Environmental Technology & Innovation: Rania Ahmed Hamza, Oliver Terna Iorhemen, Joo Hwa Tay

Environmental Technology & Innovation 5 (2016) 161–175
Contents lists available at ScienceDirect
Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti
Occurrence, impacts and removal of emerging substances of

concern from wastewater
Rania Ahmed Hamza, Oliver Terna Iorhemen ∗ , Joo Hwa Tay
Department of Civil Engineering, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
highlights
• Emerging substances of concern (ESOC) are present in water resources worldwide.
• ESOC are mutagens and carcinogens with effect on both aquatic organisms and humans.
• Conventional wastewater treatment processes are ineffective at ESOC removal.
• Membrane bioreactor technology can remove ESOC but has fouling limitation.
• Granulation technology and nano-remediation have strong potential for ESOC removal.
article info abstract

Article history: Emerging substances of concern (ESOC) have recently been detected in water resources
Received 9 September 2015 worldwide, raising human and environmental health concerns. This paper provides
Received in revised form 19 January 2016 an overview of the different classes of ESOC, their impacts, extent of removal by
Accepted 24 February 2016
conventional wastewater treatment technologies such as activated sludge process, and
Available online 2 March 2016
documented results on emerging innovative technologies. Conventional wastewater
treatment plants exhibit some limitations with respect to ESOC removal since ESOC
Keywords:
Emerging substances of concern
were not considered in their initial design. Although, advanced oxidation processes using
Granulation ozone with other oxidation agents such as UV (ultraviolet), hydrogen peroxide, titanium
Membrane bioreactor oxide, etc., prove effective, they are cost prohibitive and can produce by-products with
Nano-remediation unknown toxicity. Early results for emerging biological technologies such as membrane
Water resources bioreactors (MBRs) and granulation biotechnology indicate very promising ESOC removal.
Wastewater treatment However, membrane fouling is the main drawback of MBRs as it significantly reduces
membrane performances and membrane life resulting in an increase in maintenance
and operating costs. The main drawback of granulation technology is the deterioration
in granule stability under long-term operation and lack of a successful pilot- or full-
scale application. Thus, further research is required to abate membrane fouling in
MBRs and enhance long-term granule stability in granular systems. The technological
revolution offered by nano-materials (NMs) provides a new potential for ESOC removal
through nano-remediation. Effective removal of ESOC has been reported using nano-
adsorbents, nano-membrane filters and photocatalysts. However, the environmental fate
and the toxicological impact of NMs need to be assessed for their potential toxicity and
bioaccumulation.
© 2016 Elsevier B.V. All rights reserved.
∗ Corresponding author.
E-mail address: oliver.iorhemen@ucalgary.ca (O.T. Iorhemen).
http://dx.doi.org/10.1016/j.eti.2016.02.003
2352-1864/© 2016 Elsevier B.V. All rights reserved.
162 R.A. Hamza et al. / Environmental Technology & Innovation 5 (2016) 161–175
Contents
1. Introduction............................................................................................................................................................................................. 162
2. What are emerging substances of concern?.......................................................................................................................................... 163
2.1. Pharmaceuticals .......................................................................................................................................................................... 163
2.2. Personal care products ............................................................................................................................................................... 163
2.3. Pesticides ..................................................................................................................................................................................... 164
2.4. Surfactants................................................................................................................................................................................... 164
2.5. Disinfection by-products............................................................................................................................................................ 165
2.6. Flame retardants ......................................................................................................................................................................... 165
2.7. Perfluorinated compounds......................................................................................................................................................... 165
2.8. Nanomaterials ............................................................................................................................................................................. 165
3. Impacts of ESOC on human and environmental health ........................................................................................................................ 166
4. Removal technologies for ESOC ............................................................................................................................................................. 166
4.1. Physico-chemical treatment ...................................................................................................................................................... 166
4.2. Advanced oxidation processes ................................................................................................................................................... 167
4.3. Biological treatment ................................................................................................................................................................... 167
4.3.1. Membrane bioreactor.................................................................................................................................................. 168
4.3.2. Granulation technology............................................................................................................................................... 169
4.4. Nano-remediation ...................................................................................................................................................................... 170
5. Conclusion ............................................................................................................................................................................................... 171
Acknowledgment .................................................................................................................................................................................... 171
References................................................................................................................................................................................................ 171
1. Introduction
The purpose of wastewater treatment is to remove contaminants (pollutants) found in wastewater to acceptable levels
before discharging the treated effluent into the environment. This is to prevent human health issues and ecological hazards
arising from untreated wastewater. Over the past century, conventional technologies employed in treating municipal
wastewater include: trickling filter, activated sludge process, waste stabilization ponds, or innovative modifications of
these technologies. These technologies are effective at removing suspended solids, organics and pathogens, partial removal
of nutrients (nitrogen and phosphorus) and heavy metals. However, they are ineffective at removing a group of recently
identified substances in wastewater, collectively called emerging substances of concern (ESOC), including; pharmaceuticals,
pesticides, personal care products (PCPs), surfactants, steroids and hormones, flame retardants and plasticizers, etc.
ESOC have frequently been detected in domestic wastewaters and in almost every aquatic environment in North America,
Europe, Asia and Africa in recent years (Guerra et al., 2014; Chen et al., 2006; Richardson et al., 2005a; Sorensen et al., 2015;
Yan et al., 2015; Liu and Wong, 2013). One study showed that pharmaceuticals and PCPs were present in 80% of 139 US
streams (Onesios et al., 2009). Another study indicated that pharmaceuticals and PCPs were found to be present at high
loads reaching 80 kg/d in raw sewage in South Wales in UK (Kasprzyk-Hordern et al., 2008). In Canada, a recent Environment
Canada study identified 165 different ESOC found in Canadian water samples, and found that treated drinking water was
contaminated by excreted drugs (Crowe, 2014).
The fate and transport of many ESOC in different environmental media including soil and sediments has became a major
concern (Petrovic et al., 2008), especially with the lack of regulations on the concentration limits of ESOC in the environment
whether by the US or European Union (Bolong et al., 2009; Luo et al., 2014a; Milić et al., 2012). Only few countries
have started regulating some of these micro-pollutants. Environment Canada, for instance, has recognized nonylphenol
and nonylphenol ethoxylates as toxic substances and set limits for their concentrations in the aquatic environment, with
guideline values of 1.0 µg/L for freshwater and 0.7 µg/L for marine (CCME, 2002). In the United States, 11 disinfection
by-products (DBPs) are regulated (Richardson et al., 2007). Despite this positive development, a large number of other
unregulated DBPs exist. And recently, the United States Environmental Protection Agency (USEPA) published a new
contaminant candidate list-3 (CCL-3) to be considered for potential regulation under the Safe Drinking Water Act. The
CCL-3 contains 104 chemicals including, among others: pharmaceuticals, pesticides and their metabolites, perfluorinated
compounds, hormones, and DBPs (Richardson, 2010). In the same regard, there is a ban on perfluorooctanoic acid (PFOA)
from consumer products in Norway since 2013 (European Commission, 2011). Similarly, there is a health-based guide value
for safe lifelong exposure of PFOA for drinking water in Germany of 0.3 µg/L (Wilhelm et al., 2010).
On the global scale, many ESOC have been banned under the Stockholm Convention including aldrin, endrin,
alpha-hexachlorocyclohexane, beta-hexachlorocyclohexane, pentachlorobenzene, Chlordecone (kepone), polychlorinated
Biphenyls, etc. (UNEP, 2010). Under the same convention, the use of other ESOC have been restricted, e.g. DDT (1,1,1-
trichloro-2,2-bis (4- chlorophenyl)ethane), perfluorooctane sulfonic acid including its salts, and perfluorooctane sulfonyl
fluoride. However, considering the unavailability of adequate data, the World Health Organisation (WHO) is yet to include
most ESOC (e.g. pharmaceuticals) in its guidelines for drinking-water quality (WHO, 2011).
The aim of this paper is to identify different classes of ESOC, outline their adverse impacts on human and environmental
health, discuss the potential removal processes and identify further research needs.
R.A. Hamza et al. / Environmental Technology & Innovation 5 (2016) 161–175 163
2. What are emerging substances of concern?
Emerging substances of concern (ESOC) are a diverse group of chemical and biological agents whose health and ecological
effects are causing growing concern (Bolong et al., 2009; Estévez et al., 2012). This concern arises from the inability of
conventional municipal wastewater treatment plants (WWTPs) to remove ESOC since they were not designed to do so, and
their removal efficiency depends on the treatment technology implemented (Chen et al., 2006; Onesios et al., 2009; Petrovic
et al., 2008; Bolong et al., 2009; Luo et al., 2014a; Milić et al., 2012; Petrović et al., 2003; Esplugas et al., 2007; Kasprzyk-
Hordern et al., 2009; Chang et al., 2009; Verlicchi et al., 2012).
ESOC might not be persistent in the environment, but their high transformation and rates of removal can be offset by their
continuous introduction into the environment (Petrović et al., 2003), leading to a steady state concentration. In addition, the
disappearance of the parent ESOC does not indicate complete removal, as it can be a mere biotransformation of an unknown
degree, and the by-products formed can still be as active or toxic as the parent compound (Onesios et al., 2009; Esplugas et al.,
2007; Watkinson et al., 2007). While some ESOC themselves are not toxic, long-term exposure, even at low concentrations,
can have significant eco-toxicological effects on aquatic and terrestrial organisms (Chen et al., 2006; Petrovic et al., 2008;
Petrović et al., 2003; Esplugas et al., 2007).
ESOC enter receiving waters via municipal WWTP effluents, agricultural runoff, industrial effluents, hospital effluents,
septic tanks, subsurface storage of household and industrial waste (Chen et al., 2006). Other sources of ESOC include:
landfills, inappropriately disposed wastes and leaking sewer lines (Pal et al., 2014). They typically occur in waters at very low
concentrations, ranging from few nanograms per liter to several micrograms per liter (Luo et al., 2014a). These trace levels
of ESOC make it difficult for commonly used analytical instruments to directly detect them (Petrović et al., 2003), coupled
with the fact that ESOC exhibit a wide range of physico-chemical characteristics (Bolong et al., 2009). For instance, it has
been indicated that the absence of penicillin residues in water, despite its wide use, is attributed to the lack of sophisticated
analytical methods and equipment to detect their presence (Milić et al., 2012).
There are different groups of ESOC including pharmaceuticals, personal care products, pesticides, surfactants, disinfection
by-products, artificial sweeteners, plasticizers, flame retardants, hormones, and steroids, perfluorinated compounds,
nanomaterials etc. Some of these groups are discussed briefly below, namely: pharmaceuticals, personal care products,
pesticides, surfactants, disinfection by-products, flame retardants, perfluorinated compounds, and nanomaterials.
2.1. Pharmaceuticals
Pharmaceuticals refer to prescription and non-prescription drugs for human and veterinary use and their metabolites.
Their primary routes of entry into the environment include human excretion, veterinary usage and disposal of unused
products (Stuart et al., 2012). Many antibiotics that are used in veterinary medicine, which are FDA (Food and Drug
Administration) approved, are not merely used for therapy, but are added to the water and feed for promoting animal
growth, thus ending up in our surface and drinking waters. It is estimated that 30%–90% of these antibiotics are excreted
from the bodies of humans and animals as active substances (Chen et al., 2006).
There are different pharmaceutical sub-groups depending on usage. These include: antibiotics (e.g. amoxicillin,
chloramphenicol, ciprofloxacin, norfloxacin, and erythromycin), antidepressant (e.g. venlafaxine), antiepileptic drugs (e.g.
carbamazepine, gabapentin, and primidone), nonsteroidal anti-inflammatory drugs abbreviated as NSAID (e.g. ibuprofen,
naproxen, diclofenac, and acetaminophen), cytostatic drugs (e.g. cyclophosphamide, and ifosfamide), illicit drugs (e.g.
cocaine, and amphetamines) and hormones (e.g. 17α -estradiol, 17β -estradiol, estrone, estriol, and ethinylestradiol).
Antibiotics in particular have received special attention due to their wide application in both human and veterinary therapy
(Liu and Wong, 2013). Continuous exposure to the antibiotics group of pharmaceuticals can lead to the emergence of
resistant strains of bacteria with attendant health concerns (Zhang et al., 2009). Hormones are linked with endocrine
disrupting effect in polluted waters (Lai et al., 2002).
It is estimated that the sales of prescription drugs in Canada increased by approximately US$8 billion between 2006 and
2011 (IMS Health Canada, 2012) as cited by Guerra et al. (2014). This extensive and growing use of pharmaceuticals raises
serious concern.
2.2. Personal care products
Personal care products (PCPs) are substances applied externally on the human body. Examples of PCPs include: perfumes,
soaps, cosmetics, lotions, sunscreens, etc. Due to their external body applications, PCPs do not undergo any metabolic
changes prior to their release into the environment (Pal et al., 2014). The variety of chemicals found in PCPs have been
described as potentially hormone disrupting substances (Den Hond et al., 2013). As a result of their daily extensive use,
PCPs are continuously released into the environment via showering, bathing and cleaning (Birch et al., 2015). Thus, this
group of micropollutants are now present in the environment at increasing concentrations (Regueiro et al., 2009). Many
PCPs are bioactive, environmentally persistent and have the potential of bioaccumulation (Brausch and Rand, 2011). Just
like pharmaceuticals, the main entry route of PCPs into the environment is municipal WWTP effluents.
There are different sub-groups of PCPs including musk fragrances, antimicrobial compounds, sunscreen agents, insect
repellents, and preservatives. Two widely used musk fragrances are nitro and polycyclic musks. These substances are found
in almost all consumer products (e.g., deodorants, perfumes, cosmetics) (Pietrogrande and Basaglia, 2007).
Triclosan is a typical compound under antimicrobial compounds that is used in many consumer products (e.g., toothpaste,
detergents, toilet soaps, deodorants). Triclosan is known to exhibit acute and chronic toxicity to aquatic organisms.
A metabolite of triclosan, methyl-triclosan, is more lipophilic and environmentally persistent compared to its parent
compound (Pietrogrande and Basaglia, 2007; Lindström et al., 2002; Balmer et al., 2004).
Sunscreen agents are added to lotions and cosmetics to protect against harmful UV (ultraviolet) radiation, e.g.
methylbenzylidene camphor. Sunscreen agents are lipophilic, thus showing a potential for bioaccumulation (Pietrogrande
and Basaglia, 2007; Balmer et al., 2005). They have also been reported to show estrogenic activity (Schlumpf et al., 2001).
Under the insect repellents sub-group of PCPs, DEET (N,N-diethyl-m-toluamide) and Bayrepel (e.g., 1-piperidinecarboxylic
acid, and 1-methylpropyl ester) are the most widely used (Westerhoff et al., 2005). Though there is limited data, it has been
indicated that DEET has some toxicity to aquatic invertebrates, fish and birds (Pietrogrande and Basaglia, 2007; Trenholm
et al., 2006).
Preservatives are substances added to final products to prevent decomposition due to microbial growth or by undesirable
chemical changes (Jiménez-Díaz et al., 2014). Parabens are commonly used as preservatives. Methylparaben, ethylparaben,
propylparaben, butylparaben, and benzylparaben are the most widely used either individually or in combination due to their
synergistic effects (Figueiredo et al., 2016; Lee et al., 2005). Parabens are known to exhibit estrogenic behavior (Canosa et al.,
2006; Silva et al., 2002).
2.3. Pesticides
Pesticides are extensively used in agriculture and forestry, horticulture, parks, industrial sites, public spaces, golf courses,
educational facilities, etc. Pesticides are typically used for grass management, industrial vegetation control, and public health
uses (rodent-control areas, and mosquito-abatement) (Köck-Schulmeyer et al., 2013). They operate by repulsion, prevention,
mitigation, or destruction of pests and/or weed.
On the basis of target, pesticides can be classified into: insecticides (insects), herbicides (weed), bactericides (bacteria),
fungicides (fungi), miticides (mites and ticks), and molluscicides (slugs and snails) (Arias-Estévez et al., 2008). Others
include: nematicide (nematode), wood preservative (wood-destroying organisms), and rodenticide (rodents). Based
on the chemical structure, pesticides fall into the following classes: organophosphates pesticides e.g., fenitrothion,
chlorpyrifos, malathion, dichlofenthion and diazinon; organochlorine pesticides e.g., chlorothalonil, dichloro-diphenyl-
trichloroethane (DDT), lindane, and endosulfan; carbamates pesticides e.g. formetanate, carbetamide, carbofuran;
chlorophenol pesticides e.g., 2-,3-,4-chlorophenols, 2,5-,2,6-dichlorophenols, and 2,3,5-trichlorophenol; and synthetic
pyrethroids e.g., deltamethrin, and tefluthrin.
In the course of applying pesticides to crops, they reach the soil via precipitation, irrigation water, or wind-induced
untargeted movement of the pesticide droplets or residues (Pal et al., 2014). These pesticides then enter surface waters and
groundwater from the soil through runoff and infiltration as well as from municipal WWTP effluents. It has been indicated
that many pesticides persist for in an ecosystem for long periods; and this their persistence in the food chain can result in
biomagnifications (Arias-Estévez et al., 2008).
2.4. Surfactants
Surfactants are chemicals used extensively in a wide range of applications, including the production of detergents, resins,
paints, pesticides, lubricants, etc. On the basis of dissociation in water, surfactants can be classified into anionic, non-ionic,
cationic, and amphoteric surfactants (Salager, 2002). Anionic surfactants dissociate into an amphiphilic anion (exhibiting
both hydrophilicity and lipophilicity) and a cation, e.g., alkylbenzene sulfonates, lauryl sulfate, dialkyl sulfosuccinate, and
lignosulfonates. Non-ionic surfactants do not ionize as their hydrophilic group is the non-dissociable type, as such, they do
not react with calcium and magnesium in water. Examples of non-ionic surfactants include ethoxylated aliphatic alcohol,
polyoxypropylene glycol, and carboxylic esters. Cationic surfactants dissociate in water into an amphiphilic cation and an
anion (mostly the halogen type), e.g., quaternary ammonium salts. Amphoteric (or zwitterionic) surfactants exhibit both
cationic and anionic dissociations, e.g. betaines, sulfobetaines and phospholipids. And recently, polymeric surfactants (or
surface active polymers) have been introduced and are extensively used in the production of cosmetics, paints, foodstuffs,
and petroleum production additives. Polymeric surfactants result from the association of one or several macromolecular
structures exhibiting hydrophilic and lipophilic characters, either as separated blocks or as grafts.
Surfactants find their way into the environment as a result of domestic use (house cleaning), urban uses (street cleaning,
and industrial uses (detergent, textiles, petrochemical and pharmaceutical industries) (Borghi et al., 2011). It is estimated
that around 50% of surfactants production is emitted through WWTPs into surface waters. While some of these surfac-
tants biodegrade to non-toxic compounds before reaching the environment, concerns have been raised about alkylphenol
ethoxylates (APEs) and their degradation products as potential endocrine disrupters (Petrovic et al., 2002). APEs can be bio-
transformed into alkylphenols, e.g. 4-tert-octylphenol, and 4-nonylphenol (Pal et al., 2014; Caliman and Gavrilescu, 2009).
These metabolites are more toxic than their parent compounds (Caliman and Gavrilescu, 2009). Both the parent ethoxylates
and their metabolites, alkyl phenols and carboxylic degradation products, persist in the aquatic environment (Stuart et al.,
2012). In addition, while some surfactants are not toxic to humans, they retain their foaming properties in natural waters
in concentrations as low as 1 mg/L, which is aesthetically undesirable in drinking water (Yapijakis and Wang, 2004).
2.5. Disinfection by-products
Disinfection by-products (DBPs) are produced when disinfectants (chlorine, chloramines, chlorine dioxide, or ozone)
react with natural organic matter (NOM), anthropogenic contaminants, bromide, and iodide during water treatment
(Richardson et al., 2007). Chlorinated disinfection agents react with NOM, iodide and bromide ions to form DBPs such as the
trihalomethanes (THMs), haloacetic acids (HAAs), halonitromethanes, haloamides, haloacetonitriles, etc. Examples of THMs
are trichloromethane, bromodichloromethane, bromochloroiodomethane, chlorodiiodomethane, dibromoiodomethane,
dichloroiodomethane, etc. Examples of HAAs include: monochloroacetic acid, dichloroacetic acid, trichloroacetic acid,
monobromoacetic acid, etc.
Non-chlorinated disinfectants, despite significantly reducing or eliminating the formation of THMs and HAAs, also
produce DBPs. For instance, ozone produces DBPs such as ketones, bromates, carboxylic acids, and aldehydes.
In general, over 600 different DBPs have been identified (Richardson et al., 2007; Boorman et al., 1999). This is a concern
because DBPs have been indicated as potential endocrine disrupting compounds (EDCs) (Chang et al., 2009; Caliman and
Gavrilescu, 2009) as well as having carcinogenic potential (Pal et al., 2014). It has been indicated that brominated DBPs are
both more genotoxic and carcinogenic compared to chlorinated DBPs (Richardson et al., 2007). Iodinated DBPs, in addition
to causing medicinal tastes and odors in drinking water, are the most toxic, when compared to brominated and chlorinated
compounds (Krasner, 2009).
2.6. Flame retardants
Flame retardants are chemicals that are added to manufactured materials (e.g., textiles and plastics) and surface finishes
and coatings to inhibit combustion or delay the spread of fire after ignition (van der Veen and de Boer, 2012). These
compounds are either mixed with the base material (additive flame retardants) or chemically bonded to it through
reaction (reactive flame retardants). Flame retardants are sub-divided into: organohalogen compounds, organophosphorus
compounds, and mineral flame retardants.
Organohalogen compounds have the following as typical examples: chlorinated paraffins, tetrabromobisphenol A
(TBBPA), hexabromocyclododecane (HBCD), and decabromodiphenyl ether (decaBDE) (de Wit, 2002). Organophosphorus
compounds used as fire retardants include: triphenyl phosphate (TPP), tricresyl phosphate (TCP), and bisphenol A diphenyl
phosphate (BADP) (van der Veen and de Boer, 2012). Common examples of mineral flame retardants include: aluminum
hydroxide, magnesium hydroxide, huntite and hydromagnesite (Hollingbery and Hull, 2010; Hull et al., 2011).
Due to the inevitable use of flame retardants, they enter the environment through waste disposal to landfill and
incineration (Stuart et al., 2012). Organohalogen compounds have been found to leach out of polymers into the environment;
and some are proven EDCs (de Wit, 2002; Shaw, 2010).
2.7. Perfluorinated compounds
Perfluorinated compounds (PFCs) are anthropogenic chemicals that have been incorporated into a wide range of products
(Lindstrom et al., 2011) including wetting agents, surfactants, emulsifiers, aviation hydraulic fluids, additives, fire-fighting
foams, adhesives, paints, waxes, polishes, etc. (Pal et al., 2014). PFCs are characterized by a fully fluorinated, hydrophobic
carbon chain attached to various hydrophilic end groups with unique physicochemical characteristics, such as chemical and
thermal stability, low surface free energy and surface active properties (Fromme et al., 2009).
PFCs comprise numerous chemicals out of which the most widely used are perfluorosulfonates such as perfluorooctane
sulfonate (PFOS), and the perfluorocarboxylic acids which include perfluorooctanoic acid (PFOA) (DeWitt et al., 2012). PFOS
and PFOA have been considered to be of great concern due to their persistence, potential to bioaccumulate, and the possibility
of biomagnifications (Lehmler, 2005).
PFCs enter the environment primarily through manufacturing industries discharges and effluents from WWTPs (Pal et al.,
2014). These compounds have been detected in water bodies, drinking water and in tissues of aquatic organisms worldwide
(Fromme et al., 2009; Ahrens et al., 2009; So et al., 2007; Kannan et al., 2005; D’Eon et al., 2009). PFCs are toxic, extremely
resistant to degradation, bioaccumulate in food chains, and can have long half-lives in humans (Lindstrom et al., 2011).
2.8. Nanomaterials
Nanomaterials (NMs) are functional materials consisting of particulates with at least one dimension below 100
nanometers (nm) (Grimsdale and Müllen, 2005). NMs are at the core of an emerging technological revolution due to
their possession of unique electronic, thermal, mechanical, and biological properties not found in conventional materials
(Scida et al., 2011). Generally, the properties of NMs are significantly different from the corresponding bulk material. Silver
NMs, for example, show antibacterial activity that does not exist in silver (Grimsdale and Müllen, 2005). The combination
of the unique properties of NMs has given rise to systems with significantly enhanced performance (Engel et al., 2008).
NMs have found extensive applications in Physical and Chemical Sciences, Biological Science, Engineering, Environmental
Management and Computer Science.
There are different sub-groups of NMs including metal-based NMs, fullerenes, carbon nanotubes (CNTs), and organic
NMs. Examples of metal-based NMs include titanium dioxide, iron oxide, zinc dioxide, etc. which are used in the production
of sunscreens, cosmetics, surface coatings and some food products. Fullerenes (e.g. C60 nanoparticles) are extensively used
in biomedical applications. CNTs (single-walled, multi-walled, and functionalized CNTs) are used as additives for polymer
composites, as adsorbents in water purification and gas uptake, and in the production of batteries and fuel cells (Ravi
and Vadukumpully, 2016; Patil et al., 2016). Organic NMs are used in the production of micronized drugs and chemicals
(pigments, pharmaceuticals, vitamins) as well as polymer dispersions (Lauterwasser, 2005).
Due to their growing use, issues about risks of the possible release of NMs into the environment and subsequent impacts
on human and environmental health have taken the front burner (Hernando et al., 2011; Brar et al., 2010). Taking into
consideration the parameters that characterize nanoparticles such as size, shape, specific area, chemical composition and
the properties they possess that are very different from the bulk materials, little is known regarding the toxicological
and ecotoxicological impacts of the majority of NMs. It has been indicated that durable, biopersistent nanoparticles may
accumulate in the body, in particular in the lungs, liver, and brain (Lauterwasser, 2005). In addition, the potential interaction
of nanoparticles with the cells that they have entered raises alarming signals to possible interactions with cell structures
such as ribosomes and DNA (Lauterwasser, 2005).
Looking at the above groups of ESOC, pharmaceuticals will be continuously produced and administered on humans
and animals; pesticides will still be in continuous use; the use of surfactants, flame retardants and PCPs will not decline;
industries will continue to use chemicals for their daily activities; and nanotechnology will maintain its advancement. This
makes the search for an efficient technology for their removal a very pressing issue.
3. Impacts of ESOC on human and environmental health
ESOC affect human and environmental health due to their toxicity. They are potential mutagens and carcinogens (Milić
et al., 2012). Some adverse effects have been reported including, a growing resistance of vast groups of bacteria. Resistant
and multi-resistant bacteria have been detected in wastewater and sewage treatment plants that can enter the food chain
directly through sewage sludge, which is used as soil conditioner, or via wastewater used for irrigation (Richardson et al.,
2005a; Milić et al., 2012).
Aquatic organisms such as algae and daphnids (Dophnia magna) can be adversely affected (Milić et al., 2012; Watkinson
et al., 2007). Endocrine disruption, and abnormalities in aquatic organisms have been reported to affect the health of humans
and animals species (Chen et al., 2006; Richardson et al., 2005a; Petrovic et al., 2008; Bolong et al., 2009; Petrović et al., 2003;
Esplugas et al., 2007). Feminization and masculinization by hormones and xenoestrogens have also been reported as major
concerns (Richardson et al., 2005a).
Other documented changes include: abnormal ratios of estrogen and testosterone in juvenile alligators in Lake Apopka,
Florida, sexual abnormalities in fish living near WWTP outfalls, and impairment of immune functions and reproductive
dysfunction in fish (Bolong et al., 2009). Further adverse effects of ESOC are: amphipod population and sex ratio changes,
inhibition of cytochrome and other enzymes of gizzard shad liver cells and spotted seatrout estrogen receptor antagonist.
(Richardson et al., 2005a) as well as adverse effects regarding fish stress performances leading to possible reduced fitness
(Ings et al., 2011).
Furthermore, it has been indicated that refractory and biodegradable surfactants interfere with the self-purification
process in water bodies, with the former being inhibitory to microorganisms, and the later imposing high loading and
resulting in possibly anaerobic conditions (Yapijakis and Wang, 2004). Moreover, polyphosphate builders that are used
to enhance the action of laundry detergents contribute to eutrophication in water bodies (Khan and Ansari, 2005).
In humans, despite limited data, the USEPA has reported that PFCs and polybrominated diphenyl ethers accumulate in
human tissue or blood, and are associated with health effects including endocrine disruption (USEPA, 0000). Other human
health impacts attributed to the exposure to ESOC include: decrease in male sperm count, an increase in ovarian, prostate,
testicular, bladder, prostate and breast cancer as well as reproductive malfunctions (Joffe, 2001; Villanueva et al., 2007;
Costet et al., 2011).
It is alarming enough that these are considered early effects of exposure to ESOC. There is potential for more severe
adverse effects on humans and aquatic organisms.
4. Removal technologies for ESOC
4.1. Physico-chemical treatment
Physico-chemical treatment involves the use of physical and chemical processes in water and wastewater treatment.
Coagulation/flocculation using alum and iron salts followed by sedimentation have been reported to be ineffective at ESOC
removal (Esplugas et al., 2007; Adams et al., 2002). In a study in which seven common pharmaceuticals were evaluated,
Adams et al. (2002) reported that sorption onto powdered activated carbon (PAC), reverse osmosis, and oxidation with
chlorine and ozone were effective under typical water treatment plant operational conditions. Similarly, Westerhoff et al.
(2005) investigated the removal of 64 different ESOC using aluminum sulfate and ferric chloride coagulants or chemical lime
softening. They reported poor removal (<25%) of most ESOC; however, upon addition of 5 mg/L PAC with a 4-hour contact
time, the removal efficiency increased to 50% → 98% (Westerhoff et al., 2005). The study concluded that coagulation plus
chlorination exhibits poor ESOC removal; but the addition of PAC and/or ozone could significantly improve their removals. It
has also been reported that ESOC pass through the filtration unit operation and reach our drinking water (Milić et al., 2012;
Petrović et al., 2003; Petrie et al., 2015). For activated carbon, removal efficiencies in the range 60%–90% have been reported
for estrogens, 17α -estradiol, and 17β -estradiol (Esplugas et al., 2007).
Therefore, in general, ESOC are not significantly removed by common physico-chemical processes such as coagulation/
flocculation and media filtration.
4.2. Advanced oxidation processes
Advanced oxidation processes (AOPs) use a combination of ozone with other oxidation agents such as UV, hydrogen
peroxide, titanium oxide, etc. AOPs are usually applied after biological treatment as an effluent-polishing unit process. The
hydroxyl radical is the strongest known radical as it can oxidize almost all organic molecules into CO2 and inorganic ions
(Petrović et al., 2003; Esplugas et al., 2007; Chang et al., 2009; Kim and Tanaka, 2009). Ozonation accounts for approximately
90% of dark oxidation processes, achieving higher removal efficiencies for natural and synthetic estrogens, while substances
such as clofibric acid and X-ray contrast agents show recalcitrance to the oxidation (Petrović et al., 2003; Ikehata et al., 2008).
Studies by Rosal et al. (2008) and Rosal et al. (2010) found that ozonation of WWTP effluents achieved over 99% removal
efficiency of pharmaceuticals and some relevant metabolites. However, some PCPs were not significantly removed in the
ozonation unit process.
Another dark oxidation method is the Fenton treatment. It is considered to be a metal-catalyzed oxidation reaction, in
which iron acts as the catalyst. Fenton reagent occurs in the presence of ferrous or ferric ions with hydrogen peroxide through
a free radical chain reaction which produces hydroxyl radicals. Fenton treatment is used in industrial wastewater treatment
to treat residual pharmaceuticals in industrial effluents (e.g. hazardous hospital wastes or from drug manufacturing) with
increased organic loading. However, the major drawbacks of ferrous or ferric salts usually are: the narrow pH range (2–4)
of operation to avoid the formation and subsequent precipitation of iron oxyhydroxides, and the recovery of dissolved ions
from the treated solution, which requires an additional treatment stage (Klavarioti et al., 2009).
For light oxidation processes, UV/H2 O2 and titanium dioxide are the most commonly used. A study using light oxidation
processes for the removal of some selected ESOC reported removal efficiency higher than 98% for estrogens (17α -
ethinylestradiol, 17β -estradiol, and estrone) bisphenols and antiepileptics) (Petrović et al., 2003; Ikehata et al., 2008).
Another study reported 100% degradation of p, p′ -DDT using N-doped TiO2 catalyst under visible light (Ananpattarachai
and Kajitvichyanukul, 2015).
However for sufficient degradation (>90%), the ozone concentration has to be high enough to oxidize the dissolved
organic carbon (Petrović et al., 2003), which makes it economically unfeasible. Similarly, to achieve high removals in light
oxidation processes, large irradiation times are required compared to dark ozonation processes (Esplugas et al., 2007).
Moreover, the fate of ESOC need to be investigated as ozonation can produce by-products that may be as biologically active
(or toxic) as the parent compounds (Petrović et al., 2003).
4.3. Biological treatment
Biological wastewater treatment provides excellent economic advantages over other treatment processes not only in
terms of capital investment and operating cost (Mittal, 2011), but also the opportunity to convert waste into renewable
energy sources (Tay et al., 2010). Moreover, biological treatments can efficiently degrade industrial compounds without
generating toxic by-products (Zhao et al., 2015; Baêta et al., 2015). However, conventional biological treatment processes
exhibit some limitations including low biomass concentration and poor settling ability of microorganisms (in the form of
flocs) (Chan et al., 2012; Grady et al., 2011). In addition, anaerobic treatment suffers from low stability, high sensitivity
to toxic loadings and fluctuations in environmental conditions (Rajeshwari et al., 2000; Leitão et al., 2006), and results in
effluent quality that usually fails to comply with the standards (Ahammad et al., 2013). Furthermore, ESOC are usually not
readily biodegradable compounds which cannot be completely broken down or converted into biomass (Bolong et al., 2009).
Several studies have been conducted to evaluate the removal of ESOC via biological treatment processes. A study
conducted in Australia to assess the removal of 28 human and veterinary antibiotics in conventional activated sludge system
indicated that the concentration of antibiotics was reduced by an average of 87% in the liquid phase during conventional
primary and secondary treatment, with the majority of removal attributed to biological treatment (Watkinson et al., 2007).
On the other hand, it has been demonstrated that compounds such as steroid estrogen cannot be completely broken down
or converted into biomass. At neutral pH, most acidic pharmaceuticals appear as ions and remain in the water phase, thus
cannot be removed by or adsorbed onto the activated sludge. However, acidic conditions can promote the transfer, by
adsorption, of substances from the water phase to the sludge phase and not by biodegradation (Bolong et al., 2009). But
less than 10% removal of these compounds is attributed to adsorption.
Another study conducted by Guerra et al. (2014) in Canada on five different wastewater treatment processes: facultative
and aerated lagoons, chemically-enhanced primary treatment, secondary activated sludge, and advanced biological nutrient
removal, showed that pharmaceuticals and PCPs were detected in all WWTP influents at median concentrations of 1.5 to
92,000 ng/L, with no seasonal differences. Pharmaceuticals and PCPs were also found in all final effluents at median levels
ranging from 3.6 to 4200 ng/L with higher values during winter. Removal efficiencies ranged from 450% to 120%, depending
on the compound, WWTP type, and the season. This indicates that in some instances, the concentration of pharmaceuticals
and PCPs in the effluent increased rather than decreasing. In general, better removals were obtained in facultative lagoon
during summer, where analgesic/anti-inflammatory compounds, antibiotics, and antifungal/antibacterial compounds had
removals higher than 84%. Activated sludge and advanced biological nutrient removal processes showed high removals
(>90%) for most analgesic/anti-inflammatory compounds, yet antibiotics had removal rates lower than 50%. Plants with
chemically-assisted primary treatment processes presented the lowest removals for all pharmaceuticals and PCPs. Similarly,
Matamoros et al. (2015) studied the removal efficiency of ESOC by high-rate algal ponds (HRAPs) operated at hydraulic
retention times (HRTs) of 4 d and 8 d. Their findings indicate that the removal efficiency ranged from negligible removal to
more than 90% depending on the compound. In addition, studies using trickling filter in Canada and Brazil indicated that
the technology is ineffective at removing estrogen due to low solid retention time (SRT) and HRT (Bolong et al., 2009).
Most studies on biological treatment processes confirmed that operational conditions play a major role in ESOC removal.
Summer temperatures, long HRTs, and nitrifying conditions contribute to better removal efficiencies. In order to enhance
the capacity of biological treatments for ESOC removal, suggestions have been to operate at SRT ranging from 10–35 days
and HRT ranging from 16–27 days, depending on the temperature (Guerra et al., 2014; Bolong et al., 2009; Verlicchi et al.,
2012; Matamoros et al., 2015). Moreover, it has been reported that a long SRT promotes the adaptation of different kinds
of microorganisms, as well as the presence of slower growing species that could have a greater capacity for removing
xenobiotics (Verlicchi et al., 2012). Nitrification conditions can improve the biotransformation of xenobiotics (Guerra et al.,
2014) and some micro pollutants such as ethnylestradiol were found to be oxidized to a more hydrophobic compound
(Bolong et al., 2009).
The removal mechanism of most ESOC is attributed to biodegradation as well as sorption to sludge (Guerra et al., 2014;
Bolong et al., 2009; Verlicchi et al., 2012). It has been indicated that biodegradation is the predominant removal mechanism
for analgesic/anti-inflammatory compounds, while antibiotics and antifungal compounds tend to sorb to sludge. However,
Zhao et al. (2015) reported in their study that sludge had a weaker adsorption capacity to antibiotics as well as ibuprofen,
which appeared to be removed primarily due to degradation during the biological treatment. Moreover, some results
indicated a negative removal for antibiotics, where increase in their concentration was attributed to their re-dissolution
from bile and feaces during wastewater treatment and the presence of conjugate compounds not analyzed in the influent
which retransform into the original compound during the treatment (Guerra et al., 2014; Verlicchi et al., 2012).
For effective ESOC removal, it has been suggested that combined anaerobic–aerobic systems may provide a solution
(Ahammad et al., 2013). Such combination has been found to be able to biodegrade chlorinated aromatic hydrocarbons,
phenols, and heavy metals. The mechanism was attributed to anaerobic reduction of Fe(III) and microacrophilic oxidation
of Fe(II) with production of fine particles of iron hydroxide for adsorption of organic acids, phenols, cyanide, radionuclides,
and heavy metals (Chan et al., 2009; Tauseef et al., 2013). However, it is not known whether the treatment processes can
totally degrade ESOC to carbon dioxide and water, if the ESOC are retained in the sludge, or if they are metabolized to a
more hydrophilic but still persistent form (Richardson et al., 2005b). The mechanism of removal is still not fully understood.
In addition, work is needed on anaerobic reactor design to reduce inhibition on key methanogens in the reactor microbial
consortia for increase in biogas production (Ahammad et al., 2013).
Two recent biological treatment processes that have been indicated for the removal of ESOC are membrane bioreactor
and granulation technology. These are briefly discussed below.
4.3.1. Membrane bioreactor

Membrane bioreactor (MBR) has emerged as an efficient compact technology for municipal and industrial wastewater
treatment. An MBR is a hybrid of conventional biological treatment system and physical solid–liquid separation by
membrane filtration (Tay et al., 2007; Chang et al., 2002; WEF, 2011) in one system. The inclusion of the membrane module
in the system eliminates the need for secondary clarifier. Generally, membrane processes include: microfiltration (MF),
ultra-filtration (UF), nanofiltration (NF) and reverse osmosis (RO). For MBR applications, MF and UF are the commonly used
processes because the separation mechanism required is straining (size exclusion) (Mutamim et al., 2013); thus, allowing
for the complete physical retention of bacterial flocs and virtually all suspended solids within the bioreactor (Le-Clech et al.,
2006). MBRs have been successfully used for both municipal and industrial wastewater treatment and reclamation (Le-Clech
et al., 2006; Friha et al., 2014; Chu et al., 2006; Ueda and Hata, 1999).
Typically, an MBR provides the following advantages over the conventional activated sludge process: high-quality
effluent, higher volumetric loading rate, shorter HRT, longer SRT, low sludge production, potential for simultaneous
nitrification/denitrification in long SRTs, and smaller footprint (Vargas et al., 2008; Tchobanoglous et al., 2003; Tu et al.,
2010a; Meng et al., 2009). The MBR technology is one of the most effective technologies in biological wastewater treatment
in recent decades (Le-Clech et al., 2006; Meng et al., 2009; Thanh et al., 2013; Drews, 2010) due to its long SRT, thus,
prolonged organisms acclimatization time to toxicity and recalcitrants.
The prolonged acclimatization of organisms due to long SRTs is suitable for ESOC removal. In addition, the complete
retention of bacterial flocs prevents slow-growing microorganisms such as nitrifiers from washing out (Hai et al., 2011).
Research findings have confirmed the enhanced removal of ESOC such as halogenated hydrocarbons, phenolic compounds
and steroid hormone by nitrifying bacteria (Hamid and Eskicioglu, 2012; Kim et al., 2007; Roh et al., 2009). In terms
of removal mechanism, both biodegradation/transformation and adsorption play significant roles in ESOC removal in
MBRs with biodegradation being the principal removal mechanism for hydrophilic compounds and adsorption being most
the important pathway for hydrophobic compounds (Wijekoon et al., 2013). To assess ESOC removal in MBR, Wijekoon
et al. (2013) investigated the removal of 29 different ESOC cutting across pharmaceuticals, PCPs, and pesticides at typical
concentrations that they occur in municipal wastewater (5 µg/L). All hydrophobic ESOC showed removal efficiency in excess
of 88% from the aqueous phase while the hydrophilic ESOC exhibited removal efficiencies ranging from 80% to 100% with the
exception of four (diclofenac—27%, atrazine—36%, propoxur—58%, and carbamazepine—58%). Another study also reported
95.7%–99.5% ESOC (phenolic compounds and phthalic acid esters) removal in a two-stage MBR (Boonnorat et al., 2014). To
enhance ESOC removal, Nguyen et al. (2013b) augmented the MBR with white-rot fungus and investigated the degradation
of 30 ESOC covering pharmaceuticals, PCPs, pesticides, steroid hormones and phytoestrogens. Results from this study show
significant removal of ESOC resistant to bacterial degradation and exhibited better overall ESOC removal efficiency compared
to the conventional MBR. Other techniques for MBR enhancement to ensure satisfactory ESOC removal include: introduction
of reverse osmosis downstream of MBR (MBR-RO) (Dolar et al., 2012), inclusion nanofiltration downstream of MBR (MBR-NF)
(Chon et al., 2012), and incorporation of granular activated carbon to enhance adsorption capacity (Nguyen et al., 2013a).
However, membrane fouling is the major limitation impeding the wider application of the MBR technology (Meng
et al., 2009; Tu et al., 2010b; Kimura et al., 2005). Membrane fouling in MBRs is attributable to suspended particulates
(microorganisms and cell debris), colloids, and solutes. (Meng et al., 2009). These materials deposit on the membrane surface
and/or inside its pores leading to a decline in the permeability of the membrane. Membrane fouling significantly reduces
membrane performances and membrane life resulting in a significant increase in maintenance and operating costs (Chang
et al., 2002; Wei et al., 2011). In MBR, bacteria and their waste products, extracellular polymeric substances (EPS), have been
identified as the major foulants. (Meng et al., 2009; Chang and Lee, 1998; Lin et al., 2014; Jang et al., 2006).
One current area of research on membrane fouling abatement in MBR is the integration of a novel biotechnology – aerobic
granulation (discussed in Section 4.3.2.) – with MBR to enhance system performance (Tay et al., 2007; Tu et al., 2010b;
Li et al., 2005; Juang et al., 2011). In the aerobic granulation membrane bioreactor (AGMBR), EPS are utilized for granule
formation; and the granules provide a surface for bacteria to attach to rather than the membrane surface. Additionally, the
large size and rigid structure of the granules expectedly reduce cake-layer formation, pore blocking and surface deposition
on the membrane surface. Preliminary results show significant system improvement in terms of membrane fouling (Tay
et al., 2007; Thanh et al., 2013; Yu et al., 2009; Wang et al., 2013; Vijayalayan et al., 2014). However, AGMBR is still in the
development phase with limited data with respect to removal of ESOC.
4.3.2. Granulation technology

Granulation technology is an emerging biotechnology with a great potential to remove ESOC. Granulation was first
identified in an upflow anaerobic sludge blanket (UASB) system in the 1980s (Hulshoff Pol et al., 2004; Lettinga et al., 1980;
Hulshoff Pol et al., 1987) and aerobic granulation was developed in the late 1990s (Moy et al., 2002; Tay et al., 2001; Beun
et al., 1999). The granules are aggregates of microorganisms that form through microbe-to-microbe self-immobilization
in the absence of any medium (Beun et al., 1999). They are dense microbial consortia containing several microbial species
(typically millions of organisms per gram of biomass) that can collectively degrade pollutants in wastewater (Tay et al., 2009).
The merits of the granulation technology over conventional biological treatment systems include: small footprints, better
settling properties, high biomass retention (hence less sludge production), ability to withstand high-strength wastewater,
tolerance to toxicity and resistance to shock loading when compared to suspended cultures (Liu and Tay, 2004; Adav et al.,
2008; Luo et al., 2014b; Maszenan et al., 2011; El-Kamah et al., 2010; Saleh and Mahmood, 2003).
Researchers have emphasized the importance of microbial diversity and acclimatization of biosolids to the target
contaminants (Watkinson et al., 2007). The microbial diversity offered by granular sludge provides a great potential in
removing ESOC. In an attempt to evaluate the efficiency of aerobic granular sludge in removing pharmaceuticals, Zhao
et al. (2015) investigated the removal of five representative pharmaceuticals namely, ibuprofen, naproxen, prednisolone,
norfloxacin, and sulfamethoxazole using aerobic granular sequential bioreactor. The granular sludge effectively removed
some but not all of the initial concentrations of pharmaceuticals, with removal efficiency ranging from 45% (for ibuprofen)
to 84% (for prednisolone). It was found that although the removal efficiency was poor during the initial dosing stage, the
microbes gradually adapted to the pharmaceuticals in the system with time, and the removal of all tested pharmaceuticals
improved. Granular sludge has a great potential in removing pharmaceuticals through the exploitation of synergistic effects
of microbial communities to adapt to specific remediation requirements. Additionally, a significant correlation has been
reported between nitrate and total antibiotic concentration in wastewater, suggesting the potential for nitrate concentration
to predict total antibiotic concentration in treated effluents (Watkinson et al., 2007). It can be inferred that, due to the
enhanced nitrate removal by aerobic granulation, there is a potential for effective removal of antibiotics.
One of the major removal pathways for ESOC using granular sludge is biodegradation. It has been indicated that
mineralization of many recalcitrant pollutants such as persistent herbicides, chlorinated aromatic hydrocarbons, phenols,
and heavy metals require anaerobic, aerobic or anoxic treatment (Chan et al., 2009; Shen and Guiot, 1996). The layered
structure of aerobic granules is considered a key element for the co-existence of aerobic and anaerobic populations (Tay
et al., 2002; Adav et al., 2007; Tay et al., 2003; Ivanov et al., 2006; Show et al., 2012; Lv et al., 2014). It is suggested that oxygen
consumption by aerobic bacteria is predominant at the peripheral leading to a steep oxygen gradient across the biofilm; and
that anaerobic bacteria in the granular sludge can survive in the core of the granule. It is thought that the facultative bacteria
on the periphery drastically limit the diffusive penetration of oxygen and prevent the toxicity to the oxygen-sensitive
methanogens located in the inner layer of the granule (Shen and Guiot, 1996). Tartakovsky et al. (2005) reported that three
bacterial populations can coexist: anaerobic bacteria, aerobic heterotrophic bacteria, and aerobic methanotrophic bacteria.
Similarly, Miguez et al. (1999) indicated that methane-oxidizing bacteria (methanotrophs) live in close association with
methane-producing microorganisms (methanogens) in aerobic–anaerobic bioreactors, where the oxygen concentrations
may not exceed 1 ppm. In addition, there is no inhibition on the activity of aerobic microorganisms by the long accumulation
of the by-products produced from anaerobic degradation (Muda et al., 2013).
In addition to biodegradation, sorption to aerobic granular sludge has been identified as a removal mechanism for
ESOC. Zheng et al. (2016) reported significantly higher adsorption of 17β -estradiol (steroidal estrogen) onto granular
sludge compared to activated sludge. This indicates the potential for the removal of ESOC that are poorly removed via
biodegradation. In this regard, Ni et al. (2015) reported that the removal of polybrominated diphenyl ethers (BDE-209)
was mainly through biosorption onto aerobic granular sludge with several factors affecting removal efficiency including the
initial concentration, contact time, pH and temperature.
However, the main drawback of granulation technology is the deterioration in granule stability under long-term
operation and lack of a successful pilot- or full-scale application. (Show et al., 2012). Production of granules with sustainable
long-term structural integrity is a key area requiring further research.
4.4. Nano-remediation
Nanoremediation refers to the application of NMs for environmental (groundwater, wastewater, contaminated soil)
remediation. As applied to wastewater treatment, nano-remediation techniques employed include: adsorption, nano-
membrane filtration techniques, and photocatalysis (Qu et al., 2013).
Adsorption is usually employed to polish WWTP effluents, particularly to remove organic and inorganic recalcitrants.
Nano-adsorbents possess superior properties when compared to conventional adsorbents (e.g. activated carbon) providing
effective removal of targeted contaminants such as heavy metals, polar organic compounds, and recalcitrants (Hua et al.,
2012). These superior properties are due to their extremely high specific surface area and associated sorption sites, enhanced
reactivity, short intraparticle diffusion distance, tunable pore size and surface chemistry (Brar et al., 2010; Qu et al.,
2013). Examples of nano-adsorbents include CNTs; metal-based nano-adsorbents such as titanium dioxide, iron oxide and
alumina; and polymeric nano-adsorbents. It has been reported that CNTs exhibit higher removal efficiency of various organic
chemicals compared to activated carbon chemicals (Pan and Xing, 2008). It has also been shown that organic compounds
having –OH, –COOH, and –NH2 functional groups could also form hydrogen bond with the graphitic CNT surface that
donates electrons (Yang et al., 2008). This indicates a strong potential for the removal of phenols and anilines by CNTs
from wastewater. Ji et al. (2009) found that the electrostatic attraction of CNTs aids the adsorption of positively charged
organic chemicals (e.g. antibiotics) at an appropriate pH. This shows a potential for the removal of pharmaceuticals. The
successful removal of two herbicides (diuron and dichlobenil) from wastewater using CNTs has been reported (Chen et al.,
2011). Metal-based nano-adsorbents also show effectiveness with respect to ESOC removal. Studies have indicated that
nano-scale iron particles are very efficient for the transformation and detoxification of ESOC, e.g. organochlorine pesticides,
polychloro biphenyls, and chlorinated organic solvents. (Zhang, 2003; Mauter and Elimelech, 2008). It is also reported that
silver nanoparticles can provide complete degradation of pesticides (Pradeep and Anshup, 2009).
Nano-membranes such as nano-fiber membranes, nano-composite, and thin-film nano-composite membranes can
remove micron-sized particles from aqueous phase at a high rejection rate without significant fouling (Qu et al., 2013).
It is reported that nano-filtration and reverse osmosis achieve 95% removal of EDCs, pharmaceuticals, and PCPs (Esplugas
et al., 2007). A study found that nano-composite membranes produced from single-walled CNTs and polyethersulfone (PES)
significantly improve the removal of ESOC (bisphenol A and nonylphenol) from wastewater (Kaminska et al., 2015). It has
also been indicated that the insertion of fullerenes into certain hydrophobic polymeric membranes can adsorb estrogenic
pollutants from surface and treated waters (Scida et al., 2011). This technique was found to be ideal for removing ESOC such
as estrone, estradiol, and ethinyl estradiol which have high hydrophobicity and low volatility.
Beside nano-remediation, the application of nanotechnology in determining the presence of contaminants in water by
incorporating CNTs in solid phase extraction (CNT SPE) opens a wide field for the detection of ESOC at the nano concentration
level (Scida et al., 2011).
In general, the superior properties associated with nano-scale particles provide the potential for the use of
nanotechnology in ESOC removal. However, further research needs to be conducted to investigate the removal efficiency
of the different classes of ESOC as well as the sustainability aspects. In addition, nano-particles can have human health and
ecotoxicological impacts. Therefore, the potential impacts of nano-remediation processes and the environmental fate of
nano-particles need to be assessed.
5. Conclusion
Emerging substances of concern (ESOC) have recently been detected in water resources worldwide. ESOC have severe
adverse effects on human and environmental health including endocrine disruption and abnormalities in reproductive and
immune functions of humans and aquatic animals. Acknowledging the diverse classes of ESOC, it is necessary to develop
one system that can remove all (or most) of these contaminants.
Coagulation/flocculation and media filtration as well as biological wastewater treatment processes such as activated
sludge, are ineffective at ESOC removal to acceptable levels. Advanced oxidation processes such as the combination of ozone
with other oxidation agents (UV, titanium oxide) can enhance the removal of ESOC. However for ESOC removal efficiency
above 90%, high oxidant concentrations are required, making it cost prohibitive.
Research indicates that MBRs are effective at ESOC removal. However, finding sustainable ways of mitigating fouling
in MBRs is a key area for further research. Similarly, early results on granulation technology indicate excellent removal of
the pharmaceuticals group of ESOC. Granular sludge can provide good settling properties, less sludge production, ability
to withstand toxic and shock loadings, and a small footprint requirement. However, deterioration in granule stability over
time as well as lack of a successful pilot- or full-scale application remain major limitations. Further research is needed on
the production of granules with sustainable long-term structural integrity as well as the investigation of the removal of all
ESOC groups in granular systems.
Nano-remediation has also emerged with its unique properties of NMs that present a strong potential for the removal
of ESOC. However, nano-remediation applications are still in the development phase and require further research for
commercialization as well as the assessment of potential environmental and human risks NMs pose.
Acknowledgment
The authors acknowledge the support of the Natural Sciences and Engineering Research Council of Canada.
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Environmental Technology & Innovation: Rania Ahmed Hamza, Oliver Terna Iorhemen, Joo Hwa Tay

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Environmental Technology & Innovation 5 (2016) 161–175

Contents lists available at ScienceDirect

Environmental Technology & Innovation

Occurrence, impacts and removal of emerging substances of

article info abstract

2. What are emerging substances of concern?

2.2. Personal care products

2.5. Disinfection by-products

2.6. Flame retardants

2.7. Perfluorinated compounds

3. Impacts of ESOC on human and environmental health

4. Removal technologies for ESOC

4.1. Physico-chemical treatment

4.2. Advanced oxidation processes

4.3. Biological treatment

4.3.1. Membrane bioreactor

4.3.2. Granulation technology

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