Water Air Soil Pollut (2013) 224:1770
DOI 10.1007/s11270-013-1770-3
A Review of Pharmaceuticals and Endocrine-Disrupting
Compounds: Sources, Effects, Removal, and Detections
Jimoh O. Tijani & Ojo O. Fatoba & Leslie. F. Petrik
Received: 10 June 2013 / Accepted: 2 October 2013
# Springer Science+Business Media Dordrecht 2013
Abstract There are growing concerns about the
increasing trends of emerging micropollutants in the
environment due to their potential negative impacts on
natural ecosystems and humans. This has attracted
attention from both governmental and nongovernmental organisations worldwide. Pharmaceuticals,
personal care products, and endocrine disruptors
are continuously being released consciously or
unconsciously into water sources due to poor regulatory
frameworks especially in the developing countries. The
effects of these contaminants are poorly known. They
are not easily biodegradable and have become an
environmental nuisance and public health issue. This
has heightened the risk of exposure to their deleterious
effects in such countries where the majority of the
population are still struggling to have access to good
quality drinking water supplies and better sanitation.
With the rising fear of short- and long-term impacts of
the ever-increasing number of persistent recalcitrant
organic compounds accumulating in the environment,
their removal is gradually becoming an issue to the
water treatment industry. Hence, there is a need to
develop functional techniques for the management of
water contaminated by these emerging contaminants so
as to increase the availability and access to safe and
good-quality drinking water. We conducted a narrative
review on these emerging micropollutants and
J. O. Tijani (*) : O. O. Fatoba : L. F. Petrik
Environmental and Nano Sciences Group, Department of
Chemistry, University of the Western Cape,
Private Bag X17, Bellville, South Africa
e-mail: jtijani@uwc.ac.za
examined their various documented sources, effects, as
well as recent techniques for their effective removal.
This becomes necessary due to the increasing
occurrence of these pollutants in the aquatic and
terrestrial environment. These levels are expected to
further increase in the coming years as a consequence
of the ever-increasing population density which
undoubtedly characterizes developing economies. Our
findings show that the present reported treatment
techniques in the literature such as biological
oxidation/biodegradation, coagulation/flocculation,
ozonation, electrodialysis, reverse osmosis,
sedimentation, filtration, and activated carbon were not
designed for removal of these newly identified
contaminants, and as such, the techniques are not
sufficient and unable to completely degrade the
compounds. We therefore recommended the need for
concerted efforts to develop better techniques,
especially combined advanced oxidative methods to
address the shortcomings of and growing challenge to
current practices.
Keywords Pharmaceutical and personal care products .
Endocrine disrupting compounds . Coagulation/
flocculation . Ozonation . Electrodialysis . Reverse
osmosis . Sedimentation . Filtration . Activated
carbon . Advanced oxidation process
1 Introduction
The importance of good-quality, potable water to
human existence cannot be underestimated, and life
1770, Page 2 of 29
will be practically impossible or difficult without the
availability of safe drinking water (Swaminathan et al.
2013; Cortés Muñoz et al. 2013). Over the last few
decades, there have been tremendous improvements in
the supply of safe drinking water to growing
populations. This is through various governmental
interventions especially in developing countries that
want to meet the Millennium Development Goal target
of 2015 adopted by United Nations in 2000. This
mandate is in line with European Commission Water
Framework Directive article 4 that states that all
community waters such as surface, ground,
transitional, and coastal must be in good status by
2015 (Belgiorno et al. 2007). However, good-quality
drinking water is being threatened as a consequence of
various natural and anthropogenic inputs involving the
discharge of effluents containing priority and emerging
micropollutants that are ubiquitous in different
receiving water sources. The emerging contaminants
include persistent organic pollutants, microconstituents, cyanotoxins, pesticides and herbicides,
disinfection by-products, endocrine-disrupting
chemicals (EDCs), pharmaceuticals and personal care
products (PPCPs), and a host of other compounds. The
rapid technological advancement, rapid increase in
human population, inadequate wastewater treatment
facilities, poor agricultural practices, inadequate landuse acts, and rapid urbanization coupled with drought
occasioned by global climate change have created
water pollution problems on a level that have not been
seen before (Mara 2003; Moore et al. 2003;
Montgomery and Elimelech 2007; Johnson et al.
2008). Almost every industrial process involves the
production and release of huge quantities of half a
dozen or more of those mentioned pollutants in one
form or the other into the aquatic and terrestrial
environment. The most frequent occurrence is the
increasing accumulation of pharmaceuticals and
endocrine-disrupting compounds that have overloaded
and tainted the various receiving water bodies
(Lindqvist et al. 2005; Kasprzyk-Hordern et al.
20 09). The b uild-up a nd detection of h igh
concentrations of these micropollutants in aquatic
environments has made water unsafe for aquatic
animals and for human consumption (Moldovan
2006; Roberts and Thomas 2006; Tamtam et al.
2008; Liu et al. 2009). The number of these emerging
contaminants is still expected to increase in treated
wastewater due to higher population density. This has
Water Air Soil Pollut (2013) 224:1770
resulted in growing public health risks in the developing
countries where impacts have been noted such as
endocrine conduit disturbance in aquatic organisms,
brain damage, convulsion, carcinogenic diseases,
reproductive behavioral disorder, cardiovascular disease,
liver damage, and lung defects as well as disturbances in
gene expression resulting in feminization of aquatic
organisms (Mastin 2005; Samir et al. 2006; Campbell
et al. 2006; Ha et al. 2007; Diamanti-Kandarakis et al.
2009). The current scenario has become worse due to the
lack of adequate and efficient water treatment facilities
capable of effectively eliminating and degrading the
toxic and recalcitrant compounds to harmless substances
(Nakada et al. 2006; Gulkowska et al. 2008; Sui et al.
2010). The deterioration of water quality seriously
affects economic progress and impacts negatively on
the sustainable development of a nation (Rahman et al.
2009a, b). Therefore, in order to have a healthy
population and better society with a consequential effect
on the economy growth and sustainability, access to safe
drinking water and functional wastewater treatment
facilities should not be compromised.
Within the last 10–15 years, different analytical
techniques for the detection and quantification of
persistent organic contaminants at environmentally
low concentrations have been developed (Ternes and
Joss 2006). This was as a consequence of the
increasing discovery of PPCPs/EDCs in environmental
matrices (Kolpin et al. 2002; Tixier et al. 2003; Ashton
et al. 2004). Authors such as (Yoon and Lueptow 2005)
and (Yoon et al. 2006a, b) separately observed that
high pollution levels in the aquatic environment
were majorly attributed to the presence of low
concentrations of EDCs and PPCPs (nanograms per
liter). Although the effect of these compounds on human
beings is still under debate, their presence called for
caution regarding their chemical perseverance,
microbial resistance, and synergistic effects. The
degradation and removal of PPCPs/EDCs in aqueous
solution therefore requires different techniques which
are very diverse. Different destructive methods that
allow the efficient elimination of the pollutants from
an aqueous form could be chosen. But recent reports
suggested that more than one treatment technique may
be required to degrade these compounds, depending on
the nature of target compounds. The risk posed by these
emerging micropollutants on humans and the
environment requires further investigation. Therefore,
it becomes imperative to improve on the existing
Water Air Soil Pollut (2013) 224:1770
techniques used to remove and degrade these chemicals
in the natural ecosystems, most essentially in drinking
water, as fast as possible. To date, a review of the related
literature indicated that there is little or no information
regarding the use of combined advanced oxidation
processes to remove pharmaceuticals and endocrine
disrupting compounds from aqueous solutions.
2 Pharmaceutical and Personal Care Products
Pharmaceuticals are any synthesized chemicals
compounds or drugs designed to cure and prevent the
spread of diseases as well as adding value to humans
and animals life (Maletz et al. 2013) while personal care
products encompasses cosmetics, fragrances,
preservatives, and toiletries (Houtman 2010).
Pharmaceuticals include antibiotics, anti-diabetics,
anti-epileptic, antimicrobials, anti-anxiety medications,
etc. Personal care product includes shampoos, toiletries,
toothpaste, perfume, deodorants, etc. Pharmaceutical
and personal care products (PPCPs) are chemical
compounds that have been the subject of discussion
among scientists and the general public especially in
the developed countries such as China, USA, Germany,
and European Union since the early 1990s (Ternes et al.
2004; Ternes and Joss 2006). Their presence in the
environment poses a great threat to public health and
impacts negatively on the aquatic ecosystem. One of the
potential sources of the lingering PPCPs in the aquatic
environment is through the discharge of inadequately
treated wastewater (Daughton and Ternes 1999; Ternes
et al. 2002; Fawell and Ong 2012). Due to the partial
elimination of these pollutants by wastewater treatment
plants, many of the contaminants survive and escape
from the sewage treatment plants into surface water.
Some were however retained and adsorbed onto sewage
sludge. The sludge which is sometimes used by farmers
for agricultural soil enrichment also contains emerging
pollutants and thus represents another way these
contaminants get into soil and water. Apart from this,
the partially metabolized drugs as well as medical care
products either in original or altered form are equally
released into wastewater and later find their way to and
through the treatment plants. In spite of the municipal
wastewater treatment plants being the most widely
known source where many of PPCPs and EDCs are
released, researchers have also discovered the presence
of hundreds of EDCs and PPCPs in seawater. This
Page 3 of 29, 1770
development was ascribed to the flow of wastewater
effluents by river into various larger water bodies such
as the ocean (Liu et al. 2010; Joseph et al. 2011). This
trend was supported by Richardson and Ternes (2005)
who observed that more PPCPs exist in the aquatic
environment as a result of the increasing number of
expired drugs presently being discarded in the medical
field. The resultant harmful effects of some PPCPs are
poorly known, bearing in mind they are persistent and
bioactive, and bioaccumulate in the aquatic
environment. PPCPs also comprise synthetic hormones,
fragrances, shampoos, detergents, analgesics and their
metabolites, etc. Some of these get introduced into water
through industrial and household discharge. Although
PPCP concentration in the environmental samples is
quite low, questions were raised regarding their
microbial resistance, chemical persistence, and the
synergistic effects of various compounds (Daughton
and Ternes 1999). However, the vast majority of people
are still ignorant or not aware of the health risk
associated with exposure to these chemicals. This was
evidenced in the survey carried out in United States of
America where people carelessly disposed expired and
unused medicines into sinks and toilets instead of
returning it to pharmacies (Petrovic et al. 2004). Several
studies have shown that over 140 PPCPs of different
recommended classes were detected in different
countries (Halling-Sørensen et al. 1998; Daughton and
Ternes 1999; Kümmerer and Al-Ahmad 2010; Heberer
2002; Janex-Habibi et al. 2004; Larsen et al. 2004;
Garric and Ferrari 2005; Fent et al. 2006). Some of these
reports substantiate the concentration range values as
well as removal rate of PPCPs by the various treatment
plants. Quite a large proportion of PPCPs have been
acknowledged to exist and persist in underground,
surface, and drinking water as well as municipal sewage
sludge across the globe at low concentrations (Kim et al.
2007; Focazio et al. 2008; Kinney et al. 2008; Fick et al.
2009; Benotti et al. 2009; Wu et al. 2009; McClellan and
Halden 2010). This problem has been known for more
than a decade, yet little progress has been made to stem
the tide of such pollutants from entering the global
waterways. Information on selected representative
classes of PPCPs and EDCs most frequently found and
detected in surface waters, wastewater, and sewage
treatment plants is shown in Table 1. Some of the PPCPs
and EDCs such as bisphenol A, pesticides (e.g., 2, 2,bis-p-chlorophenyl-1-1-1-trichloroethane, atrazine),
organohalogens (such as furans, brominated fire
1770, Page 4 of 29
Water Air Soil Pollut (2013) 224:1770
Table 1 Some representative classes of EDCs and PPCPs reported in surface waters, wastewater, and sewage treatment plants
EDCs/PPCPs class
Compound detected
Use/origin
Phthalates
Butylbenzylphthalate, di-(2-ethylhexyl)
phthalate, and di-n-butylphthalate
They are found in detergents, resins,
some addictives, and monomers used
in the production of plastics
Pesticides
2,2-bis-p-Chlorophenyl-1,1-dichloroethylene Extensively used in agriculture. Insecticides,
(DDE), 2,2-bis-p-chloro-phenyl-1,1,1herbicides, and fungicides are included in
trichloroethane(DDT), deltamethrin,
this class
carbofuran, atrazine, lindane, vinclozolin,
carbendazim, and tributylin
Tributyltin and triphenyltin
Compounds used in antifouling paints on ships
Organotin compounds
Alkylphenols (surfactants)
Nonylphenol, nonylphenol etoxylate,
octylphenol, octylphenol etoxylate
They are used during the production of phenol
resins, as plastic additives, emulsifiers, in
agricultural and industrial applications
Bisphenols
Bisphenol A
Bisphenol A is used in the manufacture of
polymers (polycarbonates and epoxy resins),
flame retardants and rubber chemicals
Pharmaceuticals (synthetic steroids) Diethylstilbestrol and 17-ethinylestradiol
Synthetic steroids mainly consist of oral
contraceptives as well as steroids used for
substitution therapy during menopause
Natural hormones
Estrone, 17-estradiol
Estrogens naturally and daily excreted in human
urine and animals
Analgesics/non-steroidal
Acetaminophen (analgesic), diclofenac,
ibuprofen
NSAIDs are the most used and abused drugs in
the world today
Anti-inflammatories (NSAIDs)
Ketoprofen, naproxen, phenazone,
indomethacine
All NSAIDs have analgesic, antipyretic and
anti-inflammatory effect
Antiseptics
Triclosan and thymol
Antiseptics are chemical agents that slow or stop
the growth of microorganisms (germs) on
external surfaces of the body and help prevent
infections. Antiseptics should be distinguished
from antibiotics that destroy microorganisms
inside the body and from disinfectants, which
destroy microorganisms found on inanimate
(non-living) objects
Antibiotics/antimicrobials
Used for the treatment of bacterial infections in
both humans and animals
Antiepileptics
Sulfonamides, fluoroquinolones,
trimetoprim, chlortetracycline,
erythromycin, lincomycin,
oxytetracycline, tetracycline,
roxithromycin, tylosin
Carbamazepine
Anti-anxiety/hypnotic agents
Diazepam
Anti-anxiety/hypnotic agents are used to relieve
anxiety, nervousness, and tension associated
with anxiety disorders
Lipid regulators
Clofibrate, bezafibrate
Lipid regulators may be used to lower cholesterol
and triglyceride (fat-like substances) levels in
the blood
Antiepileptics are commonly used in medicine
to stop, prevent or control seizures
(convulsions, partial seizures, generalized
tonic–clonic seizures, etc.)
Sources: Adopted from Esplugas et al. (2007)
retardants, dioxins) phthalates, polychlorinated
biphenyls (PCBs), and polycyclic aromatic
hydrocarbons are more frequently found in wastewater
treatment plants than in natural environment. Others
such as nonylphenol and octylphenol are more
prominent in surface and groundwater (Esplugas et al.
Water Air Soil Pollut (2013) 224:1770
2007). These chemicals compounds have been
established to disrupt endocrine systems, yet they are
still unregulated and discharge carelessly into the
immediate environment most especially in the
developing countries where there is no stringent
regulatory and legal frame work.
2.1 Sources of Pharmaceuticals, Personal Care
Products, and Endocrine Disruptors
The frequency of drugs and medical care products use
has continued to increase as a consequence of the
population growth rate and as such a large quantity of
different by-products is continuously being released
into the environment, although at low concentrations
(Kolpin et al. 2002; Yu and Chu 2009). This
concentration level varies from country to country
depending on the drug consumption, usage pattern,
population index, and treatment plant potential
(Bolong et al. 2009). For instance, the concentration
of bisphenol A in North American and European water
is around 12 and 43 ppb, respectively (Klecka et al.
2009; Rogers et al. 2013). Ellis (2006) and Czech and
Rubinowska (2013) asserted that an average of 170
pharmaceuticals in excess of 1 ton per year were
projected to be used in Brussels. The presence of these
contaminants of emerging concern has been observed
to seriously affect the water quality and obviously
attract attention with regard to drinking water issues
(Heberer 2002; Trussell 2001; Yu and Chu 2009). The
structural complexity of the compounds was ascribed
to their physical and chemical properties which have
contributed greatly to their prevalent distribution into
the environment (Rosal et al. 2010). Presently, most of
the wastewater treatment plants are not designed to
effectively treat emerging contaminants. Because of
this, a high proportion of their metabolites escape and
get introduced to aquatic environment as effluents.
This occurs through physical and chemical breakdown,
during disposal and recycling operations within
wastewater treatment plants (WWTPs). Numerous
studies supported this claims that wastewater treatment
plants and untreated urban wastewater acted are the
major routes through which PPCPs and EDCs get
released into various water sources (Barnes et al.
2002; Pryor et al. 2002; Harrison et al. 2006).
Subsequently, due to their hydrophobic nature, PPCPs
and EDCs in water associated with particulate matter
and hence settle at the bottom sediments and
Page 5 of 29, 1770
accumulated continuously through electrostatic
interaction. Apart from WWTP discharges, other
sources includes animal feeding operations, landapplied bio-solids, row-crop production, on-site
wastewater disposal systems, recreational activities,
transportation or wash-off from roadways, and
atmospheric deposition (Kidd et al. 2007; BonefeldJorgensen et al. 2007; Palace et al. 2009; Sellin et al.
2009; Rogers et al. 2013). In the same vein, PPCPs and
EDCs come into the aquatic environment through the
discharge of residual chemicals by householders and
by agronomy and manufacturing industries (Fig. 1)
(Boyd et al. 2003; Bonefeld-Jorgensen et al. 2007;
Besse et al. 2008; Besse and Garric 2009; Sellin et al.
2009; Kümmerer and Al-Ahmad 2010; Vulliet and
Cren-Olivé 2011; Brausch and Rand 2011; Besse
et al. 2012; Qin et al. 2012). Houeto et al. (2012)
affirmed the presence of metabolized and partially
metabolized drug residues in various water sources
such as wastewater, groundwater, surface water, and
drinking water. Accidental spills could also be other
sources of PPCPs and EDCs in the aquatic ecosystems
(Falconer et al. 2006; Huang et al. 2008). Personal care
products enter into the aquatic environments through
recreational activities such as swimming and also
through showering and bathing as well as other
technological process (Larsson et al. 2007). According
to Brooks et al. (2006), the accidental ejection of
PPCPs and EDCs effluent to ecosystems were
responsible for some of the worst-scenario waterborne
diseases that impacted negatively on human health.
Boxall et al. (2004) also noted that livestock faeces,
residual animal medicine, and aquaculture uses are also
other routes through which PPCPs and EDCs are being
released into the environment. Some PPCPs and EDCs
enter into the groundwater through leaching and
leaking of poorly designed sewer and landfills (Fawell
and Ong 2012). In a related development, Jackson and
Sutton (2008)) detected that local sources such as poor
sanitary sewer systems at different residences,
commercial, and industrial locations in California
contained a high concentration of contaminants such
as phthalates, triclosan, and BPA. Jackson and Sutton
(2008) in their pilot study carried out established the
presence of synthetic endocrine-disruptors such as
phthalates, bisphenol A, and triclosan in the surface
waters in Oakland, USA. The authors linked the
occurrence of the pollutants to the leakage of sanitary
sewer system. According to Writer et al. (2010), the
1770, Page 6 of 29
Water Air Soil Pollut (2013) 224:1770
Industrial
activities
hospitals
Domestic
households
Animal farming
activities
direct discharge
Combined sewers
drinking water
Water
treatment
plants
Wastewater
treatment
plants
effluents
Agricultural
activities
and
manure
River
Run-of
Aquaculture
Groundwater
Fig. 1 Possible sources and routes of PPCPs/EDCs in water cycle (Petrovic et al. 2003)
occurrence of bisphenol A, 17ß-estradiol, estrone, and
4-nonylphenol in 11 selected lakes in Minnesota, USA,
was ascribed to land-use activities and lake tropic
conditions but not wastewater treatment plants. The
authors confirmed that the sources of endocrine
disruptors are wide spread and diverse in nature. In
Europe and North America, the occurrence of PPCPs
and EDCs in rivers and lakes were attributed to poor
agricultural practices and sewage effluent. Maletz et al.
(2013) identified municipal sewage treatment plants,
livestock breeding, and hospital effluents as the main
point sources through which EDCs are introduced into
aquatic environment.
In emerging and underdeveloped nations such as
those in Africa and Asia, careless refuse dumping and
untreated industrial effluent discharge into waterways
are very common. This also contributes to the high
level of PPCPs and EDCs in aquatic ecosystems
(Olujimi et al. 2010). The discharge and exposure to
small concentration of PPCPs and EDCs were reported
to be allied with endocrine gland malfunction, chronic
toxicity, and pathogen resistance (Rosal et al. 2010).
The coverage pattern of PPCPs and EDCs
manufactured for human and animal also differs. The
human PPCPs and EDCs behave as pseudo-persistent
when the effluents were discharged into aquatic
systems despite their short environmental half-life
and are likely to go back into the urban water cycle
(Daughton 2002, 2004; Ankley et al. 2007) while
animal drugs are transported to surface waters during
rainfall or discharged openly in a single quantity to
aquatic systems. Some of the PPCPs and EDCs later
find their way into receiving water systems (Boyd et al.
2003; Barnhoorn et al. 2004; Carballa et al. 2004). For
instance, in China, municipal wastewater discharge
was identified as the major contributor of EDCs and
PPCPs to riverine water (Peng et al. 2008). Also, more
than 80 PPCPs and EDCs that were detected according
to Heberer (2002) originated from reclaimed water
used for artificial groundwater recharge. Kolpin et al.
(2002) in his study established that close to 80 % of
139 streams in US were contaminated with
antimicrobial agents, fire retardants, steroidal
hormones, as well as emerging pollutants. Thus, the
growing re-use of reclaimed domestic wastewaters for
irrigation could also be central in low-level PPCPs
escaping into urban storm water runoff from the
irrigated area. Also, Dean (2007) and Lyons (2008)
reported independently that once the emerging
micropollutants are released into the environment their
harmful effects on the local ecosystems and human
residents are unlimited. Yu and Chu (2009) attributed
the wide occurrence of some PPCPs and EDCs such as
ibuprofen, bisphenol A, caffeine, triclosan, and bis
(2-ethylhexyl) phthalate along the West Prong Little
Pigeon River, in the USA, to the wastewater discharge
into the river. Ortiz de García et al. (2013) linked the
presence of PPCPs and EDCs in the natural
Water Air Soil Pollut (2013) 224:1770
environment to many factors among which were the
consumption patterns and water use as well as the
peculiarity of the wastewater treatment plants. Jin
et al. (2004) reported that there have been reports of
high concentrations of bisphenol A (BPA) in the rivers
and marine environments in China, although the
assessment of BPA has not been extensive especially
in terms of monitoring data for drinking water. Peng
et al. (2008) observed wide occurrence of 19 endocrine
disrupting pharmaceuticals in urban riverine water of
the Pearl River Delta, South China. The concentrations
of the micropollutants after analysis were discovered to
be high. The authors ascribed the large presence of
pharmaceutically active compounds in the river to
careless refuse dump and municipal wastewater
discharge.
2.2 Environmental Fate and Behavior of PPCPs
and EDCs
Most PPCPs and EDCs are polar and highly
hydrophilic with low partition coefficient (Kow) and
partially soluble in aqueous media. Their presence
and bioavailability in the aquatic environment depends
on the interactions between solids and water in sludge
and sediment. In some cases, some PPCPs and EDCs
concentration in the water was higher. This is as a
result of series of phase transformations processes
involving biodegradation, dilution, and photolysis in
water environment whereas, in other cases, persistent
organic pollutants, such as polyaromatic hydrocarbon,
or organochlorine pesticides bioaccummulate and get
adsorbed by the sludge. By and large, it could be
inferred that the hydrophobicity of a chemical
substance will determine whether PPCPs or EDCs will
bioaccumulate in the solid phase or not (Caliman and
Gavrilescu 2009). The more hydrophilic a pollutant is,
the higher the tendency of being in the aqueous phase.
Therefore, one of the most important parameters to be
considered for chemical loss during adsorption onto
sludge is the organic carbon normalized sorption
coefficient (KOC). The chemical partitioning behavior
of PPCPs and EDCs in aqueous media also depends on
the partition coefficient (Kow). Hence, the greater the
values are for both parameters, the more those
compounds sorb upon organic carbons such as
suspended solids, non-polar fats, lipids, and mineral
oils whereas leaching of PPCPs from the soil or
sediment may be attributed to low level of KOC and
Page 7 of 29, 1770
K ow. The listed mathematical expression may be
adopted as reference criteria to know if PPCPs or
EDCs will be sorbed onto sediment or sludge.
(1) if Log KOW <2.5, then it signifies low sorption
potential;
(2) if 2.5<log Kow <4.0, it means medium sorption
potential;
(3) Log KOW >4.0 may be equivalent to high sorption
ability (Jones-Lepp and Stevens 2007; Caliman
and Gavrilescu 2009). Therefore, the
environmental distribution, bioavailability,
reactivity, transport phenomenon, and toxicity
potential of PPCPs and EDCs in natural and
artificial ecosystem depends largely on the
hydrophilicity and hydrophobicity sorption
coefficient value of the contaminants (Suarez
et al. 2008). Some indicative parameters such as
estrogenic activity potency (relative to estradiol),
environmental concentration, half-life, sorption
Koc for the environmental fate, and behavior of
several EDCs and PPCPs are shown in Table 2,
which lists some information concerning the
environmental fate as well as the effects of EDCs
and PPCPs.
2.3 Effects of Pharmaceutical and Personal Care
Products
Many nations in the world today are highly concerned
about the impending environmental crisis and
substantial risk occassioned by the occurrence of
PPCPs in the environment (Bound and Voulvoulis
2005; Glassmeyer et al. 2005; Heberer and Feldman
2005; Lishman et al. 2006; Larsson et al. 2007).
Although many drugs are fashioned to respond to quite
a large range of health challenges at low physiological
doses (milligrams per kilogram), some are more
dynamic and can perform best at nanograms-perkilogram concentrations. After accomplishing the
specific functions in the body, some still interact even
at low quantity with multiple non-therapeutic receptors
over the long-term, resulting in potentially harmful
effects on non-targeted receptors in both aquatic and
terrestrial wildlife. Strauch (2011) asserted that the
effects of PPCPS on human toxicity irrespective of
their concentration in the water supply are yet to be
ascertained. Research conducted by Ternes et al.
(2004) and Topp et al. (2008)) discovered that certain
1770, Page 8 of 29
Water Air Soil Pollut (2013) 224:1770
Table 2 Properties and processes that govern the fate of endocrine disruptor PPCPs in the environment
Process
Chemical
Environmental
Retention and
transport
Transformation
Accumulation
Property
Types of EDCs/environmental fate/effects
Solubility
Ionic, water-soluble ECDs; increased transport and dispersion/dilution
Volatility
Some pesticides and industrial EDCs; global redistribution by evaporation and
atmospheric transport
Stability
Many organic halogenated compounds; persistence
in the environment
Partitioning
Non-polar EDCs that bind to solids and lipids; partition into soil/sediment
and biota (solid/liquid/gas)
pH
Affects ionic EDCs, e.g., phenolics, and cellular reaction media
Salinity
Osmoregulation; affects also fate of ionic species in coast gradients
Temperature
Governs reactions; extremes (cold) increase stress; adapted hormonal functions
Photoperiodicity
Marked effects on many hormonal cycles (diurnal, lunar, annual)
Humus content
Binder, carrier, reaction site, etc.
Sorption
On humus/minerals; on aerosol particles; on plants and other biological tissues
Precipitation
In sorbing particles or as salts; dynamic equilibria with resuspension
Complexation
With other ligands e.g., in humus
Colloid formation
With humus; may enhance transport of, e. g., heavy metals in soil
Advection/dispersion
In free air, surface water, ground water (porous soil)
Diffusion
Impermeable soils; slow but may be important overall
Active transport
By humans/animals
Acid dissolution
Of polar EDCs in particular
Hydroxylation
Important for many persistent organics, e.g., PCBs
Chemical adducts
Important for many persistent organics, e.g., PCBs
Degradation/biotic
Depends on molecular structure and environment (humidity, pH, nutrients, redox)
Degradation/abiotic
Photo-decay in atmosphere and surface water
Polymerization
For some EDCs/conditions
Bioaccumulation
Bio-accumulating EDCs in food-chains; in tissues (lipid, bone)
Other accumulation
In (deep non-turbulent) sediments and soils
Sources: (Assmuth and Louekari 2001; Caliman and Gavrilescu 2009)
PPCPs, such as estrogenic compounds, have a very high
bioaccumulation potential. This environmental
bioaccumulation exacerbates the abnormal hormonal
control causing reproductive impairments, decreased
fecundity, increased incidence of breast and testosterone
cancers, and persistent antibiotic resistance. This severe,
eco-toxic, and prolonged toxicity experienced due to the
presence of PPCPs in the environment is similar to that
of health effects caused by the presence of metallic
elements detected at concentration below 1 mg/L in
which the endocrine system are grossly affected (Sharpe
and Irvine 2004; Xia et al. 2005; Bisceglia and Roberts
2006). Lear et al. (2002) and Hileman (2005) both
submitted that contamination by certain PPCPs,
especially antibiotics, at trace level in water equally
contribute to the widespread impact and frequent
occurrence of antibacterial resistance. This rise in
antibacterial resistance has overstretched the medical
costs of communities due to re-occurrence of
hospitalization as well increased treatment cost. This is
even worse in the developing countries where income
per day is mostly less than 1 US dollar. Lin et al. (2008)
revealed that certain fractions of partially metabolized
drugs were found in waste stream, animal waste, and
pharmaceutical effluents, and some of these drugs later
undergo various degrees of transformation in the
aqueous media.
During this period, entirely new products that differ
with diverse ecotoxicological activity from the starting
material are formed. The main characteristic property
and processes linked to the occurrence and fate of the
endocrine-disrupting pharmaceuticals are summarized
Water Air Soil Pollut (2013) 224:1770
in Table 2 below. The fate and behavior of these
emerging micropollutants are quite diverse and
complex depending on the environmental factors. The
knowledge on the environmental fate of EDCs and
PPCPs are still limited.
3 Endocrine-Disrupting Compounds
Some compounds do obstruct or mimic or antagonize
the endocrine system, and these substances are known
as endocrine-disrupting chemicals. Endocrine systems
control a quite a large number of body physiological
activities such as reproductive processes like
embryonic development, sex differentiation, and
metabolic development (Flint et al. 2012). Endocrinedisrupting compounds may block the hormonal growth
in the endocrine system and affect the physiological
activities of endogenous hormones (Schug et al. 2011).
They are alternatively called environmental hormones
that cause adverse effects on aquatic and terrestrial
organisms through altering the metabolism of natural
hormones, modifying hormones receptor in a cell,
interference, or binding to receptors of the endocrine
system (Jiao and Cheng 2008; Olujimi et al. 2010).
EDCs can be natural or man-made. Others include
alkyl-phenols, dioxins, various drugs, synthetic birth
control pills, pesticides, plasticizers, and phenolic
products (Jackson and Sutton 2008). The exposure of
humans to endocrine disruptors in recent years has
received increased attention due to the high exposure
rate especially among the aquatic organisms. Ever
since, there has been increasing concern with regard
to the likely impacts of exposure to chemical
compounds with endocrine-disrupting activity in the
environment (Segner 2005; Sumpter 2005; Game et al.
2006; Mauricio et al. 2006; Xue and Xu 2006; Moder
et al. 2007; Shin et al. 2007; Hecker and Giesy 2008).
In addition, high tendencies of multiplicative and
evolving abnormalities in infants and children,
temporal descending trends in semen quality and
testosterone levels, and worldwide increased rates of
testicular and thyroid cancers among adult male
populations have been attributed to EDCs exposure
(Swan et al. 2000; Huyghe et al. 2003; Davies and
Welch 2006; Travison et al. 2007; Andersson et al.
2007). These reported health cases alerted the scientific
and public communities regarding the potential risk of
environmental EDCs to men’s health. Although the
Page 9 of 29, 1770
effect of EDCs on human health and wildlife biology
were first documented in the 1930s, the real research
progressed in the late 1970s and early 1980s (Vogel
2004; Trenholm et al. 2006; Moder et al. 2007).
Human beings exposure to EDCs could be through
dermal absorption or contaminated media such as
water, food, air, and soil. To date, no comprehensive
list of EDCs exists, because most of the new chemicals
are being manufactured continuously. There is a very
limited and incomplete evidence of endocrinedisrupting activity because more than 87,000 new
chemicals in the market have not been tested for their
endocrine toxicity (Snyder et al. 2006; Kim et al.
2007). Presently, more than 38,000 chemicals and
potentially toxic elements have been identified as
potential endocrine-disrupting pharmaceuticals. This
is an indication that more chemicals may be recognized
as endocrine disrupters as the sum of compounds
surges with unanticipated effects (Ferraz et al. 2007;
Fatoki and Opeolu 2009). This will require
identification and elimination of these compounds
from the water system. Yet again, this welldocumented knowledge of the hazards has yet to
trigger an adequate precautionary principle approach
to control and monitoring new compounds before their
release into market place and from there into the
receiving environment.
3.1 Effects of Endocrine-Disrupting Compounds
The available proof from the relevant literature
associated the abnormalities and health challenges
experienced by aquatic organisms with exposure to
low concentration of EDCs (nanograms per liter).
The toxic impacts of EDCs on the ecosystem have
continued to be the subject of research and published
data in the scientific and public health communities
over the last 20 years due to the mimicking or
disrupting potential of the endocrine system (Murray
et al. 2001; Thorpe et al. 2003). The effects of these
emerging micropollutants upon animals are well
reported (Table 3), although earlier studies stated that
there have not been primary effects upon humans and
recommended further study (Harrison 2001; Sharpe
and Irvine 2004). Many synthetic chemicals such as
pesticides, BPA, and phthalate plasticizers, and indeed
estrogens and subordinate plant metabolites have been
observed to possess endocrine-disrupting properties
(Naz 2005). Most of these EDCs bind to the cell
1770, Page 10 of 29
Water Air Soil Pollut (2013) 224:1770
receptor and antagonize the endocrine glands
responsible for hormonal secretion. Subsequently, they
block the various mechanistic signals of the endocrine
system and hence modify the hormonal receptor cells
(Olujimi et al. 2010). Some of the potential endocrinedisrupting PPCPs are shown in Fig. 2.
There are diverse opinions on the effects of EDCs
on wildlife and humans; some researchers are of the
view that there is a link between exposure and effects
of EDCs in animals and humans while some disputed
the claims (Xu et al. 2008). However, studies by
Michael (2001) discovered that exposure to EDCs have
consequential health effects on many aquatic species
which includes a low sperm count, increasing ovarian,
prostate, testicular, breast cancer, diabetes/metabolic
syndrome, and reproductive failures. These effects of
EDCs on the natural ecosystem depend on the
lipophilicity increase, exposure time, and
biotransformation mechanism. However, some EDCs
fail to degrade directly, but instead were metabolized
into other by-products, even more toxic than the original
chemicals, thereby increasing their effects on the
ecosystem. Information on the aquatic organisms
affected by exposure to EDCs and PPCPs are shown
in Table 3. Human beings and aquatic organisms get
exposed to PPCPs or EDCs through water, food, soil, or
dermal adsorption (Olujimi et al. 2010). BurkhardtHolm et al. (2005) and Kidd et al. (2007) attributed the
declining rate of fish in freshwater systems to the
widespread presence of estrogenic chemicals. Safe
(2000) also perceived that exposure of aquatic
organisms to organochlorines led to feminizations of
fishes and gulls, and sexual irregularities in alligators.
In addition, there are increasing occurrences of
reproductive and developmental abnormalities among
infants and children, pregnancy loss, birth defects,
growth retardation, ovarian failure, low semen quality,
and increased rates of testicular and thyroid cancers
(Swan et al. 2000; Huyghe et al. 2003; Davies and
Welch 2006; Travison et al. 2007; Andersson et al.
2007; Enewold et al. 2009). These deficiencies occurred
as a result of exposure to EDCs through oral ingestion
such as breast milk, infant formula, contaminated water,
food, surface, and carpet dust (Olujimi et al. 2010). This
has generated concern regarding the potential risk of
environmental EDCs to men’s health. Mackenzie et al.
(2005) and Safe (2000) ascribed the decline in sex ratios
in Canada and the United States to over exposure to
EDCs. With the recently reported cases of adverse
health implication due to exposure to EDCs, the
development of highly efficient technology is necessary
in order to maintain public health and ecosystem
stability (Lee et al. 2003; Braga et al. 2005).
4 Removal of Pharmaceuticals and
Endocrine-Disrupting Compounds—An Overview
Despite appropriate legislation framework especially
in the advanced nations to check inflow of endocrine
Table 3 Some endocrine-disrupting chemicals, hormone target, and animals affected
Compounds
Common usage
Interference hormone
Animals affected
Bisphenol A
Plasticiser
Thyroxine, cortisol
Mammals, birds, fish
Butylbenzyl phthalate (BBP),
di(2-ethylhexyl) phthalate (DEHP),
di-n-butylphthalate ( D-n-BP)
Polychlorinated biphenyl (PCBs),
dioxins, pentachlorophenol (PCP),
polychlorinated dibenzofurans (PCDFs)
p-Nonylphenol
Plasticiser
Estrogens
Mammals, birds, fish,
reptiles, amphibians
Flame retardants, unintended
by-products during
incineration
Plasticiser
Estrogens
Reptiles, amphibians
Estrogens
Mammals, birds, fish,
reptiles, amphibians
Insecticides
Estrogens and androgens
Mammals, birds, fish,
reptiles, amphibians
2,2-bis-p-chloro-phenyl-1,1,1-trichloroethane
(DDT), 2,2-bis-p-chlorophenyl-1,
1-dichloroethylene (DDE), DDE, chlordane
dieldrin, heptachloro, lindane,
endosulfan, oxychlordane, etc.
Sources: (Hill et al. 2001; Zala and Penn 2004; Olujimi et al. 2010)
Water Air Soil Pollut (2013) 224:1770
Page 11 of 29, 1770
Fig. 2 Scheme of the potential endocrine disruption PPCPs (Source: Caliman and Gaurilescu 2009)
disruptors and pharmaceuticals into drinking water, the
problem still persist (Focazio et al. 2008; Swati et al.
2008; Rahman et al. 2009a, b). Efforts were made and
still ongoing to check mate this ugly trend towards
removing or degrading the persistent refractory
pharmaceuticals and endocrine-disrupting compounds
in water and wastewater. A number of the conventional
wastewater treatment technologies have so far been
reported in the literature. However, these technologies
are not without defects in the removal of
pharmaceuticals and endocrine disruptors from
contaminated water. For instance, physicochemical
treatment such as activated carbon adsorption
(Nowotny et al. 2007; Snyder et al. 2007; Yu et al.
2008), reverse osmosis, nanofiltration and (Snyder
et al. 2007) and coagulation–flocculation, and
membrane filtration (Snyder et al. 2007; Yoon et al.
2007) were discovered not to perfectly remove EDCs
and PPCPs. Instead, they end up generating other toxic
by-products. Nevertheless, an appreciable success was
recorded when biological and physical treatments were
combined, including less generation of by-products
(Zhang et al. 2010). This was evidenced in the study
conducted by Al-Rifai et al. (2011) when combined
activated sludge, microfiltration, and reverse osmosis
were used to remove 11 pharmaceuticals and two
endocrine disruptors in a water recycling process.
The authors established 97 % removal rate when water
concentration was below 0.1 μg/L for most
compounds except bisphenol A with concentration
above 0.5 μg/L. The authors concluded that the
combined system did not only efficiently remove the
micropollutants, but also succeeded in reducing the
concentrations of some physicohemical parameters.
Hence, in order to reduce their concentration to a less
harmful level, a more sensitive and reliable technology
is needed. To date, little or no extensive compilation of
papers published on the use of combined techniques to
degrade pharmaceuticals and endocrine-disrupting
compounds from wastewater have been reviewed.
Suffice to mention that most of the reported methods
of removing emerging contaminants are categorized
1770, Page 12 of 29
into three approaches according to Liu et al. (2009);
these include physical methods, biodegradation, and
advanced oxidation processes. This review focused
most importantly homogeneous and heterogeneous
advanced oxidation processes.
4.1 Advanced Oxidation Processes
Advanced oxidation processes (AOPs) are very
effective techniques capable of completely
mineralizing the EDCs and PPCPs (Mendez-Arriaga
et al. 2008). AOPs are chemical oxidation techniques
encompassing organic pollutant removal and
degradation under the influence of highly reactive
hydroxyl radicals (Saien and Soleymani 2007; Saien
and Khezrianjoo 2008; Saien et al. 2011). The
hydroxyl radical is highly reactive and non-selective
against refractory organic pollutants with subsequent
conversion of the pollutants to CO2, H2O, and mineral
acids. In the last couple of years, AOPs have been
extensively exploited and reported in the literature for
the degradation of different wastewater containing
contaminants such as pesticides, pharmaceuticals,
endocrine disruptors, and dye molecules (Stasinakis
2008; Saien et al. 2011; Machulek Jr et al. 2013). AOPs
could be generally classified into (1) homogeneous
AOPs and (2) heterogeneous AOPs. The two
categories are reviewed as follows:
Heterogeneous Advanced Oxidation Processes This is
defined as a reaction process in which semiconductor
catalyst dissociated under the influence of photon
energy. In this case, the catalyst and the reactant exist
in different phases. Among the heterogeneous advanced
oxidation processes is the solid semiconductor TiO2
photocatalyst reviewed below.
4.1.1 Heterogeneous Photocatalysis
Semiconductor photocatalysis recently emerged
technique as one of the advanced oxidation processes
responsible for degrading recalcitrant, hazardous, and
non-biodegradable substances in wastewater and
drinking water into relatively less risky products such
as CO2, H2O, and inorganic ions. Despite these useful
functions, the post-separation of the used TiO 2
photocatalysts from wastewater treatment remains a
major challenge. Many efforts were geared towards
addressing this problem, and such efforts included
Water Air Soil Pollut (2013) 224:1770
immobilization of TiO2 upon different supports such
as silica, perlite, activated carbon, clay, zeolites, and
many others (Yao et al. 2010). Most of these support
materials are chosen because of their higher surface
area. This is to guarantee highly active reaction centers
as well as improved light penetration and reflection on
the support pores (Friedmann et al. 2010; Czech and
Rubinowska (2013). Several studies have considered
the use of titania photocatalysts or the immobilized
form of titania to degrade and mineralize organic
compounds (Nakashima et al. 2003). Some of these
are summarized as follows so as to give comparative
data to the scholars in this area. Due to the enormous
availability of treatment techniques for contaminants
of emerging concern, it is not possible to review all, but
the review will try to capture advanced oxidation
techniques involving singular and combined
photocatalytic degradation of emerging contaminants.
Chong and Jin (2012) explored the photocatalytic
ability of a titanium dioxide (TiO2) nanofiber as a pretreatment technique to degrade carbamazepine using
simulated wastewater. The findings revealed that 78 %
of CBZ, 40 % of chemical oxygen demand (COD) and
23 % of PO4 concentrations from influent
contaminated water were removed during the 4-h
reaction time. After 0.5-h treatment, the analysis by
high-performance size exclusion chromatography
(HPLC) revealed a dramatic shift of molecular weight
from higher portion (>10–1,000 kDa) to a lower level
(<10 kDa). Tsai et al. (2009) described the
photocatalytic degradation of bisphenol A conducted
using a TiO2 suspension reactor. The degradation
capability was evaluated with respect to initial BPA
concentration, TiO2 dosage, initial pH, and temperature.
The obtained first-order reaction constants (kobs)
validated the degradation of BPA during the experiments.
The photocatalytic degradation of diclofenac, metoprolol,
estrone, and chloramphenicol was conducted in a tube
reactor using different commercially available TiO2 by
Czech and Rubinowska (2013). The prepared
photocatalysts were characterized using BET, X-ray
diffraction (XRD), and scanning electron microscopy
(SEM), and it was observed that anatase TiO2
possessed the highest activity in the photocatalytic
oxidation of diclofenac, chloramphenicol, and
estrone whereas the presence of rutile only
enhanced the photooxidation of metoprolol. The
anatase TiO 2 with 21 nm crystals was highly
efficient for COD reduction in the treated water
Water Air Soil Pollut (2013) 224:1770
and the photooxidation of all studied pollutants
followed pseudo-first-order kinetics. The photocatalytic
degradation of endosulphan and lindane (endocrinedisrupting compounds) in the presence of titania was
also reported by Ashiya and Guatam (2011). The study
revealed that the presence of acetone in the reaction
mixture slowed the reaction competition for hydroxyl
radicals between pesticides and acetone. The
degradation efficiency of 95 % (endosulphan) and
98 % (lindane) coincided with the zero point charge of
the catalyst at pH 7. Chong et al. (2011) opined that
immobilized anatase titanate nanofiber and mesoporous
TiO2 infused kaolinite catalysts in a photoreactor
(SB-ASP) were responsible for the CBZ elimination
from municipal wastewater. The experiment was
investigated by varying the following parameters, batch
reactor cycles, effluent organic matter, nitrate, and
phosphate. The analyzed results as obtained from
high-performance size exclusion chromatography
revealed that the carbamazepine degradation was
achieved.
Tables 4 and 5 below have highlighted clearly the
difference between single techniques and combined
treatment, in most cases, the combination approach
appearing to be more promising in both organic
pollutant elimination and degradation, as most
combined treatment processes used were able to
completely degrade and mineralize EDCs and PPCPs
above 90 %. This makes the combined system for water
reclamation a feasible substitute for commercialization
in the nearby future.
In another study, photodegradation assisted by TiO2
was conducted for degrading estrone and 17β-estradiol
using sunlight and UV irradiation (Zhang and Zhou
2008). The study confirmed the use of UV
photodegradation to be far more efficient than solar
irradiation, and this was ascribed to the vigorous
absorbance of ultraviolet energy by EDCs, although the
method did not depend on initial chemical concentration
or sample matrix. Thus, heterogeneous photocatalysis
was confirmed as a very effective method for removal
of EDCs from water. Sin et al. (2012) in his review article
submitted that heterogeneous photocatalysis in the
presence of UV, solar light, and oxygen is highly
effective for the removal and decomposition of EDCs
in water. The authors established that the degradation
efficiency is influenced by solution pH, reaction
temperature, light intensity and wavelength, catalyst
loading, and initial substrate concentration.The study on
Page 13 of 29, 1770
the adsorption and photocatalytic degradation of 15
different pharmaceuticals by titanium dioxide (TiO2)
anatase and rutile nanowires together with commercially
available TiO2 (P25) nanoparticles in the presence or
absence of UV were investigated by Hu et al. (2012).
The UV-exposed anatase nanowires effectively
mineralized venlafaxin, atorvastatin, ibuprofen,
naproxen, and gemfibrozil while the effective removal
of fluoxetine and norfluoxetine was by rutile-phase
nanowires. The exposure to 265 nm UV effectively
decayed sulfamethoxazole and atrazine. The kinetic
studies showed that the removals of the pollutants were
completed within 20–40 min. Rengaraj and Li (2011)
established the photocatalytic degradation of bisphenol A
under UV illumination. Ultrasonic-assisted sol–gel
method was used to synthesize and characterize Agdoped titania. The characterization was done using
SEM, EDX, XRD, XPS, and UV-visible absorption
spectroscopy. The loading of Ag on TiO2 catalysts
significantly hastened the photocatalytic oxidation of
BPA in aqueous suspension. The reaction mechanism
specified that the nanosized Ag doped on TiO 2
nanocomposites acted as the center for electron capture
where the reduction of oxygen took place. This reduction
of oxygen by means of the separation in Ag–TiO2
nanocomposites was responsible for the faster BPA
degradation rate compared with pure TiO2 particles.
Also, Fabiola et al. (2008) revealed that the degradation
of naproxen in a 0.078 L Duran reactor equipped with a
1 kW Xe-lamp using TiO2 as photocatalyst did not only
confirm photocatalysis treatment as a highly efficient
technique but recommend further improvement in the
biodegradability under the operational conditions tested.
However, Zhang et al. (2010) appraised the
photocatalytic oxidation of endocrine-disruptors,
Escherichia coliform (Escherichia coli) as well as the
estrogenic activity of a secondary effluents obtainable
from a wastewater treatment plant using a photocatalytic
reactor coated with TiO 2 . Filtration followed by
photocatalysis was used to compare the reduction rate
of estrogenic activity and E. coli in both filtered and
unfiltered wastewater samples. The inactivation rate of
E. coli and estrogenic activity improved considerably
after filtration which was ascribed to the partial removal
of suspended solids which thus enhanced the
photocatalytic oxidation. Combined photocatalysis with
filtration pretreatment was reported to be effective. Lin
et al. (2013) utilized immobilized TiO2 photocatalyst
supported on a fiberglass to photo mineralize ibuprofen.
Compounds
Type of water
Combined treatment
technique
Operating conditions
Results and comments
References
Paracetamol (PPCPs)
Bi-distilled water
H2O2/UV
Low-pressure lamp (17 W, 254 nm);
CH2O2 =5 and 20 mmol/L,
pH 2.0–7.0
Andreozzi et al.
(2003a, b)
Clofibric acid (PPCPs)
Aqueous solution
H2O2/UV
17β-Estradiol,
estrone and 17αethinyestradiol (EDCs)
Sterile doubledistilled water
UV and and UV/TiO2
Low-pressure lamp (17 W, 254 nm);
Co =1.0 mmol/L, CH2O2 =
1.0 mmol/L, pH 5, Tr=60 min
High-pressure Hg lamp (152 W):
C0 =10 μg/L; TiO2 immobilized:
UVA lamp (photolysis)
Complete removal of paracetamol with
mineralization between 21 % to 40 %
by using H2O2 concentration of 5.0
and 20 mmol/L
Almost complete removal of clofibric
acid in 60 min with low concentration
Antibiotic (metronidazole)
(PPCPs)
Deionized water
UV photo-Fenton,
UV/H2O2
17β-Ethinylestradiol(EDCs)
Laboratory-grade
water, surface
water of low
alkalinity and
high alkalinity
UV/H2O2
Naproxen, iohexol,
carbamazepine,
clofibric acid
(PPCPs)
Laboratory-grade
water, surface
water
UV/H2O2
Medium-pressure UV 200–300 nm
at pH=7 1–3 μM H2O2
Diclofenac (PPCPs)
Distilled water
Phenol
Petrochemical
industrial
wastewater
Ultrasonic irradiation
with TiO2, SiO2,
SnO2, TiO2/SiO2
UV/TiO2
Phenol and chlorophenol
Aqueous solution
Sonication at 216, 617,850 KHz,
diclofenac concentration
50–100 mg/L
TiO2 nanoparticle dosage (initial
phenol concentration (30 to
110 mg/L), pH of solution (3 to 11),
contact time (0 to 300 min), UV
irradiation duration
pH of solution, initial hydrogen
peroxide concentration, TiO2
dosage, UV irradiation duration
Andreozzi et al.
(2003a, b)
Very fast removal of estrogenic activity
of the three compounds tested by
photocatalysis. The 50 % of estrogenic
activity was removed in 10 min. Removal
of 100 % was reached in 1 h of treatment.
Photolysis needs more time to remove
estrogenic activity
UV provides low degradation compared
with UV/H2O2. Photo-Fenton gives
20 % higher removal than Fenton.
Coleman et al. (2004)
Reduction in estrogenic activity occurs
faster in laboratory water than in
surface water indicating scavenging
effects and also dependence on water
alkalinity. In most cases, complete
removal occurs at ≤600 mJ/cm2 fluence
Moderate degradation at 100 mJ/cm2
fluence and >99 % at 600–1,700 Mj/cm2
depending on the drug. Lower degradation
with direct photolysis. Rates decrease in
surface water compared to laboratory water
90 % degradation after 60 min at 216 or
617 kHz and 20 % at 850 kHz without
particles. Particles enhance degradation
The highest removal efficiency of phenol
occurred at contact time (300 min) and
solution pH (3) and initial phenol
concentration (50 mg/L). Combined
UV/TiO2 improved the removal efficiency
Within 90 min irradiation time, 74.6 %
and 79.8 % phenol and chlorophenol
were destroyed. The optimum removal
conditions were pH 4, 0.5 g/L TiO2,
90 min irradiation time, 75 ml/L H2O2.
UV/H2O2/TiO2 combined system was
more efficient than UV/H202 and UV/TiO2
Linden et al. (2007)
Shemer et al. (2006)
Pereira et al. (2007a)
Hartmann
et al. (2008)
Ali Nickheslat
et al. (2013)
Dixit et al. (2010)
Water Air Soil Pollut (2013) 224:1770
UV/H2O2/TiO2
Low-pressure lamp: UV=0-600 mJ/cm2,
concentration of H2O2 =25–50 mg/L,
antibiotics (Co)=6 μmol/L;
pH (UV)=6 pH(photo-Fenton)=3.5
Low-pressure UV and mediumpressure UV, 10−5 mM H2O2
1770, Page 14 of 29
Table 4 Treatment of emerging contaminants in water by combined advanced oxidation processes
Compounds
Type of water
Combined treatment
technique
Operating conditions
Results and comments
References
Phenol
Water
O3/H2O2
Initial pH of solution, temperature,
ozone dosage, initial H2O2
concentration, rotation speed
Zeng et al. (2013)
4-Chloro-2-nitrolphenol
Aqueous solution
Photocatalytic, sonolytic,
sonophotocatalytic
Artificial UV lamp 125 W,
Solution pH, catalyst dosage,
oxidant concentration
Diethyl phthalate (DEP)
Aqueous solution
Single (sonolysis, photolysis,
photocatalysis) and
combined (sonophotolysis,
sonophotocatalysis)
UV irradiation time, photocatalyst
dosage variation ultrasonic
frequency variation
Di-(2-ethylhexyl)
phthalate (DEHP)
Synthetic and real
petrochemical
wastewater
H2O2/Fe2+
H2O2 concentration, Fe2+
concentration, and solution
pH, contact time
Diclofenac (PPCPs)
Distilled water
Fenton and photo-Fenton
Fe2+/H2O2/Sunlight at pH 6.5,
Diclofenac concentration 50 mg/L
The degradation rate increases with
increasing solution pH and rotation
speed. 100 % complete degradation of
40 mg/L phenol was achieved when
O3/H2O2 were combined.
80 % degradation was achieved in 2 h for
photocatalytic treatment. With the
integration of ultrasound, 96 % destruction
rate was achieved within 1 h 30 min.
The trends of degradation was
sonophotocatalysis>photocatalysis>
sonocatalytic>sonolysis
There was a rapid degradation and
mineralization of DEP with the
sonophotocatalytic processes more than
singular sonolysis and photolysis. The
study demonstrated the combined process
decomposed DEP faster than single
advanced oxidation process.
85.6 % degradation of DEHP was noticed
within 60 min at pH 3. The study also
suggested that the optimum concentration
condition were 90 mg/L H2O2, 5 mg/L Fe2+,
and 20 mg/L DEHP in the solution at pH 3.
Fast drug degradation was accompanied
by slower mineralization
Carbendazim
Aqueous solution
TiO2 photocatalysis
and ozonation
Variation of TiO2 concentration,
ozone dose, UV irradiation
time and solution pH
Naa et al. (2012)
Esmaeli et al. (2011).
Perez-Estrada
et al. (2005a)
Rajeswari and
Kanmani (2009)
Page 15 of 29, 1770
The results revealed that increase in ozone
dosage up to 0.48 g/h and a decreased
of TiO2 above 1 g/L at optimum pH=6,
accelerate the removal rate. 88 % chemical
oxygen demand (COD) removal in 3 h
by the combined photocatalytic ozonation
process was noticed, whereas 54 % and
67 % COD were individually removed
by photocatalysis and ozonation process.
Hence, carbendazim was effectively
mineralized by the combined photocatalytic
ozonation process. The study revealed that
combined TiO2-based photocatalysis and
ozonation significantly overwhelmed the
individual treatment technique ozonation
and TiO2 photocatalysis
Verma et al. (2013)
Water Air Soil Pollut (2013) 224:1770
Table 4 (continued)
Compounds
Type of water
Single treatment
technique
Operating conditions
Results and comments
References
17β-Estradiol,
estrone (EDCs)
Deionized water and
treated effluent
from a sewage
treatment plant
Photocatalysis
Immobilized TiO2/UV-black
fluorescent lamp, 250 μg/L
Nakashima
et al. (2003)
Clofibric acid,
carbamazepine,
iomeprol, iopromide
(PPCPs)
Abamectin
Distilled water
Photocatalysis
Suspended Degussa or Hombikat
TiO2/artificial sunlight at
pH=3.4–6.5, 0.5–10 mg/L
Aqueous solution
Photo-fenton
UV irradiation time variation,
H2O2 concentration, initial
concentration of abamectin
Paracetamol (PPCPs)
Deionized water
Photocatalysis
Suspended Degussa TiO2/UV254 nm or UV-365 at pH=
3.5–11, 2–10 mM
Gemfibrozil,
tamoxifen (EDCs)
Deionized water
Photocatalysis
Suspended Degussa or anatase
TiO2/UV-360 nm at pH=10,
2.5–47 mg/L
Chloramphenicol
(PPCPs)
Deionized water
Photocatalysis
Suspended Degussa or
anatase TiO2 or ZnO/UV(320–400 nm) at pH=5,
10–80 mg/L
Diclofenac, naproxen,
ibuprofen (PPCPs)
Deionized water
Photocatalysis
Suspended Degussa
TiO2/artificial sunlight,
25–200 mg/L
Fast degradation of both estrogens following f
irst-order kinetics. Rate increases with increasing
catalyst surface area and temperature decreasing
initial concentration. Degussa is generally
more active
First-order kinetic rates increase with increasing
catalyst loading and decreasing initial concentration.
Degussa is generally more active than Hombikat.
Determination of by-products and pathways
70 % and 60 % removal and mineralization rate of
abamectin was achieved within 60 as well as
180 min UV irradiation, respectively. The use of
advanced oxidation process such as photo-Fenton
assisted in degrading abamectin
First-order rate under UV short wave irradiation
is much faster than under UV long wave. Several
factors such as initial drug, catalyst, and oxygen
concentrations, pH, and light intensity are tested
concerning drug degradation. Identification of
by-products
Gemfibrozil undergoes only photocatalytic
degradation but not photolytic. Tamoxifen
undergoes direct photolysis but its metabolites
undergo photocatalytic degradation. Degussa is
more active than anatase. Mineralization takes
much longer than drug removal
First-order rate increases with increasing drug
concentration and catalyst loading and adding
H2O2. Degussa TiO2 and ZnO are equally active.
Complete elimination of drug activity after 90 min
corresponding to 70 % mineralization
Diclofenac and naproxen are susceptible
to photolysis but not ibuprofen. By-products
of low biodegradability accompany diclofenac
and naproxen degradation
Doll and Frimmel
(2004)
Matos et al. (2012)
Yang et al. (2008)
Yurdakal
et al. (2007)
Chatzitakis
et al. (2008)
Mendez-Arriaga
et al. (2008)
Water Air Soil Pollut (2013) 224:1770
Adopted from: Klavarioti et al. (2009); Esplugas et al. (2007)
1770, Page 16 of 29
Table 5 Treatment of emerging contaminants in water by single advanced oxidation processes
Water Air Soil Pollut (2013) 224:1770
The authors established direct relationship between
photocatalytic dosage and contaminant degradation rate.
Addition of H 2 O 2 significantly enhanced the
decomposition rate. In the same vein, Madhavan et al.
(2010) investigated the combined effect of sonolysis,
photocatalysis, and sonophotocatalysis on the
degradation of ibuprofen. The authors discovered that
the obtained degradation rate from sonophotocatalysis
was significantly higher than the individual advanced
oxidation processes studied. The synergy index value of
combined advanced oxidation was 0.3 greater than
individual sonolytic and photocatalytic process.
Equally, Frontistis et al. (2012) reported the efficiency
of the combined photocatalysis and ultrasonic
irradiation regarding 17α- ethynylestradiol (EE2)
degradation in aqueous solution. The study established
a synergistic effect rather than a cumulative action
between the two combined systems. In fact, increase in
catalyst dosage and photon flux together with a decrease
matrix complexity was responsible for estrogen
concentration changes. So far, this review has shown
that photocatalysis using titania or its immobilized form
may be useful in degrading and completely mineralizing
some of the PPCPs and EDCs in contaminated water.
4.1.2 Homogeneous Advanced Oxidation Processes
Homogeneous advanced oxidation process is a
reaction process in which both the reactant and
photocatalysis are in the same phase. Most of the
commonly used homogeneous photocatalysis are
ozone, metal oxide, metal oxide/hydrogen peroxide,
etc. The mineralization and decomposition of
emerging micropollutants by homogeneous advanced
treatment therefore exploits ozone, hydrogen peroxide,
ultraviolet light, or combined process using a
combination of ozone and hydrogen peroxide, hydrogen
peroxide, and ultraviolet light, ozone/ultraviolet
light/ferrous ions or ferric ions, ferrous or ferric
ions/hydrogen peroxide, ferrous or ferric ions/ultraviolet
light to degrade toxic pollutants. This section review
some of the previous research conducted using either
single or combined system to destroy the contaminants
of emerging concern. Xu et al. (2007) demonstrated
ozone oxidation technique to investigate the degradation
of endocrine disruptor bisphenol A in drinking water.
The effects of different ozone dosages, BPA initial
concentrations, and ozone adding time were monitored
in a reactor. The outcome of the study revealed that
Page 17 of 29, 1770
ozone dosage plays a dominant role during the process
of BPA degradation, while the impact of the contact time
could be ignored, although high ozone dosage, and
dissolved ozone concentration greatly contributed to
the extent of BPA degradation. Thus, the O3-H2O2
processes proved to have similar effects on the
degradation of BPA by ozone oxidation. Li et al.
(2011) reported the pentachlorophenol (PCP) removal
under xenon lamp irradiation in presence of metal oxide
bismuth silicate (BSO). A mineralization rate of 99.1 %
after 120 min was observed. Decrease in pH was
observed from pH 6.2 to 4.6. The electron spin
resonance results indicated that the degradation
mechanism was largely due to the presence of
superoxide radical (O2−), and the GC-MS analysis
confirmed the presence of some intermediates, mainly
aromatic compounds and aliphatic carboxylic acids.
Table 2 captures other single treatment techniques used
to remove and degrade emerging micropollutants.
Furthermore, a review conducted by Ning et al.
(2007) showed that the combination of ozone and other
ozone-based advanced oxidation process were highly
efficient in destroying steroidal estrogenic hormones
such as estrone (E1), 17b-estradiol (E2), estriol (E3),
and 17aethinylestradiol (EE2), except phthalates
suspected resist degradation by ozone. Pereira et al.
(2007) explored two homogeneous advanced
oxidation processes such as UV and UV/H2O2 to
degrade pharmaceutically active substances fond in
aqeous water. The authors discovered that integration
of hydrogen peroxide significantly enhanced the
overall degradation efficiency of the pollutants. Hence,
combined UV/H2O2 was revealed to be a viable option
for degradation of the pollutants. Giri et al. (2010)
utilized seven different advanced oxidation methods
such as UV, UV/TiO 2 , UV/H 2 O 2 , O 3 , O 3 /UV,
O3/TiO2, and O3/UV/TiO2 to remove and degrade
selected PPCPs in aqueous solution. The authors
observed four different removal patterns which include
non-degradation by any of the seven techniques,
degradation by ozone-based, and not ultraviolet,
system, degradation by ultraviolet, and not ozonebased, techniques. In addition, the degradation of the
pollutants by combined ozonation and ultraviolet was
rapid and efficient. Zelmanov and Semiat (2008)
demonstrated that iron(III) oxide nanocatalyst
combined with hydrogen peroxide could effectively
degraded water contaminated with phenol and ethylene
glycol without necessarily exposing the solution to
1770, Page 18 of 29
ultraviolet or photolight. The authors concluded that
the degradation rate of phenol and ethylene glycol was
35 times and two to four times greater than the
literature value reported for Fenton process and UV.
Kim et al. (2009) reported that H2O2 addition aided the
photodegradation of PPCPs during UV treatment and
found that the average first-order rate constant value
for all the PPCPs studied increased by a factor of 1.3
when H2O2 was added during UV treatment. The
addition of H2O2 improved the photodegradation rates
of PPCPs appreciably during UV treatment. Equally,
Nakonechnya et al. (2008) explored ozone and
hydrogen peroxide combination to degrade steroidal
hormone estrone (E1). The authors observed that the
E1 degradation was found to depend on pH and
O3/H2O2 ratio. Thus, the combination of O3/H2O2
proved to be highly efficient treatment for E1. Lopez
et al. (2003) argued that UV and UV/H2O2 treatment
methods were able to oxidize pharmaceutical
intermediates such as 5-methyl-1,3,4-thiadiazole-2methylthiol (MMTD-Me) while the direct
photodegradation of the two pharmaceutical intermediates
have shown that the intermediate with lower concentration
degraded faster. Vogna et al. (2004a) proposed diclofenac
oxidation using combined UV/H2O2 and ozonation
technique and were found to be feasible and viable in
bringing about complete mineralization of diclofenac. In
another study, the UV/H2O2 method was effective in
removing carbamazepine while UV alone was not
efficient to reduce the carbamazepine concentration
(Vogna et al. 2004b.
However, other AOPs such as ultrasonic irradiation
with widespread application of degrading organic
pollutants present in wastewater have equally been
examined (Shannon et al. 2008). These methods
oxidize the complex organic matter found to be
extremely difficult to degrade biologically into simpler
end products. The reported complete degradation and
mineralization potential was ascribed to the reactive
nature of the generated free active species most
predominantly hydroxyl radical (Giri et al. 2010).
The radical was reported to be non-selective and highly
reactive with higher oxidation potential of 2.33 V when
compared with other conventional oxidizing agents
such as H2O2 or KMnO4 (Gogate and Pandit 2004). Xiao
et al. (2013) combined continuous wave (CW) and
pulsed wave (PW) ultrasound to degrade carbamazepine,
ibuprofen, acetaminophen, sulfamethoxazole,
ciprofloxacin, propyl gallate, and diethyl phthalate. The
Water Air Soil Pollut (2013) 224:1770
findings showed that degradation rates of the pollutants
were quicker for smaller compounds but less rapid for
larger compounds by PW ultrasound than that achieved
under CW ultrasound. The introduction of hydroxyl
radical trapping agent, acetic acid, to PPCPs solutions
aided in degrading certain fractions within the bulk
solution that were positively interrelated with the molar
volume of the compound. Chong et al. (2012) joined an
integrated membrane bioreactor with titanium dioxide
photocatalyst (MBR-TiO2) to mineralize CBZ from
pharmaceutical wastewater. The individual systems of
MBR and TiO 2 photocatalytic technology were
monitored separately so as to establish the synergistic
operational effects. The respirometric test showed that
CBZ introduction acts as a chemical stressor that
influenced the biomass metabolism in the MBR which
resulted in the reduction of sludge yield. The combined
MBR-TiO2 system operated at 4:1 ratio condensed the
chemical stressor effects and a maximum of 95 % CBZ
removal efficiency was observed. However, despite the
success story of efficient degradation of emergent
contaminants by credited to various advanced oxidation
processes, high operational cost still limits it widely
acceptance especially in the emergent nations. Therefore,
the integration of less expensive treatment process such
as adsorption with advanced oxidation process will
further enhance and accelerate the degradation rate of
organic pollutants.
4.1.3 Combined Advanced Oxidation Processes
with Biological and Physical Treatment
As stated earlier, wastewater treatment containing
organic pollutants is complex, expensive, and timeconsuming. The survey of literatures revealed that most
wastewater treatment plants are not designed for
emergent pollutants removal. Therefore, a more
practical, versatile, and economical technique is needed.
Ever since the identification and detection emergent
micropollutants in terrestrial and aquatic environment,
numerous treatment processes such as biological and
physicochemical methods have been exploited and
explored. However, AOPs and other conventional
treatment option such as physicochemical treatment
have been applied to remove pharmaceuticals and
endocrine disruptors from wastewater. Advanced
oxidation process coupled with biological process is
not often effective against the target pollutants
degradation due to the inhibitory effect of hydroxyl
Water Air Soil Pollut (2013) 224:1770
radicals by the biomass. The physical treatment such as
filtration can be employed before or after the advanced
oxidation process. Thus, the application of physical and
biological methods helps to remove large insoluble
particles, reducing turbidity and interfering ions from
the aqueous matrix. Once all these are removed, the
degradation efficiency of AOPs will be improved. An
overview on the combined AOPs with physical or
biological treatment is as follows. Ozonation as one of
the AOPs is employed as a pre-oxidation step in a
combined treatment line. The combination of ozonation
and a moving-bed biofilm reactor to remove estrogenic
substances from a conventional activated-sludge
treatment was reported by Gunnarsson et al. (2009).
Ozonation was used as a pre-treatment step to enhance
anaerobic digestion stability of the modelled
compounds (Carballa et al. 2007). Not only that,
chemical oxygen demand solubilization of 60 % was
achieved, thus hastening the destruction of the soluble
organic matter during anaerobic digestion. Also, photoFenton process was integrated with a biological system
to degrade α-methylphenylglycine by Oller et al.
(2007a). It was observed that the combined system
enhanced the biodegradability and broad elimination
of bio-refractory compound (Oller et al. 2007). The
coupled technology was able to remove 95 % of total
organic carbon (Oller et al. 2011). José et al. (2010)
reported that the removal of carbamazepine, clofibric
acid, diclofenac, and diazepam from municipal
wastewater using biological treatment failed to
completely eliminate the pollutants, but incorporation
of membrane bioreactor and advanced oxidation
processes such as O3, O3/UV, O3/H2O2, and UV/H2O2
effectively achieved complete removal. Nakada et al.
(2007) studied the removal of some pharmaceuticals
and endocrine disruptors present in municipal
wastewater by combined sand filtration and ozonation.
It was stressed that the combined efforts of ozone and
sand filtration with sludge treatment enhanced the
elimination of 80 % of the model pollutants. Ozonation
was noted to play the dominant role. In another study,
combined advanced oxidation and a biological
treatment process was used to remove pesticides from
an aqueous matrix. It was observed that the biological
treatment assisted in removing the bulk of the chemical
oxygen demand while O3/UV enhanced the pesticide
decomposition (Lafi and Al-Qodah 2006). Rossnera
et al. (2009) utilized three different adsorbents such as
activated carbon, carbonaceous resin, and high-silica
Page 19 of 29, 1770
zeolite to remove EDCs, PPCPs, and flame retardant.
Activated carbon was only able to achieve a two-log
elimination of the modelled compounds. The
incorporation of advanced oxidation processes
enhanced the degradation rate. Badawy et al. (2009)
utilized combined Fenton and biological treatment
process to eliminate some pharmaceuticals from
industrial wastewater. The authors revealed that
recalcitrant toxic pollutants were partially removed by
biological treatment and successfully destroyed by the
Fenton process. Thus, the integrated system is more
advantageous and capable of completely eliminate
hazardous persistent pollutants in water and wastewater.
Liu et al. (2009) reviewed the removal mechanism of
endocrine disruptors in wastewater treatment using three
different methods such as physical, biodegradation, and
chemical advanced oxidation processes. The authors
recognized that physical and advanced oxidation
processes such as ozone/hydrogen peroxide are more
advantageous with respect to removal and degradation
efficiency while a biodegradation process among which
activated sludge treatment was observed to reduce the
level of EDCs in surface water. Hence, physical,
biological, and chemical advanced oxidation could be
combined to improve the removal performance of
EDCs.
5 Detection and Quantification of Emerging
Micropollutants
The contaminants of emerging concern are structurally
complex, and the probability of being highly present in
drinking water is increasing due to ever-increasing
population density driven by high demand of new
chemicals in the market (Marchesini et al. 2007). There
is a need to urgently adopt fast and sensitive analytical
protocols that can screen, detect, and quantify a large
diversity of composites concurrently. This becomes
necessary as the various known analytical equipment
including liquid chromatography combined with mass
spectrometry (LC-MS), high-performance-liquid
chromatography (HPLC), liquid chromatography
coupled with electrochemical detection (LC-ED),
capillary electrophoresis (CE), and gas chromatography
coupled with mass spectrometry (GC-MS) used so far
are not without some challenges (Gatidou et al. 2007;
Comerton et al. 2009; Mottaleb et al. 2009). Presently,
most of these instruments are too cumbersome in
1770, Page 20 of 29
analyzing samples, and despite the long sample pretreatment, the equipment can only detect or identify a
small range of similar contaminant at a time in the
matrices. Apart from this, long pre-concentration steps,
lack of rapid processing and detection of sample, and
time-consuming analysis negates the continuous use of
these analytical instruments. Also, lack of portability
and suitability during field work constitute another
challenge (Huertas-Perez and Garcia-Campana 2008;
Blazkova et al. 2009; Le Blanc et al. 2009). Not only
these, the sophisticated and costly nature of the
equipment, their labor–energy-intensive nature coupled
with the need of the derivatization of samples in the case
of (GC-MS) prior to analysis form the basis to develop
more simple and robust instrumental techniques that are
affordable, durable, and easy to maintain. Sensors and
biosensors are presently seen as a replacement to those
aforementioned instruments. Iwuoha (2012) established
that sensor materials were more sensitive in determining
and quantifying the emerging micropollutants than other
reported analytical equipment such as GC-MS. Sensors
and biosensors, for instance, are presently considered as
an alternative to those aforementioned expensive
instruments due to the ease of operation and elimination
of the pre-treatment steps, lower consumption time,
higher sensitivity, and fast responses (Yin et al. 2009).
Other benefits include easy determination of pollutants
in multifaceted media without rigorous sample
preparation (Rodriguez-Mozaz et al. 2006). Presently,
large numbers of biosensors developed are still in the
laboratory stage and need to be certified before bulk
manufacture and use (Rodriguez-Mozaz et al. 2006;
Farré et al. 2009). Apart from providing information
on the chemical composition of the sample, biological
activity such as toxicity and endocrine-disrupting effect
can also be obtained. The development of more sensors
and biosensors should be the top priority in the nearest
future. This should be standardized for easy detection
and quantification of emerging micropollutants.
Without functional and practicable analytical tools,
determination, and quantification of the environmental
fate, and behavior of these emergent pollutants will be a
mirage. However, despite the simplicity in the use of
biosensors to detect EDCs and PPCPs, one major
challenge is that biosensors is specific and can only
sense a micropollutant at a time. This mean a lot of
biosensors need to be developed which will require
additional cost and time. Therefore, simple analytical
technique such as total organic carbon (TOC) is
Water Air Soil Pollut (2013) 224:1770
recommended as a high level of TOC in water or
wastewater signifies huge pollutants load. Hence, the
water or wastewater necessitates treatment.
6 Conclusion and Recommended Interventions
Advanced oxidation processes can degrade these
contaminants without necessarily adding complex
chemicals. This is a much green and less complex route
than many other options, if energy consumption can be
reduced. Although free radicals are short-lived and do
the job rapidly without leaving long-term residues
when applied properly but need to be managed so as
not to leave partially degraded secondary pollutants.
The continuous reported adverse health challenges
occasioned by poor or partial elimination and
degradation of emerging micropollutants by single
treatment techniques in drinking water also require
urgent interventions. This means that the current single
treatment system has failed to do the job and instead of
detoxifying the contaminants acts as a point source of
environmental contamination. The removal of
PPCPs/EDCs from contaminated water is a challenging
task due to the complexity and persistence of the
pollutants in water. Thus, there is a need to urgently
adopt the use of combined advanced oxidation
techniques to treat wastewater contaminated by
emerging pollutants. Combined advanced oxidation
techniques offer the potential to drastically reduce the
health and environmental effects of persistent organic
pollutants and endocrine disruptors. Hence, the new
approaches will help to maintain public health together
with environmental sustainability. The combined
technology offers the hope that adequate water
purification will not only contribute to the production
of safer water for drinking purpose but also eliminate the
re-surfacing of by-products after single-stage
wastewater treatments. This will go a long way to
putting to rest the issue of heightened fears concerning
the safety of drinking water. Not only this, the task of
water regulatory agencies will also become less onerous
with regards the treatment of the contaminated water.
Emerging micropollutants are now recognized as a
problematic issue due to their bioaccumulation in the
environment owing to their accidental discharge. A lot
still needs to be done, among which is the establishment
of monitoring teams to enforce the environmental
regulations. There is also a great need to continuously
Water Air Soil Pollut (2013) 224:1770
carry out a thorough routine toxicological analysis of
drinking water so as to establish the exposure limits to
PPCPs/EDCs in humans. Water regulatory agencies
need to be informed of the proper treatment technique
to adopt while treating tainted wastewater. Future
research should also include re-designing and upgrading
conventional wastewater treatment plants in urban
centers to accommodate the latest technology of
degrading and mineralizing emerging pollutants. This
will contribute in no small measure to the quality of
drinking water. The research on emerging contaminants
should be extended to the developing countries where
the extent of the deterioration of water sources needs to
be established, which will aid the water industry and the
policy makers to choose the appropriate advanced water
treatment techniques to use for degrading PPCPs/EDCs
in water. Biosensors need to be further developed for
rapid detection of specific contaminants. In order to
have a natural ecosystem that is completely free of
pharmaceuticals and endocrine-disrupting compounds,
there is a need to introduce green chemistry in the
production and development of numerous drugs,
medical, and personal care products that are affordable
and do not persist in the environment. A regulatory
framework based on the precautionary principle should
be implemented to screen all compounds for their
ecotoxicity prior to approval for use.
Acknowledgments The authors acknowledge Environmental
and Nano Sciences Research Group, Department of Chemistry,
University of the Western Cape, South Africa, for the assistance.
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