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Environ Earth Sci (2017) 76:611

DOI 10.1007/s12665-017-6924-y


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 Keywords Pharmaceuticals  Advanced oxidation

the natural water sources has been reported as early as in processes (AOPs)  Heterogeneous photocatalysis 
the year 1980. Until now, the presence of pharmaceutical Titanium dioxide (TiO2)  Reactive oxygen species (ROSs)
compounds in the aquatic environment has been frequently
reported in the literature. Moreover, increasing evidence
suggests that these contaminants have posed a threat to Introduction
both humans and ecosystems. In this regard, the present
review paper seeks to offer an overview of this environ- Water is one of the important resources on earth where
mental issue of pharmaceutical pollution where the subject human beings and ecological systems rely on it for sur-
matters to be reviewed include the effects, sources and vival. If there is no water, there will be no life on earth.
mitigation strategies of pharmaceuticals in the aquatic Nowadays, the demand of water increases with the rapid
environment. Besides, a review of the fundamentals and growth of population and vigorous industrial development.
mechanisms of heterogeneous photocatalysis technology is High-quality water sources are necessary particularly in
also presented in this paper. Heterogeneous photocatalysis maintaining healthy ecosystems and assurance for safe
is a rapidly expanding technology which has been exten- drinking water.
sively investigated and applied in wastewater treatment for Common water pollutants including pesticides, poly-
the remediation of persistent pollutants such as pharma- chlorinated biphenyls (PCBs), poly aromatic hydrocarbons
ceutical compounds during the last decade. Furthermore, (PAHs), metals such as mercury, lead, cadmium and
the ideal photocatalyst titanium dioxide (TiO2), which can arsenic, to name a few, have been significantly reduced
collaborate and perform well in the photocatalysis treat- through the adoption of appropriate legal measures and the
ment process, is also discussed. The advantages and limi- removal of numerous dominant pollution sources (Al-
tations associated with the application of this treatment Odaini et al. 2013). Recently, the scientific community
method are summarized and discussed in details. Finally, starts to focus on a new group of pollutants, which are
this review paper focuses on the future trend of the pho- pharmaceuticals (Choina et al. 2013; Doll and Frimmel
tocatalysis technology and identifies the barriers and 2005; Putschew et al. 2000; Ternes 1998). Pharmaceuticals
lacking parts which need to be resolved in the near future. 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,
& Puganeshwary Palaniandy and their effects on the environment and human health are still poorly understood (Quadra et al. 2016; Sangion and
1 Gramatica 2016).
School of Civil Engineering, Engineering Campus, Universiti
Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia Pharmaceutical is one of the most indispensable ele-
2 ments with undeniable benefits in modern life (Blair 2016;
School of Chemical Engineering, Engineering Campus,
Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Sangion and Gramatica 2016). They are extensively and
Malaysia increasingly used as an integral component to establish and

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maintain a healthy population of both humans and live- and limitations of the photocatalysis process, were dis-
stock (Choina et al. 2013; Mozia and Morawski 2012; cussed in details in the review. The last part of this review
Wilkinson et al. 2016). However, due to the widespread concerns on the lacking part of current studies and the areas
application of pharmaceuticals and their inadequate of future research.
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 Pharmaceuticals in the aquatic environment
various aquatic compartments such as surface water,
groundwater, effluents of sewage treatment plant, seawater The most frequently detected pharmaceuticals in the water
(Daughton and Ternes 1999; Halling-Sørensen et al. 1998) sources and their concentrations are summarized in Table 1
and even in the drinking water (Doll and Frimmel 2005; (Bagheri et al. 2016; Quadra et al. 2016; Wilkinson et al.
Sacher et al. 2001; Vaizoğullar 2017). 2016). Basically, they are divided into eight main classes
The retained pharmaceuticals in different water sources based on their specific mode of therapeutic action, namely
may lead to some adverse effects on the biological balance antibiotic, analgesic and antipyretic, central nervous sys-
and human health such as aquatic toxicity, resistance tem (CNS) stimulant, iodinated X-ray contrast media,
development in pathogenic bacteria, acute and chronic antidepressant, beta blocker, hormone/steroid and lipid
damage, hormonal and endocrine disruption (Emmanuel regulator. The presence of pharmaceutical compounds as
et al. 2005; K’oreje et al. 2016; Wu et al. 2012; Yang et al. the new emerging pollutants in the natural water resources
2008a). This situation is changing from bad to worse when is becoming an issue of global concern (Mozia and Mor-
these persistent pharmaceuticals are unable to be elimi- awski 2012; Nasuhoglu et al. 2011; Wu et al. 2012). The
nated by using conventional wastewater treatment tech- main factors concerned relating to this issue are the lack of
niques due to the typical characteristics of the the baseline data and the malfunctioning of the conven-
pharmaceuticals (Achilleos et al. 2010; Al-Odaini et al. tional wastewater treatment methods.
2013; Mozia and Morawski 2012). For example, pharma- Pharmaceutical pollution has not been given a signifi-
ceuticals are lipophilic to pass membranes and facilitate the cant attention despite its increased and extensive applica-
absorption. Besides, they can escape from the biological tion for different purposes throughout the world in
treatment process since they are designed to be biologically nowadays (Choina et al. 2013; Mozia and Morawski 2012).
active and persistent to maintain their therapeutic activity Ignorance on this matter is due to the fact that pharma-
until the specific physiological function on the human and ceuticals are not regulated as environmental pollutants and
animals has been performed (Achilleos et al. 2010; Aguilar not listed as pollutants in the WHO guidelines for drinking
et al. 2011; Suarez et al. 2009; Zhang et al. 2008). water quality (Al-Odaini et al. 2013). This, in turn, leads to
Therefore, they have the properties to bioaccumulate and the lack of baseline data regarding the occurrence of
cause negative effects to aquatic or terrestrial ecosystems, pharmaceutical compounds in the aquatic environment,
such as immobilization, mortality, inhibition of growth and thus prohibiting the evaluation of public exposure and the
reproduction (Quadra et al. 2016). subsequent effects (Arpin-Pont et al. 2016; Sim et al. 2011;
The continuous input and persistence of pharmaceuticals Taylor and Senac 2014). As the effects on human health
in the aquatic ecosystem indicate an environmental chal- are unknown and the findings on the aquatic organisms are
lenge even only at low concentrations. Recently, studies are limited, the severity of this issue may be covered up and
concerning on the removal of pharmaceuticals during treat- turning to worse as day goes on (Bagheri et al. 2016). Most
ment by using heterogeneous photocatalysis wastewater probably, the hidden effects may slowly accumulate and
treatment technique (Bahnemann 2004; Lofrano et al. 2009; expose unexpectedly and irreversibly.
Sharma et al. 2012). The field of heterogeneous photocatal- Besides, studies have proven that the conventional
ysis has been expanding rapidly within the last four decades wastewater treatment plants are unable to eliminate the
(Ibhadon and Fitzpatrick 2013). Photocatalysis performs the retained pharmaceutical compounds completely (Achilleos
redox function through the transformation, deactivation and, et al. 2010; Cai and Hu 2017; Mozia and Morawski 2012;
finally, the minimization of environmentally persistent Zhang et al. 2008). This is because the conventional
compounds (Aziz et al. 2016). wastewater treatment plants such as sedimentation and
This review paper aims to give an overview of the biological treatment process are not designed to remove the
occurrence of pharmaceutical compounds in the aquatic persistent pharmaceuticals which are polar, predominantly
environment, including the sources, effects and solutions to water soluble in nature, neither volatile nor biodegradable
overcome the pharmaceutical pollution. Also, the under- (Aguilar et al. 2011; Al-Odaini et al. 2013; Bagheri et al.
standing and fundamentals of heterogeneous photocatalytic 2016; Luo et al. 2015; Maroga Mboula et al. 2012;
wastewater treatment technology, including the advantages 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
Antidepressant Controls anxiety and depression Amitriptyline Surface water (66–207) ng/L
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

(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


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


Raw water

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


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

ecosystem health (Sangion and Gramatica 2016; Wilkinson


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



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

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


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).

Environ Earth Sci (2017) 76:611 Page 5 of 19 611

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

Table 2 Review of studies examining the effects of different pharmaceutical compounds on the aquatic organisms
Therapeutic class Compound Effect Value References

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
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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.
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
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 Page 7 of 19 611

Possible sources of pharmaceuticals in the environment

Home use Industrial

Veterinary use Agriculture and farming use
(Hospital, clinic and household) (Production and manufacturing)

Unused, Husbandry, Aquaculture Land application Landfill Industrial effluents

Excretion livestock and
expired and
surplus medicines aviculture
Sediment Soil

Sewage Excretion
Household waste

Sewage treatment plant Waste dumping site Manure


Surface water


Portable water

Drinking water

Fig. 1 Possible sources and fates of pharmaceuticals in the environment. Adapted and modified from Quadra et al. (2016) and Bagheri et al.

In addition, veterinary use is also an important source of manufacturing are among the industries which have highly
drugs to the environment. Abundant of veterinary phar- contribute to the occurrence of pharmaceutical pollution
maceuticals is applied in husbandry sector as a growth through the inappropriate disposal, accidental spillage
promoter, for breeding and therapeutic purposes (Bund- during the manufacturing and distribution processes (Al-
schuh et al. 2016; LA Ioannou et al. 2011; Kümmerer Odaini et al. 2013; Yang et al. 2008a), as well as the direct
2009; Sim et al. 2011). After the consumption of phar- discharge of pharmaceutical waste into the water sources
maceutical by the livestock, part of the pharmaceutical is (Abellán et al. 2007; Emmanuel et al. 2005; Gautam et al.
excreted through the urine and feces, in either metabolized 2007; LA Ioannou et al. 2011; Kümmerer 2001).
or parent form. Without any treatment, the excreted phar- Once the pharmaceutical residue in the environment,
maceuticals get into the soil and groundwater directly their behavior can be significantly affected by some factors
(Kümmerer 2001; Quadra et al. 2016). Often, livestock’s such as solubility, chemical structure, persistence, sorption
manure is used as fertilizer in the agricultural field. The behavior, climatic factors (temperature, precipitation),
manure which contains the pharmaceutical residues can be water body properties (pH, redox potential, organic carbon
either mobilized into surface water during heavy precipi- content), composition of sediments and environmental
tation or infiltrated into the groundwater (Abellán et al. degradation. Due to this immense complexity, more
2007). Other than livestock, fish farming is also an research in this field is required to identify the behaviors of
important source of pharmaceuticals (Quadra et al. 2016). drugs in the environment (Quadra et al. 2016). Further-
The direct application of pharmaceuticals in the aquacul- more, strategies are required for the removal of numerous
ture for the prevention and treatment of microbial infec- dominant pollution sources. Besides the enactment of
tions has caused the increment of retained pharmaceuticals appropriate legal measures, a standard or guideline of
in the aquatic environment (Kümmerer 2009). pharmaceuticals wastewater effluent is also required to be
Also, pharmaceuticals are extensively applied in the invented.
agricultural and farming fields to control the bacterial
disease (Fukahori et al. 2012; Kümmerer 2009; Mozia and Pharmaceuticals mitigation strategies
Morawski 2012). These pharmaceuticals can accumulate in
farmland and eventually reach the natural water sources Pharmaceuticals are often poorly removed by conventional
through leaching and runoff (Abellán et al. 2009; Wilkin- wastewater treatment techniques (K’oreje et al. 2016). The
son et al. 2016). Last but not least, production and 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 Can avoid the pharmaceuticals from This method may only partially
(Borsuk et al. 2008; specially designed with two separate entering the sewer and aquatic capture the excreted
Lamichhane and compartments: a front compartment environment pharmaceuticals as part of it may
Babcock 2012; Lienert for urine and a larger rear Reduce the volume of wastewater remain in feces
et al. 2003) compartment for feces needed to be treated Unable to fully resolve the
The urine is collected and stored in a Can ensure the high levels of ecological risk as this solution
urine storage tank which located in pharmaceutical in urine have been only discharge some, but not all
or nearby the household. Then the treated rather than discharged pharmaceuticals
urine will be transported to a directly into the sewer
treatment unit (which located either
Aquatic environment can be
locally or centrally) to be treated
escaped from the harmful
pharmaceuticals and hormones
Can avoid nutrient pollution
Invention of Green This solution aims to create Capable to degrade faster and lessen Pharmaceutical research and
pharmaceuticals ‘‘environmentally friendly’’ impact on the environment or be development may be costly
(Daughton 2003; pharmaceuticals which equipped environmentally less harmful Least feasible option
Khetan and Collins with the following properties:
2007) Easy uptake of compound by the
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
Take-back programs Involve the returned of unused Can be an alternative solution for Unable to address the excretion of
(Becker et al. 2010; pharmaceuticals to pharmacy, improper disposal (toilet or drain pharmaceuticals and their
Blair 2016; Straub predetermined sites (such as fire disposal) and avoid the metabolites from normal use due
2016) departments, police station, pharmaceuticals from entering the to changes in temporal and spatial
hospitals), or through the mail aquatic environment usage
More effective to be applied at the Able to reduce accidental or Can be costly to implement and
sites with high pharmaceutical intentional exposure to unused manage
usage (such as hospitals, nursing pharmaceuticals Have limited access and
homes, hospice care locations) Allow the reuse of pharmaceuticals participation in many areas
where greater amounts of unused for emergencies or needy
drugs can be collected
Trash disposal (Blair As an alternative solution for take- Cost saving Could cause accidental exposure to
2016; Gibson 2010) back programs. Can avoid the potential harm from unused pharmaceuticals and
Include the removal of drugs from stockpiling the unused environmental contamination
their original containers and mixing pharmaceuticals in home Unable to address the excretion of
with kitty litter, dirt, coffee grounds pharmaceuticals and their
or other unappealing materials, metabolites
followed enclosing the mixture in a May cause leach from landfills
sealable bag, can, or container

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

Environ Earth Sci (2017) 76:611 Page 9 of 19 611

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

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
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
_ þ O2 þ OH
! OH 
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,

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
Fig. 2 Simplified mechanisms for the photoactivation of a semicon- properties such as excellent pigmentary properties, high UV
ductor catalyst (Al-Rasheed 2005) absorption and resistance to photocorrosion in aqueous

Environ Earth Sci (2017) 76:611 Page 11 of 19 611

environment, eco-friendly, low energy band gap and can be water effluent without the recovery of TiO2 since the cat-
applied individually without additional chemicals, TiO2 alyst remains confined to the packed-bed (Borges et al.
remains a benchmark among other semiconductors (Abellán 2015). Consequently, the post-processing treatment can be
et al. 2007; Al-Rasheed 2005; Belgiorno et al. 2007; Choina avoided, thereby saving time and costs (Hashim et al.
et al. 2013; Lofrano et al. 2009; Yang et al. 2008a). 2017). However, as compared to the suspended catalyst, it
Basically, TiO2 has three different crystalline forms. is reported that 60–70% of reduction in performance has
Anatase and rutile are the most common forms. Anatase is been observed in the aqueous system for immobilized TiO2
more efficient than rutile in the photocatalysis application since the latter system offers a lower reaction surface area
since the former crystalline form has an open structure and for the photocatalysis reaction to take place (Bautista et al.
exhibits higher photocatalytic activity, whereby brookite is 2015; Gaya and Abdullah 2008; Jiménez et al. 2015).
the third crystalline form which is uncommon and unsta- Besides, the immobilized catalyst is more difficult to be
ble to be used in the photocatalysis treatment process. The synthesized and it requires the inert support materials such
commercial TiO2 powder, such as anatase crystalline, and as glass or ceramic fibers, alumina pellets or molecular
the combinations of anatase and rutile (Degussa P25, 25:75 sieves (Spasiano et al. 2015). Despite aforementioned
or 80:20 anatase/rutile) have been the most extensively disadvantages, currently, coated photocatalyst and immo-
used heterogeneous catalysts in the photocatalysis treat- bilization techniques are still investigated intensively due
ment process due to their chemical stability, reproducibil- to the assumption that this system is more effective in the
ity, highest detoxification efficiencies and readily available removal of organic compound as compared to the sus-
as a catalyst for oxidation processes (Al-Rasheed 2005; pended TiO2 (Gaya and Abdullah 2008).
Spasiano et al. 2015). Besides being a promising photocatalyst in the
Suspended TiO2 powder and immobilized TiO2 are the wastewater treatment process, TiO2 is also an important
two different modes of TiO2 photocatalyst which are typ- material in many commercial products, ranging from
ically used in the photocatalytic degradation processes. drugs to foods, paints to pharmaceuticals, cosmetics to
Both of them offer their respective advantages and disad- catalysts and sunscreens to solar cells, where TiO2 is
vantages as tabulated in Table 4. The slurry or suspended applied as a desiccant, brightener and reactive mediator.
TiO2 has been the most commonly used system because of TiO2 is used as the inactive ingredients in the food
its simplicity in terms of preparation and application. The products up to 1%, as permitted by the U.S. Food and
suspended TiO2 system can provide a higher efficiency Drug Administration. The health effects associated with
than the immobilized system, mainly due to a higher ratio the consumption and application of TiO2 are still not
of catalyst active site to reaction volume. Nevertheless, an clearly known (Ibhadon and Fitzpatrick 2013). So far,
additional separation process is required to recover the only Gaya and Abdullah (2008) has mentioned on the
TiO2 powder at the end of the treatment process, by either toxic effect of the TiO2 suspension on the E. coli. Also,
filtration or centrifugation. This separation process not only the increased antibacterial inhibition is observed with the
increases the complexity and cost of the overall process, increment of TiO2 loading during the photocatalytic
but it is also time-consuming (Spasiano et al. 2015). Fur- experiment. Therefore, more studies are required to fur-
thermore, the suspended TiO2 powder tends to agglomerate ther investigate the effect of TiO2 on the environment
into larger particles at high concentration, which could and organisms. Meanwhile, the regulatory framework for
reduce the catalytic activity (Hao et al. 2012; Lalhriatpuia the use of TiO2 in the food products should be estab-
et al. 2015). On the other hand, the immobilized TiO2 lished in the near future, particularly in the developing
system allows the direct discharges of decontaminated nations (Ibhadon and Fitzpatrick 2013).

Table 4 Advantages and disadvantages of the suspended and immobilized TiO2

System Advantage Disadvantage

Slurry/suspended TiO2 Simplicity Require post-treatment for catalyst recovery

Provide higher degradation efficiencies Agglomeration of TiO2
Provide higher surface area for reaction
Immobilized TiO2 Do not require separation step Difficult to be synthesized
Time and cost saving Provide lower reaction surface area
Significant reduction in system efficiency

611 Page 12 of 19 Environ Earth Sci (2017) 76:611

Advantages and limitations of heterogeneous Chaudhuri 2010b; Gültekin and Ince 2007). Besides, the
photocatalysis purification techniques like ozonization, chlorination and
filtration too have their own limitations in terms of the
Apparently, current conventional water and wastewater energy sources consumption and the generation of harmful
treatment processes have failed to overcome the pharma- waste (Sharma et al. 2012). However, in contrast with the
ceutical pollution as they are not designed to remove the aforementioned treatment methods, heterogeneous photo-
suspended pharmaceuticals (Blair 2016). To date, hetero- catalyst which relies on the generation of ROSs is able to
geneous photocatalytic degradation using TiO2 photocata- render the complete mineralization of pharmaceuticals
lyst remains as a viable alternative in the elimination of (Kaan et al. 2012). Among the variety of ROSs, OH has
organic contaminants persistent in both aquatic and atmo- attracted the most attention. The positive characteristics of

spheric (Gaya and Abdullah 2008). Since the last decade, OH radicals are including non-selective nature, high oxi-
this wastewater treatment technique has been extensively dation potential (2.8 eV) when compared to other oxidants,
applied for the elimination of different types of pharma- ability to react with a wide range of contaminants without
ceuticals. Table 5 summarizes previous studies on the any additives, as well as rate constants normally in the
heterogeneous photocatalysis treatment technique for the order of 106–109 mol/L/s (Kanakaraju et al. 2014). During
degradation of pharmaceuticals. It is noticeable in Table 5 the photocatalysis treatment process, OH appears to be a
that the initial concentration of pharmaceutical employed strong oxidant that can react and further break down the
in the previous studies was usually higher than that typi- non-biodegradable or recalcitrant compounds (such as
cally detected in the natural water sources (lg/L–ng/L). pharmaceuticals) in water or wastewater, from complex
This is to allow the accurate determination of residual molecules into the simplest and non-hazardous end prod-
concentration and the assessment of treatment efficiency ucts such as water and carbon dioxide (Elmolla and
within a measurable time scale (Achilleos et al. 2010). As Chaudhuri 2010b; Khataee et al. 2013; Lofrano et al.
shown in Table 5, most of the TiO2 photocatalytic studies 2009). Therefore, heterogeneous photocatalysis degrada-
focused on the determination of optimal operating condi- tion process can provide promising clean water sources that
tions to attain the best performance in terms of degradation ensure the health and safety of human, living organisms
and mineralization. Markedly, the degradation rate of and the environment.
pharmaceutical is greatly affected by the operational The growth and development of the world have induced
parameters such as the type and loading of photocatalyst, several environmental issues, mainly regarding the deple-
initial concentration of the pharmaceutical under investi- tion of natural resources (Spasiano et al. 2015). It has been
gation, pH of the solution and light (source, wavelength circulated worldwide that the depletion rate of these
and intensity). Other operational parameters which can resources is increasing year by year, causing it to become
enhance the degradation rate include the addition of co- one of the major concern among humans globally. Due to
oxidants and the concentration of electron acceptors. this issue, priority is given to the sustainability concept
Moreover, the design and geometry of the photoreactor regardless of sectors. Heterogeneous photocatalyst is one
also influence the optimal degradation rate of pharmaceu- of the wastewater treatment methods which in line with the
tical (Kanakaraju et al. 2014). Due to this, different opti- concept of sustainability. The recent studies start to utilize
mum operating conditions are normally documented by the the natural UV radiation (from sunlight) instead of the
different studies for the highest pharmaceutical removal synthetic UV radiation (from UV lamp and solar simulator)
efficiency (regardless of the studied pharmaceuticals are as the source of photocatalyst excitation. Meanwhile, the
different or similar), since the degradation rate of phar- ideal photocatalyst, TiO2, is found to be water insoluble
maceutical is dictated by a great deal of aspects and under most of the environmental conditions and remains
parameters. Here, there are three main advantages associ- unchanged throughout the treatment process (Belgiorno
ated with this treatment method and could be explained et al. 2007; Choina et al. 2013; Ibhadon and Fitzpatrick
from the aspects of health and safety, sustainability as well 2013). As the main elements of UV radiation and oxygen
as the simplicity of technology. are unlimited supplied by the solar and atmosphere,
Various types of advanced treatment methods such as respectively, as well as the photocatalyst can be recovered
activated carbon adsorption, air stripping and reverse and reused after the treatment process, the photocatalytic
osmosis have been applied for the elimination of retained technology is considered to be low cost, environmentally
pharmaceuticals. Yet, studies have found out that these friendly, low energy consumption with no consumable
processes are less effective for the overall mineralization, chemicals required (Aziz et al. 2016; LA Ioannou et al.
which only transfer the pharmaceutical compounds from 2011).
one phase to another or just collecting the pharmaceutical Heterogeneous photocatalyst treatment which involves a
compounds without eliminating them (Elmolla and simple operating system with limited equipment required

Environ Earth Sci (2017) 76:611 Page 13 of 19 611

Table 5 Recent examples of pharmaceuticals photocatalytically degraded by TiO2

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

Sulfamethoxazole, TiO2 (Degussa P25), Concentration of More than 90% of sulfamethoxazole and Cai and Hu
Trimethoprim LED lamp TiO2 = 0.05 g/L trimethoprim were removed under the (2017)
Initial concentration of each optimum treatment conditions
pharmaceutical = 400 ppb Antibacterial activity study with a reference
Irradiation time = 20 min Escherichia coli strain indicated that with
every portion of trimethoprim removed, the
System flow rate = 8 mL/
residual antibacterial activity decreased by one
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
Flumequine Titanium tetrabutoxide Concentration of Photocatalytic degradation of flumequine by Vaizoğullar
(TBT, Sigma Aldrich, TiO2 = 4 g/L TiO2 under UV irradiation exhibited 23% (2017)
97%), UV lamp Initial concentration of degradation efficiency under the given
(Spectroline XX- flumequine = 10 mg/L treatment conditions.
15 N) Apparent rate constant (kapp) of flumequine
Irradiation time = 240 min
degradation in TiO2/UV system was
UV light intensity = 2 mW/
0.0009 min-1
pH 5
Diclofenac TiO2 (Degussa P25), Immobilized TiO2 Eosin-Y dye was an effective electron donor to Hashim
solar visible light (Supported on fiberglass activate the photocatalyst, making the catalyst et al.
sheets) suitable for operating under solar light (2017)
Concentration of The optimized parameters conveyed a diclofenac
TiO2 = 37.5 mg/cm2 degradation rate of 40% and 49% for 2 ppm
(low range) and 4 ppm (high range) dye
Initial concentration of
concentrations, respectively
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 93.1% of tetracycline degradation efficiency was Luo et al.
(Philips, PL-L 18 W) TiO2 = 2.09 g/L obtained under the optimum treatment (2015)
Irradiation time = 20.95 min conditions
pH 5.5 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
Paracetamol TiO2 (Degussa P25), Immobilized TiO2 TiO2 Degussa P25 showed a good photocatalytic Borges et al.
UV lamp (Supported on glass activity for the paracetamol removal from (2015)
spheres) wastewater, reaching a high photodegradation
Initial concentration of (between 99 and 100% of paracetamol removal
paracetamol = (0.05, 0.5, after 4 h of irradiation) for all the amounts of
1) g/L 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

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 Under the achieved optimal conditions of the Khataee
atenolol, 500, 30-W UV-C (Supported on ceramic operating parameters, high removals of 95.32, et al.
chlorpromazine lamp (Philips, the plates) 87.02 and 90% were obtained for (2013)
Netherlands) Initial concentration of each metronidazole, atenolol and chlorpromazine,
pharmaceutical = 10 mg/L respectively, in the solution of a mixture of the
Irradiation time = 150 min
The TOC results (90% removal after 16 h) and
UV light
ecotoxicological experiments revealed that the
intensity = 38.45 W/m
photocatalysis process could effectively
mineralize and reduce the ecotoxicity of the
pharmaceuticals from their aqueous solutions
Atenolol TiO2 (Degussa P25), Concentration of Complete degradation of atenolol was obtained Ji et al.
High-pressure mercury TiO2 = 2 g/L under the optimum treatment conditions (2013)
lamp (Philips, HPK, Initial concentration of Hydroxyl radical (OH) was determined to be the
125 W) atenolol = 37.6 lM predominant reactive species during
Irradiation time = 60 min photocatalysis by means of radical probes
pH 6.8 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
Tylosin TiO2 (Degussa P25), Immobilized TiO2 In weak concentrations, from 0.0044 to Laoufi et al.
UV lamp (Philips, Initial concentration of 0.0327 mM, the abatement of tylosin was (2013)
TLD, 18 W/08) tylosin = (0.0044–0.0327) between 90 and 96% after an exposure time to
mM radiations of 420 min
Irradiation time = 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 available photons by the contaminants will eventually
treatment method is able to attain the complete mineral- induce a lower intensity of photons to excite the catalyst
ization with no sludge generated. Therefore, the post- surface (Abellán et al. 2009; LA Ioannou et al. 2011;
treatment and disposal of sludge can be avoided (Al- Kümmerer 2009; Yang et al. 2008a). Therefore, hetero-
Rasheed 2005; Chong et al. 2015; Ibhadon and Fitzpatrick geneous photocatalysis treatment is unable to integrate
2013). Additionally, the achieved photocatalysis removal with primary and secondary treatment process, but it is
efficiencies of pharmaceuticals in the previous studies are suggested to be used as a tertiary treatment process, par-
believed to be sufficient for the actual treatment process. In ticularly for the elimination of pharmaceutical compounds
other words, the photocatalytic degradation of pharma- which are still retained in the treated wastewater (Naddeo
ceuticals in the real situation is likely to occur rapidly since et al. 2009).
the concentrations of pharmaceuticals detected in the nat- Another major limitation is that TiO2 can only be pho-
ural water sources (lg/L–ng/L) are far lower than that toexcited by the light at a wavelength of \388 nm due to
employed in the previous studies. Hence, this treatment its wide band gap (3–3.2 eV) (Achilleos et al. 2010;
method is able to perform effectively for a technical use in Daghrir and Drogui 2013). Therefore, it is important to
the wastewater treatment plant. Besides, it is a totally safe avoid any loss of solar radiation during the treatment
treatment method which is conducted under the ambient process. For better results, this treatment process can be
temperature and ordinary pressure (Aziz et al. 2016). assisted by the artificial illumination of catalyst to achieve
Despite the aforementioned advantages, there are also the degradation of contaminants in time that is practical for
some limitations associated with the application of photo- the real wastewater treatment processing (Ibhadon and
catalysis. The main limitation is that this method is unable Fitzpatrick 2013). Besides, it is suggested that the nano-
to perform well in turbid water. This is because the material should be modified so that it can utilize the visible
reduction of light transmissivity, the adsorption of con- light in solar irradiation (Kaur et al. 2016).
taminants onto the surface of catalyst or the absorption of

Environ Earth Sci (2017) 76:611 Page 15 of 19 611

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

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)
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
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-
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
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.

Environ Earth Sci (2017) 76:611 Page 17 of 19 611

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