Environ Earth Sci (2017) 76:611
DOI 10.1007/s12665-017-6924-y
ORIGINAL ARTICLE
Pharmaceutical residues in aquatic environment and water
remediation by TiO2 heterogeneous photocatalysis: a review
Chee Mei Lee1 • Puganeshwary Palaniandy1 • Irvan Dahlan2
Received: 22 December 2016 / Accepted: 17 August 2017 / Published online: 1 September 2017
 Springer-Verlag GmbH Germany 2017
Abstract The occurrence of pharmaceutical compounds in
the natural water sources has been reported as early as in
the year 1980. Until now, the presence of pharmaceutical
compounds in the aquatic environment has been frequently
reported in the literature. Moreover, increasing evidence
suggests that these contaminants have posed a threat to
both humans and ecosystems. In this regard, the present
review paper seeks to offer an overview of this environ-
mental issue of pharmaceutical pollution where the subject
matters to be reviewed include the effects, sources and
mitigation strategies of pharmaceuticals in the aquatic
environment. Besides, a review of the fundamentals and
mechanisms of heterogeneous photocatalysis technology is
also presented in this paper. Heterogeneous photocatalysis
is a rapidly expanding technology which has been exten-
sively investigated and applied in wastewater treatment for
the remediation of persistent pollutants such as pharma-
ceutical compounds during the last decade. Furthermore,
the ideal photocatalyst titanium dioxide (TiO2), which can
collaborate and perform well in the photocatalysis treat-
ment process, is also discussed. The advantages and limi-
tations associated with the application of this treatment
method are summarized and discussed in details. Finally,
this review paper focuses on the future trend of the pho-
tocatalysis technology and identifies the barriers and
lacking parts which need to be resolved in the near future.
& Puganeshwary Palaniandy
cepuganeshwary@usm.my
1 Gramatica 2016).
School of Civil Engineering, Engineering Campus, Universiti
Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
2 ments with undeniable benefits in modern life (Blair 2016;
School of Chemical Engineering, Engineering Campus,
Universiti Sains Malaysia, 14300 Nibong Tebal, Penang,
Malaysia
Keywords Pharmaceuticals  Advanced oxidation
processes (AOPs)  Heterogeneous photocatalysis 
Titanium dioxide (TiO2)  Reactive oxygen species (ROSs)
Introduction
Water is one of the important resources on earth where
human beings and ecological systems rely on it for sur-
vival. If there is no water, there will be no life on earth.
Nowadays, the demand of water increases with the rapid
growth of population and vigorous industrial development.
High-quality water sources are necessary particularly in
maintaining healthy ecosystems and assurance for safe
drinking water.
Common water pollutants including pesticides, poly-
chlorinated biphenyls (PCBs), poly aromatic hydrocarbons
(PAHs), metals such as mercury, lead, cadmium and
arsenic, to name a few, have been significantly reduced
through the adoption of appropriate legal measures and the
removal of numerous dominant pollution sources (Al-
Odaini et al. 2013). Recently, the scientific community
starts to focus on a new group of pollutants, which are
pharmaceuticals (Choina et al. 2013; Doll and Frimmel
2005; Putschew et al. 2000; Ternes 1998). Pharmaceuticals
are known as the ‘‘new emerging pollutants’’ since they are
recently detected in the environment in increasing amount.
Up to now, pharmaceuticals are not covered by regulations,
and their effects on the environment and human health are
still poorly understood (Quadra et al. 2016; Sangion and
Pharmaceutical is one of the most indispensable ele-
Sangion and Gramatica 2016). They are extensively and
increasingly used as an integral component to establish and
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maintain a healthy population of both humans and live-
stock (Choina et al. 2013; Mozia and Morawski 2012;
Wilkinson et al. 2016). However, due to the widespread
application of pharmaceuticals and their inadequate
removal from wastewater, low levels of pharmaceuticals
(ranging from the low ng/L to mg/L) have been ubiqui-
tously detected (in both original and metabolized forms) in
various aquatic compartments such as surface water,
groundwater, effluents of sewage treatment plant, seawater
(Daughton and Ternes 1999; Halling-Sørensen et al. 1998)
and even in the drinking water (Doll and Frimmel 2005;
Sacher et al. 2001; Vaizoğullar 2017).
The retained pharmaceuticals in different water sources
may lead to some adverse effects on the biological balance
and human health such as aquatic toxicity, resistance
development in pathogenic bacteria, acute and chronic
damage, hormonal and endocrine disruption (Emmanuel
et al. 2005; K’oreje et al. 2016; Wu et al. 2012; Yang et al.
2008a). This situation is changing from bad to worse when
these persistent pharmaceuticals are unable to be elimi-
nated by using conventional wastewater treatment tech-
niques due to the typical characteristics of the
pharmaceuticals (Achilleos et al. 2010; Al-Odaini et al.
2013; Mozia and Morawski 2012). For example, pharma-
ceuticals are lipophilic to pass membranes and facilitate the
absorption. Besides, they can escape from the biological
treatment process since they are designed to be biologically
active and persistent to maintain their therapeutic activity
until the specific physiological function on the human and
animals has been performed (Achilleos et al. 2010; Aguilar
et al. 2011; Suarez et al. 2009; Zhang et al. 2008).
Therefore, they have the properties to bioaccumulate and
cause negative effects to aquatic or terrestrial ecosystems,
such as immobilization, mortality, inhibition of growth and
reproduction (Quadra et al. 2016).
The continuous input and persistence of pharmaceuticals
in the aquatic ecosystem indicate an environmental chal-
lenge even only at low concentrations. Recently, studies are
concerning on the removal of pharmaceuticals during treat-
ment by using heterogeneous photocatalysis wastewater
treatment technique (Bahnemann 2004; Lofrano et al. 2009;
Sharma et al. 2012). The field of heterogeneous photocatal-
ysis has been expanding rapidly within the last four decades
(Ibhadon and Fitzpatrick 2013). Photocatalysis performs the
redox function through the transformation, deactivation and,
finally, the minimization of environmentally persistent
compounds (Aziz et al. 2016).
This review paper aims to give an overview of the
occurrence of pharmaceutical compounds in the aquatic
environment, including the sources, effects and solutions to
overcome the pharmaceutical pollution. Also, the under-
standing and fundamentals of heterogeneous photocatalytic
wastewater treatment technology, including the advantages
123
Environ Earth Sci (2017) 76:611
and limitations of the photocatalysis process, were dis-
cussed in details in the review. The last part of this review
concerns on the lacking part of current studies and the areas
of future research.
Pharmaceuticals in the aquatic environment
The most frequently detected pharmaceuticals in the water
sources and their concentrations are summarized in Table 1
(Bagheri et al. 2016; Quadra et al. 2016; Wilkinson et al.
2016). Basically, they are divided into eight main classes
based on their specific mode of therapeutic action, namely
antibiotic, analgesic and antipyretic, central nervous sys-
tem (CNS) stimulant, iodinated X-ray contrast media,
antidepressant, beta blocker, hormone/steroid and lipid
regulator. The presence of pharmaceutical compounds as
the new emerging pollutants in the natural water resources
is becoming an issue of global concern (Mozia and Mor-
awski 2012; Nasuhoglu et al. 2011; Wu et al. 2012). The
main factors concerned relating to this issue are the lack of
the baseline data and the malfunctioning of the conven-
tional wastewater treatment methods.
Pharmaceutical pollution has not been given a signifi-
cant attention despite its increased and extensive applica-
tion for different purposes throughout the world in
nowadays (Choina et al. 2013; Mozia and Morawski 2012).
Ignorance on this matter is due to the fact that pharma-
ceuticals are not regulated as environmental pollutants and
not listed as pollutants in the WHO guidelines for drinking
water quality (Al-Odaini et al. 2013). This, in turn, leads to
the lack of baseline data regarding the occurrence of
pharmaceutical compounds in the aquatic environment,
thus prohibiting the evaluation of public exposure and the
subsequent effects (Arpin-Pont et al. 2016; Sim et al. 2011;
Taylor and Senac 2014). As the effects on human health
are unknown and the findings on the aquatic organisms are
limited, the severity of this issue may be covered up and
turning to worse as day goes on (Bagheri et al. 2016). Most
probably, the hidden effects may slowly accumulate and
expose unexpectedly and irreversibly.
Besides, studies have proven that the conventional
wastewater treatment plants are unable to eliminate the
retained pharmaceutical compounds completely (Achilleos
et al. 2010; Cai and Hu 2017; Mozia and Morawski 2012;
Zhang et al. 2008). This is because the conventional
wastewater treatment plants such as sedimentation and
biological treatment process are not designed to remove the
persistent pharmaceuticals which are polar, predominantly
water soluble in nature, neither volatile nor biodegradable
(Aguilar et al. 2011; Al-Odaini et al. 2013; Bagheri et al.
2016; Luo et al. 2015; Maroga Mboula et al. 2012;
Palominos et al. 2009). Other treatment methods such as
 Table 1 Most frequently detected pharmaceuticals in water sources and their concentrations. Data taken from Quadra et al. (2016), Bagheri et al. (2016) and Wilkinson et al. (2016)
Therapeutic class Function Compound Water source Concentration

Antibiotic Inhibits or abolishes the growth of microorganisms, Sulfamethoxazole Wastewater (0.02–0.58) lg/L
such as bacteria, fungi or protozoa River 1.8 ng/L
Amoxicillin Surface water (\2.5–245) ng/L
River 17 ng/L
Erythromycin Surface water (\0.5–159) ng/L
Triclosan Surface water (140–2300) ng/L
Environ Earth Sci (2017) 76:611

Analgesic and antipyretic As pain reliever and fever reducer Acetaminophen Wastewater (10–23.33) lg/L
Surface water (110–10,000) ng/L
River 280 ng/L
Diclofenac Wastewater (0.01–510) lg/L
Surface water (\0.5–154) ng/L
River (2440–5900) ng/L
Naproxen Wastewater (0.5–7.84) lg/L
River (20–50) ng/L
Ibuprofen Wastewater (0.49–990) lg/L
Surface water (1–2370) ng/L
River 640.5 ng/L
Ketoprofen Wastewater (0.13–3) lg/L
Carbamazepine Wastewater (0.1–1.68) lg/L
Codine Surface water (12–1000) ng/L
Central nervous system (CNS) stimulant Reduces tiredness and increases alertness, Caffeine Wastewater (3.2–11.44) lg/L
competitiveness, and aggression River (200–127,000) ng/L
Tap water (0.22 ± 0.06) ng/L
Iodinated X-ray contrast media Enhances the contrast between organs or vessels Iopromide Wastewater (0.026–7.5) lg/L
examined and surrounding tissues during Iomeprol Wastewater 1.6 lg/L
radiography
Antidepressant Controls anxiety and depression Amitriptyline Surface water (66–207) ng/L
Fluoxetine
Venlafaxine Surface water (5.8–120)ng/L
(1.1–35) ng/L
Beta blocker Treats hypertension and heart failure Metoprolol Wastewater (10–390) ng/L
Surface water (\0.5–10) ng/L
Atenolol Wastewater (10–730) ng/L
Surface water (\1–487) ng/L
Page 3 of 19
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activated carbon adsorption, air stripping and reverse

(1200–1700) ng/L

(1900–3000) ng/L

(0.78–1.05) ng/L
osmosis have also been investigated for the elimination of

(0.1–200) ng/L

(\10–60) ng/L
(73–831) ng/L

(48–872) ng/L

(48–790) ng/L
Concentration

(0.3–3) lg/L
(3–9.7) ng/L
pharmaceuticals. However, these processes are just trans-

444 ng/L
275 ng/L
ferring the pharmaceutical compounds from one phase to
1 ng/L

another without eliminating them (Elmolla and Chaudhuri

2010a).

Effects of retained pharmaceuticals

Drinking water

Drinking water
Surface water

Surface water

Surface water
Surface water

Surface water
Water source

Pharmaceuticals are one of the vital substances which are

Wastewater

Wastewater
Raw water

Raw water
beneficial to our daily life, particularly in terms of therapy
and healthcare facilities. However, when the pharmaceu-
River

River

ticals are exposed to the nontarget organisms, the benefi-

cial function may not be performed. In contrary, its
biological activity may cause abundant of acute and
chronic effects which can adversely affect the wildlife and
17a-ethinylestradiol

ecosystem health (Sangion and Gramatica 2016; Wilkinson

19-norethisterone

et al. 2016). In the last three decades, the presence and

17b-estradiol

Gemfibrozil
Bezafibrate
Compound

impact of pharmaceuticals in the environment have gained

an increasing concern. Pharmaceuticals, being a large,
diverse and persistent group of emerging organic microp-
ollutants, are found to be poorly removed by conventional
wastewater treatment processes and thus have been ubiq-
uitously detected in the natural water sources and even
Used as contraceptives and in hormonal replacement

drinking water. So far, the retained pharmaceutical com-

Decreases the level of cholesterol and triglycerides

pounds in the environment are reported at concentrations

ranging from the low ng/L to mg/L (K’oreje et al. 2016).
However, it is important to highlight that these pollutants
can pose a risk for aquatic life by various mechanisms even
at low concentration (Blair 2016; Wu et al. 2012).
Pharmaceutical pollution has been verified to induce the
endocrine or hormonal disruption problem, causing the
abnormal reproduction of fish (Khataee et al. 2013; Yang
et al. 2008a). Kidd et al. (2007), who conducted the
experiment in a pristine lake at the Experimental Lakes
Area in Canada, has found out that the addition of steroid
in blood
therapy
Function

estrogen ethinyl estradiol (EE2) can lead to the feminiza-

tion of males as well as the collapse of a fish population.
Recently, Sangion and Gramatica (2016) have also repor-
ted on the same endocrine disruption problem where the
EE2 caused the feminization of male fish in river and water
bodies, even at concentrations of few ng/l. In addition, fish
with intersex gonads and feminization of males or vice
versa have been found in some rivers in the UK. The
similar incident occurred in the city of Boulder, Colorado,
where the white suckers (a type of fish) also encountered
the endocrine disruption problems such as gonadal inter-
sex, disrupted ovarian, reduced gonad size and testicular
Table 1 continued
Therapeutic class

Hormone/steroid

histopathology. These endocrine disruption problems are

Lipid regulator

caused by the long-term exposure of the aquatic organisms

to the estrogenic compounds which are retained in the
water sources (Stoner and Kosinski 2008).

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Environ Earth Sci (2017) 76:611
Furthermore, pharmaceutical residues in the aquatic
environment are reported to have some ecotoxic effects.
For example, enrofloxacin and ciprofloxacin (two different
types of fluoroquinolone antibiotics) which are frequently
detected in wastewater and surface water are toxic to algae
(Ebert et al. 2011). Besides, the antibiotic of tetracycline
has been proven to bring the toxic effects to the plants and
the early stage of aquatic organisms. It also causes the
negative impact to the sewage sludge bacteria by inhibiting
their protein synthesized process (Yahiat et al. 2011).
Moreover, diclofenac is known as the most toxic analgesics
in acute exposure studies with the growth inhibition (EC50)
below 100 mg/L (Fent et al. 2006). Again, diclofenac and
hormones have been shown to bring fatal effects on fish,
crustaceans and algae at very low doses (Bagheri et al.
2016). The developed antibiotic resistance by the patho-
genic bacteria is also one of the verified adverse effects
identified in the previous studies (Elmolla and Chaudhuri
2010b; Maroga Mboula et al. 2012). These developed
antibiotic resistance genes which could cause the genotoxic
effects to the microorganisms will then spread in the
environment and lead to the occurrence of aquatic toxicity
(Khataee et al. 2013; Yang et al. 2008a).
Further instances of the effects of different pharma-
ceutical compounds on the aquatic organisms are summa-
rized in Table 2. Based on Table 2, it is noticeable that the
pharmaceuticals can induce some negative impacts to the
flora, fauna and microorganisms in the aquatic environ-
ment. Although most of the reported half-maximal effec-
tive concentrations (EC50) and half-maximal inhibitory
concentration (IC50) are found to be higher than those
detected in the environment, these results are still con-
cerned due to the possibility of synergistic effects with
other pharmaceuticals and more intense effects at long-
term exposure (Quadra et al. 2016). For example, research
by Cleuvers (2003) has indicated that, in comparison to the
singly measured toxicities, mixture of ibuprofen and
diclofenac can cause more immobilization in Daphnia
magna (microcrustacean) and inhibition of the average
growth rate for algae, which clearly demonstrate the syn-
ergistic effect of the mixture pharmaceuticals.
Up to now, concerns still remain regarding the harm of
pharmaceutical residues to human health, particularly to a
developing fetus (Blair 2016). Somehow, it is suggested
that long-term exposure to the retained pharmaceuticals
may bring unintended effects to the human health since
pharmaceuticals are designed to be highly interactive with
the receptors of human and animals (Abellán et al. 2007;
Jelić et al. 2012). It is important to highlight that the
continuous discharge of pharmaceutical compounds will
lead to a higher retained concentration in the future time
associated with unpredictable adverse effects on human,
aquatic and terrestrial organisms. Hence, further studies are
Page 5 of 19 611
required to acquire more verified adverse effects of the
retained pharmaceutical compounds on the living organ-
isms, especially on the human being, so that it can become
a convincing fact to alert the society regarding the seri-
ousness of this pharmaceutical pollution.
Major sources of pharmaceuticals
Tons of drugs are produced every year and broadly applied
in both human and veterinary medicine (Quadra et al.
2016). More than 200 types of pharmaceutical compounds
(mainly painkillers, vascular drugs, antibiotics and antide-
pressants) are frequently detected in aquatic and terrestrial
compartments with the concentration ranging from few ng/
l to thousand lg/l (Sangion and Gramatica 2016). There-
fore, understanding the sources and fates of pharmaceuti-
cals in the environment is vital for the determination of
suitable approaches to prevent them from entering the
water supply (Bagheri et al. 2016; Helwig et al. 2016).
Pharmaceuticals may reach aquatic ecosystems through
many pathways (Quadra et al. 2016). Figure 1 illustrates
the possible sources and fates of pharmaceuticals in the
environment. Basically, there are four major sources which
contribute to the occurrence of pharmaceuticals in the
aquatic environment: human use, veterinary use, agricul-
ture and farming use, as well as the industrial production.
As shown in Fig. 1, pharmaceuticals can reach the water
sources via the emission from healthcare facilities (hospi-
tals and clinics) and households (such as private residences,
dormitories, hotels, residential care facilities) (Abellán
et al. 2007; Chang et al. 2010; LA Ioannou et al. 2011).
Among all, hospitals act as the main source of pharma-
ceuticals released to the environment particularly through
the patients’ excretions (Bagheri et al. 2016; Straub 2016).
Following human consumption, excreted residue (feces and
urines) may enter the sewer in either original parent com-
pound or metabolite (Helwig et al. 2016). Depending on
the properties of pharmaceuticals, only part of them is
removed by the ordinary microbiological treatments in
wastewater treatment plants (WWTPs), whereas the
remaining residue is discharged and dispersed in the
aquatic environment (Abellán et al. 2007; Sangion and
Gramatica 2016). Due to that, WWTPs are often recog-
nized as the main route of entry for pharmaceuticals in the
environment, leading to a ubiquitous and continuous con-
tamination (Quadra et al. 2016; Sangion and Gramatica
2016). Besides, the improper disposal of unused, expired
and surplus pharmaceuticals into the drains or toilets is
another important pathway to contaminate the environment
(Al-Odaini et al. 2013; Moctezuma et al. 2012; Wu et al.
2012). These pharmaceuticals are most probably infiltrated
into the groundwater depending on the hydrology system
(Quadra et al. 2016).
123
 Table 2 Review of studies examining the effects of different pharmaceutical compounds on the aquatic organisms
Therapeutic class Compound Effect Value References

123
Anxiolytics Diazepam Alter the expression of 51 genes in the brain of Danio rerio (zebrafish), in which 61% of genes were 235 ng/L Oggier et al. (2010)
downregulated and 39% were upregulated
611 Page 6 of 19

Stimulants Caffeine Cause lethal to 50% of Ceriodaphnia dubia (microcrustacean) in a 48-h exposure 57 ± 3.3 mg/L Moore et al. (2008)
Impair 50% of reproduction in Ceriodaphnia dubia 44 mg/L
Cause a growth inhibition in 50% of Pimephales promelas (fathead minnow) 71 mg/L
Antipyretics Acetaminophen Affect embryonic development of Danio rerio 50 lg/L David and
Pancharatna (2009)
Cause an elongation inhibition in 50% of the wheat’s root 668.8 mg/L An et al. (2009)
Cause lethal to 50% of Hyalella azteca (amphipod crustacean) in a 72-h exposure 7.7 mg/kg Gómez-Oliván et al.
(2012)
Cause a growth inhibition in 25% of Duplicaria similis, Ceriodaphnia dubia and Ceriodaphnia 4.15, 4.47 and Quadra et al. (2016)
silvestrii (three different species of microcrustacean) 2.96 mg/L
Non-steroidal anti- Dipyrone Cause a growth inhibition in 25% of Duplicaria similis, Ceriodaphnia dubia and Ceriodaphnia 3.59, 2.79 and
inflammatory drug silvestrii 1.12 mg/L
(NSAID)
B-blockers Propranolol Cause mortality and immobility in Ceriodaphnia silvestrii 2.5 mg/L Rosa (2008)
Lipid regulators Clofibric acid With the increased concentration of clofibric acid, increased number of non-viable (dead) sperm of 0.1, 1 lg/L and Runnalls et al. (2007)
Pimephales promelas and decreased swimming velocity in the fish have been observed 1 mg/L
Hormones Estriol Cause immobility in Daphnia magna (microcrustacean) 94.6 mg/L Quadra et al. (2016)
Estradiol Result in feminization of Pimephales promelas 4 ng/L Lange et al. (2009)
17a- Cause feminization of Rutilus rutilus (roach fish) 4 ng/L and Länge et al.
ethinylestradiol (2001)
Antidepressants and Fluoxetine Cause immobility in 50% of Duplicaria similis 8900 ng/L Wolff (2011)
psychiatric medicines Cause growth inhibition in 50% of Pseudokirchneriella subcapitata (microalga) 100 ng/L
Antibiotics Tetracycline Cause growth inhibition in 50% of Microcystis aeruginosa (cyanobacteria) and Selenastrum 0.09 and Daghrir and Drogui
capricornutum (microalga) 2.2 mg/L (2013)
Cause a growth inhibition in 50% of Daphnia magna, while cause mortality in 50% of Danio rerio and 6617.2, 406
Carassius auratus (goldfish) and
322.8 mg/L
Reproduction and number of descendants of Daphnia magna decreases with increment of tetracycline 0.1–5.0 mg/L Borghi and Palma
loading to each subsequent generation (2014)
Environ Earth Sci (2017) 76:611
Environ Earth Sci (2017) 76:611
Possible sources of pharmaceuticals in the environment
Home use
Veterinary use
(Hospital, clinic and household)
Unused, Husbandry,
Excretion livestock and
expired and
surplus medicines aviculture
Sewage Excretion
Household waste
Sewage treatment plant Waste dumping site Manure
Soil
Fig. 1 Possible sources and fates of pharmaceuticals in the environment. Adapted and modified from Quadra et al. (2016) and Bagheri et al.
(2016)
In addition, veterinary use is also an important source of
drugs to the environment. Abundant of veterinary phar-
maceuticals is applied in husbandry sector as a growth
promoter, for breeding and therapeutic purposes (Bund-
schuh et al. 2016; LA Ioannou et al. 2011; Kümmerer
2009; Sim et al. 2011). After the consumption of phar-
maceutical by the livestock, part of the pharmaceutical is
excreted through the urine and feces, in either metabolized
or parent form. Without any treatment, the excreted phar-
maceuticals get into the soil and groundwater directly
(Kümmerer 2001; Quadra et al. 2016). Often, livestock’s
manure is used as fertilizer in the agricultural field. The
manure which contains the pharmaceutical residues can be
either mobilized into surface water during heavy precipi-
tation or infiltrated into the groundwater (Abellán et al.
2007). Other than livestock, fish farming is also an
important source of pharmaceuticals (Quadra et al. 2016).
The direct application of pharmaceuticals in the aquacul-
ture for the prevention and treatment of microbial infec-
tions has caused the increment of retained pharmaceuticals
in the aquatic environment (Kümmerer 2009).
Also, pharmaceuticals are extensively applied in the
agricultural and farming fields to control the bacterial
disease (Fukahori et al. 2012; Kümmerer 2009; Mozia and
Morawski 2012). These pharmaceuticals can accumulate in
farmland and eventually reach the natural water sources
through leaching and runoff (Abellán et al. 2009; Wilkin-
son et al. 2016). Last but not least, production and
Page 7 of 19 611
Industrial
Agriculture and farming use
(Production and manufacturing)
Aquaculture Land application Landfill Industrial effluents
Sediment Soil
Surface water
Groundwater
Portable water
treatment
Drinking water
manufacturing are among the industries which have highly
contribute to the occurrence of pharmaceutical pollution
through the inappropriate disposal, accidental spillage
during the manufacturing and distribution processes (Al-
Odaini et al. 2013; Yang et al. 2008a), as well as the direct
discharge of pharmaceutical waste into the water sources
(Abellán et al. 2007; Emmanuel et al. 2005; Gautam et al.
2007; LA Ioannou et al. 2011; Kümmerer 2001).
Once the pharmaceutical residue in the environment,
their behavior can be significantly affected by some factors
such as solubility, chemical structure, persistence, sorption
behavior, climatic factors (temperature, precipitation),
water body properties (pH, redox potential, organic carbon
content), composition of sediments and environmental
degradation. Due to this immense complexity, more
research in this field is required to identify the behaviors of
drugs in the environment (Quadra et al. 2016). Further-
more, strategies are required for the removal of numerous
dominant pollution sources. Besides the enactment of
appropriate legal measures, a standard or guideline of
pharmaceuticals wastewater effluent is also required to be
invented.
Pharmaceuticals mitigation strategies
Pharmaceuticals are often poorly removed by conventional
wastewater treatment techniques (K’oreje et al. 2016). The
continual emission of pharmaceuticals (either in parent
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Table 3 Review of studies examining the strategies for the mitigation of pharmaceuticals in the aquatic environment
Strategy/reference Description of solution Advantage Disadvantage

Urine separating toilets In this technology, the toilet is
(Borsuk et al. 2008; specially designed with two separate
Lamichhane and compartments: a front compartment
Babcock 2012; Lienert for urine and a larger rear
et al. 2003) compartment for feces
The urine is collected and stored in a
urine storage tank which located in
or nearby the household. Then the
urine will be transported to a
treatment unit (which located either
locally or centrally) to be treated
separately
Invention of Green This solution aims to create
pharmaceuticals ‘‘environmentally friendly’’
(Daughton 2003; pharmaceuticals which equipped
Khetan and Collins with the following properties:
2007) Easy uptake of compound by the
body
Degrade well during sewage
treatment and susceptibility to
environmental biodegradation,
sorption, and photolysis
Less harmful to the environment
High pharmacological activity and
sufficiently stable in the patient’s
body
Take-back programs Involve the returned of unused
(Becker et al. 2010; pharmaceuticals to pharmacy,
Blair 2016; Straub predetermined sites (such as fire
2016) departments, police station,
hospitals), or through the mail
More effective to be applied at the
sites with high pharmaceutical
usage (such as hospitals, nursing
homes, hospice care locations)
where greater amounts of unused
drugs can be collected
Trash disposal (Blair As an alternative solution for take-
2016; Gibson 2010) back programs.
Include the removal of drugs from
their original containers and mixing
with kitty litter, dirt, coffee grounds
or other unappealing materials,
followed enclosing the mixture in a
sealable bag, can, or container
Can avoid the pharmaceuticals from
entering the sewer and aquatic
environment
Reduce the volume of wastewater
needed to be treated
Can ensure the high levels of
pharmaceutical in urine have been
treated rather than discharged
directly into the sewer
Aquatic environment can be
escaped from the harmful
pharmaceuticals and hormones
Can avoid nutrient pollution
Capable to degrade faster and lessen
impact on the environment or be
environmentally less harmful
Can be an alternative solution for
improper disposal (toilet or drain
disposal) and avoid the
pharmaceuticals from entering the
aquatic environment
Able to reduce accidental or
intentional exposure to unused
pharmaceuticals
Allow the reuse of pharmaceuticals
for emergencies or needy
Cost saving
Can avoid the potential harm from
stockpiling the unused
pharmaceuticals in home
This method may only partially
capture the excreted
pharmaceuticals as part of it may
remain in feces
Unable to fully resolve the
ecological risk as this solution
only discharge some, but not all
pharmaceuticals
Pharmaceutical research and
development may be costly
Least feasible option
Unable to address the excretion of
pharmaceuticals and their
metabolites from normal use due
to changes in temporal and spatial
usage
Can be costly to implement and
manage
Have limited access and
participation in many areas
Could cause accidental exposure to
unused pharmaceuticals and
environmental contamination
Unable to address the excretion of
pharmaceuticals and their
metabolites
May cause leach from landfills

form or metabolites) into the surface water sources not only
causes the ubiquitous contamination of freshwater sup-
plied, but it is also proved to induce some adverse effects to
the aquatic organisms particularly in terms of endocrine
disruptions (Khataee et al. 2013; Talib and Randhir 2016).
Reported strategies in this regard are thus reviewed as
tabulated in Table 3 to evaluate and compare the different
solutions which have been suggested.
Besides depending on the wastewater treatment process
such as the most promising advanced oxidation processes
(AOPs) for the mitigation of pharmaceuticals in the aquatic
environment, there are some other solutions which have
been suggested and discussed as presented in Table 3.

123
Environ Earth Sci (2017) 76:611
Among the suggested pharmaceuticals abatement strate-
gies, take-back program is the only strategy which cur-
rently exists and being the most recognized upstream
strategies (Blair 2016). This program provides plenty of
benefits by retrieving the unused pharmaceuticals, but at
the same time, its limitations are capable of restricting it
from the worldwide application. Next, source treatment
such as urine separating toilets can be an effective way of
discarding the retained pharmaceuticals in the urine, but
the pharmaceutical residues in the feces have been sadly
neglected. In this case, this treatment will be unable to
provide a thorough elimination of pharmaceuticals and can
most probably increase the complexity of the treatment
process and cost.
On the other hand, it can be observed that the trash
disposal is the simplest and cost-saving technique to be
implemented. Yet, it may not be the most secure solution
since it can induce the same environmental problem
through leaching from landfill and accidental exposure if
there is incautious handling. As for the invention of
green pharmaceuticals, although it may be costly in
terms of pharmaceuticals research and development, but
its ease to degrade and less harmful properties contribute
to the sustainable protection of aquatic resources. There
are some newly discovered strategies like starting new
prescriptions at lower dosages (Daughton 2003). In this
regard, patient is advised to start with the lowest effec-
tive dose and adjusting the dosage as necessary. This
prescript way not only reduces the patient costs and
unused pharmaceuticals disposal cost, but it also
improves the therapeutic efficacy and prevents the
unnecessary side effects to the patient, as well as avoids
the accidental exposures and emission of pharmaceuticals
to the aquatic environment. Last but not least, the mit-
igation technique which is known as ‘‘eco-directed sus-
tainable prescribing’’ is mainly about the selection of
pharmaceuticals with lower excretion rate (Daughton
2014). Unlike the former strategy (lower prescription
dose), this solution emphasizes on the metabolism and
excretion of pharmaceutical drugs rather than the initially
ingested dose by the patient, because the emission of
pharmaceuticals into the environment via sewers is dic-
tated by the excretion profile and pharmacokinetics of
the different types of pharmaceutical compounds. This
solution involves the reduction in dose of medications
with high excretion profile and replaces with another
suitable medication which is poorly excreted, if possible.
Nevertheless, the understanding on the effectiveness,
usage, participation and feasibility of this strategy is still
incomplete.
In summary, an ideal solution for the pharmaceuticals
mitigation in the aquatic environment is yet to be met. The
above-discussed strategies which equip with both
Page 9 of 19 611
limitation and strength may require further investigation to
compensate the scarcity of the information and subse-
quently identifying the most effective strategy for real
application.
Heterogeneous photocatalyst
During the last decade, AOPs appears to be a promising
wastewater treatment technology which could successfully
degrade the soluble organic pollutants and the volatile
organic compounds retained in the water and air, respec-
tively. The only chemical property which unites the dif-
ferent types of AOPs is the generation of reactive oxygen
species (ROSs), particularly the hydroxyl radical (OH),
which is a powerful oxidizing agent that possesses the
second highest oxidizing potential (2.8 eV). It can be
generated in situ to oxidize and further mineralize the
recalcitrant pollutants into the harmless end products such
as carbon dioxide and water (De la Cruz et al. 2013; Kaur
et al. 2016; Xekoukoulotakis et al. 2011; Yahiat et al.
2011).
AOPs such as Fenton, photo-Fenton, ozonation, ultra-
sound radiation, photolysis and photocatalysis are applied
for the treatment of pharmaceutical wastewater. However,
these treatment processes are found to be less effective
with the fluctuating degree of removal efficiency. The
tertiary treatment methods such as electrodialysis, acti-
vated carbon, chemical removal, coagulation, filtration and
membrane filtration are also examined for their removal
efficiency of pharmaceutical compounds retained in the
wastewater after secondary treatment. Yet, the efficiencies
of these methods are observed to be fluctuated critically
(Kaur et al. 2016).
To date, heterogeneous photocatalysis has been known
as the most distinctive, popular, effective, interesting and
promising wastewater treatment technique for the removal
of recalcitrant and persistent contaminants (Aguilar et al.
2011; Maroga Mboula et al. 2012; Yahiat et al. 2011; Yang
et al. 2008a). This treatment process is initiated by the
interaction between the UV and catalyst, where it can be
simplified as ‘‘the speeding up of photoreaction in the
presence of a catalyst’’ (Al-Rasheed 2005; De la Cruz et al.
2013). It utilizes the near ultraviolet band of the solar
spectrum (\400 nm) to excite the catalyst integrated with
the presence of oxygen and water (LA Ioannou et al. 2011).
Then, the generated ROSs are applied for the destruction of
contaminants appeared in the water body. Among the
photosemiconductors, titanium dioxide (TiO2) with anatase
phase appears to be the most extensively used photocata-
lyst due to its idealizing properties such as high stability,
cost-effective and favorable performance (Kaur et al.
2016).
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611 Page 10 of 19 Environ Earth Sci (2017) 76:611

Mechanisms of heterogeneous photocatalysis As a result of irradiation, TiO2 can act as an electron

donor or molecules acceptor. The powerful oxidant, hþ vb ,
Numerous studies have been published on the reaction 
oxidizes the water and hydroxide ion (OH ) to produce the

mechanism of photocatalytic process using TiO2 (Al- OH, whereby the reductant, e cb , reduces the oxygen to
Rasheed 2005; Elmolla and Chaudhuri 2010b; Ibhadon and form superoxide radical anion (O 
2 ). O2 then reacts with
Fitzpatrick 2013; Jaeger and Bard 1979; Moctezuma et al. þ
hydrogen ion (H ) to form hydrogen peroxide radical
2012; Yang et al. 2008a, b). Heterogeneous photocatalysis (HO2 ) and further protonated by Hþ can produce hydrogen
can be defined as the acceleration of photoreaction in the peroxide (H2O2). These oxidation and reduction processes
presence of semiconductor photocatalyst. Among the which take place on the surface of the photoexcited semi-
variety of catalyst, TiO2 is mostly preferred in the photo- conductor not only generate abundant of ROSs such as
catalysis process for features such as chemical stability, 
OH, O 
2 , HO2 and H2O2 which takes part in the contam-
acceptable band gap, ability to adsorb electrons and low inant degradation process, but also prevent the recombi-
cost (Gani and Kazmi 2016). Figure 2 illustrates the sim- nation of hþ 
vb and ecb . The following chain reactions have
plified mechanisms for the photoactivation of a semicon- been widely postulated (Al-Rasheed 2005):
ductor photocatalyst, TiO2. As shown in Fig. 2, the valence
and conduction bands of a TiO2 are separated by a band TiO2 ðhþ _
vb Þ þ H2 O ! TiO2 þ OH þ H
þ
ð2Þ
gap or energy gap. In order to initiate the degradation TiO2 ðhþ  _
vb Þ þ OH ! TiO2 þ OH ð3Þ
process, TiO2 requires photoexcitation with light at a
wavelength of \387 nm, to exceed the band gap of the TiO2 ðe
cb Þ þ O2 ! TiO2 þ O
2 ð4Þ
active anatase phase of 3.2 eV and rutile phase of 3.0 eV O þ 
2 þ H ! HO2 ð5Þ
(Ibhadon and Fitzpatrick 2013). In other words, photo-
catalysis over a TiO2 is initiated by the absorption of HO2 þ Hþ þ TiO2 ðe
cb Þ ! H2 O2 ð6Þ
photons with energy equal to or greater than its band gap. O þ O þ
þ 2H ! H2 O2 þ O2 ð7Þ
2 2
This promotes the movement of electron from the valence
band to the conduction band of TiO2. Subsequently, it On the other hand, the cleavage of H2O2 by one of the

reactions below can also generate OH:
generates the positive valence band hole hþvb and negative



conduction band electron ecb : _
H2 O2 þ hv ! 2OH ð8Þ
TiO2 þ hv ! e
cb ðTiO2 Þ þ hþ
vb ðTiO2 Þ ð1Þ H2 O2 þ O
2
_ þ O2 þ OH
! OH 
ð9Þ
The electron and hole can recombine when there is a H2 O2 þ TiO2 ðe _ 
cb Þ ! OH þ OH þ TiO2 ð10Þ
lack of oxygen to react with the electron for the formation
of O The ROSs (OH,O  þ
2 , HO2 and H2O2) including hvb and
2 . During the recombination, the absorbed light
energy released as heat with no chemical reaction takes e
cb then degrade the organic compounds adsorbed on the
place (Ibhadon and Fitzpatrick 2013). surface of photocatalyst and suspended in the solution.
Although the degradation commences with a partial
degradation, the term photocatalytic degradation usually
refers to the complete photo mineralization or oxidation,
essentially to the harmless end products of water and car-
bon dioxide (Saadati et al. 2016). OH is verified to be the
most abundant and dominant oxidizing species since it
degrades the organic compounds directly in a TiO2 aqueous
suspension (Moctezuma et al. 2012; Yang et al. 2008a).

Titanium dioxide (TiO2) as photocatalyst

Among the photosemiconductors (ZnO, ZrO2, MgO, MoO3,

Fig. 2 Simplified mechanisms for the photoactivation of a semicon-
ductor catalyst (Al-Rasheed 2005)
CdS, SnO2, WO3, etc.), TiO2 is the most extensively used
photocatalyst due to its biological and chemical inertness,
non-toxicity, low cost, high catalytic efficiency and photo-
chemical stability (Abellán et al. 2009; Aguilar et al. 2011; Ji
et al. 2013; Laoufi et al. 2013). Besides, with the ideal
properties such as excellent pigmentary properties, high UV
absorption and resistance to photocorrosion in aqueous

123
Environ Earth Sci (2017) 76:611
environment, eco-friendly, low energy band gap and can be
applied individually without additional chemicals, TiO2
remains a benchmark among other semiconductors (Abellán
et al. 2007; Al-Rasheed 2005; Belgiorno et al. 2007; Choina
et al. 2013; Lofrano et al. 2009; Yang et al. 2008a).
Basically, TiO2 has three different crystalline forms.
Anatase and rutile are the most common forms. Anatase is
more efficient than rutile in the photocatalysis application
since the former crystalline form has an open structure and
exhibits higher photocatalytic activity, whereby brookite is
the third crystalline form which is uncommon and unsta-
ble to be used in the photocatalysis treatment process. The
commercial TiO2 powder, such as anatase crystalline, and
the combinations of anatase and rutile (Degussa P25, 25:75
or 80:20 anatase/rutile) have been the most extensively
used heterogeneous catalysts in the photocatalysis treat-
ment process due to their chemical stability, reproducibil-
ity, highest detoxification efficiencies and readily available
as a catalyst for oxidation processes (Al-Rasheed 2005;
Spasiano et al. 2015).
Suspended TiO2 powder and immobilized TiO2 are the
two different modes of TiO2 photocatalyst which are typ-
ically used in the photocatalytic degradation processes.
Both of them offer their respective advantages and disad-
vantages as tabulated in Table 4. The slurry or suspended
TiO2 has been the most commonly used system because of
its simplicity in terms of preparation and application. The
suspended TiO2 system can provide a higher efficiency
than the immobilized system, mainly due to a higher ratio
of catalyst active site to reaction volume. Nevertheless, an
additional separation process is required to recover the
TiO2 powder at the end of the treatment process, by either
filtration or centrifugation. This separation process not only
increases the complexity and cost of the overall process,
but it is also time-consuming (Spasiano et al. 2015). Fur-
thermore, the suspended TiO2 powder tends to agglomerate
into larger particles at high concentration, which could
reduce the catalytic activity (Hao et al. 2012; Lalhriatpuia
et al. 2015). On the other hand, the immobilized TiO2
system allows the direct discharges of decontaminated
Table 4 Advantages and disadvantages of the suspended and immobilized TiO2
System Advantage
Slurry/suspended TiO2 Simplicity
Provide higher degradation efficiencies
Provide higher surface area for reaction
Immobilized TiO2 Do not require separation step
Time and cost saving
Page 11 of 19 611
water effluent without the recovery of TiO2 since the cat-
alyst remains confined to the packed-bed (Borges et al.
2015). Consequently, the post-processing treatment can be
avoided, thereby saving time and costs (Hashim et al.
2017). However, as compared to the suspended catalyst, it
is reported that 60–70% of reduction in performance has
been observed in the aqueous system for immobilized TiO2
since the latter system offers a lower reaction surface area
for the photocatalysis reaction to take place (Bautista et al.
2015; Gaya and Abdullah 2008; Jiménez et al. 2015).
Besides, the immobilized catalyst is more difficult to be
synthesized and it requires the inert support materials such
as glass or ceramic fibers, alumina pellets or molecular
sieves (Spasiano et al. 2015). Despite aforementioned
disadvantages, currently, coated photocatalyst and immo-
bilization techniques are still investigated intensively due
to the assumption that this system is more effective in the
removal of organic compound as compared to the sus-
pended TiO2 (Gaya and Abdullah 2008).
Besides being a promising photocatalyst in the
wastewater treatment process, TiO2 is also an important
material in many commercial products, ranging from
drugs to foods, paints to pharmaceuticals, cosmetics to
catalysts and sunscreens to solar cells, where TiO2 is
applied as a desiccant, brightener and reactive mediator.
TiO2 is used as the inactive ingredients in the food
products up to 1%, as permitted by the U.S. Food and
Drug Administration. The health effects associated with
the consumption and application of TiO2 are still not
clearly known (Ibhadon and Fitzpatrick 2013). So far,
only Gaya and Abdullah (2008) has mentioned on the
toxic effect of the TiO2 suspension on the E. coli. Also,
the increased antibacterial inhibition is observed with the
increment of TiO2 loading during the photocatalytic
experiment. Therefore, more studies are required to fur-
ther investigate the effect of TiO2 on the environment
and organisms. Meanwhile, the regulatory framework for
the use of TiO2 in the food products should be estab-
lished in the near future, particularly in the developing
nations (Ibhadon and Fitzpatrick 2013).
Disadvantage
Require post-treatment for catalyst recovery
Agglomeration of TiO2
Difficult to be synthesized
Provide lower reaction surface area
Significant reduction in system efficiency
123
611 Page 12 of 19
Advantages and limitations of heterogeneous
photocatalysis
Apparently, current conventional water and wastewater
treatment processes have failed to overcome the pharma-
ceutical pollution as they are not designed to remove the
suspended pharmaceuticals (Blair 2016). To date, hetero-
geneous photocatalytic degradation using TiO2 photocata-
lyst remains as a viable alternative in the elimination of
organic contaminants persistent in both aquatic and atmo-
spheric (Gaya and Abdullah 2008). Since the last decade,
this wastewater treatment technique has been extensively
applied for the elimination of different types of pharma-
ceuticals. Table 5 summarizes previous studies on the
heterogeneous photocatalysis treatment technique for the
degradation of pharmaceuticals. It is noticeable in Table 5
that the initial concentration of pharmaceutical employed
in the previous studies was usually higher than that typi-
cally detected in the natural water sources (lg/L–ng/L).
This is to allow the accurate determination of residual
concentration and the assessment of treatment efficiency
within a measurable time scale (Achilleos et al. 2010). As
shown in Table 5, most of the TiO2 photocatalytic studies
focused on the determination of optimal operating condi-
tions to attain the best performance in terms of degradation
and mineralization. Markedly, the degradation rate of
pharmaceutical is greatly affected by the operational
parameters such as the type and loading of photocatalyst,
initial concentration of the pharmaceutical under investi-
gation, pH of the solution and light (source, wavelength
and intensity). Other operational parameters which can
enhance the degradation rate include the addition of co-
oxidants and the concentration of electron acceptors.
Moreover, the design and geometry of the photoreactor
also influence the optimal degradation rate of pharmaceu-
tical (Kanakaraju et al. 2014). Due to this, different opti-
mum operating conditions are normally documented by the
different studies for the highest pharmaceutical removal
efficiency (regardless of the studied pharmaceuticals are
different or similar), since the degradation rate of phar-
maceutical is dictated by a great deal of aspects and
parameters. Here, there are three main advantages associ-
ated with this treatment method and could be explained
from the aspects of health and safety, sustainability as well
as the simplicity of technology.
Various types of advanced treatment methods such as
activated carbon adsorption, air stripping and reverse
osmosis have been applied for the elimination of retained
pharmaceuticals. Yet, studies have found out that these
processes are less effective for the overall mineralization,
which only transfer the pharmaceutical compounds from
one phase to another or just collecting the pharmaceutical
compounds without eliminating them (Elmolla and
123
Environ Earth Sci (2017) 76:611
Chaudhuri 2010b; Gültekin and Ince 2007). Besides, the
purification techniques like ozonization, chlorination and
filtration too have their own limitations in terms of the
energy sources consumption and the generation of harmful
waste (Sharma et al. 2012). However, in contrast with the
aforementioned treatment methods, heterogeneous photo-
catalyst which relies on the generation of ROSs is able to
render the complete mineralization of pharmaceuticals
(Kaan et al. 2012). Among the variety of ROSs, OH has
attracted the most attention. The positive characteristics of

OH radicals are including non-selective nature, high oxi-
dation potential (2.8 eV) when compared to other oxidants,
ability to react with a wide range of contaminants without
any additives, as well as rate constants normally in the
order of 106–109 mol/L/s (Kanakaraju et al. 2014). During
the photocatalysis treatment process, OH appears to be a
strong oxidant that can react and further break down the
non-biodegradable or recalcitrant compounds (such as
pharmaceuticals) in water or wastewater, from complex
molecules into the simplest and non-hazardous end prod-
ucts such as water and carbon dioxide (Elmolla and
Chaudhuri 2010b; Khataee et al. 2013; Lofrano et al.
2009). Therefore, heterogeneous photocatalysis degrada-
tion process can provide promising clean water sources that
ensure the health and safety of human, living organisms
and the environment.
The growth and development of the world have induced
several environmental issues, mainly regarding the deple-
tion of natural resources (Spasiano et al. 2015). It has been
circulated worldwide that the depletion rate of these
resources is increasing year by year, causing it to become
one of the major concern among humans globally. Due to
this issue, priority is given to the sustainability concept
regardless of sectors. Heterogeneous photocatalyst is one
of the wastewater treatment methods which in line with the
concept of sustainability. The recent studies start to utilize
the natural UV radiation (from sunlight) instead of the
synthetic UV radiation (from UV lamp and solar simulator)
as the source of photocatalyst excitation. Meanwhile, the
ideal photocatalyst, TiO2, is found to be water insoluble
under most of the environmental conditions and remains
unchanged throughout the treatment process (Belgiorno
et al. 2007; Choina et al. 2013; Ibhadon and Fitzpatrick
2013). As the main elements of UV radiation and oxygen
are unlimited supplied by the solar and atmosphere,
respectively, as well as the photocatalyst can be recovered
and reused after the treatment process, the photocatalytic
technology is considered to be low cost, environmentally
friendly, low energy consumption with no consumable
chemicals required (Aziz et al. 2016; LA Ioannou et al.
2011).
Heterogeneous photocatalyst treatment which involves a
simple operating system with limited equipment required
Environ Earth Sci (2017) 76:611
Table 5 Recent examples of pharmaceuticals photocatalytically degraded by TiO2
Type of Type of photocatalyst, Treatment conditions
pharmaceutical UV source
Sulfamethoxazole, TiO2 (Degussa P25), Concentration of
Trimethoprim LED lamp TiO2 = 0.05 g/L
Initial concentration of each
pharmaceutical = 400 ppb
Irradiation time = 20 min
System flow rate = 8 mL/
min
Flumequine Titanium tetrabutoxide Concentration of
(TBT, Sigma Aldrich, TiO2 = 4 g/L
97%), UV lamp Initial concentration of
(Spectroline XX- flumequine = 10 mg/L
15 N)
Irradiation time = 240 min
UV light intensity = 2 mW/
cm2
pH 5
Diclofenac TiO2 (Degussa P25), Immobilized TiO2
solar visible light (Supported on fiberglass
sheets)
Concentration of
TiO2 = 37.5 mg/cm2
Initial concentration of
diclofenac = 25 mg/L
Eosin-Y dye
concentration = 2 mg/L
Irradiation time = 5 min
UV light
intensity = 750 mW/cm2
Tetracycline TiO2, UV lamp Concentration of
(Philips, PL-L 18 W) TiO2 = 2.09 g/L
Irradiation time = 20.95 min
pH 5.5
Paracetamol TiO2 (Degussa P25), Immobilized TiO2
UV lamp (Supported on glass
spheres)
Initial concentration of
paracetamol = (0.05, 0.5,
1) g/L
Page 13 of 19 611
Main findings References
More than 90% of sulfamethoxazole and Cai and Hu
trimethoprim were removed under the (2017)
optimum treatment conditions
Antibacterial activity study with a reference
Escherichia coli strain indicated that with
every portion of trimethoprim removed, the
residual antibacterial activity decreased by one
portion
Chronic toxicity studies conducted with Vibrio
fischeri exhibited 13–20% of bioluminescence
inhibition during the decomposition of 1 ppm
sulfamethoxazole and 1 ppm trimethoprim, no
acute toxicity to Vibrio fischeri was observed
during the photocatalytic process
Photocatalytic degradation of flumequine by Vaizoğullar
TiO2 under UV irradiation exhibited 23% (2017)
degradation efficiency under the given
treatment conditions.
Apparent rate constant (kapp) of flumequine
degradation in TiO2/UV system was
0.0009 min-1
Eosin-Y dye was an effective electron donor to Hashim
activate the photocatalyst, making the catalyst et al.
suitable for operating under solar light (2017)
The optimized parameters conveyed a diclofenac
degradation rate of 40% and 49% for 2 ppm
(low range) and 4 ppm (high range) dye
concentrations, respectively
93.1% of tetracycline degradation efficiency was Luo et al.
obtained under the optimum treatment (2015)
conditions
Photocatalytic degradation of tetracycline
followed a pseudo-first-order reaction rate
Apparent rate constant (kapp) and half-life of
tetracycline degradation in TiO2/UV system
were 0.0604 min-1 and 11 min, respectively
TiO2 Degussa P25 showed a good photocatalytic Borges et al.
activity for the paracetamol removal from (2015)
wastewater, reaching a high photodegradation
(between 99 and 100% of paracetamol removal
after 4 h of irradiation) for all the amounts of
photocatalyst tested
Photocatalytic degradation of paracetamol
followed a pseudo-first-order reaction rate
Apparent rate constants (kapp) of paracetamol
degradation in TiO2/UV system were 0.036,
0.045 and 0.042 min-1 for 0.05, 0.5 and 1 g/L
of paracetamol concentration, respectively
123
611 Page 14 of 19 Environ Earth Sci (2017) 76:611

Table 5 continued
Type of Type of photocatalyst, Treatment conditions Main findings References
pharmaceutical UV source

Metronidazole, Millennium TiO2 PC- Immobilized TiO2
atenolol, 500, 30-W UV-C (Supported on ceramic
chlorpromazine lamp (Philips, the plates)
Netherlands) Initial concentration of each
pharmaceutical = 10 mg/L
Irradiation time = 150 min
UV light
intensity = 38.45 W/m
Atenolol TiO2 (Degussa P25), Concentration of
High-pressure mercury TiO2 = 2 g/L
lamp (Philips, HPK, Initial concentration of
125 W) atenolol = 37.6 lM
Irradiation time = 60 min
pH 6.8
Tylosin TiO2 (Degussa P25), Immobilized TiO2
UV lamp (Philips, Initial concentration of
TLD, 18 W/08) tylosin = (0.0044–0.0327)
mM
Irradiation time = 420 min
Under the achieved optimal conditions of the Khataee
operating parameters, high removals of 95.32, et al.
87.02 and 90% were obtained for (2013)
metronidazole, atenolol and chlorpromazine,
respectively, in the solution of a mixture of the
pharmaceuticals
The TOC results (90% removal after 16 h) and
ecotoxicological experiments revealed that the
photocatalysis process could effectively
mineralize and reduce the ecotoxicity of the
pharmaceuticals from their aqueous solutions
Complete degradation of atenolol was obtained Ji et al.
under the optimum treatment conditions (2013)
Hydroxyl radical (OH) was determined to be the
predominant reactive species during
photocatalysis by means of radical probes
Atenolol photocatalytic degradation followed the
pseudo-first-order kinetic (R2 = 0.993)
The pseudo-first-order rate constant (kapp) was
determined to be 0.057 min-1
In weak concentrations, from 0.0044 to Laoufi et al.
0.0327 mM, the abatement of tylosin was (2013)
between 90 and 96% after an exposure time to
radiations of 420 min
The values of the kinetic constant, the pseudo-
first-order constant (kapp) and the equilibrium
constant of adsorption were, respectively,
equals to 0.000444 mol/L min, 0.00653 min-1
and 14.69 L/mol

could potentially be used as a standalone treatment. This
treatment method is able to attain the complete mineral-
ization with no sludge generated. Therefore, the post-
treatment and disposal of sludge can be avoided (Al-
Rasheed 2005; Chong et al. 2015; Ibhadon and Fitzpatrick
2013). Additionally, the achieved photocatalysis removal
efficiencies of pharmaceuticals in the previous studies are
believed to be sufficient for the actual treatment process. In
other words, the photocatalytic degradation of pharma-
ceuticals in the real situation is likely to occur rapidly since
the concentrations of pharmaceuticals detected in the nat-
ural water sources (lg/L–ng/L) are far lower than that
employed in the previous studies. Hence, this treatment
method is able to perform effectively for a technical use in
the wastewater treatment plant. Besides, it is a totally safe
treatment method which is conducted under the ambient
temperature and ordinary pressure (Aziz et al. 2016).
Despite the aforementioned advantages, there are also
some limitations associated with the application of photo-
catalysis. The main limitation is that this method is unable
to perform well in turbid water. This is because the
reduction of light transmissivity, the adsorption of con-
taminants onto the surface of catalyst or the absorption of
available photons by the contaminants will eventually
induce a lower intensity of photons to excite the catalyst
surface (Abellán et al. 2009; LA Ioannou et al. 2011;
Kümmerer 2009; Yang et al. 2008a). Therefore, hetero-
geneous photocatalysis treatment is unable to integrate
with primary and secondary treatment process, but it is
suggested to be used as a tertiary treatment process, par-
ticularly for the elimination of pharmaceutical compounds
which are still retained in the treated wastewater (Naddeo
et al. 2009).
Another major limitation is that TiO2 can only be pho-
toexcited by the light at a wavelength of \388 nm due to
its wide band gap (3–3.2 eV) (Achilleos et al. 2010;
Daghrir and Drogui 2013). Therefore, it is important to
avoid any loss of solar radiation during the treatment
process. For better results, this treatment process can be
assisted by the artificial illumination of catalyst to achieve
the degradation of contaminants in time that is practical for
the real wastewater treatment processing (Ibhadon and
Fitzpatrick 2013). Besides, it is suggested that the nano-
material should be modified so that it can utilize the visible
light in solar irradiation (Kaur et al. 2016).

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Environ Earth Sci (2017) 76:611
Last but not least, heterogeneous photocatalysis process
must be operated cautiously to avoid the incomplete min-
eralized organic contaminants to be released into the water
sources. It is important to highlight that the ultimate goal of
the treatment process should be emphasized on the com-
plete mineralization of pollutants, since the previous
studies have reported that the metabolites and intermedi-
ates generated during the treatment process can be more
toxic than the parent compounds (Kümmerer 2009; Maroga
Mboula et al. 2012; Nasuhoglu et al. 2011). For instance,
Szabo and his co-researchers have reported that the inter-
mediates of paracetamol (e.g., acetamide, hydroquinone)
have posed a higher toxicity level as compared to parac-
etamol itself (Szabó et al. 2012). Besides, the phenolic
intermediates of paracetamol which are classified as the
persistent organic pollutants are found to be toxic for both
environment and human beings (Torun et al. 2015).
Future trends
Maroga Mboula et al. (2012) indicated that the complete
mineralization of contaminants under the heterogeneous
photocatalyst treatment method is associated with a high
operating cost caused by the excessive consumption of
energy and TiO2. In order to minimize the overall cost of
photocatalysis treatment process and to overcome the
depletion of non-renewable energy resources, scientists are
currently searching for a new energy resource that is clean,
renewable and alternative to the fossil fuels. Among the
alternative sources, solar, which is derived from the sun-
light, was recognized as the most promising natural energy
source. This potential energy can be converted into
chemical energy by natural solar photoassisted reactions
(Spasiano et al. 2015). Table 6 shows the recent studies
applying the solar radiation for the photocatalysis degra-
dation of pharmaceuticals. It can be observed that the solar
heterogeneous photocatalysis has been an efficient tech-
nique for the elimination of pollutants from aqueous. As
photocatalysis makes use of sunlight for UV radiation, the
technology is inexpensive, environmentally friendly and
can be applied worldwide. Also, it requires only minimal
equipment, which is highly deployable and appropriate for
developing countries and remote sites with no access to
electricity (Ibhadon and Fitzpatrick 2013).
TiO2 remains as a benchmark and excellent photocata-
lyst among other semiconductors due to its ideal properties
(Kaan et al. 2012). The main drawback which currently
restricts its wider commercial application is the limited
solar spectrum to be used (limited to ultraviolet region),
which is only about 3–4% of the solar energy reaching the
terrestrial surface. Therefore, much effort has been devoted
to the development of visible-light-harvesting
Page 15 of 19 611
photocatalysts through the reduction in catalyst’s band gap
to increase the amount of visible sunlight which TiO2 can
absorb (Spasiano et al. 2015). Other inventions include the
increment of catalyst surface area, active site and photon
energy absorption (Al-Rasheed 2005; Ibhadon and Fitz-
patrick 2013). Additionally, the retrieval and reuse of TiO2
is also an essential issue to be resolved. There are a few
TiO2 retrieval methods which have been suggested for the
recovery of TiO2 suspended in the reaction mixture in
aqueous slurry systems. Ultracentrifugation and membrane
filtration separation methods are efficient in the separation
of nanomaterials, but both of them have their own limita-
tion of high energy consumption and easily to be blocked,
respectively. Compared to the aforementioned methods,
the magnetic separation method is considered a rapid and
effective technique for the recovery of nanoparticles
(Bagheri et al. 2016). Nevertheless, Saadati et al. (2016)
have mentioned that future studies should focus on the
immobilized system, where the photocatalyst is immobi-
lized on suitable support matrices to avoid the post-sepa-
ration and recovery of the catalyst particles at the end of
the treatment process. Overall, each of the recovery
methods equipped with advantages and disadvantages. The
selection of method should be based on the quality stan-
dards which have to be met, efficiency and cost (Bagheri
et al. 2016).
Besides the replacement of artificially generated photons
with the natural solar irradiation and the modification of
TiO2, there are some barriers and lacking parts which still
need to be overcome in the near future:
• Although solar photocatalysis has produced significant
interest in research on nowadays, so far, there is a lack
of ‘‘in situ’’ experiments on the long-term reliability of
solar operation (Spasiano et al. 2015).
• Photoreactor is a specific device which is used to
convey the solar photons and chemical reagents to in
contact with the photocatalyst efficiently. Unlike the
classic chemical reactors, solar photoreactors more
concern on the physical geometry to ensure the
effective collection of solar radiation for the optimal
photocatalytic treatment process, as well as the uniform
distribution of sunlight inside the photoreactor, as the
poor distribution may reduce the overall efficiencies of
the photochemical process. However, studies have
found out that the design and scale-up of a solar
photoreactor is one of the major problems associated
with the application heterogeneous photocatalyst treat-
ment method, where it is very difficult to reproduce the
same ratio of irradiated surface to total volume during
scale-up (Aziz et al. 2016; Spasiano et al. 2015).
• Future research should prioritize on the investigation of
AOPs under real treatment conditions since the
123
611 Page 16 of 19 Environ Earth Sci (2017) 76:611

Table 6 Recent studies applied the solar radiation for the photocatalysis degradation of pharmaceuticals
Type of Type of Main findings Reference
pharmaceutical photocatalyst

Paracetamol TiO2 Heterogeneous photocatalyst treatment method which associated with the application of (Lee et al.
CPCR and solar radiation was able to eliminate 97.2–99.7% of paracetamol under pH 4–7 2015)
and TiO2 concentration of 0.5–1 g/L
Tetracycline In2S3 Under the optimal conditions (pH 7.0, In2S3 dosage of 2.5 g/L and tetracycline loading of (Ai et al. 2015)
20 mg/L), the degradation efficiency of tetracycline approached 100%
Paracetamol Immobilized More than 83% of 2.65 9 10-4 M paracetamol was degraded under solar irradiation and the (Jallouli et al.
TiO2 present of TiO2 2014)
Propranolol TiO2 81% of propranolol degradation and 30% of mineralization were attained after 240 min of (De la Cruz
(Degussa solar irradiation et al. 2013)
P25)
Formaldehyde Vanadia– Complete mineralization of formaldehyde was obtained using V2O5/TiO2 thin-film catalyst (Akbarzadeh
titania under sunlight irradiation et al. 2010)

literature about real field applications of AOPs is very further research should focus on the possible disruption
scarce, which may limit the wider application of so far to other biological systems (such as nervous and
obtained data (Gani and Kazmi 2016). immune systems), especially in system development
• More investigation should be conducted to acquire during pre-/perinatal exposure periods (Wilkinson et al.
more data on the environmental occurrence of human 2016).
and veterinary pharmaceuticals in use today, so that a
proper estimation of exposure to pharmaceuticals in
environmental and drinking water, and their potential
Conclusion
risks to the ecosystem and human health can be
assessed (K’oreje et al. 2016).
Water pollution by persistent pharmaceutical compounds is
• So far, there is a notable lack of evidence regarding
an ever-increasing environmental problem concerned
the harmfulness of the retained pharmaceuticals,
globally. In this regard, more research is crucially required
particularly on the human health. Although informa-
to obtain more information about the effects of pharma-
tion on the potential environmental risks of pharma-
ceuticals in both parent and metabolites forms, in single
ceuticals is available, this effect cannot be easily
and mixture conditions, as well as in low-level and long-
extrapolated to the human harm. Therefore, extra
term exposure. These findings are particularly important to
findings on the potential biota and human health
human being as it can become a convincing fact to alert the
effects are required, in both low-level and long-term
society regarding the seriousness of the pharmaceutical
exposure. Besides, information regarding the impact
pollution. On the other hand, while the solar photocatalysis
of pharmaceuticals in drinking water (often in the ng/
treatment process has emerged as a reliable, sustainable,
L range) is also incomplete (Blair 2016; Quadra et al.
environmentally friendly and economical treatment tech-
2016).
nology, its application is constrained by several major
• Abundant of studies deals with the removal of
technical issues mainly related to the main elements in the
pharmaceutical individually instead of pharmaceuticals
photocatalysis process such as photocatalyst, solar UV
mixture which simulates the real wastewater matrix
source and photoreactor. Further investigation, modifica-
(Rizzo et al. 2009). In this regard, the extra concern
tions and improvements on these important elements can
should be given to the synergistic effects of the multiple
be implemented to increase the industrial acceptance as
compounds on both ecological and human health (Ji
well as the effectiveness and practical application of this
et al. 2013). In addition, Nasuhoglu et al. (2011) have
treatment technique in the real wastewater treatment
indicated that the intermediates generated during the
system.
pharmaceuticals treatment process are found to be more
toxic and higher retained concentrations as compared to Acknowledgements The authors would like to acknowledge Min-
the parent compounds. Therefore, the pharmaceutical istry of Higher Education (MOHE) for funding this project under
metabolites should also be given the similar attention to grant Fundamental Research Grant Scheme (FRGS); Grant number:
identify their hidden toxic potential on both ecological 203/PAWAM/6071256 as well as the support of Universiti Sains
Malaysia (USM) for providing the Intensif Grant and USM
and human health. Besides the endocrine disruption, Fellowship.

123
Environ Earth Sci (2017) 76:611
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