and effective. Chlorine dioxide is
likewise used to eliminate sulfamethoxazole, 17 α-ethinylestradiol, and diclofenac
(Khetan & Collins, 2007a). The degradation of bisphenol A, 17 α-ethinylestradiol, and
17 β-estradiol and estrogenicity byproduct from purified water through the combination
of chlorination and ozonation process have demonstrated consistent result in
comparison with ozonation process culminating in a 75-99% removal rate (Alum et al.,
2004). Amidst the process of chlorination, Sulfamethoxazole, diclofenac,
fluoroquinolone, and acetaminophen become oxidized, all other compounds will also
be metabolized. These pharmaceuticals, including acetaminophen, generate toxic by-
products such as N-acetyl-p-benzoquinone imine and 1,4-benzoquinone, while
chloramines, one of the oxidizing compounds are released as a toxic by-product of
sulfamethoxazole and metoprolol (Pinkston & Sedlak, 2004). Chloramines are
commonly considered carcinogenic compounds.

1.2.4. Adsorption method

This method involves the collection and removal of organic pollutants from wastewater
using the absorbent solids to evacuate toxic contaminants, thus disinfecting the effluent
(Li & Li, 2015). This separation technique enhances the further removal of foul stench,
discoloration from organic matter and toxic substances by transferring contaminants
from the dissolved liquid phase to the adsorbent surface and allowing them to
accumulate for elimination to occur (Ikehata et al., 2006). Hence, the activated carbon
adsorption is extensively utilized for the treatment of wastewater, often applied as a
granular or powdered activated feed. TC adsorption on silica was investigated and the
study indicated that the adsorption enthalpy and entropy were nearly -16 and -25 J/mol
accordingly (Turku et al., 2007).

Fe-incorporated SBA15 (Fe-SBA15) of varying Fe content (III) was fabricated to

improve the adsorption efficiency of TC and the study demonstrated that Fe-SBA15
had higher adsorption capability of TC than SBA15, however, tetracycline was not
completely removed (Zhang et al., 2015).

10
1.2.5. Photolysis

Solar radiation photolysis has been acknowledged to be among the most effective
method to degrade antibiotics in the aquatic ecosystems (Andreozzi et al., 2003).
Photolysis is simply the direct disintegration of chemical compounds through light
absorption (Legrini et al., 1993), however, some pharmaceutical products have been
found to be highly resistant to photolytic alterations, in particular APIs which are not
prone to absorb light at wavelengths greater than 290 nm (Khetan & Collins, 2007b).
In general, the existence of organic contaminants in the water habitats is ascertained by
various physicochemical (abiotic) and biological processes. Abiotic transitions of any
pollutant as well as pharmaceutical substances in the aquatic environment occurs
through hydrolysis and even photolysis. As the norm, pharmaceuticals, typically
intended for oral ingestion are hydrolysis-resistant, thereby signifying the techniques of
indirect photolysis as a default route to their inorganic form in surface water environs.
Whilst, organic compounds which absorb solar light directly become photolyzed
(Richard G. Zepp & Cline, 1977), indirect photolysis process incorporates nitrate and
humic acid photosensitizers which occurs naturally in the environment, however when
the sun is irradiated, naturally occurring strong oxidants such as hydroxyl radicals are
produced (R. G. Zepp et al., 1981).

1.2.6. Electrochemical oxidation

Electrochemical oxidation has been tested on a lab-scale and pilot plant scale to degrade
organic compounds in aqueous solutions, however, due to its relatively high operational
cost, this process is not being used commercially. The transmission of electrons within
the electrodes which provides a clean reactor system is among the major benefits of this
process because it restricts the surge in the number of organic molecules involved
(Martínez-Huitle & Ferro, 2006). However, they have certain limitations including the
fact that in cost comparison with several other processes, the electrochemical oxidation
process is rather expensive and the water mechanism is even more complex. Therefore,
if the effluents do not have sufficient conductivity, salt has to be incorporated into the
flux to be processed. There are three phases for the mechanism of electrochemical

11
oxidation process to be completed namely; Electrocoagulation, Electro-flotation and
Electro-oxidation (O’Shea & Dionysiou, 2012)

−e− (1)
RH → RH +

−H+ (2)
RH + → R●

R● + R● → R − R (3)

The anodizing reaction is usually regarded as a precise process that implies the exact
transition to the electrode by an electron from the organic compound thereby emitting
a cationic radical. The cationic radical products generated are significantly impacted by
the existence and pH of the electrodes. Studies involving the anodic oxidation process
using a boron-doped diamond electrode and a graphite cathode to treat acetaminophen
on a small scale have been shown to be effective (Brillas et al., 2005). This is due to
the production of high amounts of hydroxyl radicals (OH ● ) from the electrodes which
allows a total solubilization of the acetaminophen to be achieved at lower
concentrations. The properties of the BDD included optical clarity, good electrical
conductivity, and inertness (G. Chen, 2004).

This literature review summarized the biological, physical, and chemical methods
utilized for the elimination of pharmaceuticals stating their advantages and limitation
as listed in Table 1.1.

12
 Table 1.1. The advantages and limitations of various methods utilized for the
treatment of wastewater

Methods Functions Advantages Limitations References

AS Processes large Cost-efficient Bulk load (New et al.,

volume of and widely affects its 2000)
organic matter utilized durability and
efficiency
MF Filtration Well combined Biofouling (Snyder et
with membrane- Quite al., 2007)
based treatment ineffective for
technologies the
degradation
of many APIs
Chlorination Use of chlorine Highly effective Releases (Alum et
primarily for for disinfecting carcinogenic al., 2004)
disinfection water disinfection
end products
Adsorption Adsorb and Economical PAC: mainly (Ikehata et
separate for low al., 2006)
organic
wastewater
Photolysis Disintegration Cheap and The (Legrini et
of recalcitrant reasonably efficiency al., 1993)
compounds efficient for could vary
into APIs based on the
biodegradable biodegradation geographical
matter by light area with a
absorption lower supply
of sunlight
Electrochemical Anodic More effective Expensive (O’Shea &
Oxidation oxidation for breaking and effluent Dionysiou,
process which down APIs to has to be 2012)
generates OH ● non-toxic highly
which allows compounds conductive
mineralization
of APIs

Difficulties observed within the discussed treatment methods have resulted in the rapid
development of AOPs as the ideal technology for water and wastewater treatment.

13
1.3. Advanced oxidation processes

AOPs are a treatment alternative for a wide variety of recalcitrant micro pollutants.
AOPs generate a sufficient quantity of highly reactive radicals (in particular hydroxyl
radicals) which have an especially important reactive effect on organic molecules.
These technologies for the rehabilitation of soil, air and wastewater comprising of
recalcitrant contaminants are considered to be highly promising methods (Glaze et al.,
1987). AOPs degrade contaminants in rudimentary, biodegradable form, rendering their
treatments in traditional processes more cost-effective.

Besides, AOPs can be in homogenous and heterogeneous phases. Homogeneous

processes usually involve the use of certain chemicals called homogeneous advanced
oxidation whilst, heterogeneous processes utilized some catalysts known as
heterogeneous advanced processes of oxidation or catalytic processes, to increase the
rate of degradation reaction. Some of the most frequently AOPs studied for water
treatment applications are UV/O3 process, UV-H2O2, heterogeneous photocatalysis,
Fenton and Photo-Fenton reaction, supercritical water oxidation, etc.

1.3.1. UV/O3 method

The UV / O3 method provides a valuable means of oxidizing and destroying organic

pollutants in water. Specifically, UV radiation of 253.7 nm irradiates aqueous
conditions with ozone saturation. The coefficient of extinction at O3 is 3,300 L.mol-
1.cm-1 at 253.7 nm, much greater than the coefficient of hydrogen peroxide (18.6 L.mol-
1.cm-1). The ozone depletion level is nearly 1,000 times higher than H2O2 (Duguet et
al., 1992). Photolysis of ozone is necessary for the AOP with UV and ozone radiation
to occur. The ozone-based photodecomposition creates two hydroxyl radicals that do
not recombine to create hydrogen peroxide (Glaze et al., 1982)
ℎ𝑣 (4)
𝐻2 𝑂2 + 𝑂3 → 2HO● + 𝑂2

2HO● → 𝐻2 𝑂2 (5)

This treatment method entails hydrogen peroxide, UV radiation and ozone for the

14
formation of hydroxyl radicals and oxidation of pollutants during corresponding
reactions to occur. Hence, the most common treatment methods such as biological
degradation do not have to be substituted, wherever possible.

1.3.2. UV/O3 /H2O2 method

This method is a very effective technique of drastically reducing TOC by accelerating

the ozone breakdown thereby increasing the generation rate of HO● radicals. (Mokrini
et al., 1997) showed that the optimal H2O2 concentration and at varying pH values, a
40% reduction in TOCs were demonstrated. The integration of UV radiated ozone and
peroxide proved higher efficiency than single ozone in degrading nitrophenols,
enhancing reaction rate, and reduce the consumption of ozone by using low pH levels
(Trapido et al., 2001).

1.3.3. Fenton method

Fenton’s method entails the formation of hydroxyl radicals due to the chemical reaction
of hydrogen peroxide in the presence of iron (Carey et al., 1976). The UV light greatly
improves the production of hydroxyl radicals by reducing ferric ions (Fe (III)) to ferrous
ions (Fe (II)) as shown in equation 6. Moreover, given the vast availability and non –
toxic nature of iron, Fenton’s chemical reaction would seem to be feasible for the
treatment of wastewater (Ruppert et al., 1993).

ℎ𝑣 (6)
𝐹𝑒 3+ + 𝐻2 𝑂 → 𝐹𝑒 3+ + HO●

Fenton process was reportedly used to degrade nitrobenzene, phenol, 2,4-

dichlorophenol and 4- chlorophenol, this process was observed to improve biological
degradation and reduce toxic compounds (Chamarro et al., 2001). The UV-Vis/
ferrioxalate / H2O2 method has reportedly been modified and observed to be more
effective for the removal of organic pollutants than the photo–assisted Fenton processes
(Richard G. Zepp et al., 1992).

1.3.4. Heterogeneous Photocatalysis process

This process involves the photoexcitation of the semiconductor photocatalyst in the

presence of oxygen under UV radiation thereby oxidation occurs which then produces

15
hydroxyl radicals and free holes are generated. There are two stages involved, the solid
and liquid phase, so this process can be termed to be heterogeneous. The wavelength
shorter than 380nm along the solar spectrum makes this system ideal to be utilized on
a large scale (Kositzi et al., 2004). Although several catalysts had been tested however
the anatase form of TiO2 has the most advantageous properties including relatively great
stability, high efficiency with lower cost, subsequently, the disadvantage is that its
fouling with organic substances (Andreozzi et al., 1999). Azeez et al investigated the
photocatalytic degradation of MB with Nano titania and a complete mineralization of
MB with TiO2 NPs was observed (Azeez et al., 2018). Tsai et al also reported that in
the presence of UV-A, the number of antibiotic-sensitive and antibiotic-resistant
microbes were reduced effectively by TiO2 photocatalysis (Tsai et al., 2010). In recent
years, the trend has been to initiate photocatalytic degradation in the presence of the
catalyst in order to create hydroxyl radicals, and thus, it is not mandatory to add an
oxidizer to the medium. The photocatalysis process has been shown in industrial
effluent and potable drinking water to be a potential approach for the disintegration of
toxic and recalcitrant organic substances. A total oxidative degradation of pollutants
was ascertained in most cases and the byproducts comprise of CO 2, H2O, and other
inorganic molecules. Nonetheless, due to its economic viability, it's simple operation at
massive scale and process efficiency, solar illumination for photocatalysis process has
been such a tremendous booming advancement.

Table 1.1. The removal efficiencies of various target pollutants using different kinds
of photocatalyst

Name of photocatalyst Light Target pollutant % of References

condition removal
TiO2 – SBR process UV Antibiotic wastewater 57 (Elmolla &
containing amoxicillin Chaudhuri,
and cloxacillin 2011)
TiO2 UV and Tetracycline 50 (Reyes et al.,
solarium 2006)
lamp

Natural zeolite Natural Safranin-T dye 84.5 (Abukhadra

heulandite/polyaniline Sunlight et al., 2018)
@nickel oxide

16
composite
(Hu/PANI@Ni2O3)
Multi-walled carbon 6W UVC Tetracycline 92 (Ahmadi et
nanotubes and TiO2 lamp al., 2017)
nanoparticles
(MWCNT/TiO2
nanocomposite)
TiO2 UV Antibiotic oxolinic 60 (Giraldo et
acid al., 2010)
ZnO Simulated Antibiotic 67 (Palominos
solar light Tetracycline et al., 2009)
Nano-ZnO–TiO2 UV Phenolic solution 70–80 (Prabha &
composite particles Lathasree,
2014)
Copper(I) oxide- Solar Orange II dye 85 (Koiki et al.,
graphitic carbon simulator 2019)
nitride heterojunction
(Cu2O-g-C3N4)
TiO2 UV-A Antibiotic-resistant 99 (Tsai et al.,
bacteria in 2010)
suspension:
Methicillin-resistant
Staphylococcus
aureus (MRSA),
Multidrug-resistant
Acinetobacter
baumannii (MDRAB)
and Vancomycin-
resistant Enterococcus
faecalis (VRE)
ZnO UV Methyl red 93 (Comparelli
et al., 2005)

1.4. Mechanism of photocatalysis

The aim of the heterogeneous photocatalysis with the utilization of semi conductive
catalyst TiO2 is to perform a series of redox reactions on the catalyst surface (Haque &
Muneer, 2007). The mechanism of photocatalysis is the process associated with the
formation of holes and electrons by the absorption of photons by a semiconductor. The
valence band (VB) consists of the highest occupying (h-bonding) band entailing the
semi-conductor energy levels and the conduction band (CB) is the lower unoccupied
band. Both VB and CB are partitioned by the bandgap energy. As shown in Figure 1.1,

17
when photon energy (hν) of greater than or adequate to the bandgap energy of TiO2
illuminated onto the catalyst surface (usually 3.2 eV - anatase or 3.0 eV - rutile) (Huang
et al., 2016), free electrons are transferred from the VB to the CB. Thus, pairs of
“electron hole” are formed (e– - h+) as seen in equation (6).

𝑇𝑖𝑂2 + ℎ𝑣 → 𝑇𝑖𝑂2 (𝑒𝐶𝐵 − + ℎ𝑉𝐵 + ) (6)

If electron scavengers are not present, the photo-excited electron is recombined with
the valence band within a few nano-second with simultaneous heat dispersion.
Therefore, for efficient photocatalytic reaction and elongation of recombination, the
inclusion of electron acceptors such as oxygen is highly essential

Figure 1.1. Schematic diagram of detailed mechanism of photocatalytic reaction

Chain redox reactions which occur on the surface of the photocatalyst are clearly
described by the following equations (7) – (15):

18
  The oxidation reaction of the formed holes with adsorbed water molecules to
generate hydroxyl radicals
(7)
h+ + OH → OH

h+(VB) + H2O(adsorbed) → OH + H+ (8)

 Dissolved oxygen with excited electrons undergoes the reduction reaction to

create radical superoxide anions which will in turn through various series of
redox reactions produce H2O2

   →  

   →  

→ 


 →  

 → 

 The photo excited hydrogen peroxide is then further disintegrated to produce

hydroxyl radicals

→ 

→ 

The major oxidants which include OHand radical superoxide anion can trigger
a series of chemical degradation reactions. They are known to be resilient, non-selective
oxidants. The chemical degradation of organic compounds continues through various
redox processes which creates a substantial number of intermediates, eventually leading
to the production of CO2, H2O, and inorganic ions as the final degradation products.

19
 CHAPTER 2. MATERIALS AND METHODS
2.1. Materials

Commercial Titanium dioxide, Anatase with a purity of 99.7% was purchased from
Aldrich and used throughout the experimental study. The hydrochloric acid and sodium
hydroxide solution used to adjust the pH of the model pharmaceutical pollutants were
of analytical standard. Tetracycline crystalline powder was obtained from Alfa Aesar
by Thermo Fisher Scientific and its chemical structure with other properties was listed
in Table 2.1.

Table 2. 1. Chemical Structure and the properties of Tetracycline (TC)

Chemical Structure of Tetracycline

Molecular Formula C22H24N2O8

Molecular Weight 444.4 g/mol

Melting Point 172-174°

Solubility Limited solubility in water,

Soluble in 1M HCl with heating
Form Crystalline powder

Storage and Sensitivity Keep cold

20
 A b c
Figure 2.1. Images of some chemicals and apparatus used during the experiments,
a) Tetracycline crystalline powder b) Titanium (IV) oxide, anatase powder c) the
500mL volumetric glass handmade dark beaker

2.1.1. Preparation of glassware and apparatus

The deionized water used in cleaning all the glass and plastic laboratory wares that were
utilized during every experimental process was obtained from the double-distilled water
equipment (A4000D, Bibby, England) situated in the MEE laboratory. The handmade
dark beaker, as shown in Figure 2.1, was a 500 mL Pyrex griffin volumetric glass beaker
which was taped around with black elastic tape to create a dark condition, more so to
repel the interference of the surrounding light atmosphere during the chemical reaction,
while being stirred with a Magnetic stirrer. The other glassware used includes 200mL
graduated measuring glass cylinder, thermometer, 125 mL of volumetric conical flask,
45 mL Centrifuge tubes, 25 mL Terumo syringe, and safety goggles to protect the eyes
from UV Light radiation.

2.1.2. Preparation of sample solution

For each experiment conducted, sample solutions were prepared by dissolving

appropriate quantities of TC in double-distilled water. Standard solutions with
concentrations of 40, 60, 80, and 100 ppm were prepared in the 500 mL volumetric
flask and used as samples for optimization of the pollutant’s initial concentration.

21
2.1.3. Equipment Used

IKA C-Magnetic Stirrer UV Spectrophotometer Thermo scientific

High Speed
(Shimadzu UV-1280) Sorvall legend XTR
Centrifuge

S220-Kit Mettler Toledo JSM – IT 100 Scanning Jasco FT/IR -

pH meter electron microscope 4600typeA
spectroscopy

MS 12002TS/A00 IKA HS 26 0 basic UVC TNE Ultraviolet

Horizontal Shaker Light
Precision weighing scale

Figure 2.2. The equipment used during this research

22
2.2. Methodologies

2.2.1. Survey Methodology

Antibiotic resistance is a significant threat to public health. The general public

awareness is considered to be a necessity for the safe and proper use of antibiotics, also
to restrict the spread of antibiotic resistance. So as part of the objectives of the research
study, a survey was undertaken. The main purpose of the survey was to ascertain the
behavior and level of awareness of residents concerning pharmaceutical products and
wastewater pollutants in Hanoi, Vietnam. A cross-sectional questionnaire-based study
was carried out between students from Vietnam Japan University, Hanoi University of
Science, members of Hanoi International Fellowship, and friends from other provinces
in Vietnam.

The questionnaire comprised the following 1) personal information including age,

educational level (two statements), 2) attitude towards antibiotic use such as practices
of using antibiotics with regards to their daily routine and health (three statements), 3)
knowledge of antibiotics and treatment of pharmaceutical effluents (five statements).
The survey questionnaire was distributed to participants electronically across various
social platforms including emails, Facebook, etc., direct face-to-face interviews were
also conducted, participation in the survey was voluntary and over a hundred responses
were received back. The sample of the questionnaire used for this survey has been
included in Appendix A.

2.2.2. Characterization of the TiO2 material

The SEM images were obtained by using the JSM – IT 100 Scanning electron
microscope to evaluate the size and morphological structure of the photocatalyst. The
Energy dispersive x-ray spectroscopy (EDX) device which features as an SEM integral
function was used to determine the elemental composition of the material. This
experiment was conducted at the Nanotechnology laboratory, VNU - Vietnam Japan
University, Vietnam. The functional group present in the photocatalyst and their
absorption bands were evaluated using Jasco FT-IR-4600typeA spectroscopy. This
FTIR analysis was conducted at VNU, Hanoi University of Science, Vietnam.

23
 2.2.3. Experimental design and set-up

The adsorption and photocatalysis processes were carried out in a laboratory-scale

system with the set-up comprising of UV-C emitting light bulb TNE UV Lamp 20W,
(Ho Chi Minh, Vietnam) with a wavelength of 360 𝑛𝑚 placed in the center of the
photocatalytic reactor at a distance of 18cm from the sample in the handmade beaker
positioned on the IKA C-Magnetic Stirrer High speed which was set to a temperature
of 25℃ and speed of 200 rpm. The photo-reactor system was enclosed with a hard
cardboard to keep out any kind of illumination by ambient light. The schematic
illustration of the photochemical reactor system is displayed in Figure 2.3.

Figure 2.3. Schematic illustration of the set-up of the photocatalytic experiment

24
 2.2.4. Experimental procedure

The degradation experiment with TC was carried out in a 200 mL aqueous solution
containing the antibiotics (40 mg/L, 200 mL) and TiO2 photocatalyst (0.1g/Loading).
As shown in Figure 2.4, for photocatalytic degradation to occur, the sample solution
was kept in the dark with constant stirring on the magnetic stirrer at a speed of 200 rpm
to allow the adsorption of the TC molecules on the surface of the TiO 2 photocatalyst,
and after 60 minutes, the maximum adsorption equilibrium was achieved. The UV lamp
was thereafter turned on after 60 minutes of adsorption in the dark and the
photocatalytic process started. The influence of different parameters on the
photodegradation process was investigated. The experiments were performed at
different initial concentration (40, 60, 80, 100 ppm), different TiO2 dosage (0.1, 0.3,
0.5g/L), pH levels (3, 7, 9), and temperature (25, 35, 45℃). Each photodegradation
process during this study was conducted for 3 hours as illustrated in Figure 2.4.

25
Step 1 Step 2 Step 3

Calibration of TC to Adsorption of TiO2 Photocatalytic activity under

different concentration in the dark condition the UV light

Step 4

Aliquot was centrifuge for 20 min at a speed of

10, 000 rpm using K Model PLC-012E universal

centrifuge

Step 5

Unico S 2150 UV spectrophotometer was used to

measure absorbance

Figure 2.4. Overview of the experimental procedure

26
2.3. Analytical methods

The aliquot samples were taken after the required irradiation time which is 15 min,
afterward centrifuged, the solution was then carefully extracted with a 25 mL Terumo
syringe to separate the particles of the photocatalyst and the resulting solution was
analyzed by UV spectrophotometer (Shimadzu UV-1280) at the maximum wavelength
of 357 nm. The removal efficiency of TC (%RTC ) was expressed as
𝐶0−𝐶𝑒
%RTC = ×100%
𝐶0

Where 𝐶0 is the initial concentration of the TC pollutant, 𝐶𝑒 is the concentration of TC

in the photocatalytic reactor at time t (min).

The standard calibration curve of TC concentrations as shown in Figure 2.5,

demonstrated strong linearity of R2 > 0.9963. All the experiments were repeated in
triplicates to verify and ensure that the data collected were satisfactory. In addition, all
the data points represented were the mean values from the three repetitions.

0.8

Abs
0.6

0.4
Abs

0.2

0.0
0 5 10 15 20
TC concentration (ppm)

Figure 2.5. Showing the standard calibration curve of TC

27
 CHAPTER 3. RESULTS AND DISCUSSION
3.1 The analysis of the survey carried out during the study

This study assessed the knowledge and awareness regarding the use of antibiotics and
the treatment of pharmaceutical wastewater pollutants in Vietnam. A total of 123
responses were received with most of the participants (92.7%) belonging to 20-30 years’
age group (Figure 3.1), furthermore, a good number of the participants (90%) had higher
educational levels (Figure 3.2). Simultaneously, as shown in Table 3.1, more than half
of the respondents (55%) ingested antibiotics as a daily routine, which could over time
result in overdose, presumably leading to antimicrobial resistance.

Figure 3.1. Distribution based on age groups

Figure 3.2. Distribution based on educational qualifications

28
 Table 3.1. Questions and responses of the survey participants, total number of
participants = 123

Do you use antibiotics for your daily life (Bạn có sử dụng thuốc kháng sinh
trong cuộc sống hàng ngày không)?
Yes / Có 68 (55.3%)
No / Không 43 (35%)
Not sure / Không rõ 12 (9.7%)
When you fall ill, how do you treat the sickness (Bạn sẽ làm gì khi gặp vấn đề
về sức khỏe)?
Go to the hospital to seek for doctor’sadvice (Đến bệnh viện/phòng 55 (44.7%)
khám đểgặp và nghe theo lời khuyên của bác sĩ)
Go to the pharmacy to buy antibioticdrugs directly (Đến hiệu thuốc 55 (44.7%)
để muathuốc theo lời khuyên của bác sĩ)
Self-medicate with drugs at homewithout any prescription (Tự chữa 13 (10.6%)
bệnhtại nhà không theo lời khuyên của bácsĩ)
After you get better, how do you dispose of the remaining unused antibiotics
(Nếu bạn sử dụng thuốc kháng sinh còn dư, bạn sẽ)?
Throw away with other domestic wastein the refuse dump (Vứt bỏ 104 (84.6%)
cùng vớicác rác thải sinh hoạt thông thườngkhác)
Flush down the kitchen sink or toilet (Xảxuống bồn rửa bát hoặc 3 (2.4%)
nhà vệ sinh)
Specific disposal technique, forexample, return unused pack to 16 (13%)
thepharmacy (Có biện pháp xả thải đặcbiệt, ví dụ như đem hoàn trả
lại hiệuthuốc/công ty sản xuất thuốc)
Do you know about the side effects of over-using antibiotics without the
doctor’s advice, for example, over-use of tetracycline has been known to be
the cause of yellow teeth in children?
(Bạn có từng nghe qua/có biết về các hậu quả của việc sử dụng thuốc kháng
sinh không theo chỉ định của bác sĩ, ví dụ, sử dụng tetracycline có thể gây hư
hỏng men rang hoặc vàng răng ở trẻ em)?
Yes, I know / Có biết 61 (49.6%)
No, I do not know / Không biết 34 (27.6%)
I know, but not sure / Có biết,nhưng không rõ 28 (22.8%)
Do you know about the specific rule or of Vietnamese standard guiding
pharmaceutical products and industries (Bạn có biết luật/quy định hay tiêu
chuẩn nào ở việt Nam về sản xuất thuốc kháng sinh)?
Yes, I know / Có biết 12 (9.8%)
No, I do not know / Không biết 88 (71.5%)
Not sure / Có biết,nhưng không rõ 23 (18.7%)
Do you know that wastewater generated from pharmaceutical product/
industry are needed to be treated in a specific way (Bạn có biết nước thải từ
hoạt động sản xuất thuốc kháng sinh cần được xử lý đặc biệt không)?

29
 Yes, I know / Có biết 38 (30.9%)
No, I do not know / Không biết 43 (39%)
I think so, not sure / Có, nhưngkhông chắc là xử lý theo cách nào 37 (30.1%)
Do you have the knowledge about the method by which pharmaceutical
wastewater is being treated (Bạn có biết về phương pháp mà nước thải có
thuốc kháng sinh được xử lý không)?
Yes, I know / Có biết 12 (9.8%)
No, I do not know / Không biết 86 (69.9%)
I think there are specific treatments, but not sure / Khôngbiết chính 25 (20.3%)
xác
Do you think that untreated wastewater from pharmaceutical
product/industry will have an adverse effect or is safe in our environment
and human health (Bạn cho rằng nước thải chưa qua xử lý từ hoạt động sản
xuất thuốc có thể có tác động xấu đến môi trường và sức khỏe con người
không)?
Yes, I think it will have adverse effect / Có, tôi cho rằng có 107 (87%)
ảnhhưởng xấu
No, I think it is safe / Không, tôinghĩ là an toàn, không ảnh hưởng 3 (2.4%)
I’m not sure / Tôi không chắc 13 (10.6%)
However, based on the survey result, 45% of respondents took antibiotics from drug
stores and pharmacies while some of the participants (45%) sought the medical
personnel’s recommendation, which thereafter revealed that the younger generation
would usually go directly to the pharmacy rather than consulting the doctor for
prescriptions and merely close to 11% of the respondents had actually taken antibiotics
without professional advice. The use of antibiotics has been said to be strongly affected
by the easy availability of medication and regulatory enforcement, as well as the belief
amidst the independent pharmacy owners and distributors in several countries that if
antibiotics are not sold without prescriptions, they would incur losses and businesses
might be lost, as patients would most likely just go somewhere (Holloway et al., 2017).
This result is quite similar to the findings of the survey conducted across the Pan-
European region which reported that the issue of self-medication amidst their
respondents ranged between 0.1% - 21% (Grigoryan et al., 2007). Besides, majority of
the respondents (85%) had attested to disposing of their unfinished pharmaceuticals
together with domestic waste, 2.4% dispose by flushing down their toilets together with
the human waste, thereby permitting the existence of antibiotic waste in the
environment. Moreover, the current study showed that the lack of knowledge and
awareness regarding the method of treating pharmaceutical effluent varied between 43-

30
86%. Similarly, amidst 123 participants, 87% agreed that untreated pharmaceutical
effluents deem unsafe and could have adverse effects on the environment and human
health.

The problem of antibiotic resistance is an underrated health concern in most developing

nations and more attention should be paid to the dispensation of antibiotics.
Subsequently, one efficient strategy of combating self-medication could be to avoid
left-overs by dispensing only the specific amount prescribed and reduce reusing the
same medications for similar ailment. Simultaneously, enhancing the laws and policies
regarding the pharmaceutical industry, so also creating higher awareness campaigns to
educate the general public on the appropriate use of antibiotics, the possible adverse
environmental and human health effects especially an emphasis on resistance to
antibiotics may deter the increased existence of antibiotics in the environment.

3.2. The characterization result of the photocatalyst

3.2.1. Morphology analysis using Scanning Electron Microscope (SEM)

The images from the SEM and EDX analysis of the photocatalyst can be seen in Figures
3.3 and 3.4. As shown in Figure 3.3(a), the TiO2 material was observed to be relatively
uniform in distribution and size with the particle size found to be within the micrometer
scale with a diameter of 1.5 𝜇m, more so the shape of the particle was found to be
spherical. Also, the EDX spectra showed high peaks of Ti and O (Figure 3.3c) in the
sample with the elemental composition percentage (Figure 3.3d) as 87.09% and 12.91%
respectively, thereby confirming that the photocatalyst is purely TiO2 without other
elemental impurities. To further investigate the elemental composition, one area of the
sample was selected during SEM analysis, and EDX mapping analysis was conducted.
Invariably from Figure 3.4, the two elements Titanium and Oxygen were detected, the
images revealed a uniform distribution of these elements and can be attributed to
confirm the presence of Ti and O in the sample.

31
 A b

Formula Atom Mass

% %

O 87.09 2.43

Ti 12.91 1.08

C d

Figure 3.3. The SEM images and EDX spectra of TiO2 particle

32
 a b c
Figure 3.4. The mapping images of a) TiO2 material consisting of b) titanium and c)
oxygen elemental particles

3.2.2. Fourier Transform Infrared Spectroscopy (FTIR) analysis

Figure 3.5 shows the FTIR spectra of the TiO2 photocatalyst. The functional group and
composition of the TiO2 material were analyzed within the infrared (IR) spectra
frequency range of 400 - 4000 cm-1 with resolution 4cm-1. In transmittance (% T), these
IR spectra provides qualitative data on how the adsorbed molecules are bound to the
surface. The spectrum displayed several absorption peaks however, the pure TiO 2
sample exhibited the Ti – O – Ti bending vibrations at 638 cm-1 – 521 cm-1
(Mahalingam et al., 2017). While the absorption peaks at 1105 cm-1 indicates the
characteristics of surface adsorbed water and the peak at 3448 cm-1 corresponds to the
bending vibrations of the hydroxyl functional groups (Vetrivel et al., 2015).

33
 Figure 3.5. The Fourier transform infrared spectra of TiO2 material using the FT/IR-
4600typeA machine

3.3. Photodegradation of Antibiotic pollutant

3.3.1. Effect of initial concentration on the removal of TC with TiO2

The chemical composition of different organic molecules tends to have an impact on

the photocatalytic degradation rate as a result of the chemical reactions of these organic
compounds with different photocatalysts. One of the essential aspects to consider in
photodegradation processes is the effect of TC initial concentration (Prabha &
Lathasree, 2014). The initial concentration of TC varying from 40, 60, 80, and 100 ppm
was investigated and as displayed in Figure 3.6, after 180 mins, the decrease in the
removal efficiency was observed to range between 98.9, 87.9, 76.4, and 18% with
increasing TC concentrations respectively. This is because the increase in the
pollutant’s initial concentration causes more molecules to be adsorbed to the surface of
TiO2 by the Vanderwaal force, thereby diminishing the adsorption ability of hydroxyl
ions which will inhibit the production of hydroxyl radicals (Lu et al., 2013).
Furthermore, at higher concentrations, more molecules will be adsorbed until TiO 2

34
particle cannot adsorb anymore which would compel the molecules of the pollutant to
block the photons, hence the removal efficiency would decrease. However, at low
concentration of 40 ppm, TC was completely degraded and chosen as the optimum
pollutant initial concentration.

Dark Light

Dark Light

Figure 3.6. The effect of initial concentration on TC removal efficiency, Volume of

the sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm,
temperature= 25℃, Total reaction time = 180 min, absorbance wavelength for TC =
357 nm

3.3.2. Effect of catalyst dose on the degradation efficiency of TC with TiO2

The dosage of photocatalyst highly affects the rate of heterogeneous photodegradation

reaction, as significant increases are usually detected. Overall, to prevent wasteful use
of the catalyst, the optimum dosage must be estimated so as to achieve maximum
absorption of effective photons (Prabha & Lathasree, 2014). For this experiment,
varying photocatalyst ranging from 0.1g/L, 0.3g/L, and 0.5g/L were investigated to
determine their effects on the removal of 40 ppm TC pollutants. As seen in Fig.3.7, the
percentages of TC removal were 98.9%, 92.9%, and 78.7%, thus there was no

35
significant increase in the degradation rate when the TiO2 dosage was increased, rather
it indicated a negative effect. Similarly, (Mozia et al., 2013) reported a decline in the
removal efficiency of diclofenac TiO2 loading was increased to 0.3g/L, but no
substantial influence on degradation was observed for catalyst dose ranging between
0.05 – 0.2g/L.

100
0.1 g/L
0.3 g/L
0.5 g/L
80
Removal Efficiency (%)

60

40 Dark Light

20

0
0 20 40 60 80 100 120 140 160 180 200
Time (min)

Figure 3.7. The effect of catalyst dose on TC removal efficiency, Volume of the
sample solution= 200 mL; TC concentration= 40 ppm, temperature= 25℃, Total
reaction time = 180 min, absorbance wavelength for TC = 357 nm

Although, other findings have claimed that “catalyst loading tends to have both benefits
and limitations to the process of photodegradation”, however, reducing the catalyst load
had shown to decrease both the amount of photons absorbed as well as, increases the
rate of degradation process. The reduction in the amount of catalyst loading also
enhances the transparency of the sample solution which further enables easy penetration
of the light intensity, thus, improving the photochemical reaction (Bagheri et al., 2017).
Hence, to avoid unnecessary excess catalyst and also ensure appropriate absorption of
light photons for utter degradation, 0.1g/Loading was selected as the optimum catalyst

36
dose for subsequent experiments.

3.3.3. Effect of pH value on the degradation efficiency of TC with TiO2

The most significant parameter in ensuring effective photodegradation is the pH value,

as hydroxyl radical formation is greatly dependent on the influence of pH (Jiao et al.,
2008), so also alters the surface of the photocatalyst, dissociates the pollutant and
changes the structure of the pollutants in the aqueous solution (Etacheri et al., 2012).
The point of zero charge (pHpzc) is commonly used to depict where the pH value of a
photocatalyst at the surface charge density is equal to zero. Initial pH is amongst the
most crucial parameters in the photodegradation activities due to its influence on the
photocatalyst’s surface charge and ionizing nature. As shown in Figure 3.8a, the effect
of pH on TC removal efficiency was determined by evaluating different initial pH
values ranging from 3-9, whilst other parameters remained constant. After 120 mins of
irradiation, 62%, 97%, and 22% of TC were removed at pH 3.0, 7.0, and 9.0,
respectively. Evidently, TC in the neutral solution showed quicker degradation than in
the acidic and alkaline solution. Similar findings were reported by other study that
MWCNT/TiO2 nano-composite were used to study the enhanced photocatalytic
degradation of tetracycline and real pharmaceutical wastewater (Ahmadi et al., 2017).
Nevertheless, the effects of pH values on the process of TC photodegradation are quite
complex to interpret due to its numerous functions such as influencing the adsorption
rate of TC on the surface of the TiO2 catalyst. The pHpzc for anatase TiO2 was evaluated
at 6.2 using the salt addition method (Figure 3.6b) which corresponds to the value
reported by other researcher (Zeng, 2013). Thus, at pH solution > pHpzc, the charge
on the surface of the catalyst is negative, and for pH solution < pHpzc, the charge on
the surface of the catalyst is positive as shown in equation (17) and (18) (Zeng, 2013)

Ti-OH + OH- ↔ TiO- + H2O (17)

Ti-OH + H+ ↔ TiOH2+ (18)

The neutral surface charge will be when pH solution = pHpzc. Thus, in the acidic and
neutral pH medium, degradation of TC was more favorable than in the alkaline medium.
Therefore, in this study, the neutral pH =7 is the optimal and most favorable medium

37
with a removal efficiency of 97%

100
pH 3
pH 7 (a)
80 pH 9
Tc Removal efficiency (%)

av
60

40
Dark Light

20

Dark Light
0
0 20 40 60 80 100 120 140 160 180 200
Time (min)

4
pH (b)

2
bv
Initial
- pH

0
Final
pH

Point of Zero charge = 6.2

-2

-4
2 4 6 8 10 12
pH
Initial

Figure 3.8. a) Effect of pH on the removal efficiency of Tc, Volume of the sample
solution= 200 mL; TiO2 dosage = 0.1 g/L, TC concentration = 40 ppm, temperature=

38
25℃, Total reaction time = 180 min, absorbance wavelength for TC = 357 nm, b) the
pH0 vs 𝒑𝑯∆ 2using the salt addition method

3.3.4. Effect of temperature on the degradation efficiency of TC with TiO2

Temperature has been considered to be a valuable parameter while investigating the

conditions that influence the photodegradation of pollutants (Behnajady et al., 2006).
This study examined the effects of varying temperatures ranging from 25 oc, 35oc, and
45oc with 0.1g/L of TiO2 on the removal of 40 ppm TC pollutants, and 98.5%, 99.1%,
99.7% of TC were degraded respectively which could be said to show a slight increment
as the temperature changes. But, the optimal temperature was observed at 45 oc with a
removal efficiency of 99.7%. The result as seen in Figure 3.9 showed that as the
temperature increased, a significant rise in the reaction rate was observed thereby
enabling a faster removal efficiency, which has been the case in numerous findings
ascertaining that temperature is directly proportional to the rate of the chemical reaction.
However, at a very high temperature, the reaction pathway is hindered, and adsorption
capability becomes low thereby weakening the oxidation of the direct hole on the
surface of the TiO2 photocatalyst which may cause desorption to occur (C. Chen et al.,
2011).
100
Temp. = 25OC
Temp. = 35OC
Temp. = 45OC

80
Removal Efficiency (%)

60

Dark Light
40

20
Dark Light

0 20 40 60 80 100 120 140 160 180

Time (mins)

Figure 3.9. Effect of temperature on the removal efficiency of Tc, Volume of the
sample solution= 200 mL; TiO2 dosage = 0.1g/L, TC concentration= 40 ppm,

39
 temperature= 25℃, 35℃, 45℃ Total reaction time = 180 min, absorbance wavelength
for tetracycline = 357 nm

3.3.5. The removal of TC with the optimized conditions

This study conducted quite several experiments to optimize the following experimental
variables; at an initial concentration of 40 ppm, 0.1g/L of TiO2 photocatalyst, pH =7,
and temperature at 25oC. The result obtained as shown in fig.3.10 indicated that under
optimum conditions, the removal efficiency was 99.7% after 180 mins in the presence
of oxygen. Thus, utter degradation was observed.

100
Degradation efficiency

80
Removal Efficiency(%)

60

40

Dark
Light
20

0
Dark
Light
0 20 40 60 80 100 120 140 160 180

Time (mins)

Figure 3.10. the optimized condition on the removal efficiency of Tc, Volume of the sample
solution= 200 mL; TC concentration= 40 ppm, TiO2 dosage = 0.1g/L, pH = 7, Temperature= 45℃,
Total reaction time = 180 min, absorbance wavelength for tetracycline = 357 nm

40
 CHAPTER 4 CONCLUSION
This research provides an overview of the basic concepts and mechanisms of the
photocatalytic process, methods, and how experimental variables affect the efficiency
of this process.

Firstly, the survey analysis identified the behavior, knowledge, and attitude of the
respondents, and it could be speculated that to reduce the spread of antimicrobial
resistance, appropriate antibiotic dispensation and increased awareness should be
encouraged to educate the general public. Furthermore, this study applied the photo-
catalytic process in removing tetracycline using commercial TiO2 material and the
optimal condition for TC removal: TC concentration 40 ppm, catalyst dose 0.1g/L, pH
7. The optimum degradation efficiency was 99% of TC within 180 minutes. Thus, the
results obtained from SEM, EDX, and FTIR analysis confirmed that the purchased
commercially produced material was TiO2 with high purity and uniformity.

The result presented in this laboratory-scale study clearly shows the application of the
TiO2 photocatalyst to degrade antibiotics- laden wastewater in a sustainable way and
would definitely protect the environment as well.

41
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 APPENDICE
Appendix A

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