Applied Catalysis A: General 510 (2016) 134–155

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Applied Catalysis A: General

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

Heterogeneous photocatalytic studies of analgesic and non-steroidal

anti-inflammatory drugs
Amandeep Kaur a , Ahmad Umar b,c,∗ , Sushil K. Kansal a,∗∗
a
Dr S.S. Bhatnagar University Institute of Chemical Engineering & Technology, Panjab University, Chandigarh 160014, India
b
Department of Chemistry, College of Science and Arts, Najran University, PO Box-1988, Najran 11001, Saudi Arabia
c
Promising Centre for Sensors and Electronic Devices (PCSED), Najran University, PO Box-1988, Najran-11001, Saudi Arabia

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

Article history: The presence of pharmaceutical compounds in natural water is considered as an environmental problem
Received 23 July 2015 due to their regular input in aquatic system and hence their removal becomes a challenging task. The
Received in revised form 21 October 2015 present study provides information about the occurrence of pharmaceutical contaminants in water and
Accepted 6 November 2015
their treatment. The advancement of distinct treatment processes for the removal of active pharmaceu-
Available online 6 December 2015
tical ingredients in wastewater has been described. The main objective of this study is to summarize the
latest studies of the degradation of analgesic and anti-inflammatory drugs by heterogeneous photocatal-
Keywords:
ysis. This study also highlights the effect of various operational parameters on degradation efficiency,
Analgesic
Anti-inflammatory drugs
kinetics and mineralization of various pharmaceutical compounds during the process.
Advanced oxidation processes © 2015 Elsevier B.V. All rights reserved.
Photocatalysis
Titania

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
1.1. Occurrence of pharmaceuticals in the aquatic environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
2. Pharmaceutical wastewater treatment processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2.1. Conventional treatment processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2.2. Advanced oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3. Treatment of analgesic and non-steroidal anti inflammatory drugs by heterogeneous photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3.1. Ibuprofen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3.2. Diclofenac . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3.3. Paracetamol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.4. Naproxen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3.5. Other drugs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

1. Introduction

Water, a natural resource is essential for the existence of life.

∗ Corresponding author at: Department of Chemistry, College of Science and Arts, Although water is present in abundance, but only a limited amount
Najran University, PO Box-1988, Najran 11001, Saudi Arabia. of usable water is available. The level of ground water is decreasing
∗∗ Corresponding author at: Dr. S.S. Bhatnagar University Institute of Chem-
day by day because of more industrialization, improved agriculture,
ical Engineering & Technology, Panjab University, Chandigarh 160014, India.
Fax: +91 172 2534920.
inappropriate disposal techniques, excessive population growth
E-mail addresses: ahmadumar786@gmail.com (A. Umar), sushilkk1@pu.ac.in, and change in climatic conditions [1]. Therefore, the optimum uti-
sushilkk1@yahoo.co.in (S.K. Kansal). lization of the limited water available becomes utmost priority

http://dx.doi.org/10.1016/j.apcata.2015.11.008
0926-860X/© 2015 Elsevier B.V. All rights reserved.
 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
and this could be done only by improving the quality of water
and removing unwanted organic, inorganic and mineral substances
from water streams.
Pharmaceuticals have been identified as potential contami-
nants in aquatic environments among various water pollutants
throughout the world [2–5], and pollution by these drugs increased
noticeably with their incessant use over the years. The consump-
tion rate of the drugs has been increasing in the USA, Japan,
France, Spain, United Kingdom and Italy by 11.9% every year.
There are around 3000 compounds used as pharmaceuticals; anti-
inflammatory/analgesic and antibiotics being the most common
drugs consumed for therapeutic use [6].
In the 1960s, existence of pharmaceutical contaminants was
detected in wastewater in Europe and United States for the first
time. Since then contamination of the environment with these
pharmaceuticals has been acknowledged worldwide [7]. The phar-
maceutical industry uses active pharmaceutical ingredients (APIs)
for the production of desired drugs, which are pharmacologically
active, toxic in nature [8], resistant to degradation, chemically per-
sistent in aqueous media, and has adverse happenings in water
bodies and adverse impact on living beings. These compounds
enter into natural water streams from a number of sources such as
pharmaceutical industrial discharge, personal care products, hos-
pital effluents, therapeutic drugs, sewage systems and excretion
from livestock etc. [9]. They remain in the environment, enter
into the food chain, bioaccumulate, biomagnify and have danger-
ous effects on humans and wildlife. Few adverse health effects of
these pharmaceutical contaminants are genotoxicity, resistance in
microorganisms, toxicity in aquatic environments and hormonal
disruption [10,11]. The existence of these drugs, even in low con-
centration in water for a prolonged duration is very dangerous and
their removal is a challenging task [12–15]. In addition, there are
no legally permissible limits for these pharmaceuticals in waste
water as the exact impact of chronic exposure of pharmaceuti-
cals on aquatic environment still remains unknown [7]. It has been
estimated that about 50 percent of the pharmaceutical wastewater
produced throughout the world is released into the environment
without any proper treatment [16]. These pharmaceuticals may
also be released into the environment by excretion of partially
transformed active pharmaceutical ingredients by human beings
and animals [7,9,17].
Treatment of pharmaceutical wastewater is necessary because
it not only stabilizes the environment and protects the living
beings from various water borne diseases, but also makes water
available for use in numerous applications such as agriculture irri-
gation, washing purposes and non-potable municipal use [18,19].
Most of the pharmaceutical compounds present in wastewater are
polar micropollutants which are not easily removed by wastewater
treatment plants (WWTPs) [20]. Consequently, these micropollu-
tants pass through the surface water and after leaching they enter
into the ground water. The WWTPs which receive the pharma-
ceutical polluted water from sewage plants are not capable of
removing these micropollutants because they are designed only
for the removal of oxygen demand, suspended solids, pathogens,
and nutrients from wastewater. There are many studies which
clearly mention that conventional treatments such as adsorption,
coagulation, ion flotation and sedimentation used in WWTPs have
limited degradability of active pharmaceutical compounds and
therefore their end product requires further treatment [15,21]. Bio-
logical treatment methods have been traditionally used for the
management of pharmaceutical wastewater [22]. These treatment
procedures are limited only to effluents which mainly consist of
biodegradable compounds and are not hazardous to the biological
culture [23,24].
Current literature shows that the advanced oxidation processes
(AOPs) are far more effective and efficient in removal of pharma-
135
ceutical contaminants. In general, all AOPs possess similar chemical
property, i.e. generation of reactive oxygen species which are non
selective in nature and have an ability to oxidize recalcitrant com-
pounds by hydroxylation or dehydrogenation which are further
mineralized into end products as CO2 and H2 O [25–30]. The treat-
ment of pharmaceutical wastewater by AOPs such as photolysis,
photocatalysis, ozonation, ultrasound radiation, fenton and photo-
fenton, etc. exhibit fluctuating degree of removal efficiency [31–38].
Among all AOPs, heterogeneous photocatalysis is the most distinc-
tive technique for the removal of persistent contaminants from
wastewater. Several toxic organic or inorganic water pollutants can
be completely mineralized into more biologically degradable and
harmless substances at comparatively lower costs using heteroge-
neous photocatalysis [39].
Recent studies demonstrate that non-steroidal anti-
inflammatory drugs (NSAIDs) are frequently found in surface
water, sewer water, ground water and even in drinking water
as pharmaceutically active compounds [21,40–42]. The NSAIDs
consists of a heterogeneous family of drugs having analgesic
and anti-inflammatory features. Among NSAIDs, diclofenac and
ibuprofen are the most commonly consumed drugs and are usually
found in surface water. The main aim of this review is to assess the
acquirable information on the occurrence and the removal of anal-
gesic and NSAIDs from wastewater through photocatalysis process.
1.1. Occurrence of pharmaceuticals in the aquatic environment
The production of pharmaceutical compounds is grabbing con-
siderable attention for promoting better health care facilities
worldwide and longer life expectancy of people. As a result, the
consumption of various pharmaceutical compounds has increased
drastically over the years and has led to generation of large volumes
of waste water whose treatment is a problem in itself. Thou-
sand tons of pharmaceuticals are readily taken up by humans and
animals which are released into the municipal treatment plants
through metabolic excretion and various inappropriate disposal
techniques. Besides, solid waste excreted by animals which is used
as manure for agriculture enters the food chain through crops. The
unused and expired drugs from household, hospitals, industries
and others sources are also continuously released into the envi-
ronment. Though, a small proportion of these drugs are reduced
through incineration, but still major quantity of these drugs have
been discarded to waste disposal area or flushed down via toi-
let into municipal sewer [43,44]. As these drugs are partially or
impartially soluble in water, they pass through the water treat-
ment plants without being eliminated completely. Moreover, the
pharmaceuticals which make their way through the soil via differ-
ent means remain intact as they are unabsorbed by the soil because
of their polar nature and hence possess strong potential to get into
the environment [45–48].
Another source of pharmaceutical pollution is the effluent
from manufacturing units which is treated in effluent treatment
plant (ETP). ETP is an assembly of various treatments which are
arranged in such a manner that the final product of one stage is
used as input of the next stage for remediation. The various stages
include preliminary, primary, secondary and tertiary treatment.
In addition, disinfectant (chlorine) is added after the tertiary
treatment to eliminate the pathogens which are responsible for
various diseases. After disinfection, this partially treated water
containing remnants of pharmaceutical contaminants enters into
surface and ground water which leads to their potential existence
in drinking water as well. Fig. 1 shows possible sources and
pathways of pharmaceutical compounds entering into the aquatic
environment. The presence of these pharmaceutical compounds
and their metabolites even in minute quantities in water are a risk
to aquatic and human life [49]. The unfavorable effect on aquatic
136 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
Fig. 1. Possible sources and pathway of pharmaceuticals compounds into the aquatic environment.
environment includes feminization of male fish, renal failure and
impairment of gill and lever in fish.
2. Pharmaceutical wastewater treatment processes
2.1. Conventional treatment processes
The conventional treatment processes consist of physical, chem-
ical and biological methods which include various procedures
such as preliminary, primary, secondary and tertiary treatment
[50]. Primary treatment partially eliminates pharmaceutical con-
taminants from wastewater [21] which require further advanced
treatment. The dissolved organic compounds in water can be oxi-
dized by biological treatment method. The biological treatment
process involves the use of microorganisms which consume a vari-
ety of organic compounds [51]. Activated sludge (AS) process has
been by far the most preferred biological method for degradation
of pharmaceutical wastewater due to its large hydraulic retention
time [52]. Temperature, dissolved oxygen, pH, hydraulic reten-
tion time, organic load, microorganisms and existence of harmful
substances are the various factors that affect the efficiency of AS
process [53]. AS process has a lower installation cost and lesser
operational needs as compared to more advanced methods. It is
more eco-friendly than chlorination but has some disadvantages as
well, like high energy consumption, difficult to operate and gener-
ates huge amount of sludge [54]. The pharmaceutical contaminants
remain ineffective in AS process under standard operating con-
ditions [55]. However, higher concentrations of pharmaceuticals
force it to be restrictive. AS treatment is inefficient where COD con-
tent in wastewater is more than 400 mg/L [22]. These biological
methods do not completely remove the high concentration of pol-
lutants present in wastewater. The removal efficiency of diclofenac
varied from 0 to 75% with AS treatment method, while that for car-
bamazepine was usually below 10% shown in Fig. 2 [56,57]. The
primary sedimentation technique eliminated ibuprofen from 12%
to 45%. The concentration after primary treatment decreased from
20 to 43% with biological treatment technique [58]. Stumpf et al.
[59] investigated the higher removal efficiency of diclofenac (75%),
ibuprofen (75%), ketoprofen (69%), naproxen (78%) and clofibric
acid (34%) with activated sludge process.
The specific pharmaceutical compounds which are retained
in the wastewater after secondary treatment are eliminated by
tertiary treatment methods such as coagulation and filtration,
 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155 137

Fig. 2. Removal efficiency distributions of carbamazepine and diclofenac in WWTPs.

activated carbon, membrane separation, chemical removal and Table 1

Classification of advanced oxidation processes.
electrodialysis. However, the efficiency of these methods fluctuates
critically. Activated carbon is another tertiary treatment method Advanced oxidation processes
which is used for removal of natural and synthetic organic species
Homogeneous process Heterogeneous process
from wastewater. It is reported that activated carbon has high ten-
With or without light source • Photocatalytic ozonation
dency to adsorb pharmaceutical contaminants from wastewater
• Heterogeneous photocatalysis
[60–62]. But, the separation of carbon from water is a difficult task. • Photolysis
These methods have various operational difficulties in addition • H2 O2 photolysis
to high capital costs. Thus, these methods may not be appropri- • Fenton and Photo fenton
ate for the complete removal of pollutants from the environment. • O3 /UV
• O3 /H2 O2 /UV
Therefore, there is a significant need to develop a wastewater treat- • O3 /H2 O2
ment process which can remove the pollutants effectively by simple • Catalytic ozonation
method.

2.2. Advanced oxidation processes
As we know, conventional treatment methods are incapable
enough to treat various toxic and non biodegradable pollutants and
in the last couple of decades, a lot of researchers have prominently
adopted advanced oxidation processes for the degradation of these
organic pollutants which are difficult to treat. This clearly signi-
fies the importance of AOPs in removing recalcitrant pollutants
from wastewater under ambient conditions [63]. The production
of hydroxyl radicals (• OH) or other species of same reactivity is the
characteristic feature of most AOPs. This highly reactive hydroxyl
radical react with all kinds of natural and synthetic organic pollu-
tants non-selectively and rapidly, thereby oxidizing the recalcitrant
organic matter and eventually transforming them into their min-
eralized products [13,64]. The highlight of this process is that it can
propose various approaches for the production of hydroxyl radicals,
hence enabling suitable agreement with the typical requirements
of treatment methods AOPs can be used as both pretreatment as
well as post-treatment option in biological processes [65].
Advanced oxidation processes can be classified on the basis of
phase systems, i.e., homogeneous and heterogeneous processes,
both of which can be performed with or without the use of light
source [66]. These processes make use of different light source, oxi-
dants and catalysts to produce highly reactive hydroxyl radicals for
the treatment of wastewater. A list of various possible types of AOPs
is given in Table 1.
Photolysis involves the breakdown of a target molecule by
the absorption of light and leads to its photolytic decomposi-
138 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
tion to intermediate products whose degradation ultimately gives
mineralized end products [67,68]. However, limited studies have
been reported to understand the behaviour of pharmaceutical
substances and their photochemistry in aquatic environments is
largely undiscovered [33,69,70]. Many pharmaceutical compounds
are very sensitive to photolytic transformation [71]. The perfor-
mance of the photolytic process can be improved by combining
light source with hydrogen peroxide (H2 O2 ), followed by photolytic
dissociation which produces hydroxyl radicals, thereby facilitating
oxidation process. The important role of hydrogen peroxide is to
promote the photolysis by using UV light ( < 300 nm) as shown
in recent studies [33,71,72]. The photolysis with H2 O2 is gener-
ally accomplished with high intensity mercury vapor lamp with
low and medium pressure so as to reduce the required amount of
H2 O2 required. The advantage of this process can be ascribed to
the fact that H2 O2 , effective source of • OH, is completely soluble
in water and requires no separation after treatment [73,74]. Alalm
et al. [75] investigated the complete degradation of diclofenac and
paracetamol achieved at acidic pH (pH 3) in 120 and 60 min of
irradiation respectively. However, at higher pH the degradation
efficiency of these drugs decreased remarkably. This could be due
to poor rate of oxidation of H2 O2 at pH > 4, which leads to lesser
generation of • OH. The organic content present in the water may
also reduce the radical production, thereby decreasing degradation.
Another study compared the degradation efficiency of ibuprofen
by different photochemical processes. The results demonstrated
that UV-C irradiation facilitates only 53% of TOC (total organic car-
bon) removal, while H2 O2 photolysis exhibited an increase in TOC
removal upto 90% for ibuprofen. It is fascinating to study that even
though the mineralization of ibuprofen obtained by UV-C photol-
ysis is insufficient for wastewater treatment [76], this TOC value
is really higher than that achieved by Mendez-Arriaga et al. [77]
under UV-A irradiation.
Fenton process is another type of AOPs used for the treatment
of wastewater [78]. In this process, fenton’s reagent oxidizes in the
presence of ferrous salt and H2 O2 in a simple redox reaction. This is
a metal catalyzed based oxidation reaction in which iron (Fe2+ ) act-
ing as a catalyst gets oxidized to Fe3+ . The efficiency of this process
can be significantly increased by increasing the number of hydroxyl
ions produced in the presence of UV irradiations and hence so called
“photo-Fenton” process [79]. Its efficiency depends on the various
factors such as reaction time, pH of the solution (ranging between 2
and 4), H2 O2 concentration, nature and quantity of organic contam-
inants present in wastewater [80]. The advantage of this process is
that the degradation of toxic organic pollutants is possible under
UV light as well as solar light [81], Also, it requires simple apparatus
from bench to large scale at normal temperature and pressure [82].
Less toxic and biodegradable intermediates are produced as final
product which further needs biological post treatment [83]. Rad
et al. [84] studied the degradation of paracetamol in aqueous phase
using photoFenton in a binary system. The degradation efficiency
for 20 mg/L concentration of paracetamol and phenol were found to
be 85 and 95% with cobalt ferrite (0.2 g/L) and H2 O2 (50 mmol/L) at
pH 3.5 respectively. In a study conducted by Loaiza-Ambuludi et al.
[76], 96% mineralization of ibuprofen (0.2 mM, pH 3) was achieved
using Fe3+ (0.25 mM) and H2 O2 (10 mM) after 8 h of UV-C irradia-
tion. Ravina et al. [85] investigated the removal of diclofenac with
photoFenton oxidation using 400 W low pressure mercury lamp in
photoreactor. About 90% TOC removal of diclofenac was achieved
within 1 h using Fe2+ (14 mg/L), H2 O2 (340 mg/L) at pH 2.8. de Luna
et al. [86] observed the reaction kinetic for the degradation of parac-
etamol by varied ferrous iron to H2 O2 ratio using Fenton oxidation.
It was observed that the diclofenac degradation followed 2nd order
reaction kinetics. The intermediates such as hydroquinone, ben-
zaldehydes, benzoic acids and several non-aromatic organic acids
were identified during fenton oxidation and further converted into
mineralized products such as NH4 + , CO2 and H2 O.
Ozone (O3 ), a very selective oxidant, has gained noteworthy
attention in remediation and purification of wastewater [87]. It
removes the micropollutants as well as reduces its color, foam and
odour [88]. In water, it either decomposes itself to produce very
reactive hydroxyl radicals, which brings out the indirect oxidation
of organic pollutants or attacks specifically on particular functional
groups of organic moieties via an electrophilic mechanism [89].
This process has been implemented to improve the biodegradabil-
ity and performance of the treatment method [90]. In addition, the
efficiency of ozone process is increased by combining ozone with
hydrogen peroxide, UV irradiations and catalyst [13]. The limita-
tion of this process is that it enhances the energy requirement by
40–50% in comparison to the conventional treatment process.
Over the last ten decades, a number of studies have been
reported on the degradation of pharmaceutical wastewater using
ozone [91,92]. Aguinaco et al. [93] studied the complete degra-
dation of diclofenac (10−4 M) using 1.5 g/L of TiO2 , 10 mg/L O3
concentration with flow rate of 30 L/h in 6 min and 65 to 75% TOC
removal was obtained after 60 min of reaction. About 32% mineral-
ization of diclofenac was reached in 90 min with single ozonation
[94]. Another study investigated the kinetic parameter studies with
O3 and O3 /H2 O2 for the removal of pharmaceutical compounds
from water [95]. The degradation of drugs like ibuprofen, clofib-
ric acid and diclofenac has been studied with O3 /H2 O2 bringing
out almost 98% of mineralization [96]. Several sulfonamides and
trimethoprim were removed (>90%) from river water by ozonation
(O3 dose = 7.1 mg/L) in 1.3 min [97]. The required quantity of ozone
depends on various parameters such as alkalinity, pH of wastew-
ater, properties of dissolved organic matter and desired removal
performance of target compounds [98]. pH plays an important role
in ozonation process, as both the absorption and reaction rates of
ozone get influenced by lowering the pH [99]. This process has few
disadvantages as well, which restricts its use worldwide as it is
an energy demanding process and is expensive to implement [88].
Also, the target compounds which are not fully treated can be sim-
ply transformed into another phase resulting in the production of
more other harmful substances [92]. The efficiency of this process
can be enhanced by combining it with H2 O2 and UV light, which
is expected to stimulate the elimination rate considerably by gen-
erating more hydroxyl radicals in the treatment procedure [65].
Ozone based processes such as O3 /H2 O2, O3 /UV and O3 /UV/H2 O2
may produce • OH in different ways. These combined methods are
considered to be most efficient processes for removal of recalcitrant
organic pollutants.
Recently, catalytic oxidation using ozone has emerged to be
very noteworthy and valuable research area [100–103]. The pro-
cess includes both homogeneous and heterogeneous catalytic
ozonation. The principal of homogeneous catalytic ozonation is
stimulation of ozone in the presence of metal ions such as Fe(II),
Mn(II), Ni(II), Co(II), Cd(II), Cu(II), Ag(I), Cr(III), and Zn(II), by
generating hydroxyl radicals [100,103,104]. Heterogeneous pho-
tocatalytic ozonation employs the use of catalysts such as metal
oxide and supported metal oxides, over which adsorption of ozone
takes place which further decomposed into surface-obligated rad-
icals and hydroxyl radical on the catalyst surface [100,105]. In this
heterogeneous process, the initial performance of hydroxyl radicals
is principally influenced by the variation in surface characteristics
of catalysts, keeping in view that the decomposition of ozone sig-
nificantly depends on point of zero charge of catalyst, which is also
important for the initiation. The point of zero charge and density
of hydroxyl groups present on the surface of the catalyst varies
indigenously with the modification of the catalyst with metals. pH
plays a crucial role in the determination of charge properties of
the hydroxyl groups catalyst/water interface [102,106,107]. The
 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
Fig. 3. Schematic mechanism of photocatalytic reaction for the degradation of drug
using TiO2 photocatalyst.
hydroxyl groups, mostly have no surface charge, when the pH of
an aqueous solution is close to the point of zero charge, on the con-
trary, when the pH is above or beneath the point of zero charge, the
oxide surface undergoes protonation and deprotonation. This het-
erogeneous mechanism is under controversies as different catalysts
are used and its pathway is so complicated. The variation is basi-
cally due to the differences in the performance of the catalyst, the
characteristics of target compounds and the optimum conditions by
different authors, thereby arising the difficulties in understanding
the mechanism of catalytic ozonation. Yang et al. [108] studied the
TOC removal of diclofenac. Authors observed that TOC removal effi-
ciency was about 20% and 90% with single ozonation and catalytic
(MnOx /Al2 O3 ) ozonation with 1.5 g/L of catalyst concentration and
30 mg/L of ozone concentration.
The use of heterogeneous photocatalysis in the presence of
semiconductor to degrade recalcitrant compounds is reported
primarily in 1980s [109]. After that, this study has gained atten-
tion predominantly among other AOPs. This mechanism is based
on the stimulation of solid semiconductor under the irradia-
tions of suitable wavelength. A large number of catalysts were
used in photocatalysis, but TiO2 with anatase phase have some
important characteristics, such as high stability, cost effective,
favorable performance and commercially available. TiO2 absorbs
light below 400 nm wavelength which facilitates the use of solar
light [110]. TiO2 photocatalysis has become an attractive pro-
cess to promote the degradation of contaminants in the aquatic
environment since it removes pollutants rapidly and efficiently
from water through photocatalytic transformations [63,111–113].
Degussa TiO2 is widely used as photocatalyst in environmental
applications and it shows high reactivity under UV light during
heterogeneous photocatalysis.
From a mechanistic point of view (Fig. 3), when semiconductor
(TiO2 , ZnO, CdS, WO3 etc.) is exposed to light, the electrons (e− )
get the valence band (VB) is promoted into the conduction band
(CB) of the photocatalyst, leaving photo-generated holes (h+ ). These
generated electron–hole pairs may either undesirably recombine
liberating heat or make their separate ways to the surface of the
catalyst where they react with species absorbed on the surface of
the catalyst. When the photocatalytic process takes place in aque-
ous solution, holes react with water and hydroxide ions to form
139
Fig. 4. General Structure of NSAIDs.
hydroxyl radicals (• OH), while electrons react with oxygen and
reduce it into superoxide radical anions [114]. Hydroxyl radicals
are used as the primary oxidant in the phtotcatalytic oxidation of
organic compounds. It has been displayed that repeated attacks of
organic compounds by • OH leads to complete oxidation of these
pollutants to CO2 and H2 O [115–117].
Various parameters affect the performance of photocatalytic
reactions such as catalyst dose, solution pH, concentration of the
catalyst, light intensity, pH of solution and H2 O2 concentration so
on. The use of renewable energy sources is beneficial for photo-
catalysis by economical point of view. Also, the number of studies
on the degradation of pharmaceutical compounds using solar light
photocatalysis has been reported [67,118,119].
3. Treatment of analgesic and non-steroidal anti
inflammatory drugs by heterogeneous photocatalysis
A considerable part of pharmaceutical contaminants in wastew-
ater are comprised of analgesic and NSAIDs, which are extensively
used to relieve pain and reduce inflammation. In 1899, first NSAID,
aspirin was manufactured by German Bayer Company. Currently,
more than hundred drugs come under the category of NSAIDs and
they are familiar to be mostly used all over the world as a pain
killer [50]. NSAIDs structurally comprise of acidic moieties which
are coupled to a planar, aromatic functional groups (Fig. 4). From the
mechanistic point of view, they inhibit the activity of cyclooxyge-
nase (COX) and thereby transfer arachidonic acid to prostaglandins
and thromboxane thereby relieving from ongoing pain and fever.
About 30 million people consume NSAIDs every day. In Germany,
about 180 tons of ibuprofen, 75 tons of diclofenac and 500 tons
of aspirin were used in 2001 [120]. More than 78 tons of aspirin,
345 tons of ibuprofen and 86 tons of diclofenac were consumed
in England in 2000 [121], And 400 tons of ibuprofen, 37 tons of
naproxen, 10 tons of diclofenac and 22 tons of ketoprofen were
used in France in 2004 [122]. Ibuprofen, diclofenac, paracetamol,
naproxen, aspirin, mefenamic acid and ketoprofen are the most sig-
nificantly used NSAIDs, among these, dicolfenac is highly toxic in
nature and its acute effects are examined at concentrations less
than 100 mg/L [23].
In most of the studies, the attention has been on the estima-
tion of optimum conditions for the degradation and mineralization
of pharmaceutical compounds. The% degradation efficiency can be
determined using the following formula:
% efficiency = % conversion = % abatement = extent of degrada-
tion (%) = (C0 − C)/C0 × 100
C0 and C are the initial and final concentrations of drug. The
study of operational parameter includes the type of catalyst, solu-
tion pH, catalyst loading, initial drug concentration, wavelength,
light intensity have also been investigated. Authors also discussed
the proposed degradation pathway for selected active pharmaceu-
tical ingredients by using mass spectrometry.
3.1. Ibuprofen
Ibuprofen (IBP) is one of the most commonly used NSAID and
analgesic drug present in water. About 75–90% of the drug gets
eliminated in the wastewater treatment plants [123]. It is biolog-
ically active and even its small traces have a negative impact on
the environment [124]. It has been extensively used for treatment
140 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
of migraine, fever, muscle ache and tooth ache. Several tons of
ibuprofen is prepared worldwide because of its excessive use in
the treatment of above mentioned ailments. The most prominent
metabolites of IBP, namely carboxyl and/or hydroxyl IBP, have been
found as toxic byproducts [125]. This is one of the most frequently
used drugs, and consequently, there has been gained concern to the
photocatalytic degradation of IBP.
Achilleos et al. [126] investigated the photocatalytic degrada-
tion and mineralization of ibuprofen (IBP) and carbamazepine (CBZ)
in aqueous phase by TiO2 under UV-A and simulated solar illu-
mination. TiO2 degussa P25 (mixed phase) exhibited maximum
conversion of IBP and CBZ in 120 min of irradiation among other
six types of TiO2 . About 65% and 61% of IBP was degraded with
optimum catalyst dose of degussa P25 TiO2 under both UV-A and
solar light respectively. About 74% of CBZ was degraded with opti-
mum catalyst loading after 120 min of irradiation. This may be due
to its structure having both phases such as anatase and rutile. This
behavior may be due to lesser electron-hole recombination rate in
anatase phase. The study also proposed that this treatment can be
employed as a post-secondary treatment in WWTPs.
The studies have revealed that IBP can be completely elimi-
nated during photocatalytic degradation of IBP, (DCF and NPX) with
UV/TiO2 . Maximum conversion of IBP (200 mg/L) has been achieved
with a catalyst dose of 1 g/L TiO2 after 240 min of irradiation and
it follows the first order rate constant of 9.1 × 10−3 min −1 . Also,
Biological treatment after a photocatalytic process is feasible for
the elimination of IBP. This IBP transformation is due to • OH attack
on the methylpropyl phenyl positions and/or propanoic acid moi-
ety. Different organic acids with m/z (162, 178, and 133) such as
formic, propionic or hydroxypropionic acid or sodium salts have
been identified by LC–MS during decarboxylation and demethyla-
tion processes (Fig. 5) [35]. Propionic acid biodegrades initialy to
formic acid and acetic acid and then to carbon dioxide and water.
Hence, it is finally degraded to simpler and less toxic compounds.
Wang et al. [127] synthesized Ag-AgBr/TiO2 composite by
one pot method and estimated its photocatalytic activity for the
degradation of ibuprofen (IBP) under visible light. Almost 98%,
80%, 97% and 62% degradation of Ibuprofen was observed with
Ag–AgBr/TiO2 after 2 h illumination with white, blue ( = 465 nm),
green ( = 523 nm), and yellow ( = 589 nm) respectively. The
higher removal efficiency of IBP was attained with white and blue
LED light as compared to yellow and green LEDs as Ag and AgBr
were photoactive under white and blue irradiations. This could
be due to efficient charge transfer and separation of photoexcited
charge carriers in three component system. Mineralization of IBP
reached upto 80% under LED irradiations of 6 h (Fig. 6) and it also
decreased the toxicity and aromaticity of the degraded products.
A smaller extent of formic acid was identified in IBP solution after
360 min of photocatalytic reaction. Further, it was evaluated that
composites were highly effective for Escherichia coli inactivation
as compared to conventional Ag–AgBr/P25 and pure titania under
white LED irradiation.
The performance of Zr-doped titania photocatalyst on IBP degra-
dation was observed by changing operational reaction parameters
such as substrate concentration, catalyst concentration, pH, cata-
lyst to substrate ratio and catalyst reuse. Conversion of ibuprofen
increased with increase in catalyst to substrate ratio from 1:1 to 4:1
which was due to diminished effect of catalyst poisoning by using
catalyst in large amount. Simultaneously, more intermediates were
generated. However, concentration of intermediates decreased as
a result of higher catalyst dose after 180 min of photocatalytic
reaction. Results confirmed that Zr-doped titania exhibited high
catalytic activity at smaller catalyst dose as compared to pure tita-
nia. The photocatalytic degradation of IBP increased by a factor of 6
with decreased in pH from 9 to 2 as shown in Fig. 7. This improve-
ment in photocatalytic activity is observed due to alteration in
surface properties of titania after Zr doping. After doping, cata-
lyst behaves like hydrophobic compound. Thus, polar hydrophilic
intermediates are generated, which are readily discharged from the
surface of catalyst into drug solution [128]
In another study, photodegradation of IBP was evaluated
together with tetracycline (TC) using different sizes of ZnO
nanoparticles which were synthesized using ethanol (ZnOe ) and
water (ZnOw ) as solvents. TEM images (Fig. 8(a,b)) shows that ZnOe
nanoparticles were in slighter agglomerated form and particle size
was found to be 30 nm. Besides, the large (100 nm) particles of ZnOw
were obtained. The influence of catalyst loading, initial concen-
tration of drug, pH and role of adsorption was investigated. The
abatement of TC was larger than IBP with ZnOe as compared to
ZnOw nanoparticles because of zwitterionic and amphiphilic nature
and higher polarity of TC as compared to IBP. ZnOe smaller particles
show an improved performance in the degradation of drugs, due to
the high specific surface area. The formation of IBP by-product is
more with ZnOe than ZnOw after 240 min of photocatalytic treat-
ment. These intermediates are benzene derivatives and aliphatic
acids. It is proposed that transformation products like benzene
derivates are oxidized to radicals and quinonic structure which
are easily fragmented to aldehydes, ketones, alphatic alcohols and
amines (molecular mass <100) and then easily mineralized into CO2
and H2 O [129] (Table 2).
3.2. Diclofenac
Diclofenac (DCF) is a derivative of phenylacetic acid which con-
sists of phenyl and acetic acid moieties [134]. It is commonly used as
antirheumatic, antiarthric and analgesic and approximately around
15% of it is excreted without conversion after human ingestion
[126]. The presence of diclofenac has been found both in water as
well as in sewage effluent which causes different adverse effects
[135,136]. The vulture population declines in Pakistan causing eco-
logical imbalance due to DCF residues in dead animals [137].
Calza et al. [138] studied the degradation of DCF under simulated
solarlight using TiO2 as catalyst, intermediate and mechanistic
study was also carried out to access the decomposition of phar-
maceutical drug. Response surface methodology was employed to
evaluate the optimum values of operational parameters such as
catalyst dose and drug concentration for the degradation of target
compound. Complete mineralization of compound was accom-
plished within 2 h of irradiation. There were total 11 photoproducts
with four transformation compounds of same m/z ratios at 312 pro-
duced from hydroxylation process (Fig. 9). Simultaneously, aminic
group was entirely converted into inorganic ions with the for-
mation of nitrate and ammonium ions. Moreover, Vibrio fischeri
was used in assessing the ecotoxicity of photocatalytically treated
solutions. Results demonstrated that toxicity of treated solution
decreased reached a final value less than 1% showed the efficiency
of the photocatalytic process in the detoxification of the irradiated
solution.
Achilleos et al. [139] investigated the effect of various param-
eters such as different types of TiO2 , catalyst loading, H2 O2
concentration, initial concentration and water matrix on the degra-
dation of diclofenac (DCF). All experiments were performed in UV-A
light affixed immersion well type reactor at pH of 6 with continu-
ous oxygen supply. TiO2 degussa P25, Tronox AK-1 and Hombikat
exhibited 85% conversion of DCF in 4 h of irradiation among other
types of TiO2 shown in Fig. 10. This may be due to its structure
having both phases such as anatase and rutile. Mixed phase TiO2
(anatase:rutile::75:25) has higher photocatalytic activity than pure
crystalline phase for degradation of drugs in aqueous phase. Pure
anatase is more active than rutile phase. This behavior may be due
to several reasons (i) the distinct position of the conduction band,
(ii) lesser electron-hole recombinations in anatase phase and (iii)
Table 2
Summary of heterogeneous photocatalytic studies on ibuprofen (IBP).
Compound
Ibuprofen (IBP), diclofenac
(DCF) and
naproxen(NPX)
Ibuprofen (IBP)
Ibuprofen (IBP)
Ibuprofen (IBP) and
Carbamazepine(CBZ)
Ibuprofen (IBP)
Ibuprofen (IBP)
Ibuprofen sodium salt
(IBP-Na)
Ibuprofen
Ibuprofen (IBP) and
Diclofenac (DCF)
Ibuprofen (IBP) and
tetracycline (TC)
Water matrix Catalyst with optimum
concentration
Milli-Q water TiO2
C[TiO2] = 1 g/L
— TiO2 Degussa P25
C[TiO2] = 0.1 g/L
Milli Q water TiO2 Degussa P25 and
Fe(NO3 )3 .9H2 O
C[TiO2P25] = 1 g/L
C[Fe 3+ ] = 0.045 Mm
Milli Q water and Aeroxide P25
treated domestic
Wastewater
Deionized water Ag-AgBr/TiO2
C[Ag-AgBr/TiO2] = 0.5 g/L
Ultrapure water TiO2 (99% anatase)
C[TiO2] = 120 mg/L
Ultra pure water TiO2 Degussa P25
C[TiO2P25] = 40 mg/L
Ultra pure water Zr-TiO2
C[TiO2P25] = 40 mg/L
Ultra pure water TiO2 Aeroxide P25
C[TiO2] = 500 mg/L
Ultra-pure water ZnO nanoparticles (ZnOw )
and (ZnOe )
C[ZnOw] = C[ZnOe] = 10 mg/L
Reactor with light source
Solar simulated reactor
with Xe-Op lamp (1 Kw,
290–400 nm)
- Solar pilot plant reactors
(CPC-35,CPC-6 and PC-
1.5)
- Solar irradiation
- 4KJ/L-5KJ/L solar energy
consumption
Xenon arc lamp, 450 W
- Solar simulator, 1000 W
- UV-A lamp (9 W,
350-400 nm)
- Vis-LED photoreactor
- white, blue LED
( = 465 nm), green
( = 523 nm), and yellow
( = 589 nm)
- UV-C Germicidal lamp (9
W, 200–280 nm)
- UV-A Dark light lamp
(9 W, 315–400 nm)
Four UV–vis solarium lamp
(15 W, 320–400 nm)
Four UV–vis solarium lamp
(15 W, 320–400 nm)
- Immersion well lab scale
reactor
- UV-A lamp (9 W,
350–400 nm)
- Solar simulated xenon
lamp (1 kW, 290 nm)
- Four UV–vis solarium
lamp (60 W)
Process parameters
C[IBP] = 25–200 mg/L,
C[TiO2] = 1 g/L,
C[IBP] = 20–200 mg/L,
C[TiO2] = 0.1–1 g/L
C[IBP] = 0.02–0.09 mM,
C[TiO2] = 1 g/L,
C[Fe 3+ ] = 0.05–0.045 mM
C[IBP] = 5–20 mg/L,
C[TiO2] = 50–800 mg/L,
pH 3–10,
H2 O2 dose = 0.07–1.4Mm
C[IBP] = 10 mg/L,
C[Ag-AgBr/TiO2] = 0.5 g/L
C[IBP] = 5 mg/L,
C[TiO2] = 120 mg/L
C[IBP] = 5–60 mg/L,
C[TiO2P25] = 10–40 mg/L,
pH: 3-9
C[IBP] = 10–60 mg/L,
C[Zr-TiO2] = 10–40 mg/L,
pH :2–9
C[IBP] = 10 mg/L,
C[TiO2] = 500 mg/L,
pH: inherent pH
C[IBP] = C[TC] = 5–60 mg/L,
C[ZnOw] = C[ZnOe] = 10 mg/L,
pH: 3–9
Discussion Reference
- The maximum photocatalytic degradation of ibuprofen was [35]
achieved with catalyst dose of 1 g/L
- Role of dissolved oxygen on photodegradation of IBP was
investigated
- 4 kJ/L of energy supplied for the complete degradation of IBP [130]
(20 mg/L) with TiO2 dose of 0.1 g/L
- H2 O2 accelerates the photodegradation process, 50% of IBP
(200 mg/L) was eliminated in 120 min with 0.1 g/L of TiO2 ,
1028 mg/L of H2 O2 , 4.75 kJ/L
- Highest degradation rate achieved by combined UV/TiO2 with [124]
ultrasound process and rate was found to be 108.4 × 10 −7 min−1
- The ratio of IBP to Fe3+ was kept at 1:0.5
A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
- Performance of photocatalytic process depends on various factors [126]
such as catalyst dose, pH and drug concentration were investigated
- UV-A light and simulated solar were effective for IBP degradation,
mainly in the presence of TiO2 Degussa P25
- Three component systems (Ag–AgBr/TiO2 ) revealed better [127]
photocatalysis results as compared to one and two component
systems
- Degradation of IBP with Ag–AgBr/TiO2 was about 98% under white
LED light
- TiO2 /UV-C photocatalytic process was more efficient for IBP [131]
degradation and mineralization
- Generation of OH radical played important role in IBP degradation
with first order rate constant of 0.054 min −1
- Complete degradation of IBP-Na (10 mg/L) was achieved with [132]
40 mg/L TiO2 Degussa P25 under 120 min of irradiations
- TiO2 degussa P25 was adequate catalyst to degrade the IBP under
analyzed conditions
- About 85% ibuprofen (10 mg/L) was degraded with Zr-TiO2 (40 mg/L) [128]
in 180 min
- ESMS confirmed the degradation of ibuprofen with Zr-TiO2 was
higher but polymeric compounds are formed partially
- Higher drug degradation (90% for DCF, 85% for IBP) was achieved in [133]
2 h, with sonophotocatalysis as compared sonocatalytic and
sonolytic degradation
- DCF and IBP decomposition followed pseudo first order kinetic
model
- ZnOe showed better photocatalytic degradation as compared to [129]
ZnOw
- Intermediates such as benzene and phenolic derivatives were
identified during photocatalytic degradation of IBP by negative
ESI-TOF-MS. These derivatives were oxidized to radials and quinonic
structure and easily converted to CO2 and H2 O
141
142 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155

Fig. 5. Photodegradation pathway of ibuprofen with TiO2 .

Fig. 6. IBP and TOC removal efficiencies under different colour of light irradiations.

higher oxygen adsorption capacity of anatase as a result of higher
density of superfacial hydroxyl groups. Furthermore, pure anatase
has more surface area as compared to rutile phase and this can also
lead to an improved activity. The results revealed that abatement
as well as mineralization of DCF was effective under UV-A/TiO2
treatment.
Another study on degradation of DCF under UV/TiO2 and
direct photolysis was investigated by Martinez et al. [140]. In
this, effect of various parameters such as catalyst loading, dis-
solved oxygen and H2 O2 concentration on process kinetics were
compared. UV light was more effective for degradation of tar-
get compound than near UV–vis. Complete removal of diclofenac
was achieved under optimal conditions (0.5 g/L of synthesized
 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155 143

Fig. 7. Effect of pH on abatement of IBP (10 mg/L) with Zr-doped titania (20 mg/L) under UV–vis irradiation.

Fig. 8. TEM images of ZnO nanoparticles precipitated from (a) ethanol (ZnOe) and (b) water (ZnOw ).

Fig. 9. Photocatalytic degradation pathways followed diclofenac (DCF).

144 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155

Fig. 10. Effect of types of TiO2 on DCF degradation.

anatase, 50% O2 (v/v)) under UV light, with apparent rate con-

stant 0.9 min−1 . Oxygen increases the photodegradation process
by reducing the unfavourable electron-hole recombination. Eight
photoproducts were formed during the photolysis of diclofenac
with decarboxylation, photocyclization and dehalogenation. The
byproduct, monohalogenated carbazole was observed by photo-
cyclization pathway and this product is highly phototoxic.
Bagal et al. [141] examined effect of operational parameters
such as inlet pressure of fluid (2-4 bar), pH of drug solution (4–7.5),
TiO2 loading (0.05-0.3 g/L) and H2 O2 concentration (0.05-0.3 g/L)
on the decomposition of DCF, with combinational approach of
hydrodynamic cavitation (HC) and heterogenous photocatalysis. A
slit venturi was used as cavitation device in hydrodynamic reactor.
About 95% DCF degradation and 76% TOC reduction was obtained
with HC/UV/TiO2 /H2 O2 system as compared to UV and UV/TiO2
individually under optimized conditions (TiO2 loading = 0.02 g/L,
H2 O2 loading = 0.02 g/L, inlet fluid pressure = 4 bar, pH 4) and
depicted in Fig. 11 and it followed first order kinetic model for DCF
degradation.
By-products generated during photocatalytic oxidation of DCF
were determined. All products have lower retention time than DCF,
proposed that products were less polar than parent compound.
The chromatograph of degraded products and parent compound
disappeared after 60 min of photocatalytic membrane oxidation.
However, it is possible that smaller molecules were formed during
process, recalcitrant compounds could not be detected and TOC
removal was about 70% under optimized conditions (0.5 g/L TiO2 , Fig. 11. Exent of degradation of diclofenac (DCF) using HC/TiO2 /H2 O2 ,
UV/TiO2 /H2 O2 and combined process of HC/UV/TiO2 /H2 O2 .
2.5 mg/L of DCF concentration at pH 6) [145] (Table 3)

even death. It has been detected as one of the anthropogenic com-

3.3. Paracetamol
Paracetamol also called as 4-hydroxyacetanilide (ACT) or
acetaminophen (APAP), which was initially introduced into medi-
cation as an analgesic/antipyretic by Von Mering in 1893 and has
been used as pain reliever for house medication more than 30 years
[147]. It is the most widely used drug after aspirin as a substitute
in many countries. Its composition cures more than hundred prob-
lems. But its use in excessive amount may cause liver failure and
pound in ground and surface water even after its treatment [148].
Concentration of APAP up to 120 ␮g/L was noticed in ground water
was reported in study [149]
There are number of studies carried out on the elimination of
APAP by heterogeneous photocatalysis. Desale et al. [150] opti-
mized the catalyst dose and pH of the APAP solution (50 mg/L),
using TiO2 degussa P25 in bath reactor. Complete degradation and
72% mineralization of APAP (50 mg/L) was achieved under opti-
mized conditions (2 g/L of TiO2 degussa P25, pH 3) in 240 min
Table 3
Summary of heterogeneous photocatalytic studies on diclofenac (DCF).

Compound Water matrix Catalyst with optimum Reactor with light source Process parameters Discussion Reference
concentration

Diclofenac (DCF)
Ultra pure water
TiO2 - Fluorescence lamp with
C[TiO2] = 0.2 g/L black light (125 W,
300-420 nm)
C[DCF] = 5–80 mg/L,
C[TiO2] = 0.2–1.6 g/L,
pH: 2–9
- Experimental data was found to be fit in pseudo first [138]
order kinetic model
- Higher concentration of DCF (40 - 80 mg/L) with 1.6 g/L
catalyst loading was able to fit in second order kinetic
model

Diclofenac Deionized water, municipal
waste water treatment
effluent and ground water
- TiO2 samples: Degussa Immersion type batch C[DCF] = 5–20 mg/L, - Degussa P25 was more effective catalyst for degradation [129]
P25, Hombicat UV100, photoreactor, Radium C[TiO2] = 50–1600 mg/L, of diclofenac as compared to other catalysts
Aldrich, Tronox AK-1, UV-A lamp (9 W, H2 O2 dose = 0.07–1.4 mM, - Performance of photocatalytic process depends upon
Tronox TRHP-2, Tronox 350–400 nm) pH: 6 various factors such as catalyst to substrate ratio,
TR reaction time, catalyst and water matrix
- C[TiO2P25] = 50 mg/L

Diclofena Milli pore water - TiO2 Degussa P25 UV light -Medium pressure C[DCF] = 8 mg/L, - The effect of light irradiation, catalyst dose, H2 O2 dose [140]

A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155

Diclofenac sodium
C[DCF] = 20 mg/L
Distilled water
- C[TiO2P25] = 0.5 g/L mercury lamp, 366 nm,
NUV-vis light–low
pressure mercury lamp,
254 nm
TiO2 -Hydrodynamic cavitation
C[TiO2] = 0.2 g/L (HC) reactor with
photocatalysis
- UV light source, 250 W
C[TiO2P25] = 0.1–2 g/L,
pH:6,
H2 O2 dose = 0–5 mM
C[DCF] = 20 mg/L,
C[TiO2] = 0.05–0.3 g/L,
H2 O2 dose = 0.05–0.3 g/L,
pH: 4–7.5
on photocatalytic degradation of DCF was investigated
- The radical scavengers study demonstrated that free [141]
radical attack was important for the degradation of
diclofenac
- Degradation of diclofenac by photocatalysis was almost
two times higher than HC/TiO2
- Photodegradtion data was found to be fit first order rate
constant

Diclofenac(DCF),
Amoxicillin(AMX) and
Carbamazepine(CBZ)
Diclofenac
Urban waste water, Milli
pore water
Ultra pure water and urban
waste water
TiO2 - Fluorescence lamp with
C[TiO2] = 0.8 g/L black light (125 W,
300–420 nm)
TiO2 Degussa P25 (70% - Borosilicate glass photo
anatase, 30% rutile) reactor, High pressure
mercury lamp 313 nm
(TQ 718)
C[AMX] = 10 mg/L, - Degradation of DCF alone and in mixture with AMX and [142]
C[CBZ] = 5 mg/L, CBZ was examined
C[DCF] = 2.5 mg/L, - Degradation rate was slower in real wastewater as
C[TiO2] = 0.2–0.8 g/L, compared to spiked distilled water
pH: 2–9
CDCF = 10−4 –2.7 × 10−4 M, - Complete degradation of DCF was accomplished within [143]
Ccat = 0.5–2.5 g/l, 6 min and 60–75%
CO3 = 5–30 mg/l, - TOC removal was noticed after 60 min of reaction even
pH: 7 in deionized and urban waste water

Diclofenac (DCF), Ibuprofen Milli-Q water, river water, -Aeroxide tiatnia P25 - Glass bowl batch reactor 2.50 mg/L of drug mixture. - Various composites were produced from TiO2 [144]
(IBP), Carbamazepine sea water, effulent from - C[TiO2P25] = 500 mg/L - UV-A light, 315–400 nm Equal amount of each drug. nanoparticles and their absorption-photocatalytic
(CBZ), Sulfamethoxazole waste water treatment - UV-B light, 280–360 nm C[Drug] = 0.5 mg/L, studies were carried out
(SMX) and Clofibric acid plant - UV-C light, 220–280 nm C[TiO2] = 500 mg/L - UV-C light source was more effective for the removal of
(CFA). drugs in deionized and river water

Diclofenac Ultra pure water, ground TiO2 -Photocatalytic membrane C[DCF] = 2.5 mg/L, - Degradation and mineralization of diclofenac with TiO2 [145]
C[DCF] = 2 mg/L water and tap water C[TiO2] = 0.5 g/L reactor C[TiO2] = 0.3–0.75 g/L, was about 99.5% and 69% under optimized conditions
-4 black light lamp, 24 W, pH: 6 - Effect of water matrix on photodegradation on
365 nm photodegradation of DCF was estimated

Diclofenac, Indigo Double distilled water TiO2 /Nb2 O5 Philips UV lamp, 36 W, 50 mL of stock of mixture: - Tentative path for the photodegradation of DCF, IC and [146]
carmine(IC), artazine C[TiO2/Nb2O5] = 0.6 g/L 200–400 nm C[DCF] = C[IC] = C[ATR] = 5 mg/L, ATR were investigated
C[DCF] = 5 mg/L C[TiO2] = 0.6 g/L - Results demonstrated that composite not only enhanced
C[IC] = 5 mg/L the degradation rate, mineralization was also
C[ATR] = 5 mg/L accomplished

145
146 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155

Fig. 12. Photocatalytic degradation of APAP (50 mg/L) by TiS, 0.1Cu-TS, 1Cu-TS and 10Cu-TS under visible light. The inset is the plot of ln (C0 /C) versus the irradiation time.

Fig. 13. Photodegradation pathway of APAP.

of irradiation. The rate of photocatalytic degradation of APAP
decreased with increased in pH from 3 to 11. This is due to repul-
sion between TiO2 and negatively charged APAP and similar study
of pH effect was conducted by Zhang et al. [151]. Several interme-
diates such as hydroquinone, benzoquinone, p-aminophenol and
p-nitrophenol were generated during the degradation of APAP at
different time periods. The p-aminophenol was easily oxidized to
p-nitrophenol and then converted into nitrocatechol and hydro-
quinone. Low molecular weight carboxylic acids were obtained
as the end products. Another study reported that Cu-doped TiO2
spheres (CU-TS) exhibited higher photocatalytic degradation as
compared to undoped TiO2 . Photocatalytic degradation efficiency
increased with Cu doping (0.1 wt%) but decreased when doping
reached to 1 wt%. The optimum Cu-TS loading (0.1 wt%), yielded
 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
Fig. 14. Photocatalytic degradation efficiency with different scavengers: 20 mmol/L
isopropanol, 0.2 mmol/L sodium oxalate, 0.1 mmol/L TEMPOL (4-hydroxy-2,2,6,6-
tetramethylpiperidinyloxy) and N2 in the photodegradation of APAP over
as-synthesized ␤-Bi2 O3 nanospheres.
the 100% degradation after 3 h of visible light irradiations shown in
Fig. 12 [148].
Degradation mechanism Fig. 13 and parameter optimization of
APAP under UV/TiO2 was described by Yang et al. [152,153]. In this
study, photocatalytic oxidation of APAP using TiO2 (Degussa P25
TiO2 , Germany) as catalyst, under UVA (365 nm) and UVC (254 nm)
light sources were compared. It was found that complete degrada-
tion of APAP (4.0 mM, pH 5.6) was observed with UV-C/TiO2 . The
mineralization rate was found to be 60% in 300 min (up to 80% in
450 min) of reaction. The degradation rate was found to increase
from 11 × 10−3 min−1 to 16.5 × 10−3 min−1 with an increase in cat-
alyst loading upto optimum dose (0.8 g/L), light intensity, addition
of oxygen and by varying the pH. However, after the pH value of 9.5,
the degradation was significantly decreased due to the repulsion
between APAP and negatively charged TiO2 . This study also iden-
tified an intermediate products including carboxylic acid, aliphatic
compounds through hydroxylation, as well ammonium and nitrate
were formed.
Xiao et al. [154] prepared highly pure and spherical ␤-Bi2 O3
nanospheres of diameter approximately 70 nm by solvothermal
process. A maximum conversion of APAP (10 mg/L) was obtained
with ␤-Bi2 O3 (1 mg/mL) under 180 min of visible irradiation with
a first order rate constant of 0.01387 min−1 . The degradation
was mainly due to holes which were confirmed by conduct-
ing scavenger experiments with sodium oxalate, N2 , TEMPOL
(4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy) and isopropanol.
With the addition of sodium oxalate, the photodegradation effi-
ciency increased significantly as shown in Fig. 14. Further results
showed that 89.5% of TOC removal was attained after irradiation for
240 min. The apparent reaction rate constant for the degradation of
APAP with prepared ␤-Bi2 O3 was higher as compared to N-doped
TiO2 , synthetic ␣-Bi2 O3 and Degussa TiO2 P25. Intermediate study
observed the presence of hydroquinone after the photocatalytic
oxidation of APAP. Then, the aromatic structures of intermediates
were oxidized into carboxylic acid and CO2 . Ultimately, the APAP
was mineralized into small inorganic molecules.
Alvarez et al. [155] synthesized magnetic nanoparticles such
as TiO2 /SiO2 /Fe3 O4 and TiO2 /Fe3 O4 by ultrasonic-assisted sol–gel
method and used as photocatalyst for the degradation of APAP
mixtures from aqueous phase under UV-A light. TiO2 /SiO2 /Fe3 O4
nanoparticles were more stable in aqueous solution under UV light
as compared to TiO2 /Fe3 O4 nanoparticles. Results demonstrated in
Fig. 15, that synthesized magnetic nanoparticles showed almost
comparable catalytic activity to TiO2 degussa P25. Even though,
TiO2 degussa P25 was most commonly used photocatalyst for the
147
treatment of wastewater, the problem in its separation because of
its small size stimulates the search of alternative materials. The
complete conversion of APAP was achieved in 5 h by any of these
catalysts. But mineralization of APAP was found to be 43.5%, 39.7%
and 30.8% with degussa P25 TiO2 , TiO2 /SiO2 /Fe3 O4 and TiO2 /Fe3 O4
nanoparticles respectively.
Recent research in the heterogeneous photocatalysis demon-
strated that UV-A/LEDs can be used in the place of conventional
mercury lamps. These lamps are eminent for their high energy cost
and amalgamation of noxious energy [156,157]. Gootostos et al.
[158] synthesized a novel photocatalyst K3 [Fe(CN)6 ]/TiO2 via a sol-
gel method and used it for decomposition of APAP under visible
light using LED lights. The study reported the effect of operational
parameters such as initial concentration of drug solution, catalyst
concentration, solution pH, temperature and number of LED lights
for the decomposition of APAP. The experimental results exhib-
ited that much higher degradation efficiency and rate apparent
were obtained with K3 [Fe(CN)6 ]/TiO2 as compared to commer-
cially available TiO2 degussa P25 catalyst. About 98% and 64%
of APAP was degradaed with K3 [Fe(CN)6 ]/TiO2 under blue LED
( = 450 nm) and green LED ( = 550 nm) respectively. The degra-
dation efficiency increased with the increase in number of LED
lights because that leads to increase in number of photons that
could react with catalyst. It also generates more electron-hole pairs,
that increases the photocatalytic degradation. The degradation effi-
ciency of APAP decreased with increase in initial concentration of
APAP and temperature. This can be due to increase the feasibility
of recombination of charge carriers and desorption of drug species
at the surface of catalyst. Also, rate constant increased when intial
pH of solution was increased from 5.6 to 6.9, further it lowered at
a high pH (pH 8.3). Moreover, the degradation efficiency enhanced
with catalyst dose up to 1 g/L. The degradation of APAP followed
pseudo-first order kinetics (Table 4).
3.4. Naproxen
Naproxen (NPX) belongs to 2-arylpropionic acid group which is
a typical NSAID and extensively used for muscle pain or inflamma-
tory disorders. NPX has been found repeatedly in water bodies [44].
Approximately 29 percent of NPX is not eliminated by the sewage
treatment plant (STP) which consequently enters into the aquatic
environment thereby, releasing toxic substances and affects the
water adversely [21,160]. Considerable information on degradation
of naproxen by photocatalysis in comparison to direct photolysis
is still not available [161]. The photolysis studies have been inves-
tigated under UV light, vaccum ultraviolet (VUV) light and direct
solar irradiations [162–164]. The effect of oxygen on photodegra-
dation of NPX and their kinetic study under aerated and deaerated
conditions was investigated by Marotta et al. [165]. It was reported
that more toxic derivatives were produced by photodegradation
than the actual compound [166]. This study compared the degrada-
tion of NPX by photolysis and photocatalysis under simulated solar
light. About 40% removal with 20% mineralization and 90% removal
with 5% mineralization of NPX solution were achieved by pho-
tocatalysis and photolysis respectively. Percentage degradation of
NPX by means of photocatalysis decreased due to low adsorption of
drug on catalyst surface or reduction of hydroxyl attack. The degra-
dation rate of NPX increased with TiO2 dose (0.1–1 g/L) for initial
concentration (0.8 mmol/L) of NPX. The intermediates formed after
180 min of photocatalytic reaction were identified by LC/ESI-TOF-
MS. Demethylation and decarboxylation were two prime pathways
recommended for the degradation of NPX. The toxicity of the par-
tially decomposed NPX sample was increased that can lead to the
production of end products which are more toxic than parent NPX
compound [167].
 148
Table 4
Summary of heterogeneous photocatalytic studies on acetaminophen (APAP).

Compound Water matrix Catalyst with optimum Reactor with light source Process parameters Discussion Reference
concentration

Acetaminophen (NSAID)
Distilled water TiO2 Photochemical Reactor. C[APAP] = 25–100 ␮M, - About 95% of [151]
C[TiO2] = 1 g/L -Metal Halide lamp C[TiO2] = 0.25–1.0 g/L, paracetamol (100 ␮M)
(250 W, ␭ ≥ 365 nm) pH: 3–11 was degraded with a
TiO2 dose of 1.0 g/L
under 100 min of
irradiation.
- Pseudo first order rate
constant for different
pH:
At pH 3.5, k = 8.09 ␮M min
−1

A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155

Acetaminophen Millipore Q water TiO2 Degussa P25(80%
anatase and 20% rutile)
C[TiO2] = 0.4 g/L
Photochemical reactor
(annular cylindrical reactor
with a quartz sleeve)
- Black light blue UVA lamp
(8 W, 365 nm) and UVC
lamp (15 W, 254 nm)
C[APAP] = 2–10 mM,
C[TiO2] = 0.25–1.0 g/L,
pH: 5.1–5.6
pH 6.9, k = 2.84 ␮M min −1
pH 9.5, k = 2.96 ␮M min −1
- In the presence of UV-A [152]
light, no degradation of
acetaminophen was
accomplished without
catalyst
- TOC removal was found
to about 60% after
180 min (up to 85% in
450 min) of irradiation
(UV-C) with TiO2
Degussa P25

Acetaminophen Not given ␤-Bi2 O3 Photochemical reactor C[APAP] = 10 mg/L, - Photodegradation of [154]
C[␤-Bi2O3] = 1 g/L - Xenon lamp (1000 W, C[TiO2] = 1 g/L APAP over ␤-Bi2 O3
420 nm cutoff filter) under visible light was
evaluated and compared
with Degussa P25
- Photodegradation data
was found to be fit in
pseudo first order kinetic
model

Acetaminophen Distilled water TiO2 / KAI(SO4 )2 and TiO2 /
NaAIO2
- C[TiO2/KAI(SO4) 2] = 1.0 g/L
-C[TiO2/NaAIO2] = 1.0 g/L
Lab scale reactor
-Blue color LED
(440–490 nm), Green color
LED, (510–550 nm)
C[APAP] = 0.1–1.0 mM,
C[TiO2/KAI(SO4) 2] = 0.5-1.5 g/L,
C[TiO2/NaAIO2] = 0.1–1.0 g/L,
pH: 3–8.1
- Degradation of APAP [159]
with TiO2 / KAI(SO4 )2
was higher than other
catalysts such as
Degussa-P25, TiO2 /
NaAIO2 and undoped
TiO2 under blue LED light
- Kinetic study showed
that degradation of APAP
followed first order
kinetic model
 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
Fig. 15. Photodegradation of acetaminophen in aqueous solution in the absence (blank) and presence of different nanoparticles, Reaction conditions: T ∼ 25◦ C; pH 7;
CAC ,0 = 30 mg/L; catalyst and dose; (䊐) none (blank experiment); (䊏) magnetic iron oxide, 1.0 g/L; (䊉) Degussa P25 TiO2 , 0.5 g/L; () TiO2 /Fe3 O4 , 1.16 g/L; () TiO2 /SiO2 /Fe3 O4 ,
1.34 g/L.
Fig. 16. The schematic representation of formation process of the SiO2@Au@TiO2
core–shell nanostructures.
Couple of studies on photocatalytic degradation of NPX com-
bined with other drugs was reported in literature [168,169]. Ye
et al. [170] studied the degradation of naproxen with prepared
SiO2 @Au@TiO2 core shell nanostructures under visible light irra-
diations. This experiment was performed in a batch photoreactor
and irradiated with xenon lamp (<420 nm). In this study, firstly
monodisperse SiO2 cores were synthesized and then decorated
with Au nanoparticles under ultrasonication. The deposition of Au
nanoparticles produces the visible light energy by their plasmonic
effects and intensifies the charge separation. Finally, TiO2 layer was
coated on the surface of SiO2 @Au collide and after calcination at
500◦ C for 2 h (shown in Fig. 16), the amorphous TiO2 is converted
into anatase TiO2. TiO2 coating in nanostructure reduces the loss of
Au nanoparticles after use. About 77% photocatalytic degradation of
naproxen was achieved in 6 h of irradiation with 0.1 wt% Au loaded
SiO2 @Au@TiO2 . This facilitates charge separation by acting as elec-
tron reservoir and because of plasmonic effects Au loading leads
to enhanced spectral response into visible light region. A photo-
catalytic degradation study on NPX with other three drugs namely
ibuprofen, clofibric acid and diclofenac revealed that first order rate
constant for naproxen was higher than others.
149
A recent study investigated the photodegradation of naproxen
and three other compounds in water using P25-TiO2 /tetraethyl
orthosilicate (TEOS) film under visible light. The effect of various
parameters such as initial pH of drug solution, catalyst dose, adsorp-
tion, and irradiation time of photocatalytic reaction was studied.
The maximum degradation of naproxen, ibuprofen, diclofenac and
salicyclic acid under optimum conditions (pH 6, 4 pieces of P25-
TiO2 /TEOS films) were 94%, 85%, 65%, and 76% respectively shown
in Fig. 17. This is due to change in surface charge of catalyst (the
pH of TiO2 solution is below 6.5 which is above the pKa values
of NSAIDs). TiO2 surface is positively charged and NSAIDs being
anionic in nature are adsorbed on the surface of catalyst because of
electrostatic attraction and ultimately leading to maximum degra-
dation. It was examined that the degradation of drugs increased
with irradiation time and maximum degradation was achieved in
10 h of photocatalytic reaction. The photocatalytic degradation of
drugs followed first order kinetics. The intermediate study exhib-
ited that naproxen is photdegraded into nontoxic micromolecules
with P25-TiO2 /TEOS film [171].
3.5. Other drugs
Ketoprofen comes under the category of pharmaceutically
active compounds, extensively used for the treatment of pains
during musculoskeletal fractures. Wastewater treatments plants
do not completely eliminate this compound by sorption process
because of its hydrophilic nature; its separation being mainly
dependent on biological and chemical processes. Feng et al. investi-
gated the complete degradation and kinetic study of ketoprofen by
electro-fenton and anodic oxidation methods [172]. The degrada-
tion of ketoprofen followed second order rate constant with a value
of 2.8(±0.1) × 109 M−1 s−1 . Kim et al., exhibited that the degrada-
tion of ketoprofen under UV light (intensity 0.384 mW/cm2 and
0.388 mW/cm2 ) was about 90% in 10 min of irradiation [173].
Aspirin comes under the category of NSAIDs and is used for the
treatment of fever, pain and arthritis etc. Aspirin is also very effec-
tive on blood platelets as it avoids the formation of blood clot inside
the arteries especially in patients suffering from atherosclerosis due
to its anti platelet effect in the blood. This property of aspirin is very
150 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
Fig. 17. Photodegradation of four drugs under optimized conditions (pH 6, 4 pieces of P25-TiO2 /TEOS films) in 10 h.
crucial in avoiding heart attack and stokes. About 40,000 tons of this
drug is consumed every year and its some residues are getting into
the surface water.
Investigation on photocatalytic degradation of aspirin with TiO2
nanoparticles was performed under UV light, the effect of various
process parameters such as catalyst dose, temperature, pH and time
on degradation was studied as well [174]. Optimum conditions for
degradation were determined by using response surface method-
ology. About 73% of aspirin (5 mg/L, pH 5.5) was decomposed in
50 min with a catalyst dose of 50 mg/L.
Recent studies highlighted the effect of cross linked bonding of
TiO2 immobilized polymeric catalyst on aspirin degradation under
both UV and solar light irradiations.TiO2 is able to use sunlight and
air to produce many reactive species, but filtration of TiO2 slurry
from purified water is expensive and time consuming. In this study,
photocatalytic degradation of aspirin was carried out in batch reac-
tor with five types of polymeric/TiO2 catalyst films. These five types
of polymeric cross linked films were prepared by different methods
such as freeze dried, heat treated, UV treated, acetaldehyde treated
and freeze dried UV treated Fig. 18. Observation showed that freeze
dried cross linked film had a porous structure and high degradation
efficiency in comparison to others [175].
Li et al. [176] studied the degradation of acyclovir with g-
C3 N4 /TiO2 under visible light. Results exhibited that complete
degradation of acyclovir was achieved with g-C3 N4 /TiO2 in 240 min
of irradiation, while very slight degradation was observed with TiO2
in 300 min. Authors suggested that, maximum degradation may
be due to low rate of electron-hole recombination in g-C3 N4 /TiO2 .
Additionally the generated electron produce reactive species such
as H2 O2 and • O2 . These reactive species decompose acyclovir drug.
However, this degradation process generates three intermediates
namely P1 (m/z 214), P2 (m/z 205) and P3 (m/z 152). The photo-
catalytically degraded by-products P1 and P2 were not harmful for
three tropic levels such as daphnia, fish and algae as compared
to parent compound as confirmed by acute and chronic toxicity
tests. The aquatic toxicity for intermediate P3 (guanine) on Daph-
nia was twice than acyclovir and was toxic in nature. Another study
reported complete degradation of acyclovir achieved with TiO2 P25
in 120 min of irradiation but the inhibition efficiency of treated
sample was about 10.8%, 7.2% and 14.4% for Selenastrum capricor-
nutum (96 h), Photobacterium phosphoreum (15 min) and Daphnia
magna (48 h), respectively shown in Fig. 19. However, the toxic
product could be removed with further increase in the irradiation
duration and toxicity of treated sample decreased considerably as
TOC reduction, but the final degraded solution had small inhibition
effect on aquatic life [177].
Yang et al. [178] investigated degradation of three ␤-
blockers (metoprolol, propranolol and atenolol) with UV/TiO2 and
found that propranolol degraded effectively than metoprolol and
atenolol. These three ␤-blockers (100 ␮M, pH 7) were eliminated
completely in 40 min of irradiation using 2.0 g/L of TiO2 and the
degradation kinetics found to be fit the pseudo-first-order kinetic
model. The degradation of ␤-blockers were mainly due to • OH.
The byproducts were completely mineralized into NH4 + , and NO3
(smaller extent) in 240 min of reaction.
Limited research has been dedicated so far for the treatment of
drug ketorolac tromethamine using quantum dots (QDs). Though, it
can give very good results. Kaur et al. carried out experiments using
TiO2 QDs for degradation of ketorolac tromethamine and found
that about 99% of ketorolac tromethamine (10 mg/L, pH 4.4) was
degraded with TiO2 QDs (0.5 g/L) under solar light. The effect of
operational parameters such as catalyst dose and pH was studied
and shown in Fig. 20. The degradation efficiency increased from
83.7% to 97% with increased catalyst dose from 0.25 g/L to 0.5 g/L.
This was due to increased available active sites on the surface of
catalyst. Afterwards, there was decrease in degradation efficiency
due to decrease in the penetration of light in the drug suspen-
sion. The maximum degradation efficiency was achieved at natural
pH of drug solution i.e., pH 4.4 The smaller molecules such as K1
(m/z 178), K2 (m/z 228) and K3 (m/z 212) were identified dur-
ing the photocatalytic degradation of parent compound, ketorolac
tromethamine [179].
Table 5
Summary of heterogeneous photocatalytic studies on naproxen (NPX) and other drugs.

Compound Water matrix Catalyst with optimum Reactor with light source Process parameters Discussion Reference
concentration

Equal concentration of 15 Deionied water Anatase TiO2 , rutile TiO2 , Low pressure Hg lamp C[DRUG] = 0.2 mg/L, - More mineralization of [168]
pharmaceutical and TiO2 degussa P25 (264–365 nm) C[TiO2] = 1 mg/L, drugs achieved by TiO2
compounds; Naproxen C[TiO2] = 1 mg/L pH 7.4 photocatalysis as
(NPX) compared to UVC
photolysis
- Antase TiO2 was more
effective to degrade
naproxen, atorvastatin,
ibuprofen, lincomycin,
venlafaxin, diclofenac,
gemfibrozil and
trimethoprim as
compared to rutile TiO2

A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155

Naproxen, malachitegreen, carbamazepineandtheophylline. Water type is not given TiO2 Middle pressure Hg lamp C[NPX] = 15 mg/L, - Photodegradation of [169]
C[TiO2] = 0.2 g/L (100 W, 365 nm) C[TiO2] = 0.2 mg/L, theophylline with TiO2
pH 6.8 under UV light was fast
as compared to naproxen
and carbamazepine
- Effect of initial
concentration of
substrate, pH and
temperature on
degradation was
investigated

Naproxen (NPX) Deionized water SiO2 @Au@TiO2 with
different doping
concentration of Au
(0.05–1.0 wt%)
Batch photoreactor, Xenon 50 mL of stock of mixture: - SiO2 @Au@TiO2 with [170]
lamp (250 W,  < 420 nm) C[NPX] = 1.0 × 10−5 mol/L, doping concentration of
C[TiO2] = 1.0 g/L, (TiO2 Au (0.1 wt%) having
dose ∼ 0.30 g/L) better photodegradation
results as compared to
other doping amounts

Naproxen (NPX) and three Water type not given P25-TiO2 /TEOS films
other drugs Dose: 1–5 pieces of glazed
ceramic tiles
(2 mm × 2 mm × 5 mm)
Visible light incubator 20 mL of drug solution - The degradations of [171]
(10,000 ± 1000 lx) C[NPX] = C[IBP] = C[DCF] naproxen, ibuprofen,
= C[APAP] = 5 mg/L, diclofenac and salicylic
P25-TiO2 /TEOS films (4 acid, under optimum
pieces of glazed tile), conditions was 94%, 85%,
pH: 6 65%, and 76%
respectively

Ketoprofen (KP) Milli Q water Nanocrystalline TiO2 - Glass immersion C[KP] = 4.8–59 ␮M, - Reaction rate decreased [182]
C[KP] = 59 ␮M C[TiO2] = 0.5 g/L photochemical reactor. C[TiO2] = 0.5–1.0 g/L, with increase in KP
- Medium pressure Hg pH: 7 concentration
lamp, 366 nm. -Low - Photodegradation of KP
pressure Hg lamp, /254 was slower in the
nm presence of oxygen
- Photodegradation of KP
was 1.4 times quicker in
the presence of
synthesized anatase TiO2

151
152 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155

Fig. 18. Effect of different cross-linked TiO2 films on the degradation of aspirin under UV light (C0 = 2 mg/L, pH 4.5).

Fig. 19. Growth of acute toxicity assessed with Photobacterium phosphoreum, (b) Selenastrum capricornurum, and (c) Daphnia magna, and (d) TOC reduction and photo-
catalytic degradation of acyclovir.

Chong et al. [180] studied the degradation of carbamazepine in
synthetic hospital wastewater and suggested that the COD concen-
tration in synthetic wastewater is less than real hospital effluent.
This study also formed an important basis for future studies based
on real hospital (mixed) effluents. Choi et al. [181] studied the
degradation of simulated pharmaceutical waste water. They car-
ried out degradation experiments for the simulated waste and real
pharmaceutical waste at similar conditions of pH. The studies car-
ried out by the authors showed that the TiO2 pre-treatment system
was capable of removing 78% of carbamazepine, 40% of COD and
23% of PO4 3− concentrations from the wastewater within 4 h of
reaction. The proposed treatment poses a combined effect on PO4 3−
ions reduction and conversion of toxic nitrogen containing com-
pounds in wastewater into stable NO3− ions. The studies indicated
that there is need to study the optimization of parameters for the
degradation of mixture of drugs in water, predominantly at the
pilot scale and for application to real wastewater treatment. Thus,
it is concluded that TiO2 based system has a high potential to be uti-
lized as a sustainable pre-treatment system for hospital wastewater
containing drugs and other toxic compounds (Table 5).
4. Summary
The occurrence of the pharmaceutical substances in the envi-
ronment, specifically in the water bodies has been under the
scanner of the scientific community for over the last couple of
decades. Pharmaceutical substances in the water bodies repre-
sent a threat to the ecosystem, due to the fact that they affect
the human health adversely and their exact impact on aquatic
life still needs to be discovered. Pharmaceutical compounds being
biologically active substances generally do not biodegrade eas-
ily and therefore, are capable of accumulating and persisting in
 A. Kaur et al. / Applied Catalysis A: General 510 (2016) 134–155
Acknowledgements
the UGC Major Research Project Scheme from UGC, Government of
India through a project grant F. No. 41-364/2012(SR) and TEQIP-II
grant of Dr S. S. Bhatnagar UICET, Panjab University, Chandigarh.
Ahmad Umar would like to acknowledge the Ministry of Higher
Education of Saudi Arabia for research fund.
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Fig. 20. The effect of (a) catalyst dose of and (b) pH of drug solution on the solar-light
induced degradation of ketorolac tromethamine (20 mg/L).
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153
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