Desalination 239 (2009) 229–246

A review of the effects of emerging contaminants in wastewater

and options for their removal
N. Bolonga,b,c, A.F. Ismaila*, M.R. Salimb, T. Matsuurad
a
Membrane Research Unit, Faculty of Chemical and Natural Resources Engineering,
b
Department of Environmental Engineering, Faculty of Civil Engineering,
Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia
Tel. +607 5535 592; Fax:+607 5581 463; email: afauzi@utm.my
c
Civil Engineering Programme, School of Engineering and IT, Universiti Malaysia Sabah,
88999 Kota Kinabalu, Sabah, Malaysia
d
Department of Chemical Engineering, University of Ottawa,
161 Louis Pasteur St, PO Box 450, Stn A, Ottawa, Ont.Canada K1N 6N5

Received 6 April 2007; Accepted 14 March 2008

Abstract
The occurrence of emerging or newly identified contaminants in our water resources is of continued concern for
the health and safety of consuming public. The existing conventional water treatment plants were not designed for
these unidentified contaminants. The endocrine disrupting chemicals (EDCs) comprise pharmaceuticals, personal
care products, surfactants, various industrial additives and numerous chemicals purported to be endocrine disrupter.
These have become a threat to our water supply network. The current wastewater treatment system is not effective
in elimination of these different classes of emerging contaminants as these have not been monitored due to the
absence of stringent regulation specific to these contaminants. These undesirable compounds are being released,
knowingly or unknowingly, into the aquatic environment that affect the whole living organism. The paper discusses
adverse effects of these emerging contaminants to water consumers and discusses the potential removal processes.
The use of activated carbon, oxidation, activated sludge, nanofiltration and reverse osmosis membranes, and their
efficiencies in removal of these pollutants, are reviewed. In particular, the nanofiltration removal mechanism is
emphasized because of its utmost importance in eliminating micropollutants.

Keywords: Emerging contaminants; Environmental impact; Advanced wastewater treatment; Nanofiltration

*Corresponding author.

0011-9164/09/$– See front matter © 2008 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2008.03.020
230 N. Bolong et al. / Desalination 239 (2009) 229–246
1. Introduction
The revolutionized development of resources
and technologies has produced more chemicals
and compounds which consequently increased the
number of compounds that were identified as
possessing potential environmental threats to the
livings. This ever-increasing number of surrep-
titious compounds poses potential environmental
threat to the living organism. The pharma-
ceuticals and personal care products (PPCPs),
surfactants, various industrial additives and
numerous chemicals purported to be endocrine
disrupter are not metabolized and discharged into
sewers and wastewater treatment plants
(WWTPs). These pose challenges to the designers
of future treatment plants and related method-
ology for their eradication. The issues associated
to these emerging compounds are discussed here
to highlight the challenges in tackling the
problems.
The first issue is that of nonexistence of limit-
ing regulations, especially for new compounds,
by-products, pharmaceuticals and PPCPs as
related to the water and wastewater treatment
industry. The industrial and technological break-
throughs have outpaced the regulatory practices.
None or very few precautions and monitoring
were taken to ensure these unregulated or new
compounds and by-products, specifically the
micro-range pollutants, from being released to
water sources. Yet some actions have been
actively taken; for instance, by the European
Commission that has developed strategies to deal
urgently with endocrine disrupters. One of them
is the amendment of the European Community on
Risk Assessment and Directive on the classifi-
cation of dangerous substances [1], whilst in the
US no maximum limit of these substances in
drinking or natural waters has been regulated.
However, the Food and Drug Administration
(FDA) does require ecological testing and evalu-
ation of pharmaceuticals when environmental
concentration exceeds 1 µg/L [2]. In 1996, the
Food Quality Protection Act (FQPA) and amend-
ments to the Safe Drinking Water Act (SDWA)
have authorized the US Environmental Protection
Agency (US EPA) to screen all chemicals and
formulation on any potential endocrine activity in
manufacturing or processing where drinking
water and/or food supply line could be con-
taminated [2,3]. This small sample of regulatory
practices indicates that there is no coordinated
ordinance that is accepted by the global com-
munity and nations. Moreover, limits and regula-
tion on pharmaceuticals and personal care
products and new compounds have not yet speci-
fically been made for water and wastewater
treatment criteria.
The second issue of concern is that endocrine
disrupting compounds (EDCs) are comprised of
an extensive and expanding spectrum of com-
pounds. This is not surprising as the endocrine
system has a complex function and involves a
variety of compounds, as documented by various
worldwide organisations including the World
Health Organisation (WHO), the European Union
(EU), US EPA, to name a few. These organi-
zations have developed their own characterization
lists and acceptable ranges of endocrine dis-
rupters. For example, the EDC priority list was
first reported by the EU–Strategy for Endocrine
Dis-rupters committee for 66 chemicals (includ-
ing 60 that are considered likely to be exposed to
humans). Then, a further 52 chemicals were
identified and recently the total list included 564
chemicals. However, out of this total, 147 com-
pounds are likely to be persistent in the environ-
ment [4].
As our knowledge of endocrine disrupters
increases, so does the list of chemicals that
exhibits these endocrine disrupting properties.
This means that more substances will be iden-
tified as endocrine disrupters as the number of
chemicals increases. This will necessitate identi-
fication and removal of these compounds from
the water system. Furthermore, removal of these
compounds from the wastewater treatment
 N. Bolong et al. / Desalination 239 (2009) 229–246 231

process has not necessarily been effective due to such as sludge and wastewater are difficult to
their relatively low concentrations and the asso- analyze and could seriously affect their extrac-
ciated difficulty in analysis [5]. The problem tion and analysis. A highly sensitive mea-
seems to be continuing and thus we need to surement is essential.
upgrade the existing water and wastewater treat-
ment system to cater to and solve these newly Thus, the development of a rapid, simple and
unregulated pollutants. low-cost procedure for detection of EDCs,
Thirdly, these compounds are different in their specifically for their estrogenic activity in waste-
form and mechanism of actions. Thus, the identi- water samples, is still a growing and interesting
fication and evaluation of these compounds from research area. Some of the few examples of
the environmental matrixes have provided a studies to determine EDCs in municipal waste-
unique challenge [6]. This made the measurement waters, surface and drinking water [7–10] are
and detection of EDCs difficult, for they some- summarized in Table 1.
times include biological and instrumental The concentration level would certainly vary
methods. The accuracy of the determination from one plant to the other due to the difference
methods is also still debated and progressively in the loading level of the treatment plant, plant
under research. In relation to measurement and size, population background etc. The studies
detection of EDCs in water and wastewaters, shown were mostly done in the developed
some of the problems associated are listed below: countries and thus the levels probably are much
C Detection of EDC compounds in water is at higher compared to the Malaysian scenario. Yet,
trace levels (µg/L or even ng/L); most analy-
tical instruments are unable to directly detect
Table 1
compounds at these low levels. Usually, Occurrence level of several EDCs detected in municipal
extraction is used to concentrate the target wastewaters, surface waters and drinking waters
compounds. However, this method has a
limitation for the amount of contaminant Type of Location Compounds Conc.,
subjected to the analysis that can be reduced. water detected (ng/L)
For instance, in the case of solid phase extrac- Municipal UK [7] Nonylphenol 1.2–2.7
tion, water samples are passed through a wastewaters Estrone (E1) 15–220
cartridge that is then dried by passing nitrogen Estradiol (E2) 7–88
or air. This is further followed by an elution Germany Nonylphenol 199
process using a solvent. Such a series of pro- [8] Estrone (E1) 3.4
cesses of extraction can be detrimental for Estradiol (E2) 0.9
certain types of instrumental analysis. Ethinylestradiol 1.4
(EE2)
C EDCs have a broad range of physiochemical
Japan Nonylphenol 80–1240
characteristics; there is no standard or com- [9] Estradiol (E2) 2.7–48
mon method for EDC monitoring. Each Surface Germany Nonylphenol 34
compound requires specific analysis by dif- waters [8] Estrone (E1) 0.7
ferent techniques. Estradiol (E2) 0.6
C Improved and advanced analytical and bio- Japan Nonylphenol 250
analytical technologies that enable the detec- [10] Estradiol (E2) 2.1
tion of more xenobiotics at an even lower Drinking Germany Nonylphenol 8
range of concentrations are required. water [8] Estrone (E1) 0.4
C The low level pollutants in complex matrices Estradiol (E2) 0.3
232 N. Bolong et al. / Desalination 239 (2009) 229–246
in a study carried out by Mohd et al. [11], three
Malaysian rivers have been monitored and
estradiol was detected in the Klang River where
the level was consistent with the range detected in
river water in other parts of the world. It was also
stated that the levels of estrogen detected was
high enough to be responsible for vitellogenin
induction observed in the fish caught in the river
[11].
The occurrence of these emerging compounds
in the water sources creates a great concern to
humans and biota in general; thus the next section
of this paper is to give an overview of the adverse
effects of these emerging contaminants to water
users and to discuss the advanced treatment
process alternatives for the removal of these
pollutants.
2. Adverse effects of EDCs
2.1. Water as exposure pathway
The pollution of the aquatic environment by
EDCs has become a major concern due to
increasing evidences by which exposure to EDCs
was linked to their reproductive and health effects
on humans and other living things. These are
because the water resources always act as a sink
for many types of pollution. Thus the aquatic
environment (streams, rivers, marine and even
groundwater) becomes susceptible to the effects
Fig. 1. Sources of endocrine disruptor compounds.
of most contaminants. EDCs enter the environ-
ment, specifically into the receiving waters,
through a variety of pathways that can be cate-
gorised as point source (such as municipal
sewage, industrial wastewaters, landfill) and non-
point source (such as agricultural run-off, wash-
off from roadways, underground contamination).
This is illustrated in Fig. 1.
Most of the previous research concentrates on
point source pollution, especially discharges of
EDCs via sewage treatment [12]. This is because
one of the main sources of these contaminants
comes from untreated wastewater and wastewater
treatment plant (WWTP) effluents. As expressed
by Petrovic et al. [13], most of current WWTPs
are not designed to treat these types of substance
and a high portion of emerging compounds and
their metabolites can escape and enter the envi-
ronment via sewage effluents. Thus, it is obvious
that the development of more advanced technolo-
gies may be crucial to fulfill the requirements.
2.2. Environmental effects
The issue of endocrine disruption has received
a great deal of attention since the last decade
because these compounds disturb the endocrine
system by mimicking, blocking or also disrupting
function of hormone, affecting the health of
humans and animals species. Additionally, EDCs
are exogenous substances which interfere with
 N. Bolong et al. / Desalination 239 (2009) 229–246
Table 2
Environmental effects of EDCs and PPCPs
Endocrine disrupting compounds
Bisphenol A (BPA) — used in epoxy resin and
polycarbonate plastics (in food and drink
packaging)
Butylated Hydroxyanisole (BHA) — used as a food
antioxidant
Alkylphenols (ie nonylphenol)— used in detergents
Phthalates — used as plasticizers in plastic, PVC
baby toys, flooring
Pesticides
Polychlorinated biphenyls (PCBs) —– used
in electrical equipment (capacitors and
transformers)
Estrone and 17-β estradiol (steroidal estrogens) and
17-α ethynylestradiol (synthetic contraceptive) —
contained in contraceptive pills
Antibiotics (such as penicillin, sulfonamides,
tetracylines)
Fragrances (musk)
Preservatives, i.e., parabens (alkyl-phdroxybenzoate)
— used for anti-microbiological preservatives in
cosmetics, toiletteries and even foods
Disinfectants/antiseptics, .i.e., triclosan —
used in toothpaste, handsoaps, acne cream)
233
Health effects
Proven to have estrogenic effects in rats [17] and hormonal
effects which increase breast cancer risk in human [18]
Reported to act as anti-androgen [19] that causes feminising
side-effects in men.
Estrogenic to breast cancer cells, rainbow trout estrogen
receptor and stimulates human estrogen receptor [20]
Mimicking estrogen and disturbing reproduction by
increasing number of eggs produced by Minnos and
vitellogenin levels [21]
Exposure to high levels reported to cause miscarriage and
pregnancy complication [22]
Dichloro-diphenyl-trichloroethane (DDT) — an insecticide
that has cause hormonal effect such as thinning of eggshells,
damage male reproductivity and behavioural changes [23]
Lindane — an organochlorine pesticides that shows
vitellogenin and zona radiata (egg shell protein) in liver cells
of Atlantic Salmon [24]
Penconazole — a fungicide that can affect thyroid, prostate
and testes weight [25]
Prochloraz — a fungicide that can affect pituitary weight
[25]
Propiconazole—– a fungicide that can affect steroid
metabolism [25]
Tridemorph — fungicide that can cause cyctic ovaries [25]
Epoxyconazole — a fungicide that affects sex hormone
balance and cause ovarian tumours [25]
The metabolites able to mimic estradiol (female hormone)
[26] and cause carcinogenic [22]. Exposure was reported to
cause delayed brain development and IQ decrease in children
[27]
Cause feminization which observed for fish in sewage
treatment [28]. The discharge causes mimicking
estrogen/hormone effect to non-target
Shown to cause resistance among bacterial pathogens [28],
that lead to altered microbial community structure in the
nature and affect higher food chain [29]
Musk xylol — proved carcinogenic in a rodent bioassay and
significantly absorbed through human skin [30]
Musk ambrette may damaging the nervous system [31]
Shows weak estrogenic activity [32]
Found in the receiving waters [33], that cause toxic, biocide
(kill microorganism) and also cause bacteria resistance
development towards triclosan [34]
234 N. Bolong et al. / Desalination 239 (2009) 229–246
the normal hormones at very low concentration in
the human body [14]. This implies that although
EDCs may be present in effluent at trace concen-
trations, adverse effects have been found in
aquatic biota and hence they may have health
impact to humans [15]. The major exposure route
both for humans and animals is by ingestion of
EDCs via food/drink intake which leads to bio-
accumulation and biomagnification, especially
towards species at top level of food chain. For
example, in the case of fish eating birds and
marine mammals, it has been found that they may
contain concentrations of persistent organic pol-
lutants (POPs) many times higher than those
found in fish on which they feed [16]. More of
the selected EDCs and its health effect to the
livings are shown in Table 2.
Many studies have highlighted and reported
the evidence in terms of abnormalities observed
in aquatic organisms such as disorganized repro-
ductive tissues and abnormal ratios of estrogen
and testosterone in juvenile alligators in Lake
Apopka, Florida [35], sexual abnormalities in fish
living near WWTP outfalls (male fish producing
female yolk precursor protein vitellogenin) [36],
echnologies may be crucial to fulfill the
requirements.
2.2. Environmental effects
The issue of endocrine disruption has received
a great deal of attention since the last decade
because these compounds disturb the endocrine
system by mimicking, blocking or also disrupting
function of hormone, affecting the health of
humans and animals species. Additionally, EDCs
are exogenous substances which interfere with
inter-sex in white suckers downstream of a
WWTP effluent [37] and many more as follows
[16]:
C Reproductive and immune function impact in
Baltic seals causing population decline due to
exposure to organochlorine (i.e., PCBs, DDT)
C Eggshell thinning and altered gonadal
development (syndrome of embryonic abnor-
malities) in birds exposed to DDT resulting in
severe population declines
C Reproductive endocrine function and altera-
tion in fishes due to living in sewage and
industrial effluents
C Masculinization of marine gastropods exposed
to TBT has resulted population declines
The effects of EDCs toward animals are well
reported, although the direct effects to humans
are still debated and require more studies [38,39].
However, few studies suggest that the effect of
EDCs exposure on human health includes a
decrease in male sperm count, an increase in
testicular, prostate, ovarian and breast cancer and
reproductive mulfunctions [40]. The significant
concern is toward fetuses and newborn babies
since they are the most vulnerable [39].
Currently, most researchers are focusing on
persistent, bio-accumulating, toxic substances
(also termed as priority pollutants), that were still
found in birds, fish and mammals, even though
these substances (i.e., dioxins, PCBs, organo-
chlorine pesticides) have been reduced or banned.
This category of substances is no doubt is toxic
and dangerous to life. On the other hand, more
attention goes to substances that are persistent
and also discharged or widespread in the environ-
ment although they occur at low levels. Typical
examples are pharmaceuticals and personal care
products. These substances can affect growth,
reproduction and development of organisms in
the ecosystem.
Since the endocrine system itself is complex,
it is not surprising that the substances that cause
endocrine disruption are wide and diverse. Thus,
this paper primarily focuses on estrogenic hor-
mones and other micropollutants such as pharma-
ceuticals and personal care products as they are
most relevant in municipal wastewaters.
Estrogenic hormones are the most endocrine
disrupting chemicals because the disrupting
potency can be several thousand times higher
 N. Bolong et al. / Desalination 239 (2009) 229–246
than other chemicals such as nonyl phenol [41].
This implies that natural and synthetic estrogens
can be biologically reactive even at low nano-
gram per liter levels [36]. Consequently, although
they are in low concentrations, the elimination of
these trace contaminants from entering our water
resources is required.
3. Treatment technologies
Certainly the existing water and wastewater
treatment plants have been designed for the best
in treatment and removal of contaminants and
eutrophicating pollution loads, especially those
which are specified in the existing regulations.
However, the occurrence of the new “unregu-
lated” micro-contaminants such as EDCs and
PPCPs requires advanced treatment. Furthermore,
we should be aware that EDCs and PPCPs
possess a wide range of chemical properties and
thus success in removal varies greatly depending
upon their particular properties.
Wastewater treatment is a much more com-
plicated process than water treatment due to
highly polluted wastewater characteristics.
Wastewater must be thoroughly treated before it
can be safely integrated back to the environment.
The dilution of wastewater effluent upon dis-
charge into water bodies results in a significant
decrease in the concentration of these com-
pounds, either by degradation or through binding
to natural organic matter or soil along the
riverbank, resulting in lower concentrations down
stream [42,43]. Yet, the occurrence of these
substances ranges from µg/L to ηg/L in drinking
water (Table 1) and gives an insight into its
capability in passing through conventional water
treatment.
3.1. Physicochemical treatment
Physicochemical treatment as a coagulation–
flocculation process was generally found to be
unable to remove EDCs and PPCPs. A study
235
conducted by Westerhof [44] using a bench-scale
simulation water treatment plant model and
natural waters spiked with 30 pharmaceuticals to
80 different EDCs provided the results which are
summarized in Table 3. His study yielded no
significant removal except using activated carbon
(powder) and oxidation via chlorination and ozo-
nation. Chemical treatment such as coagulation,
flocculation or lime softening shows ineffective
removal for EDCs and PPCPs. These findings
were also made by Adams et al. [45] where
compounds tested (carbadox, sulfadimehoxine,
trimethoprim) were not removed by metal salt
coagulants (aluminium sulfate and ferric sulfate).
Petrovic et al. [46] as well as Vieno et al. [47]
reached a similar conclusion for diclofenac,
carbamazepine for the elimination of ibuprofen
and ketoprofen.
Some research results [3,44] indicated that
adsorption by activated carbon and advanced
oxidation (i.e. ozon, UV) were effective for
removing some EDCs and PPCPs. An activated
carbon adsorption system is advantageous in
terms of its hydrophobic interactions in elimi-
nating most organic compounds, especially non-
polar compounds (compounds with Kow>2) [48].
Since the fate of these trace contaminants is
largely dependent on particle-contaminant inter-
actions, the competitive effects for surface sites
and/or pore blocking (with other particulates)
have lowered the extent of removal by activated
carbon. Yet, powdered activated carbon appears
to be the most effective adsorbent especially for
those substances containing refractory organic,
non-biodegradable compounds [49]. Schafer et al.
[50] stated that the potential of EDC removal by
powdered activated carbon may be up to 90%. A
comparative study on coagulation and sorption
(activated carbon) in eliminating estrogens by
Bodzek and Dudziak [51] has proven that sorp-
tion by powdered activated carbon and granular
activated carbon was more efficient than
coagulation, even in a hybrid system with nano-
filtration membranes.
236 N. Bolong et al. / Desalination 239 (2009) 229–246

Table 3
Removal performance of EDCs by selected treatment processes [44]

Treatment process Removal performance

Coagulation by alum or ferric <20% of compound removed, specially associated with particulate matter
sulphate Presence of hydrophobic dissolved organic carbon enhances removal and provides
partitioning
Lime softening <20% of compound concentration was removed at pH 9 -11
Powder activated carbon >90% of many EDCs removed (at 5 mg/L dose PAC of 4 hour contact time)
(PAC) Yet some EDCs (ibuprofen, sulfamethoxazole, meprobamate) had lower removals
(40–60%)
Hydrophobic compounds (octanol-water partition co-efficient, log Kow >5) have
better removal than polar compounds
Biofilm Removal depends on biodegradability of compounds but removal rate is unclear
Chlorination Able to remove >90% for more reactive compounds containing aromatic structures
with hydroxide functional groups
Not suitable because it produces chlorine by-product (react with EDCs) and should
be avoided
Ozonation Oxidized similar to chlorination but at slightly higher removal rates
Addition of hydrogen peroxide during ozone addition slightly increased the EDCs
removal

Oxidation is a promising removal mechanism,
especially using chlorine or ozone. However,
careful selection is needed as reaction of these
chemicals was found to be reactive and produce
byproducts, of which the effects are unknown.
Oxidation is effective in degrading EDCs/PPCPs
in low dissolved organic carbon (DOC) as DOC
has strong influence on the application of the
ozonation process [52]. Ozone oxidizes substrates
either directly or by producing hydroxyl radicals
that react with other entities. Both are strongly
reactive and have been proposed by Huber et al.
[52] as promising options for the removal of
EDCs/PPCPs. They claimed that, although sus-
pended solids increased ozone demand, the influ-
ence was minor. Five mg/L ozone doses were
sufficient but higher doses were necessary for
higher suspended solid concentrations.
3.2. Biological treatment
Johnson and Sumpter [53] revealed that the
essential sewage treatment system such as acti-
vated sludge and biological trickling filters can
rapidly convert aqueous organic compounds into
biomass that is then separated from the aqueous
phase by settlement (clarifiers). Even though this
is acknowledged as a remarkable achievement,
unfortunately, not all compounds such as steroid
estrogens are completely broken down or con-
verted to biomass. Additionally, although best
available technology is adopted, biological treat-
ment removes only a part of a wide range of
emerging contaminants, particularly polar ones
which are discharged via the final effluent [13].
In an activated sludge studied by Urase and
Kikuta [54] in the removal of three estrogens, two
endocrine disrupters and pharmaceuticals, the fate
of the target compounds in wastewater treatment
processes was found to be the determinant factor
controlling their concentrations in water environ-
ments. They stated that at neutral pH, pharma-
ceuticals (acidic pharmaceuticals such as clofibric
acid, ibuprofen, diclofenac etc) appeared as ions
and remained in the water phase, not removed or
adsorbed in the activated sludge. The limiting
 N. Bolong et al. / Desalination 239 (2009) 229–246
stage for removal was the transfer of substances
from water phase to sludge phase. The preferred
condition for the removal in the activated sludge
was in the acidic conditions to ensure the transfer
by adsorption of substances from water phase
into sludge phase, and not by biodegradation.
Similarly, according to Mastrup et. al [55], less
than 10% of natural and synthetic estrogens are
removed via biodegradation process, and
although a considerable amount is adsorbed to the
sludge, most of the compounds remain soluble in
the effluent. On the other hand, Johnson and
Sumpter [53] observed that steroid estrogens
were removed in the activated sludge, the degree
of removal being consistent with their hydro-
phobicity and most removal involved adsorption
to the organic-rich solid phase as it was not easily
biodegraded.
Biodegradation processes such as in the trick-
ling filter case studied in Canada [56] and Brazil
[57] were found incapable to remove estrogens
due to their low sludge retention time (SRT) and
hydraulic retention time (HRT) properties since
this treatment method applies solid contact and
attached growth process. Thus, suggestions were
made toward biological treatment with longer
HRT and SRT, which could increase the extent of
the removal of the compounds. Similarly, Clara et
al. [58] pointed out that low effluent wastewater
treatment plant concentration could be achieved
at operating SRT higher than 10 days (tempera-
ture of 10EC). Servos et. al. [56] observed that
apparent highest removal was shown at plants
having HRT >27 days and SRT >35 days. Both
of the time-dependent design operating para-
eters imply that a longer time would be able to
partially “treat” these compounds, yet they also
influence the water treatment plant size and other
design criteria.
Nitrification degree was also shown to affect
biological treatment system and has potential on
estrogens removal [56]. This is an indication of
an improve biological diversity and growth
conditions which could increase biological trans-
237
formation and thus lead to higher removal of the
compounds (especially organics). Layton [59]
also found that sludges that failed to nitrify also
significantly failed to degrade ethinylestradiol.
Vader [60] examined sludge under both con-
ditions (nitrifying and non-nitrifying) and found
no degradation of ethinylestradiol at non-
nitrifying environment, whereas at nitrifying
conditions, ethnylestradiol was found to be oxi-
dized to a more hydrophobic compound. The
nitrification degree in biological treatment, how-
ever, depends on many factors such as pH, oxy-
gen, temperature, etc., to ensure the growth of
nitrifying bacteria.
3.3. Advanced treatments
Advanced treatment options for removing
EDCs include ultra-violet (UV) photolysis, ion-
exchange and membrane filtration. While UV and
ion-exchange do improve the removal of EDCs
and PPCPs, they are insufficient to be considered
as feasible removal options. This was shown by
Adams et al. [45] where UV photolysis removed
50–80% of the target compounds but required a
dose a hundred times that of the typical disin-
fection dose.
Membrane filtration technology such as
reverse osmosis (RO) and nanofiltration (NF) has
demonstrated itself as a promising alternative for
eliminating micropollutants [61–63]. Compara-
tively, the NF membrane is “looser” than RO.
Therefore, RO will give almost complete removal
but the higher energy consumption makes it more
unfavorable. Based on Braeken et al. [64], trans-
port during NF is produced by different mechan-
isms, namely convection, diffusion (sieving) and
charge effects. Convection occurs due to the
applied pressure difference over the membrane
whereas diffusion mechanism happens due to
concentration gradient across the membrane. The
third mechanism that is the charge effects is due
to electrostatic repulsion between a charged mem-
brane and a charged organic compound. This
238 N. Bolong et al. / Desalination 239 (2009) 229–246
uniqueness has made NF an attracting removal
technology specifically for micropollutants such
as EDCs.
4. Nanofiltration removal mechanisms for
EDCs
It is well known that the removal mechanism
of EDCs by NF membranes occurs via a combi-
nation of processes. The dominant mechanisms
linked to EDCs removal are adsorption, size
exclusion and charge repulsion. These three main
mechanisms were so much interrelated and have
significant influence on EDCs rejection that in
turn causing the removal performances can be
very different and varied from compound to
compound. Therefore, understanding the removal
mechanisms and it interrelation to the controlling
parameters of compounds-NF-and the separation
operation system are the key element to optimize
the rejection of EDCs by NF.
4.1. Adsorption mechanism
At the early stage of filtration in NF, the
dominant mechanism of removal of various
PPCPs and EDCs is adsorption by the membrane
[41,62,63,65], and then it reaches equilibrium
(due to limited adsorptive capacity of the mem-
brane). This preliminary removal was yielding
false removal/retention results [66]. However,
adsorption is quick and is not the rate determining
step in the separation process [62]. Simul-
taneously, a cake develops on the surface of the
membrane that decreases the pore size to below
the nominal rating, thus improving the removal
[41,63, 67] and latter develops fouling. Fouling
has adverse effects by decreasing rejection [68].
Additionally, Nghiem and Schafer [66] stated that
the adsorption is partially irreversible and can
impact the performance/life of the membrane
being used. Several researchers have proposed the
adsorption mechanism for removal of estrogens
(estrone) is hydrogen bonding [50,69]. Polyamide
on polysulfone thin film composite (e.g. TFC–S,
TFC–ULP) membranes were found desirable for
the removal of estrogens (estrone) since adsorp-
tion was the dominant removal mechanism [66].
The retention was initially good and once the
membrane became saturated, the permeate con-
centration remained lower than the feed, indi-
cating sieving occurred. No decline in estrone
retention occurred after adsorption had stopped
when using polyamide on urea TFC. This is
because the X-20 RO membrane has a smaller
pore size than TFCs. There is no breakthrough
curve for the tighter membrane since diffusion is
the dominant mechanism and separation is
accomplished via sieving [66,69].
The adsorption mechanism has been correlated
with solute–membrane hydrophobic interactions
[63,66,69]. Hydrophobic interaction between
membrane and solutes is one of nanofiltration’s
important rejection mechanisms. Hydrophobicity
of membranes is usually characterized by their
contact angle whereas hydrophobicity of solutes
can be correlated and quantified with logarithm of
octanol-water partition (log Kow). Molecules with
log Kow>2 are usually referred to hydrophobic
ones [48,70]. Octanol/water partition coefficient
values are determined as log [ratio of the concen-
tration in the octanol phase to the concentration in
the aqueous phase at adjusted pH] in such that the
predominant form of the compound is un-ionized.
According to the work by Yoon et al. [63],
hydrophobic adsorption (to hydrophobic NF) that
takes place during the initial operational period
depends on hydrophobicity of compounds to be
separated. Hydrophobic properties have an influ-
ence on the sorption mechanism where strong
hydrophobic compounds as aromatic pesticides,
non-phenylic pesticides and alkyl phthalates were
highly rejected even by the lowest desalting
membrane [71]. However, the retention decreases
as sorption reduces after the saturation of the
membrane. This shows that the initial adsorption
of hydrophobic molecules on NF membranes will
be high, which causes a high initial rejection
 N. Bolong et al. / Desalination 239 (2009) 229–246
which will then come to equilibrium and then the
rejections are influenced by molecular size of the
solute. As studied by Braeken et al. [72], hydro-
philic molecules are better rejected than hydro-
philic molecules after long-term operation due to
the hydration of the hydrophilic molecules which
increases the compound effective size by forming
hydrogen bonds with water molecules. Addi-
tionally, after the membrane is saturated, hydro-
phobic solutes are easily absorbed and permeated
through membranes whereas, since for hydro-
phobic compounds that are less hydrated, the
retention is lower, especially when molecular
weight is not substantially higher than the
MWCO of membranes [72].
4.2. Sieving mechanism
The diffusion or steric exclusion rejection
mechanism is accomplished by a membrane hav-
ing a smaller pore size than the target compound
(physical blocking). This typical mechanism
implies that the compounds whose sizes are larger
than the membrane pore size are rejected and
permeation through the membrane is prevented.
Molecular size of compounds was reported in
various works [73–75] to be the most important
factor in determining retention of EDCs in NF.
The size exclusion rejection mechanism has been
determined and referenced to solutes parameters
such as molecular weight, molecular structure,
i.e., size and geometry including the compound
stokes radius [72,76,77]. The EDC rejection of
uncharged or neutral compounds in NF was
found to increase with an increase in molar mass.
This implies that uncharged compounds with a
molecular size larger than the pore size of the
membrane will be well rejected due to this
sieving effect of the polymer matrix [78].
Concerning the size exclusion removal
mechanism, according to Nghiem et al. [41], the
membrane pore size affects the retention of
estrogenic compounds where retention by porous
membrane decreases with adsorption. Addition-
239
ally, retention of micropollutants by NF mem-
branes can be enhanced by the existence of
organic matter as it interacts or absorbs and hence
increases molecular weight of the contaminant in
the water. It was found that larger organics have
a great influence and improves molecular weight
of the contaminants in the water [41].
Rejection quantification of EDCs mass trans-
fer through the NF sieving mechanism mostly
uses MWCO, desalting degree, porosity and sur-
face characteristics and morphology via atomic
force microscopy and scanning electron micro-
scopy [79]. The summary of the quantification
method via rejection due to sieving mechanism is
given in Table 4. Several researchers [73,75]
found that the MWCO of NF membrane cannot
be precisely used to predict and quantify for EDC
rejection due to the variation in MWCO deter-
mination. This is because the MWCO variation
depends on filtration protocols, solute character-
istics and concentration and as well as operating
conditions. (i.e dead end, cross flow filtration)
[79]. Verliefde et al. [78] stated that MWCO of
membrane gives an underestimation of the
MWCO for hydrophobic compounds and an over-
estimation MWCO for hydrophilic molecules.
4.3. Electrostatic interactions
In electrostatic repulsion mechanism, the
rejection relies on relative charge interaction and
not just on molecule size. According to Hilal et
al. [80], rejection of organics, colloids and large
molecules depends on the sieving parameter
(solute and pore size), while ionic components
and lower molecular weight organics are rejected
due to charge interactions between membrane
surfaces. In this manner, EDC retention could be
a combination or either size exclusion or the
charge repulsion mechanism. The negatively
charged compounds studied by Verliefde et al.
[81] were more highly rejected than neutral and
positive compounds. Berg et al. [76] obtained the
same results where charge organic were rejected
240 N. Bolong et al. / Desalination 239 (2009) 229–246

Table 4
Rejection quantification of EDC through nanofiltration via the sieving (mass transfer) mechanism [79]

Parameter Quantification mode Rejection mechanism

Molecular weight Filtration of solute (e.g PEG, PVP etc) at 90% rejection Sieving effect increases for
larger molecules
Desalting degree Filtration of sodium chloride or magnesium chloride at Higher rejection for higher
varied desalting degree, i.e., 500–2000 mg/L desalting degree
Membrane porosity Density of pores or effective number of pores calculation Rejection data fitted with
in membrane using mathematical transport models transport model
Surface morphology Physical surface area and surface roughness via atomic Discrete-small pore structure
microscopy force microscopy and scanning electron microscopy increases selectivity of
membrane

higher than non-charged organics of the same size
(molecular weight). Kimura et al. [82] investi-
gated the rejection of organic micropollutants
categorized as DBPs and pharmaceutically active
compounds using polyamide NF/RO membranes
based on bench-scale filtration experiments. Their
results clearly showed that charged compounds
could be rejected to a great extent (i.e., >90%)
regardless of physicochemical properties of the
tested compounds. In contrast, rejection of non-
charged compounds was found to be influenced
mainly by the size of the compounds. This rejec-
tion mechanism occurs as the negatively charged
solutes and the negatively charged membrane
surface prevent solutes from approaching and the
solutes are not allowed to permeate through the
membrane. The negative properties of membrane
surface usually are contributed by the sulfonic
and/or carboxylic acid groups which are depro-
tonated at neutral pH [78,79]. Different pH con-
ditions will substantially change the membrane
surface charge. Studies [83,84] revealed that by
increasing pH, the negative surface charge of
membranes would be increased and thus higher
rejections would be expected especially for
negatively charged compounds.
Changing pH not only changes the membrane
surface but also affects the disassociation state of
elecrolite solutes [85] as well as solute orientation
and solubility [74]. Each target compound has at
least one dissociation constant (pKa) (for exam-
ple, sulfamethoxazole has two, pKa1 = 1.7, pKa2=
5.6). By modifying the pH of the solution and
surpassing the pKa value, the charge of the target
compound can be changed in order to enhance
rejection [68]. In the study by Nghiem et al. [74],
carbamazepine, with a pKa of 2.3, became nega-
tively charged when the experiment was con-
ducted at pH 8.0. Drewes et al. [68] proved that
non-ionic compounds were inconsistently re-
moved even in the presence of natural organic
matter (NOM), illustrating that the negative
charge of NOM is insufficient to cause an effect
or compensate for the neutral property of the
target compound. However, at the test pH, rejec-
tion for both sulfamethoxazole and ibuprofen was
increased as the compounds became negatively
charged causing electrostatic interaction and
repulsion mechanisms.
4.4. Influence of NF operating conditions on
removal performance
In spite of the influences of the properties of
the compounds to be removed and NF membrane
characteristics in EDCs rejections, the operating
conditions and the water feed matrix also play an
important role. For example, high rejections
would be observed at higher operational pres-
sures, whereas a high amount of permeate
 N. Bolong et al. / Desalination 239 (2009) 229–246
Fig. 2. Factors influencing rejection performance of NF membranes.
produced per unit feed will cause a decrease in
rejection [78]. The influence of pH variation on
feed solution discussed above shows the influ-
ence of pH towards the charge of the membrane
as well as the compounds to be removed. On the
other hand, temperature of the water feed matrix
also affects the rejection performance. An in-
crease in solution temperature causes an increase
in diffusivity and convective flux of compounds.
This produces high permeability and water, flux
which at the same time reduces retention [86]. A
study by Kimura et al. [82] also found that con-
centration range of solutes (i.e. contaminants)
might influence the rejection efficiency of a
membrane because they observed that at the low
concentration of ng/L range the rejection effi-
ciency was lower compared to the concentration
at µg/L range. Degree of salinity in the feed
matrix will cause the effective pore radius of a
charged pore of NF membranes to increase as the
ionic strength of the surrounding liquid increases
[85]. Therefore, the rejection of monovalent ions
will decrease as their concentration in the feed
solution increases. The rejection of divalent ions
will be affected to a lower extent.
In the NF process, the complexity and unique-
ness of the rejection mechanisms promote inter-
related factors which are influenced by the
241
compounds themselves, as well as membrane
properties and its characteristics. Furthermore, the
composition of feed water and its operating
parameters have affected the rejection on each or
combination of the compounds. Thus, the perfor-
mances of NF in eliminating EDCs are influenced
by several factors, which are illustrated in Fig. 2.
5. Conclusions
The occurrence of micro-pollutants as EDCs
in receiving waters should not be ignored and
must be continuously monitored. The adverse
effect of these emerging contaminants to fauna—
specifically to aquatic life and their corre-
spondence to humans—has been highlighted by
a number of studies. The impact of EDCs on the
health and environment has urged the removal of
these compounds, not only in drinking water, but
also in the wastewater treatment process to avoid
the release to receiving waters. Besides, the
occurrence of micro-pollutants is highly signifi-
cant in water reuse as these contaminants could
be accumulated during the process if not properly
removed. The technology options in eliminating
these contaminants such as activated carbon,
oxidation via chlorination and ozonation, bio-
logical process (activated sludge treatment) and
242 N. Bolong et al. / Desalination 239 (2009) 229–246
membrane filtration have been discussed and
employed in several parts of the world. Each
removal option has its own limitation and benefit
in removing trace contaminants such as EDCs,
yet in this particular case, treatments via activated
carbon and membrane processes were shown to
have potential as removal technologies. Mem-
brane processes such as NF may have a signifi-
cant impact on EDC removal.
Several key parameters for EDC properties in
wastewater were identified to boost its removal
through NF by properly controlling those key
parameters. Additionally, a combination or a
hybrid process (i.e., NF-activated carbon) will be
able to enhance the removal performance,
particularly if a process that is able to accumulate
these trace-contaminants by a phsicochemical are
a component of such a hybrid process. This is
related to the study on the fate and kinetics of
these contaminants and their reactions in the
wastewaters. Unfortunately, most conventional
wastewater treatment plants do not have treatment
processes such as activated carbon, ozonation or
membrane treatment, and therefore these emerg-
ing micro-pollutants are not removed but are
easily released to the receiving natural waters.
Future wastewater treatments should be up-
graded in order to cater to these fast-growing
issues. Development towards a more compact and
efficient treatment such as membrane technolo-
gies will have a stronger impact in the future.
Moreover, increased water consumption has
triggered the consideration of wastewater reuse.
This requires an effective and practical tech-
nology such as membrane separation processes
because they have an advantage of purifying
wastewater without using extensive chemicals
and concentrating the refuse that has the potential
for further reuse or recycling as a resource.
Consequently, more exploration of advanced
wastewater treatment technologies that are able to
eliminate these new unregulated micro-pollutants
is highly desirable, not only to provide advan-
tages to human, but also for the benefit of other
living things. The question of whether these
advanced technologies should be employed has
become important, not only due to regulation
requirements but also due to the sustainable
development.
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