Ahmed Respap

Journal of the Department of Chemical and Environmental Engineering:
University of Nottingham 2018
TREATMENT OF CHEMICALS IN PHARMACEUTICAL WASTEWATERS USING OZONE

BASED ADVANCED OXIDATION PROCESSES
Mahmood Ahmed a
a
MSc Environmental Engineering, Department of Chemical and Environmental Engineering,
University of Nottingham
Executive Summary
Contamination of wastewaters with pharmaceutical chemicals has become an emerging concern
over the past two decades. Conventional wastewater treatment facilities do not have the
appropriate specifications and design to treat these chemicals of non-biodegradable and “pseudo-
persistent” nature. It is essential that pharmaceutical wastewaters are treated prior to their
discharge in order to tackle this rising concern and save the environment from becoming toxic,
while meeting stringent regulatory standards at local and international levels. Researchers have
previously reported the use of technologies such as activated carbon, nanofiltration, and reverse
osmosis as possible solutions for treating pharmaceuticals in wastewaters, however these are
temporary solutions as they produce concentrates that require further treatment. Advanced
Oxidation Processes (AOPs) have been reported as promising solutions for the treatment of
pharmaceuticals in wastewaters. This study investigates the use of Ozone-based AOPs for the
treatment of pharmaceutical chemicals in water. The degradation efficiencies of two groups of
pharmaceuticals, namely Caffeine (psychostimulant) and Paracetamol (mild analgesic), were
studied and the effect of Ozonation and Peroxone-process (O3/H2O2) at two alkaline conditions
(pH 8 and pH 11) on the degradation efficiency was determined. The ozone concentration was
kept constant throughout all experiments at approximately 17 µg/ml. The results showed that
ozonation alone is not as effective as the peroxone-process as concentration of caffeine reduced
by a percentage of 8% at pH 8 and 38% at pH 11, whereas it degraded by 26% and 53% at pH
8 and pH 11 respectively with the peroxone-process in 1 hour. The peroxone experiment was
repeated by reducing the volume of the wastewater at pH 11, resulting in Caffeine degradation
to up to 63% in 1 hour. On the contrary, Paracetamol degradation efficiency was relatively lower
than Caffeine. Paracetamol degraded by only 4% and 10% at pH 8 and pH 11 respectively when
exposed to ozonation alone, while it degraded by 8% (pH 8) and 16% (pH 11) in the peroxone
experiment in 1 hour. Similarly, when the peroxone experiment was repeated in a smaller volume
at pH 11, Paracetamol degraded by only 23% in 1 hour.
The research indicates that the peroxone-process with highly alkaline conditions (pH 11) is more
effective when compared to ozonation alone.
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Treatment of Chemicals in Pharmaceutical Wastewaters using Ozone based Advanced Oxidation Processes
Contents
1) INTRODUCTION ............................................................................................................. 3
2) AIMS AND OBJECTIVES ................................................................................................... 4
3) RESEARCH METHODOLOGY .............................................................................................. 5
3.1) Experimental setup ................................................................................................... 5
3.2) Analytical methods .................................................................................................... 5
3.3) Studied pharmaceuticals ............................................................................................ 5
3.4) Preparation of standard solutions ................................................................................ 5
3.5) Experimental procedure ............................................................................................. 6
4) RESULTS ....................................................................................................................... 7
5) DISCUSSION ............................................................................................................... 12
5.1) Pharmaceutical oxidation by ozonation ...................................................................... 12
5.2) Impact of peroxone-process for treatment of pharmaceuticals in water.......................... 12
5.3) Effects of initial pH .................................................................................................. 13
5.4) Reactor volume ...................................................................................................... 13
6) CONCLUSIONS AND RECOMMENDATIONS ....................................................................... 14
Acknowledgments............................................................................................................. 15
References ...................................................................................................................... 15
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1) INTRODUCTION
Conventional Wastewater Treatment Plants or Potable Water Treatment Plants are generally
designed to treat specific parameters in wastewaters prior to their discharge in respective water
bodies. Active pharmaceutical ingredients (APIs) in pharmaceuticals are designed to treat various
ailments in humans and animals, however their frequent presence in surface water, groundwater,
urban wastewater, and drinking water have shown a negative impact on the environment
(Kanakaraju, et al., 2018). This is because pharmaceuticals do not readily biodegrade which makes
them persist and consequently create a toxic environment. Water is one of the most essential
requirements for any living organism on earth. Since pharmaceuticals are being detected in
wastewaters, this poses potential health and environmental risks. In the past twenty years,
extensive research directed towards the presence of pharmaceuticals in the environment has led to
the classification of these organic compounds as emerging contaminants. Pharmaceuticals classified
into the environmentally concerning groups include non-steroidal anti-inflammatory drugs
(NSAIDs), antibiotics, betablockers, antiepileptic drugs, blood lipid-lowering agents,
antidepressants, hormones, and antihistamines (Khetan & Collins, 2007). As wastewater treatment
plants collect discharges from industries, hospitals, pharmacies, veterinaries, and households, they
become the main source of these pharmaceuticals. There are also indications that groundwater
contamination with pharmaceuticals could be due to anthropogenic activities such as dumping of
sludge or manure containing high concentrations of these pharmaceuticals and or the migration of
contaminated surface water through riverbank filtration into the groundwater (Almomani, et al.,
2016).
Considering the status of pharmaceutical pollution, various legislative actions have been undertaken
by environmental agencies of several countries such as the United States Environmental Protection
Agency (US EPA), and the environmental agencies of the European Union (EU). Most APIs and
pharmaceuticals with endocrine disruptive properties (EDCs) have however remained unregulated,
although the United States of America (USA) and the European Union (EU) and have shown great
interest in combating the presence of pharmaceuticals in the environment (Esplugas, et al., 2007).
This has led to the formation of several directives and frameworks such as the community program
of research on endocrine disrupters and environmental hormones (COMPREHEND), ecotoxicological
assessments and removal technologies for pharmaceuticals in wastewater (REMPHARMAWATER),
environmental risk assessment of veterinary medicines in a slurry (ERAVMIS) and European
Directives such as 2013/39/EU and EU 2015/495 and an endocrine disruptor screening program
(EDSP) by the USEPA (Esplugas, et al., 2007). The formation of these directives and frameworks
clearly indicate the severity pharmaceutical pollution in different water sources and that stringent
regulations are imminent soon. Pharmaceutical companies should consider these emerging reforms
and plan to operate in compliance.
Conventional treatment processes, as mentioned before, tend to be ineffective in the removal of

pharmaceuticals in wastewaters due to their non-biodegradable nature and “pseudo persistence”.
For example, antibiotics are known to be not effectively removed by conventional methods
(Kanakaraju, et al., 2018). Treatment processes such as activated carbon, nanofiltration, and
reverse osmosis have been reported as effective treatment processes, however these processes are
considered temporary solutions, as they only move or transfer the pharmaceuticals to the solid
phase or concentrate them in a small volume of aqueous solution, which then requires further
treatment. (Almomani, et al., 2016).
Advanced Oxidation Processes (AOPs) present great potential in the treatment of these emerging
contaminants (pharmaceuticals in this case) among different water treatment technologies
employed so far. AOPs involve the in-situ generation of highly reactive oxygen species (ROS) with
low selectivity such as hydroxyl radicals (HO•), H2O2, O3 and superoxide anion radicals (O2•-),
providing pathways of complete mineralization to CO2, H2O and inorganic ions or acids (Dalrymple,
et al., 2007). AOPs consist of five types; Ozone-based AOPs, UV-based AOPs, Electrochemical AOPs,
Catalytic AOPs, and Physical AOPs (Miklos, et al., 2018).
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The focus of this research was on Ozone-based AOPs for the treatment of pharmaceuticals such as
Caffeine and Paracetamol in wastewaters. The use of ozone as an oxidant and disinfectant has been
well-known for long. As an oxidant, ozone is very selective and attacks primarily electron-rich
functional groups and since its reactions in real aqueous solutions often involve the formation of
HO•, ozonation itself is often considered an AOP or AOP-like process (Miklos, et al., 2018). Ozonation
itself might somewhat be ineffective or slow in some situations, and therefore methods to actively
initiate formation of radicals includes the ozonation at elevated pH and the combinations O3/H2O2
(also called Peroxone-process) have been previously studied and been used in full-scale
applications.
Caffeine and Paracetamol are some of the most common chemicals produced by pharmaceutical
companies, and their presence in wastewaters is inevitable. In order to keep the environment safe
from such pharmaceuticals, certain measures would be required by pharmaceutical companies to
operate and discharge their wastewaters to respective water bodies within regulatory standards.
Hence, commissioning a small-scale water treatment facility using Advanced Oxidation Process
technologies could be beneficial.
2) AIMS AND OBJECTIVES

The aim of this project was to treat pharmaceutical wastewater effluents for small scale water
treatment using Advanced Oxidation Processes (AOP). Initially, the following aims and objectives
were proposed in the Individual Research Plan.
1) Studying the efficiency of ozonation for the treatment of pharmaceuticals in wastewater.

a) Measuring the concentration of pharmaceuticals at the influent and effluent points.
2) Optimization of the process to determine the appropriate design considerations for maximum
efficiency.
a) Determining the required flow rate of ozone for optimal operation.
b) Determining the appropriate concentration of ozone required for maximum efficiency.
c) Determining the required reaction time for maximum degradation of pharmaceuticals.
d) Studying the effects of feed pH on the overall performance of the system.
The above-mentioned aims and objectives were based on designing a continuous treatment unit,
whereby the wastewater is constantly circulated and treated with ozone to achieve maximum
degradation of the pharmaceutical chemicals. However, the initial proposed experimental setup was
dropped as the reactor volume was not proportionate with the capacity of the ozone generator, and
hence the experiments would have been extremely time consuming. To tackle the situation, instead
of a continuous process, a batch process was setup in which the effects of ozone exposure was
studied within a known volume of wastewater. Unfortunately, the ozone concentration regulator
was not functioning, therefore the effect of varying ozone concentrations/flowrates could not have
been studied.
Since ozonation itself might not be efficient, the peroxone-process (O3/H2O2) was also studied by
adding a certain amount of H2O2 in the water. Furthermore, the effects of pH on the overall
performance was also determined. The following amendments were made within the aims and
objectives of the project.
- The required volume of reactor compatible with the ozone generator.

- The effects of H2O2 in the overall performance.
- The effects of pH on ozonation alone, and the peroxone-process.
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3) RESEARCH METHODOLOGY
3.1) Experimental setup
The experimental set up used to carry out the ozonation experiments is presented in Figure 1. The
setup includes an ozone system consisting of an ozone generator (1) with an oxygen gas flow
controller (2) at the inlet to meet the generator specifications. The batch reactor system consisted
of diffuser (3), and a magnetic stirrer (4) to ensure uniform distribution of the ozone bubbles and
achieve optimum mass transfer. The experiments were carried out near a window so that the area
is well ventilated and to minimize ozone exposure. A pH meter (5) was also utilized to determine
the initial pH of the sample.
Figure 1: Experimental setup
3.2) Analytical methods

The initial concentration of the sample was known, as the samples were prepared in the lab and
diluted accordingly. To measure the degradation/reduction in concentration, UV-VIS Spectrometry
was used using quartz cuvettes.
3.3) Studied pharmaceuticals

Table 1 presents the name, chemical formula, initial concentration of pharmaceuticals used in
ozonation experiments.
Table 1: Name, chemical formula, initial concentration of pharmaceuticals used in ozonation

experiments.
Initial concentration used

Name (Chemical Formula) Use
(ppm)
Caffeine (C8H10N4O2) Psychostimulant 30
Paracetamol/Acetaminophen
Mild analgesic 30
(C8H9NO2)
3.4) Preparation of standard solutions

In order to correlate the absorbance values with that of the concentrations of caffeine and
paracetamol, standard solutions were prepared. A stock solution of 1000 ppm and 500 ppm of
Caffeine and Paracetamol respectively were prepared and diluted accordingly. The absorbances
were noted in descending order of concentration. The following calibration curves, figures 2 and 3,
were produced. The corresponding absorbance will be used with the calibration curve to determine
the concentration at a given time. Based on literature, the wavelength for Caffeine and Paracetamol
were 273 and 243 nm respectively.
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Calibration curve (Caffeine), 273 nm

3
2.5 y = 0.0427x + 0.002
R² = 0.9997
2
abs.
1.5
1
0.5
0
0 10 20 30 40 50 60 70
Conc. (ppm)
Figure 2: Calibration curve (Caffeine)
Calibration curve (Paracetamol), 243 nm

3
2.5 y = 0.0622x - 0.0032
R² = 0.9992
2
1.5
abs.
1
0.5
0
0 10 20 30 40 50
-0.5
Conc. (ppm)
Figure 3: Calibration curve (Paracetamol)
3.5) Experimental procedure

For each experiment, 100 ml of 30 ppm concentration of Caffeine and Paracetamol samples were
prepared. All experiments were carried out at room temperature and at pH of 8 and 11. It should
be taken into consideration that the formation of hydroxyl ions is favored in alkaline conditions,
therefore acidic conditions were not experimented. The prepared aqueous solution was charged in
the reactor (beaker) and mixed for a few minutes. The ozone generator (Ozone Lab OL80 Series)
was switched on and then left for approximately 5-7 minutes to reach steady-state ozone
production. Ozone concentration was kept constant throughout all experiments at 17 µg/ml. The O2
gas used to produce O3 in the ozone generator was controlled and set by the flowmeter at 1 LPM
(as per the ozone generator specification). The ozone gas was continuously fed into the reactor via
a porous ceramic diffuser placed at the lower half of the reactor. The mixture was constantly stirred
to ensure uniform distribution of the ozone bubbles and achieve optimum mass transfer. In order
to maintain constant pressure and avoid any build up of pressure due to the ozone gas bubbles, the
ozone gas was discharged to the atmosphere by keeping the reactor uncovered. Ozone was bubbled
until no significant reduction in absorbance was observed in the UV-VIS Spectrometer (60 minutes).
Samples were withdrawn from the reactor at time intervals of 10 minutes, and the absorbance was
analyzed in the UV-VIS Spectrometer. To determine the corresponding concentration of the
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chemical at a given time, the calibration curves (Figure 2 and 3) were utilized. Similar protocol was
followed for the peroxone-process (O3/H2O2). 1 ml of 6% H2O2 w/v was used in each 100 ml solution.
Furthermore, it was observed that the O 3/H2O2 process was more efficient than ozonation alone,
and hence the experiment was repeated on a smaller volume of sample (25 ml) to determine if
degradation takes place more efficiently. 250 µl of H2O2 of the same concentration was used in this
case. The results and discussion of all experiments are presented in Sections 4 and 5 respectively.
4) RESULTS
The following figures show the reduction in Caffeine concentration with respect to time in three
different process setups. The experiments were carried out at pH 8 and 11. It can be observed that
the degradation of Caffeine with ozonation alone (Figure 4) at pH 8 and 11 was 8% and 38%
respectively in 60 minutes, which indicates that highly alkaline conditions are more favorable with
respect to degradation. Furthermore, when Caffeine was exposed to the peroxone-process,
degradation at pH 8 and 11 was 26% and 53% respectively. This proves that the peroxone-process
is relatively more efficient than ozonation itself. Finally, the peroxone-process was repeated for a
25 ml solution at pH 11, where 63% degradation of Caffeine was achieved. The results will be
further discussed in Section 5 of this report.
In comparison to Caffeine, although slight reduction in concentration was observed, Paracetamol

did not degrade as efficiently. With ozonation alone, at pH 8 and 11, only 4% and 10% reduction in
Paracetamol was achieved in 60 minutes. In the peroxone-process, at pH 8 and 11, 8% and 16%
Paracetamol degraded. When the peroxone-process was used in a 25 ml solution at pH 11,
Paracetamol only degraded by 23%, which is relatively insignificant.
Table 2: Ozonation of Caffeine at pH 8 and 11 for 100 ml batch reaction
Concentration (ppm)
Time (min)
pH 8 pH 11
0 30.0 30.0
10 29.6 26.9
20 28.3 23.6
30 27.8 21.6
40 27.7 20.5
50 27.7 20.4
60 27.6 18.7
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Ozonation (Caffeine)
35.000
30.000
Conc. (ppm) 25.000

20.000
15.000
10.000
5.000
0.000
0 10 20 30 40 50 60
Time (min)
pH 8 pH 11
Figure 4: Ozonation of Caffeine at pH 8 and 11 for 100 ml batch reaction
Table 3: O3/H2O2 process for caffeine at pH 8 and pH 11 for 100 ml batch reaction
Concentration (ppm)
Time (min)
pH 8 pH 11
0 30.0 30.0
10 28.3 26.5
20 26.5 23.6
30 23.6 20.5
40 22.5 18.2
50 22.2 14.3
60 22.2 14.2
Peroxone-process (O3/H2O2) (Caffeine)

35.000
30.000
25.000
Conc. (ppm)
20.000
15.000
10.000
5.000
0.000
0 10 20 30 40 50 60
Time (min)
pH 8 pH 11
Figure 5: O3/H2O2 process for caffeine at pH 8 and pH 11 for 100 ml batch reaction
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Table 4: O3/H2O2 process for caffeine at pH 11 for 25 ml batch reaction
Concentration (ppm)
Time (min)
pH 11
0 30.0
10 21.3
20 19.5
30 14.4
40 11.6
50 11.1
60 11.1
Peroxone-process (O3/H2O2) (Caffeine)

35.000
30.000
25.000
Conc. (ppm)
20.000
15.000
10.000
5.000
0.000
0 10 20 30 40 50 60
Time (min)
Figure 6: O3/H2O2 process for caffeine at pH 11 for 25 ml batch reaction
Table 5: Ozonation of Paracetamol at pH 8 and 11 for 100 ml batch reaction
Concentration (ppm)
Time (min)
pH 8 pH 11
0 30.0 30.0
10 29.2 28.8
20 29.0 28.1
30 28.8 27.3
40 28.8 27.2
50 28.7 26.9
60 28.7 26.9
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Ozonation (Paracetamol)
31.000
30.000
Conc. (ppm) 29.000
28.000
27.000
26.000
25.000
0 10 20 30 40 50 60
Time (min)
pH 8 pH 11
Figure 7: Ozonation of Paracetamol at pH 8 and 11 for 100 ml batch reaction
Table 6: O3/H2O2 process for Paracetamol at pH 8 and pH 11 for 100 ml batch reaction
Concentration (ppm)
Time (min)
pH 8 pH 11
0 30.0 30.0
10 29.0 28.3
20 28.3 27.7
30 27.9 26.7
40 27.8 25.6
50 27.8 25.3
60 27.7 25.3
Peroxone-process (O3/H2O2) (Paracetamol)

31.000
30.000
29.000
Conc. (ppm)
28.000
27.000
26.000
25.000
24.000
23.000
22.000
0 10 20 30 40 50 60
Time (min)
pH 8 pH 11
Figure 8: O3/H2O2 process for Paracetamol at pH 8 and pH 11 for 100 ml batch reaction
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Table 7: O3/H2O2 process for Paracetamol at pH 11 for 25 ml batch reaction
Concentration (ppm)
Time (min)
pH 11
0 30.0
10 27.0
20 25.6
30 24.2
40 23.1
50 23.1
60 23.1
Peroxone-process (O3/H2O2) (Paracetamol)

35.000
30.000
25.000
Conc. (ppm)
20.000
15.000
10.000
5.000
0.000
0 10 20 30 40 50 60
Time (min)
Figure 9: O3/H2O2 process for Paracetamol at pH 11 for 25 ml batch reaction
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5) DISCUSSION
Based on the individual research proposal, the experiments were to be carried out to design a
continuous process wherein the wastewater would be constantly circulated within the reactor, where
it would be exposed to ozone and subsequently the pharmaceutical chemical would be oxidized and
degraded. The aim of the experiment was to enhance maximum mass transfer within a short span
of time while optimizing the process to determine the appropriate ozone concentration/flowrate,
flowrate of water circulation, and pH of solution. Preliminary studies were done to determine the
effect of ozone concentration on the degradation efficiency by altering the settings of the
concentration regulator on the ozone generator. No substantial difference was observed in
degradation and it was concluded that the regulator is dysfunctional. Hence the concentration was
set to a maximum. Based on the ozone generator supplier specification sheet the concentration of
ozone at the output (at maximum setting) was 17 µg/ml. In addition, due to the unavailability of a
calibrated ozone analyzer, the output concentration at the ozone generator could not be measured
for verification purposes. Therefore, it was assumed that the ozone concentration was in fact 17
µg/ml based on the supplier specification sheet. Oxygen was provided to the ozone generator at 1
LPM, which corresponded to a production of ozone at approximately 1020 mg/hr as per the supplier
specification sheet. Although an odor of ozone could be sensed near the apparatus, the functionality
of the ozone generator remained the major uncertainty throughout the project, considering it was
one of the main contributors in all the experiments conducted. Moreover, within the preliminary
studies, when the water containing the pharmaceutical was charged into the initially planned reactor
tube for a continuous reaction, no degradation was observed. It was concluded that the reactor
volume (approximately 1 L) might be too large for the ozone generator to have an effect. Hence,
the experiments were conducted on smaller volumes (100 and 25 ml) of water as a batch process.
5.1) Pharmaceutical oxidation by ozonation

Ozonation has been considered as a capable technology for treating different organic chemicals
effectively in water and wastewater (Gerrity, et al., 2012). One of the oxidation pathways consist
of the action of radical species generated from ozone decomposition that subsequently form
hydroxyl ions. This leads to a very fast reaction with organic compounds (Almomani, et al., 2016).
Similarly, the hydroxyl ions have the tendency to oxidize pharmaceutical compounds, given that
the ozone completely decomposes in the mixture. When caffeine, a stimulant, was bubbled into the
reactor with ozone alone, only 8% degraded while Paracetamol concentration reduced only by 4%
in 1 hour at a pH 8. The same experiments were conducted at pH 11, in which caffeine and
paracetamol degraded by 38% and 10% respectively. The generation of hydroxyl ions via ozonation
is relatively low, and that is why additional measures such as H2O2 dosing might become necessary
for the generating OH• (Sillanpaa, et al., 2017). Furthermore, to promote the decomposition of
ozone in water, a higher dose of ozone might be required, therefore 17 µg/ml concentration proves
to be insufficient. Hence, in the case of pharmaceutical oxidation by ozonation alone, caffeine and
paracetamol did not degrade very efficiently due to the low concentration of ozone.
5.2) Impact of peroxone-process for treatment of pharmaceuticals in water

To enhance the formation of hydroxyl ions, the peroxone-process was implemented to determine
the degradation efficiency of caffeine and paracetamol in water. (Antoniou & Andersen, 2012)
reported that the addition of H2O2 to the ozonation process helps enhance the degradation of organic
pollutants by accelerating ozone decomposition into highly reactive and nonselective OH • by the
following reaction.
H2O2 + 2O3 → 3O2 + 2OH•
This phenomenon is reflected when at pH 8 the degradation efficiency of caffeine and paracetamol
increased to 26% and 8% respectively in a reaction time of 1 hour. Similarly, at pH 11, caffeine and
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paracetamol degradation were 53% and 16% respectively. (Tubic, et al., 2011) conducted a pilot-
scale experiment to study the effect on the removal of natural organic matter of various O 3/H2O2
ratios. Their main finding was that higher ratios of O3/H2O2 resulted in higher removal efficiencies
of NOM as compared to lower ratios. In all the experiments, H2O2 was added to the solution with a
ratio 100:1, as in 1 ml of 6% w/v H 2O2 was added to each 100 ml solution of caffeine and
paracetamol. Any further addition of H2O2, or a higher concentration of H2O2, caused excessive
interference in the UV-Vis Spectrometer at wavelengths of 273 nm (caffeine) and 243 nm
(paracetamol). However, based on this, if a higher concentration of ozone was bubbled through the
reactor, caffeine and paracetamol may have degraded more efficiently.
5.3) Effects of initial pH

Based on the results presented in Section 4, initial pH of the sample had a significant effect on the
degradation efficiency of both caffeine and paracetamol. According to (Elovitz & von Gunten, 1999),
at elevated pH, ozonation is considered as an AOP if the generation of OH • is intentionally favored.
(Miklos, et al., 2018) suggested that the abundance of hydroxide ions (at higher pH levels) directly
influences the generation of hydroxyl radicals. It is well known that ozone chemistry is controlled
by the pH of the solution, as elevated pH levels promote ozone decomposition into hydroxyl radicals
that are more reactive and less selective than the molecular ozone. Therefore, the peroxone-process
at pH 11 was more effective compared to other scenarios as the presence of H 2O2 and hydroxide
ions due to high pH favored the formation of hydroxyl radicals that subsequently resulted in
relatively higher degradation efficiency.
5.4) Reactor volume

One of the most important aspects of any reaction, are the reactor volume and residence time. In
a chemical reaction, it is essential to have adequate mass transfer in order to obtain positive results.
Since the peroxone-process at highly alkaline conditions gave a positive response compared
ozonation alone with regards to the degradation efficiency of both caffeine and paracetamol, the
experiment was repeated with reducing the reactor volume by 75%. The volume was reduced from
100 ml to 25 ml. 250 µl of the same H2O2 was added to the solution based on the same ratio of
100:1. The idea behind this was to enhance the oxidation of caffeine or paracetamol by hydroxyl
radicals, as the distribution of OH • would take place in a confined environment, which would
subsequently increase mass transfer. A reduction in reactor volume had a positive impact on both
pharmaceuticals when compared to all other conducted experiments. Caffeine concentration
reduced from 30 ppm to 11 ppm (63% degradation), while paracetamol reduced from 30 ppm to
23 ppm (23% degradation).
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6) CONCLUSIONS AND RECOMMENDATIONS

The research conducted indicates that ozone-based Advanced Oxidation Processes possess the
potential of treating pharmaceutical wastewaters. With the current design considerations caffeine
and paracetamol can be degraded up to 63% and 23% respectively. Within the ozone-based AOPs,
the peroxone-process in highly alkaline conditions is relatively better compared to ozonation alone.
On the other hand, it should be noted, that paracetamol degradation was only up to 23% which is
relatively insignificant. The reason for such low degradation efficiency could be that the
concentration of ozone was insufficient in this scenario and the hydroxyl radicals produced were not
enough to oxidize paracetamol. By exposing paracetamol to higher concentrations of ozone
relatively positive results can be expected. To enhance the degradation efficiencies of both caffeine
and paracetamol, and for obtaining more accurate results, the following amendments to the
experimental setup are recommended.
- Using an ozone generator that can produce higher concentrations of ozone. This would
subsequently allow more decomposition of ozone that would produce hydroxyl radicals, and
hence higher degradation efficiencies of caffeine and paracetamol can be achieved. The
ozone generator should consist of an ozone concentration regulator, with which the
concentration can be altered, and the process can be optimized. With this type of ozone
generator, larger volumes of wastewater can be treated as well.
- Within the experimental setup, a calibrated ozone analyzer should be used at the output of
the ozone generator. Frequent monitoring of ozone concentration would allow us to produce
the relevant data for the comparison of ozone concentration and degradation efficiency.
- Using High Performance Liquid Chromatography (HPLC) for analysis in addition to UV-Vis.
Although UV-Vis spectrometry is considered as less time consuming and economical, HPLC
produces more accurate and precise results, and this would improve the overall accuracy in
research.
- A wider range of pharmaceuticals should be studied. This could include pharmaceuticals such
as antibiotics and estrogens that are frequently produced and readily detected in
wastewaters.
- Furthermore, using actual pharmaceutical wastewaters instead of samples produced in lab
for experimentation would allow us to study other factors that might influence the efficiency
of the applied AOP.
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Acknowledgments
The author wishes to acknowledge and appreciate the efforts and support provided by Dr. Jacob
Uguna and Prof. PJ Cullen of the Department of Chemical and Environmental Engineering at the
University of Nottingham for the completion of this project. In addition, the author acknowledges
his project team members, Mr. Yifan Ding, Mr. Hzien Siew, and Mr. Joshua Ho for their teamwork
and making this project a lifelong memorable experience.
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Journal of the Department of Chemical and Environmental Engineering:

University of Nottingham 2018

TREATMENT OF CHEMICALS IN PHARMACEUTICAL WASTEWATERS USING OZONE

Conventional treatment processes, as mentioned before, tend to be ineffective in the removal of

2) AIMS AND OBJECTIVES

1) Studying the efficiency of ozonation for the treatment of pharmaceuticals in wastewater.

- The required volume of reactor compatible with the ozone generator.

Figure 1: Experimental setup

3.2) Analytical methods

3.3) Studied pharmaceuticals

Table 1: Name, chemical formula, initial concentration of pharmaceuticals used in ozonation

Initial concentration used

3.4) Preparation of standard solutions

Calibration curve (Caffeine), 273 nm

Figure 2: Calibration curve (Caffeine)

Calibration curve (Paracetamol), 243 nm

Figure 3: Calibration curve (Paracetamol)

3.5) Experimental procedure

In comparison to Caffeine, although slight reduction in concentration was observed, Paracetamol

Table 2: Ozonation of Caffeine at pH 8 and 11 for 100 ml batch reaction

Conc. (ppm) 25.000

Figure 4: Ozonation of Caffeine at pH 8 and 11 for 100 ml batch reaction

Peroxone-process (O3/H2O2) (Caffeine)

Table 4: O3/H2O2 process for caffeine at pH 11 for 25 ml batch reaction

Peroxone-process (O3/H2O2) (Caffeine)

Figure 6: O3/H2O2 process for caffeine at pH 11 for 25 ml batch reaction

Table 5: Ozonation of Paracetamol at pH 8 and 11 for 100 ml batch reaction

Figure 7: Ozonation of Paracetamol at pH 8 and 11 for 100 ml batch reaction

Peroxone-process (O3/H2O2) (Paracetamol)

Table 7: O3/H2O2 process for Paracetamol at pH 11 for 25 ml batch reaction

Peroxone-process (O3/H2O2) (Paracetamol)

Figure 9: O3/H2O2 process for Paracetamol at pH 11 for 25 ml batch reaction

5.1) Pharmaceutical oxidation by ozonation

5.2) Impact of peroxone-process for treatment of pharmaceuticals in water

H2O2 + 2O3 → 3O2 + 2OH•

5.3) Effects of initial pH

5.4) Reactor volume

6) CONCLUSIONS AND RECOMMENDATIONS

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