Journal of Industrial and Engineering Chemistry 27 (2015) 1–11

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Review

Removal of endocrine disrupting compounds, pharmaceuticals, and

personal care products in water using carbon nanotubes: A review
Chanil Jung a, Ahjeong Son b, Namguk Her c, Kyung-Duk Zoh d, Jaeweon Cho e,
Yeomin Yoon a,*
a
Department of Civil and Environmental Engineering, University of South Carolina, 300 Main Street, Columbia, SC 29208, USA
b
Department of Environmental Science and Engineering, Ewha Womans University, 52 Ewhayeodae-gil, Seoul, Seodaemun-gu, 120-750, South Korea
c
Department of Chemistry and Environmental Sciences, Korea Army Academy at Young-Cheon, 135-1, Changhari, Kokyungmeon, Young-cheon, Gyeongbuk
770-849, Republic of Korea
d
Department of Environmental Health, School of Public Health, Seoul National University, Seoul, 151-742, Republic of Korea
e
School of Civil and Environmental Engineering, Yonsei University, 50 Yonsei-ro, Seoul, Seodaemun-gu 120-749, South Korea

A R T I C L E I N F O A B S T R A C T

Article history: Endocrine-disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have
Received 30 September 2014 been extensively detected in various surface water and wastewater. Carbon nanotubes (CNTs) have
Received in revised form 23 December 2014 aroused great research attention as a new type of adsorbent due to their unique properties and potential
Accepted 26 December 2014
applications for the removal of various inorganic and organic EDCs and PPCPs. This review summarizes
Available online 3 January 2015
the current research on the removal of EDCs and PPCPs with various CNTs, and provides valuable
information for CNT applications in the water industry. The removal of various EDCs and PPCPs was
Keywords:
reviewed based on the existing literature to address the effects of process parameters, including CNT
Carbon nanotubes
Endocrine-disrupting compounds
properties, EDC/PPCP properties, and water chemistry conditions. Regulatory issues, analytical methods,
Pharmaceuticals and personal care products and EDC/PPCP removal in water and wastewater treatment processes were also briefly addressed.
Adsorption Additionally, further research work on CNTs is suggested for the removal of EDCs and PPCPs from water.
Water treatment ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Regulatory issues and analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Regulatory issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Removal of EDCs and PPCPs in water and wastewater treatment plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Removal in water treatment plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Removal in wastewater treatment plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4. Removal mechanisms of various EDCs and PPCPs by CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1. Removal influenced by the adsorption properties of CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1.1. CNT properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1.2. Process parameters influencing CNT adsorption properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.2. Removal of selected EDC/PPCP by CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.2.1. EDCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.2.2. PPCPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. Conclusions and areas of future study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

* Corresponding author. Tel.: +1 803 777 8952; fax: +1 803 777 0670.
E-mail address: yoony@cec.sc.edu (Y. Yoon).

http://dx.doi.org/10.1016/j.jiec.2014.12.035
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
2 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11
1. Introduction
While there are several opinions as to what defines an
‘‘endocrine-disrupting compound’’ (EDC), the United States
Environmental Protection Agency (USEPA) has defined environ-
mental EDCs as exogenous agents that interfere with the
‘‘synthesis, secretion, transport, binding, action, or elimination
of natural hormones in the body that are responsible for the
maintenance of homeostasis, reproduction, development, and/or
behavior’’ [1]. The first concerns about the potentially adverse
effects of pharmaceuticals in municipal wastewater were
expressed by Stumm-Zollinger and Fair in 1965 and Tabak and
Bunch in 1970, after showing that steroids were not completed
removed during wastewater treatment [2,3].
Numerous EDCs, pharmaceuticals and personal care products
(PPCPs) contaminants have been discovered in various surface and
ground waters, and wastewaters globally, some of which have
been linked to ecological impacts, even at trace concentrations [4–
11]. Reports on EDCs and PPCPs for environmental risk and public
health assessments have raised substantial concerns among both
the public and regulatory agencies [12–15]. Most EDCs and PPCPs
are more polar than ‘traditional’ contaminants and may possess
several acidic and/or basic functional groups [16]. These proper-
ties, coupled with occurrence at trace levels (i.e., <1 mg/L), create
unique challenges for both analytical detection and removal.
EDCs and PPCPs in municipal wastewater can be removed
during wastewater treatment, during their passage through
surface or groundwater (e.g., natural attenuation), or during water
treatment. Over the last decade, numerous studies have examined
the fate of EDCs and PPCPs in drinking and wastewater treatment
[4,17–26]. Conventional water treatment plants (WTPs) typically
consist of coagulation, using alum, ferric chloride, and/or synthetic
polymers, followed by flocculation, sedimentation, filtration, and
disinfection. In the United States, chlorine and chloramines are
typically used for disinfection, while ozonation is more common in
most European countries. Coagulation would be expected to
remove only hydrophobic EDCs and PPCPs with high organic
carbon content associated with particulate or colloidal material
[27]. Oxidation preferentially attacks compounds with electron-
activating functional groups (e.g., thiols, amines, hydroxyl) located
near C5 5C bonds (e.g., benzene rings) [27]. Generally, organic
compounds react more rapidly with ozone than chlorine dioxide or
chlorine. During wastewater treatment, EDC/PPCP removal has
been found to occur primarily due to biodegradation, adsorption to
sludge, and/or oxidation by chlorine, but this varies according to
the compound in question [17].
Various conventional and advanced water and wastewater
treatment processes have been investigated in terms of removal of
EDCs and PPCPs in the aqueous phase, including adsorption with
high-binding adsorbents, including activated carbon (AC), carbon
nanotubes (CNTs), biochars, and zeolites [27–35]. Among them,
CNTs have drawn much attention because of their unique
properties and potential applications.
Since their discovery in 1991, CNTs have demonstrated such
extraordinary mechanical, electrical, thermal, and chemical
properties that they have become candidates for numerous
applications, including nanocomposites, energy storage, micro-
electronics, and medical devices [36,37]. Several studies projected
the production of CNTs at millions of tons in 2010, and a $1 trillion
worldwide market for nanoproducts by 2015 [38,39]. While many
researchers believe that CNTs may not be practical for large-scale
applications due to their high cost, CNTs have high adsorption
capacities for heavy metals [40–42], methyl orange [43], red dye
[44], phenols [45], and other organic chemicals [46]. Additionally,
continuous mass production may provide large quantities of CNTs
at economically viable prices for large-scale applications in the
near future, although the price of CNTs is at present higher than
that of other adsorbents (e.g., powdered activated carbon, PAC)
[47].
Removal of inorganic and organic compounds by CNTs has been
studied and reviewed [48,49]. However, because the unique
properties of EDCs and PPCs in terms of size, shape, pKa, functional
group, and hydrophobicity (typically assessed in terms of the
octanol-water partition coefficient, ‘‘KOW’’) affect their removal by
CNTs, a broader review of EDC/PPCP removal by CNTs with various
properties (size, shape, surface area, average pore diameter and
volume, morphology, and functional group) is necessary. Thus, this
review provides a comprehensive analysis of the removal of
various inorganic and organic EDCs and PPCPs by various CNTs in
water and wastewater. Additionally, this review briefly surveys
recent publications on regulatory issues on EDCs and PPCPs,
analytical methods for EDCs and PPCPs, and EDC and PPCP removal
in drinking water and wastewater.
2. Regulatory issues and analytical methods
2.1. Regulatory issues
EDCs and PPCPs are potential contaminants of drinking water,
particularly with wastewater reuse, due to their potentially
adverse impact on human health and the ecology of the natural
environment. In the US, regulation of contaminants in drinking
water began in 1962 with the Public Health Services Standards
[16]. These regulations covered several compounds now known to
be endocrine disruptors, such as arsenic, cadmium, and some
phenols.
For EDCs, the USEPA announced the establishment of the
Endocrine Disruptor Screening Program (EDSP) in 1998, which
used a tiered approach to identify substances that have the
potential to interfere with the endocrine system, to confirm that
potential, and characterize the effects of these substances
[50]. EDSP recommended that human and wildlife impacts be
considered, and that estrogen, androgen, and thyroid end points be
examined. The conceptual framework devised by EDSP consisted of
(i) Tier 1, including an autotrophic screen, a Hershberger screen
(male rodent-based tests for androgenic activity), a rodent
pubertal female screen, a rodent pubertal male screen, estrogen
and androgen receptor reporter gene screens, a fish reproduction
screen, and a frog metamorphosis screen, and (ii) Tier 2 including a
two-generation mammalian reproduction and development test
and a mysid shrimp reproduction test. In addition to discrete
chemicals, EDSP recommended the evaluation of mixtures of
chemicals in breast milk, baby formulas, hazardous waste sites,
pesticides and fertilizers, drinking water disinfection byproducts,
and gasoline.
There are currently no federal regulations for pharmaceuticals
in drinking or natural waters; the US Food & Drug Administration
requires ecological testing and an evaluation of a pharmaceutical
only if the environmental concentration in water or soil is expected
to exceed 1 mg/L or 100 mg/kg, respectively [51]. However, only
three of the numerous EDCs and PPCPs (17b-estradiol (E2), 17a-
ethinyl estradiol (EE2), and erythromycin) are currently listed in
the USEPA’s ‘‘Drinking Water Contaminant Candidate List 3’’
[52]. When municipal wastewater effluent is used for indirect
potable reuse, the State of California has considered the possible
impacts of EDCs and PPCPs: ‘‘Each year, the planned groundwater
recharge reuse project (PGRRP) will monitor the recycled water for
EDCs and PPCPs specified by the Department, based on a review of
the PGRRP engineering report and the affected groundwater
basin(s)’’ [16]. Large volumes of domestic sewage are collected and
treated at municipal wastewater treatment plants (WWTPs). Due
to the growing use of sewage sludge for fertilizer and soil
 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11
amendments, the US National Research Council in 2002 recom-
mended investigating the occurrence of PPCPs in sewage sludge
[53].
2.2. Analytical methods
The first difficulty in developing an EDC/PPCP analytical
approach is determining what EDCs and PPCPs actually are, and
which compounds should be used as target analytes. Additionally,
because EDCs and PPCPs represent an extremely broad spectrum of
compounds, the development of analytical techniques is challeng-
ing. Currently, biological and instrument methods (e.g., in vitro and
in vivo assays, gas chromatography (GC)/liquid chromatography
(LC)-mass spectrometry (MS)-MS, inductively coupled plasma
(ICP)-MS, and immunosorbents) are available for the detection and
quantitation of these emerging contaminants in water.
In vitro bioassays have been used as screening tools for
measuring the estrogenic or androgenic activity of single
compounds or complex mixtures [54–56], because they are rapid,
inexpensive, and fairly reproducible. For these reasons, accurate
estimates of the relative potency of many samples or compounds
can be obtained in a short period of time. While in vitro assays are
an attractive option for screening and mechanistic studies, they
may miss effects that would occur only in whole organisms. In
in vitro bioassays, the range of responses can include anything from
simple receptor binding, to the expression of endogenous or
exogenous genes, to cell proliferation and differentiation. The most
widely studied EDCs are estrogenic and anti-estrogenic due, at
least in part, to the role of estrogens in breast cancer. In fact, some
of the most commonly used cellular bioassays for estrogens were
developed for breast cancer research (e.g., the MCF-7 cell
proliferation assay) [57]. In such a study, a human breast cancer
cell line (MCF-7) was used to investigate the cumulative
estrogenicity profiles elicited during the oxidation of three
estrogenic compounds: bisphenol A (BPA), E2, and EE2. While
estrogen and androgen cell lines are used most commonly in EDC
testing, cell lines capable of detecting impacts on the thyroid have
also been developed and are needed for EDC screening [58,59].
For direct measurements at trace levels (sub-mg/L), an
extraction step is typically used to concentrate the target
compounds to a detectable level. Conventional extraction techni-
ques such as liquid-liquid [60–62], Soxhlet [63–65], and steam
distillation [66–68], have been used to extract EDCs and PPCPs
from water; however, solid-phase extraction (SPE) is by far the
most common technique used for sample improvement. SPE uses a
stationary phase that binds target compounds as the liquid phase,
in this case water, is passed through the SPE device.
GC has long been used for chemical analyses. Conventionally,
GC involves injecting a liquid sample into a heated injection
chamber, where the compounds are rapidly vaporized and swept
by a carrier gas, usually helium, onto a long, thin coated silica
chromatography column (e.g., 30-m long by 0.25-mm diameter)
coated internally with a stationary phase [69].
Some mass analyzers (i.e., ion trap, triple quadrupole) can
perform tandem mass spectrometry (MS/MS). In MS/MS, the
analyte is ionized and then fragmented to produce product ions.
MS/MS transitions are exclusive for a given compound and result in
lower background noise and higher signal-to-noise ratios, and thus
MS/MS methods are favored in the analysis of complex matrices,
such as wastewater effluents. Numerous studies have reported
detection of various EDCs and PPCPs at very low concentrations
(sub-mg/L) by GC-MS/MS [70–73].
Although GC/MS has many advantages over other analytical
techniques, the instrumentation is costly and difficult to operate
and maintain. These disadvantages have resulted in the increased
popularity of other analytical methods, such as LC/MS. LC has been
3
used extensively in the analysis of organic compounds in water.
Unlike GC/MS, the separation of analytes in LC/MS occurs in the
liquid phase. Thus, analytes reach the mass spectrometer as a
liquid rather than as a gas. Three main types of ionization are used
in LC/MS: electrospray ionization, atmospheric pressure chemical
ionization, and atmospheric pressure photoionization. While
LC/MS has facilitated the analysis of many compounds, it has
several limitations. LC/MS systems are expensive and specialized
training and experience are necessary. Analysis time is one of
the important factors for EDC/PPCP analysis. A method for the
analysis of 36 EDCs and PPCPs using ultra-high performance (UHP)
LC-MS/MS was developed recently [74]. UHPLC-MS/MS in both
positive and negative electrospray ionization modes was used to
achieve optimum sensitivity while reducing sample analysis time
(<20 min), compared with previously published methods.
3. Removal of EDCs and PPCPs in water and wastewater
treatment plants
To evaluate the potential for exposure of humans to EDCs/PPCPs
and to design more effective treatment systems, environmental
professionals must understand the mechanisms by which EDCs
and PPCPs are attenuated in engineered systems. Over the last
decade, many studies have reported on the behavior of EDCs and
PPCPs in drinking water treatment [4,27,72,73,75] and wastewater
treatment processes [7,11,49,76]. While monitoring studies of
EDCs and PPCPs provide insight into the fate and transport of the
compounds in WTP and WWTPs, many have shown that
conventional drinking and wastewater treatment plants can not
remove many EDCs and PPCPs completely. More insight into
removal processes has been obtained by examining specific
treatment processes [16]. Table 1 lists the anticipated perfor-
mances of different unit processes, based on literature reports with
specific classes of compounds or similarities to other trace
pollutants that have been studied in more detail.
3.1. Removal in water treatment plants
As mentioned previously, conventional WTPs typically consist
of coagulation followed by flocculation, sedimentation, filtration,
and disinfection. Metal salts (e.g., aluminum sulfate, ferric
chloride) are commonly added to destabilize particles present in
the water and/or to precipitate new particles (coagulation),
aggregate particles (flocculation), and improve the settling
characteristics of particles (clarification). Previous studies have
shown that the use of coagulation removes a small percentage of
the EDCs and PPCPs in aqueous solutions [27,77]. However, more
EDC/PPCP could be removed if these compounds partitioned onto
the particulate matter originally present in the source water or
partition/adsorb onto metal (hydr)oxide or carbonate precipitates
formed through coagulation. For hydrophobic compounds, parti-
tioning can be predicted based on KOW [78]. Under the conditions
encountered during water treatment, only those EDCs and PPCPs
with relatively high KOW values (i.e., >105) will be removed to an
appreciable degree by this mechanism.
Activated carbon can be used to remove numerous pesticides,
pharmaceuticals, and estrogenic compounds [27,77,79]. The
removal performance of activated carbon is governed by
the physicochemical properties of the sorbent (surface area, pore
size distribution, surface charge, oxygen content) and the properties
(shape, size, charge, and hydrophobicity) of the solute. Hydrophobic
interactions are the main mechanism of removal for most organic
compounds in activated carbon adsorption systems. As a result of
the hydrophobic attractions, activated carbon removes most non-
polar organic compounds (i.e., those compounds with log KOW > 2)
effectively. However, ion exchange interactions can result in the
4 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11

Table 1
Unit processes and operations used for EDC and PPCP removal.

Group Classification AC BAC CNT O3/AOPs UV Cl2/ClO2 Coagulation/ Softening/metal NF RO Degradation

flocculation oxides {B/P/AS}*

EDCs Pesticides E E G–E L–E E P–E P G G E E {P}

Industrial chemicals E E F–E F–G E P P–L P–L E E G–E {B}
Steroids E E G–E E E E P P–L G E L–E {B}
Metals G G F–G P P P F–G F–G G E P {B}, E {AS}
Inorganics P–L F P–L P P P P G G E P–L

PhACs Antibiotics F–G E F–E L–E F–G P–G P–L P–L E E E {B}G–E {P}
Antidepressants G–E G–E F–E L–E F–G P–F P–L P–L G - E E G–E
Anti-inflammatories E G–E F–E E E P–F P P–L G - E E E {B}
Lipid regulators E E G–E E F–G P–F P P–L G - E E P {B}
X-Ray contrast media G–E G–E P–F L–E F–G P–F P–L P–L G - E E E {B and P}
Psychiatric control G–E G–E F–E L–E F–G P–F P–L P–L G - E E G–E

PCPs Synthetic scents G–E G–E F–G L–E E P–F P–L P–L G–E E E {B}
Sunscreens G–E G–E F–G L–E F–G P–F P–L P–L G–E E G–E
Antimicrobials G–E G–E G–E L–E F–G P–F P–L P–L G–E E F {P}
Surfactants/detergents E E G–E F–G F–G P P–L P–L E E L–E {B}

Source: Modified from [16].

PhACs = pharmaceuticals; PCPs = personal care products; BAC = biological activated carbon; AOPs = advanced oxidation processes; UV = ultraviolet; NF = nanofiltration;
RO = reverse osmosis; *B = biodegradation, P = photodegradation (solar); E = excellent (>90%), G = good (70–90%), F = fair (40–70%), L = low (20–40%), P = poor (<20%).

removal of polar solutes [80]. A previous study showed that a linear
regression analysis yielded the following relationship: [percentage
removal] = 15  [log Kow] + 27% (n = 22; R2 = 0.88) for various EDCs
and PPCPs [27]. However, the log KOW value is estimated only for the
neutral molecular form, and predictions of log KOW have been
criticized [81].
In the US, free chlorine (i.e., HOCl and OCl) is used widely for
both disinfection and the oxidation of reduced inorganic species.
Free chlorine reacts quickly with phenolic compounds, mostly
through the reaction between hypochlorous acid and the
deprotonated phenolate anion [57,82]. A previous study examined
various drinking supplies that were spiked with 62 different EDCs
and PPCPs before chlorination [27]. In that study, ionized
functional groups in the EDCs and PPCPs had substantial effects
on chlorine reactivity; deprotonated groups generally had second-
order rate constants several orders of magnitude greater than
those of protonated groups [83]. In a separation study, it was
observed that polyaromatic hydrocarbons (PAHs) containing
aromatic benzene rings had high reactivity with chlorine
[84]. However, several studies have shown that organic com-
pounds react more rapidly with ozone than chlorine [4,27,85].
In ozonation, two strong oxidants (molecular ozone, O3, and
hydroxyl radicals, HO.) can cause the transformation of EDCs
and PPCPs and other organic compounds [86]. Preliminary data for
a set of EDC/PPCP compounds showed a wide range of reactivity
for reactions with ozone: for example, roxithromycin (4.5  106
1/M s), diclofenac (>105 1/M s), ethynylestradiol (>105 1/M s),
carbamazepine (0.78–3  105 1/M s), sulfamethoxazole (105
1/M s), bezafibrate (590 1/M s), ibuprofen (6 1/M s), diazepam
(0.95 L/M s), and iopromide 0.8 1/M s) [87]. Common structural
properties existed for the most highly reactive compounds among
the 62 EDCs and PPCPs, generally including activated aromatic
ring structures (i.e., hydroxyl or amine functionalities) and low
pKa values [27]. Additionally, deprotonated species reacted more
rapidly with electrophilic ozone, because they are stronger
nucleophiles, while additional compounds in this group included
other substituted (chlorine, methyl, aldehydes) aromatics and
PAHs. From those previous studies, certain generalizations
were observed in the reactivity of chlorine and ozone
[16]. First, aromatic compounds were more reactive than aliphatic
compounds. Second, the general order of reactivity from highest
to lowest for aromatic or aliphatic compounds was:
thiols > amines > hydroxyl > carboxyl. Finally, dissociated acidic
compounds were more reactive than protonated forms (i.e.,
reactivity increased with pH), but non-dissociated bases are more
reactive when not protonated.
3.2. Removal in wastewater treatment plants
Numerous studies have reported the removal of EDCs and
PPCPs in WWTPs with ‘conventional’ biological processes, such
activated sludge (AS), biofiltration, and soil aquifer treatment
[88–97]. While those processes show limited EDC/PPCP removal,
the studies demonstrated that the removal efficiency of these
compounds varied greatly depending on several factors, including
the physicochemical properties of the pollutants (e.g., pKa and
KOW) and the type of wastewater treatment technology used (e.g.,
dilution of wastewater effluent, rainfall, and temperature).
However, it remains challenging to examine the removal mecha-
nisms, such as biodegradation, adsorption to sludge, and oxidation
by chlorine and ozone. EDCs and PPCPs widely detected in WWTPs
are typically classified as pesticides, steroids, antibiotics, analge-
sics, anti-inflammatories, contrast agents, synthetic scents, and
antimicrobials. Among them, antibiotics, such as triclocarban,
triclosan, trimethoprim, and sulfamethoxazole, were found
commonly in WWTP samples [17,98,99]. The relatively high
removal efficiency (>80%) found for triclocarban was due
mainly to its high hydrophobicity (log KOW = 4.90) [17], so it is
presumably due mainly to absorption to sludge [99], although it is
not readily biodegradable [98]. It was somewhat unexpected that
relatively hydrophilic sulfamethoxazole (log KOW = 0.89) also
showed fairly high removal efficiency, although this was presum-
ably due to oxidation during chlorination [27]. However, hydro-
philic trimethoprim (log KOW = 0.91) showed very low removal
efficiencies due to its low biodegradability [88] and poor
adsorption to sludge [100], although trimethoprim can be removed
to some degree by chlorine treatment in a WWTP [27]. Analgesics
and anti-inflammatories, such as diclofenac, naproxen, and
ibuprofen, have been widely detected at high concentrations
(>1000 ng/L) in WWTPs [7,11,17]. These high concentrations are
due primarily to their high usage in the community, because their
removal efficiencies are actually very high (>90%). These high
removal efficiencies can be explained by a combination of the three
mechanisms: biodegradability, adsorption to sludge, and oxidation
by chlorine [17]. While diclofenac has low biodegradability and
adsorption to sludge [101,102], the high removal efficiency is
 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11
achieved mainly through chlorination. Additionally, while a
previous study reported that analgesics, including naproxen and
ibuprofen, are readily removed from wastewater due to their
biodegradability [93], some removal may also occur through
adsorption to activated sludge, due to the moderate partition
coefficients of these hydrophobic compounds [102].
4. Removal mechanisms of various EDCs and PPCPs by CNTs
Compared with ‘conventional’ adsorbents (granular activated
carbon, GAC, and PAC) commonly used in water treatment plants,
much less is known about the behavior of EDCs and PPCPs with
CNTs. Thus, the purpose of this section is to summarize existing
removal mechanisms with adsorption of EDCs and PPCPs by CNTs
having various physicochemical properties and to predict the
behavior of different classes of EDCs and PPCPs, based on their
physicochemical properties.
4.1. Removal influenced by the adsorption properties of CNTs
4.1.1. CNT properties
Compared with AC, CNTs have significantly different physico-
chemical properties that are far more well-defined and uniform.
For example, understanding parameters (e.g., pore diameter
distribution and adsorption energy distribution) is necessary to
determine adsorption on ACs, whereas for CNTs, the various well-
defined adsorption sites available to the adsorbed molecules can be
considered directly [49].
The adsorption properties of CNTs depend on various factors,
including adsorption site, surface area, purity, and surface
functional groups [103]. There are four potential sites in CNT
bundles for the adsorption of different pollutants: (i) ‘‘internal
sites,’’ the hollow interior of individual nanotubes (available only if
the caps are removed and the open ends are unblocked), (ii)
‘‘interstitial channels,’’ the channels between individual nanotubes
in the bundles, (iii) ‘‘grooves,’’ the grooves present on the periphery
of a nanotube bundle and the exterior surface of the outermost
nanotubes, where two adjacent parallel tubes meet, and (iv) the
‘‘outside surface,’’ the curved surface of individual nanotubes on
the outside of the nanotube bundles [104,105].
Additionally, the fraction of opened and unblocked nanotubes
can influence the overall adsorption capacity significantly, because
opened CNT bundles provide more adsorption sites than capped
CNTs [49]. While the theoretical specific surface area (SSA) of
nanotubes is very large, and can reach 2600 m2/g, the nanotube
cylinders are closed, and their SSA is, in fact, as much as 20 times
lower, due to tangling and aggregation [106].
A CNT that contains one layer of a rolled graphite sheet is called
a single-walled carbon nanotube (SWNT), whereas when several
SWNTs with different diameters are nested concentrically
together, it is called a multi-walled CNT (MWNT) [107]. The
distance between the layers of MWNTs is too small for any organic
compounds to fit into [108]. CNTs tend to aggregate together as
bundles due to van der Waals interactions [109]. A previous study
showed that the experimental analysis of nanotube sorption
capacity concurs with results obtained in the study of SSA,
indicating that for the three nanotube types, the sorption capacity
for an EDC (e.g., BPA) increases in the following order: MWNTs-
COOH < MWNTs < SWNTs [110]. As briefly described above, the
difficulty in stabilizing SWNTs is due to their propensity to
aggregate, particularly in aqueous systems, due to non-specific
hydrophobic interaction between tubes, as well as substantial van
der Waals attractions [111,112].
Ultrasonication (US) enhances the dispersion and debundling of
CNTs greatly [113]. The degradation rates of acetaminophen (AAP)
and naproxen (NPX) were studied in the absence and presence of
5
SWNTs under ultrasonication conditions [114]. The degradation
rates of AAP and NPX were higher for US/SWNT reactions than US
reactions. The presence of SWNTs increased the degradation rates
of AAP and NPX under conditions of SWNT adsorption and US/
SWNT reactions compared with US reactions. The findings
suggested that the dispersion of SWNTs facilitated rapid adsorp-
tion, because small, dispersed particles would provide additional
sites for adsorption.
While it is known that both morphology and impurities
influence the surface area and pore volume of CNT bundles, purity
is often neglected. There is a general issue that impurities can
readily coat the surfaces of CNT bundles, consequently, influencing
the adsorption on the external surface of the outermost nanotubes
of bundles [115]. The lower uptake (on a mass basis) of the
Carbolex and Carbon Solutions SWNTs for atrazine, versus Cheap
Tubes SWNTs, is likely caused by metal impurities, leading to a
lower carbon content (of the order of 60–70%, versus nearly 95% for
the Cheap Tubes) [116]. The impurities contribute a significant
mass but do not provide strong adsorption sites.
It is known that oxygen-containing functional groups (i.e., –OH,
–C55O, and –COOH) of CNTs influence the maximum adsorption
capacity. These functional groups can be added intentionally by
oxidation using various acids [117–119], ozone [120,121], and
plasma [122] or be removed by heat treatment [123]. While
functionalization of CNTs is aimed at easy processing, the
adsorption properties for organic chemicals can also be changed
greatly [107]. Functional groups can alter the wettability of CNT
surfaces, and thus make CNTs more hydrophilic and appropriate
for the adsorption of somewhat lower molecular weight and polar
compounds [124]. The influence of oxygen on the sorption of
atrazine was evaluated using three MWNTs, MWNT-O (0.85%),
MWNT-O (2.2%), and MWNT-O (7.1%), containing variable oxygen
contents but having otherwise similar physical properties
[125]. Maximum capacity was negatively related to the carboxylic
groups and surface oxygen content of the MWNTs. The mechanism
responsible for this was attributed to a more negatively charged
MWNT surface due to deprotonation of carboxylic groups at the
equilibrium sorption pH 6, where water adsorption is more active
than that of atrazine.
4.1.2. Process parameters influencing CNT adsorption properties
While CNT properties, including adsorption site, surface area,
purity, and surface functional groups, are significant for adsorp-
tion, process parameters, such as pH, ionic strength/background
ions, contact time, initial solute concentration, temperature, and
competition, also play important roles in determining the sorption
rate of EDCs and PPCPs onto CNTs.pH: The pH of the solution is a
significant factor influencing the sorption process because of its
effect on the stability and chemical form of EDCs and PPCPs and
also on the surface characteristics of CNTs. A decrease in the
sorption potential of the nanotubes at higher pH values occurred
for BPA (a well-known EDC) in wastewater [110]. BPA is a weak
acid, with a pKa value of 9.6–10.2 [79]. Therefore, in alkaline
wastewater, it releases a proton and forms bisphenolate anions.
Reduction of adsorption for BPA when pH > pKa was apparent, due
to growing repulsion forces and a reduction in p–p interactions
between bisphenolate anions and the surface of the MWNTs-COOH
[110]. The effects of pH on the adsorption of BPA and EE2 in young
(pH 5 and conductivity 12,500 mS/cm) and old (pH 7.5 and
conductivity 3250 mS/cm) landfill leachates were evaluated
[30]. In that study, an increase in the pH of the leachates from
3.5 to 7.5 had no effect on the adsorption of BPA, regardless of the
type of leachate. Decreased adsorption of BPA was observed in both
young and old leachate samples when the pH was increased to
11. Changes in the pH resulted in minimal adsorption variation of
EE2 (<2%) in the young leachate. In old leachate, however, the
6 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11
adsorption of EE2 decreased, by 32%, with an increase in pH, from
3.5 to 11. The contrast between the reduction in the adsorption of
EE2 (log KOW =  10.5) and BPA (log KOW = 9.6–10.2) with varying
pH levels may be attributable to the different log KOW values of the
compounds [126]. In a separate study, the sorption of atrazine
(pKa = 1.68) on both MWNTs-O (0.85%) and MWNTs-O (2.2%)
remained constant over the pH range 3.5-9, while the sorption of
atrazine on to MWNTs-O (7.1%) decreased slowly between pH
3.5 and pH 5, and there was no additional decrease beyond pH 5
[125]. Atrazine would not be protonated and weak forces, such as H
bonding and hydrophobic attraction, may become significant at
those pH ranges.
Ionic strength, background ions, and NOM: The effects of ionic
strength on the adsorption of BPA and EE2 by SWNTs were
determined in landfill leachate [30]. Increases in the NaCl
concentration, from 0 to 320 mM, did not significantly change
the adsorption of either BPA or EE2 in either leachate solution.
Many researchers have found that increasing the ionic strength
had no significant effect on the adsorption of various organic
chemicals [127]. The adsorption of BPA and EE2 from the young
leachate by SWNTs was not affected by increasing the concen-
tration of Ca2+, while using the old leachate conditions, an
increase in the Ca2+ concentration from 0 to 150 mM increased
the adsorption of BPA and EE2 by 12% and 19%, respectively
[30]. One explanation for this could be a ‘‘salting-out’’ effect,
which refers to the reduced solubility of organic compounds in
aqueous salt solutions [128]. The adsorption of BPA and EE2 could
be improved by the interactions between the chemicals and the
complexes that can form between the humic acid and the Ca2+
ions [30]. In the same study, an increase in the concentration of
glucose (i.e., hydrophilic) did not have a significant effect on the
adsorption of BPA and EE2, while removal efficiencies of 15% for
BPA and 20% for EE2 were achieved with humic acid (i.e.,
hydrophobic) only, indicating that hydrophobic interactions
between BPA/EE2 and humic acid contributed to their removal.
The concentration of these complexes increased with higher
concentrations of Ca2+, and with the hydrophobic nature of humic
acid, these complexes may facilitate additional hydrophobic
interactions among BPA and EE2 by providing additional surfaces
that can serve as adsorption sites.
The effects of NOM (Suwannee River fulvic acid, SRFA) on the
sorption of ibuprofen (IBU) and triclosan (TCS) were determined on
SWNTs, MWNTs, and MWNTs-O. The adsorption of IBU with SRFA
decreased 2.3, 6.7, and 5.5 times, respectively, compared with IBU
alone. This is presumably because SRFA competes with organic
contaminants through two major mechanisms on the CNTs [129]:
(i) SRFA may compete with IBU and TCS for sorption sites on CNT
surfaces through direct site competition, and (ii) large SRFA
molecules may be sorbed to the entrances of the internal edges of
CNTs, which are capable of sorbing IBU and TCS, resulting in
blockage of these sorption sites. The direct site competition of SRFA
and IBU would be lower for SWNTs than MWNTs, because SWNTs
have higher surface areas and larger entrances to internal edges
[130].
Much current research is focused on the sorption of EDCs and
PPCPs by CNTs in isolation and ignores any potential interactions
between mixtures of metals and organic contaminants that may
influence sorption. A previous study showed that oxygenated
functionalities, mainly carboxylic groups on MWNTs-O surfaces,
reduced the sorption of atrazine [125]. In that study, metal cations,
including Cu2+, Pb2+, and Cd2+, decreased the sorption of atrazine,
depending on the density of the oxygenated functionalities,
presumably due to the formation of surface or inner-sphere
complexes of those metals through carboxylic groups and
hydration. In a separate study, the co-adsorption of Pb2+ with
diuron or dichlobenil suggested that Pb2+ significantly suppressed
the adsorption of diuron or dichlobenil on MWNTs-O (7.58%), and
had slight effects on the adsorption of herbicides onto MWNTs-O
(2.66%) and MWNTs-O (1.52%) [131].
Temperature: The adsorption of BPA and E2 to SWNTs and acid-
treated SWNTs (t-SWNTs) was examined at various temperatures
over an equilibration period of 72 h [119]. In this study, in total,
19.4, 15.4, and 14.3 mg/g of BPA were adsorbed on SWNTs, while
8.0, 6.4, and 5.1 mg/g were adsorbed on t-SWNTs at 280, 295, and
315 K, respectively. This decrease in BPA sorption with increasing
temperature can be attributed to the associated exothermic
reaction mechanism described elsewhere [132]. In a separate
study, an increase in temperature resulted in a corresponding
decrease in the sorption of atrazine [133]. This also indicated that
the uptake of atrazine on CNTs was an exothermic process. The
observed negative DH0 suggested an exothermic sorption,
supported by the observation that sorption of atrazine onto
MWNTs decreased with increase in temperature. All the DH0
values, 36.87, 28.39, and 37.24 kJ/mol, were less than 40 kJ/
mol, indicating that the sorption of atrazine onto MWNTs (MWNT-
O (0.85%), MWNT-O (2.2%), and MWNT-O (7.1%)), respectively, was
mainly a physisorption process [38,39].
4.2. Removal of selected EDC/PPCP by CNTs
The characteristics of EDCs and PPCPs play a key role in their
removal rate in aqueous solutions. It is generally accepted that the
three major classes of endocrine-disruption endpoints are
estrogenic (compounds that mimic or block natural estrogen),
androgenic (compounds that mimic or block natural testosterone),
and thyroidal (compounds with direct or indirect impacts on the
thyroid) [16]. Pesticides, steroids, metals, and perchlorate are
typical EDCs that have been found commonly in water and
wastewater. Table 2 presents removal information by CNTs on
selected representative classes of EDCs and PPCPs, based on
literature reports. The removal efficiency was found to vary by
compound, and is described in turn for each group of compounds
below.
4.2.1. EDCs
Bisphenols: The adsorption of BPA by the SWNTs differed greatly
between the young and the old landfill leachates, which have
different water chemistry conditions, as described previously. In
young leachate (pH 5 and conductivity 12,500 mS/cm), the removal
of BPA reached 69%, while in the old leachate (pH 7.5 and
conductivity 3250 mS/cm), the removal was much lower, 33%
[30]. In addition to the water chemistry effects on the charge and
hydrophobicity of BPA and SWNTs, which may influence its
adsorption, it was also assumed that SWNTs aggregates were
considerably more compact in the old leachate (higher Ca2+ and
hydrophobic dissolved organic carbon (DOC)) than those in the
young leachate (lower Ca2+ and hydrophobic DOC). Such compact-
ness may have also reduced the interstitial spaces and groove areas
in the SWNT aggregates [119]. Among the SWNT adsorption sites
[105]–(i) inside the tubes, (ii) interstitial channels, (iii) external
groove areas, and (iv) external surfaces of aggregates–a previous
study suggested that the groove areas and interstitial spaces were
the most suitable places to accommodate ‘butterfly shaped’ BPA
molecules [126]. As noted above, the compactness of the SWNT
bundle ultimately eliminates the groove areas and interstitial
spaces, and thus BPA adsorption by SWNTs would be expected to
be reduced significantly in the old leachate.
Hormones: As described previously, the adsorption of EE2 was
significantly higher than that of BPA between the young and old
leachates [30]. Overall, a significantly larger fraction of EE2 was
removed from both leachate solutions than of BPA. The higher
adsorption of EE2 over BPA can possibly be explained by its larger
 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11 7

Table 2
Summary of selected EDC and PPCP removal by CNTs.

EDC/PPCP class Adsorbent Surface area (m2/g) Co (mg/L) Source water qm (mg/g) Reference

Analgesics
Ibuprofen SWNTs, MWNTs, MWNTs-O 1020, 283, 287 50–2000 Synthetic water 232, 81, 19 [130]
Diclofenac MWNTs 162 NA Pure water, 41.4, 22.3 [155]
WW effluent
Antibiotics
Oxytetracycline MWNTs 58–357 2500 Synthetic water 41–7,910a [162]
ASulfapyridine MWNTs 300 210–7300 Synthetic water 103–104b [157]
MWNTs 174 100,000 Synthetic water 600–800b [169]
Sulfadimethoxine MWNTS 174 100,000 Synthetic water 1300–1500b [169]
Sulfamethoxazole MWNTs 300 380–2500 Synthetic water 102–103b [157]
SWNTs, MWNTs 410–653, 157–422 810–48,000 Synthetic water 38,900–83,400, [159]
3780–24,100b
Tetracycline SWNTs, MWNTs 410–653, 157–422 1400–84,000 Synthetic water 34,100–55,500, [159]
12,500–45,300b
Tylosin MWNTs 157–422 2900–174,000 Synthetic water 11,300–33,900b [159]
MWNTs-H 228 20,000–100,000 Synthetic water 85 [170]
Antiepileptics
Carbamazepine MWNTs-COOH 200–400 90,000 Synthetic water 13.9c [28]
SWNTs 380 10–20,000 Synthetic water 130 [171]
including DOM
MWNTs 58–357 2500 Synthetic water 30–190a [162]
MWNTs/Al2O3 237 3658 Synthetic water 37.2 [172]
Antiseptics
Triclosan SWNTs, MWNTs, MWNTs-O 1020, 283, 287 50–2000 Synthetic water 558, 435, 106 [130]
MWNTs 281 1000–12,000 Synthetic water 155–166 [165]
Bisphenols
Bisphenol A SWNTs, MWNTs, MWNTs-COOH 467, 456, 338 1000 Synthetic WW 58.7, 18.7, 21.4 [110]
SWNTs 407 2280 Synthetic landfill 22.6–44.8 [30]
leachate
SWNTs, acid treated SWNTs 407 228 Synthetic water 52.8, 41.4 [119]
SWNTs 407 228 Synthetic seawater, 13.4–16.1 [29]
brackish water
SWNTs 380 10–20,000 Synthetic water 359 [171]
including DOM
Bisphenol AP MWNTs, MWNTs-OH, >500 20,000 Synthetic water 136–162 [173]
MWNTs-COOH
Hormones
17a-ethinyl estradiol SWNTs 407, 233 2960 Synthetic landfill 24.9–120 [30]
leachate
SWNTs, acid treated SWNTs 407 296 Synthetic water 115, 101 [119]
SWNTs 407 296 Synthetic seawater, 35.6–35.7 [29]
brackish water
MWNTs 84.3 5000 Synthetic water 0.472 [174]
SWNTs, MWNTs 541, 174 300–3,300 Synthetic water 276, 119 [126]
Perchlorate SWNTs, MWNTs, DWNTs 418, 176, 619 1000 Synthetic water 1.13, 0.29, 1.50 [151]
SWNTs 364 20,000 Synthetic water 10.0–13.6 [152]
Pesticides/herbicides
Atrazine SWNTs 407 100 Synthetic water 4.97c [116]
MWNTs-O 167, 178, 185 500–20,000 Synthetic water 47.6, 36.1, 20.1 [125]
(0.85, 2.16, 7.07%) including Cu, Pb,
or Cd
MWNTs-O 167, 178, 185 1000–8000 Synthetic water 60.3, 33,3, 24.0 [133]
(0.85, 2.16, 7.07%)
MWNTs 189 1000–30,000 Synthetic water 61–67 [175]
Magnetic MWNTs 163 5000 Synthetic water 42 [176]
SWNTs, MWNTs 167, 300 30,000 Synthetic water 33, 110 [177]
Diuron MWNTs-O 159, 157, 161 600–22,000 Synthetic water 50.3, 48.0, 29.8 [134]
(1.52, 2.66, 7.58%)
Dichlobenil MWNTs-O 159, 157, 161 600–13,000 Synthetic water 39.4, 37.2, 23.5 [134]
(1.52, 2.66, 7.58%)
Isoproturon MWNTs 162 NA Pure water, 16.3, 8.1 [155]
WW effluent
Stimulant
Caffeine MWNTs 162 NA Pure water 41.6 [155]

Co = EDC/PPCP initial concentration; WW = wastewater; NA = not available; qm = maximum sorption capacity.

a
Sorption capacity from Polanyi–Manes.
b
Distribution coefficient (L/kg) calculated from the Freundlich model.
c
KF = Capacity factor (mg/g)/(m3/mg) for the Freundlich model.

log KOW values, suggesting that hydrophobic interactions of the
EDCs with the SWNTs are the dominant adsorption mechanism. A
separate study reported that the K/KHW (adsorption coefficient/
hexadecane-water partition coefficient) values of EE2 for the
SWNTs and MWNTs were six orders of magnitude higher than
naphthalene, phenanthrene, pyrene, which is consistent with the
order of benzene ring numbers [126]. While this finding suggests
that p–p bonding is a significant force for PAH adsorption on
carbon nanomaterials (CNMs), the difference in benzene ring
numbers does not explain the higher adsorption of EE2. Because
8 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11
the phenol group is a charge donor, and CNMs can be donors or
acceptors [109], the p–p bond formed between EE2 and CNMs is a
donor-acceptor system, and much stronger than that between
PAHs and CNMs.
Pesticides and herbicides: The adsorption of diuron and
dichlobenil (herbicides) on MWNTs–MWNT-O (1.52%), MWNT-O
(2.66%), and MWNT-O (7.58%)–was determined [134]. The findings
suggested that the adsorption of diuron and dichlobenil increased
with increasing surface areas and pore volumes of MWNTs. The
values of adsorbed amount and surface coverage of diuron were
larger than those of dichlobenil, although the surface area,
molecular volume, and water solubility of dichlobenil are smaller.
This may be attributable to larger van der Waals interactions for
diuron (log KOW = 2.85) than for dichlobenil (log KOW = 2.74), due
to the relatively greater dipolar moment [131]. These data indicate
that the surface coverage of both herbicides is >1, suggesting that
the adsorption of both on MWNTs was multilayer. The adsorption
of atrazine by surfactant-dispersed SWNTs and MWNTs showed
that surfactant treatment inhibited atrazine adsorption signifi-
cantly [135]. The modified CNTs may have become more
hydrophilic, because the hydrophilic fraction of the surfactant
micelles faces the water, which reduces the adsorption of atrazine
to a great extent. In that study, the inhibitory effects of cationic
(cetyltrimethylammonium bromide, CTAB) and anionic (sodium
dodecylbenzene sulfonate, SDBS) surfactants on the adsorption of
MWNTs were similar, while the inhibitory effect of SDBS on SWNTs
was somewhat greater than that of CTAB. For the SWNTs of lower
purity and containing more oxygen atoms, the existence of
oxygen-containing functional groups may then have affected the
affinity of cationic and anionic surfactants, and given rise to the
difference in inhibition of atrazine adsorption, as observed.
However, the high hydrophobicity of MWNTs surfaces created
an equal affinity for cationic or anionic surfactants, and therefore
the inhibitory effects on atrazine adsorption were similar with
either surfactant. Additionally, the surfactant treatment increased
the dispersion of MWNTs, and consequently an adsorption surface
area increase would be expected [135].
Metals and perchlorate: The sorption mechanisms between
metal ions and CNTs are very complex, including electrostatic
interactions (i.e., attraction), sorption-precipitation, and chemical
interactions between the metal ions and the surface functional
groups on the CNTs. A previous review summarized the technical
feasibility of various types of raw and surface- oxidized carbon
nanotubes (CNTs) for the sorption of divalent metal ions (Cd2+,
Cu2+, Ni2+, Pb2+, and Zn2+) from aqueous solution [48]. In that study,
it was shown that the sorption mechanisms appeared to be due
mostly to chemical interactions between the metal ions and the
surface functional groups (–OH, –C5 5O, and –COOH) of the CNTs.
The functional groups, oxidized by NaOCl, HNO3, KMnO4, or H2O2,
strongly enhanced the sorption capacities of CNTs [136–139].
Perchlorate (ClO4), a commonly known anionic EDC, has been
detected widely at various concentrations (<1–100 mg/L) in
drinking water and seawater [140], tea and soft drinks [141],
dairy milk [142–145], saliva [146], rice [147], leafy vegetables
[148], seaweeds [149], and wastewater effluent [150]. While there
are many studies on metal ion removal by CNTs [31,136–139], only
a few relate to perchlorate removal by CNTs [151,152]. The overall
adsorption of ClO4 varied, depending on the different CNTs–
double-walled CNTs (DWNTs, 619 m2/g) > SWNTs (418 m2/
g) > MWNTs (176 m2/g) [151] – whereas the specific adsorption
capacity on a per-meter-squared basis of CNTs sample decreased
as SWNTs > DWNTs > MWNTs. This indicates that the surface area
of SWNTs is more efficient than that of DWNTs for perchlorate
adsorption. However, previous studies indicated that surface
charge, rather than specific surface area, was the vital parameter in
controlling perchlorate adsorption [153]. Background anions,
including SO42, NO3, and Cl, reduced ClO4 adsorption by
the CNTs significantly, while the co-existence of Fe3+ and
cetyltrimethylammonium cations enhanced ClO4 adsorption by
two- to three-fold [151]. Also, in that study, ClO4 adsorption was
promoted by oxidized DWNTs due to the introduction of more
oxygen-containing functional groups, which served as additional
adsorption sites.
4.2.2. PPCPs
Analgesics: The maximum sorption capacity of IBU for MWNTs
was ca. threefold less than for SWNTs [130]. Compared with
MWNTs (283 m2/g), SWNTs (1020 m2/g) have higher SSA and pore
volume due to the single layer. Often, the SSA for SWNT is higher
than that for MWNT due to the difference in layer number (and,
consequently, the diameter of the CNTs). In the application of
adsorption for wastewater treatment, the treated solution will
usually be a mixture of many compounds rather than a single one.
Interactions of those compounds may enhance or inhibit the
adsorption capacity of the adsorbent [154]. In the case of
wastewater treatment plant effluent, the matrix is dominated
by humic acids, proteins, carbohydrates, inorganic compounds,
and other biological building blocks. All these compounds compete
with diclofenac for binding sites on the MWNTs, decreasing the
availability of the binding sites for trace compounds [155]. In that
study, it was also observed that the adsorption capacity of
diclofenac alone is greater than the capacity of the compound in
the wastewater, suggesting that the background NOM had a
greater influence on the adsorption process [156].
Antibiotics: Sulfapyridine exhibited much higher adsorption
nonlinearity than sulfamethoxazole for the MWNTs within the
tested concentration ranges (8.4  104 to 1.1  102 mmol/L for
sulfapyridine and 1.5  103 to 2  102 mmol/L for sulfamethox-
azole), suggesting a more heterogeneous distribution of the
adsorption (interaction) sites for sulfapyridine [157]. Both sulfa-
pyridine and sulfamethoxazole have one benzene ring and one
aromatic heterocyclic group, which likely interact with the
polarized aromatic rings on the surface of MWNTs through
the mechanism of p–p electron coupling. A previous study
proposed a mechanism of p–p electron donor-acceptor (EDA)
interaction between p-electron acceptor compounds (nitroaro-
matic compounds, tetracycline) and the p-electron-rich regions on
the graphene surface of MWNTs [158]. In addition to dispersion
(p–p stacking) attraction forces, the substituted benzene ring and
the aromatic heterocyclic group of sulfonamides may cause extra
p–p EDA interactions with the graphene surface of carbonaceous
adsorbents [157]. A separate study reported that three antibiotics
(sulfamethoxazole, tetracycline, and tylosin) interacted with
the polarized electron-depleted or electron-rich regions on the
graphitized carbon surfaces of KOH-activated SWNTs and MWNTs
via the mechanism of p–p EDA interactions [159]. Among those
compounds, the protonated amino group in the tetracycline and
tylosin molecules may facilitate strong cation-p bonding with
p-electrons on the graphitized carbon surfaces [160]. The several
functional groups and structures in the tetracycline and tylosin
molecules cause a variety of specific adsorptive interactions on the
surface of CNTs, and thus higher degrees of adsorption nonlinearity
were induced.
Anti-epileptics: An isotherm study has shown that the isotherm
patterns begin to level off, or have already leveled off, as sorbed
concentrations approach the expected coverage for one monolayer
of carbamazepine (CBZ) for MWNT-COOH [28]. Monolayer cover-
age is expected to be between 181–195 mg/g depending on planar
CBZ orientation. The mechanism of p–p stacking may best explain
CBZ physisorption with surfaces. Like many organic sorbates
with one or more benzene rings [116], CBZ has planar conjugated
p-electron systems that can overlap with surface p orbitals of CNTs
 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11
in a favorably attractive geometric configuration. CBZ benzene ring
structures are also expected to act as a p-electron acceptor due to
the electron-withdrawing capabilities of the amide group; the N
atom and with the heterocyclic ring N are in sp2 configurations
with their lone pairs of electrons delocalized in bonds with the
electron-withdrawing carbonyl group [161]. However, incremen-
tal desorption of CBZ from MWNTs was observed [162]. This is
presumably because strong and weak surface sites exit on MWNTs,
based on kinetic modeling, which could allow different degrees of
desorption. Additionally, the formation of covalent bonds, such as
those observed between the functional groups on organic
chemicals and CNTs, could possibly occur between the amide
group of CBZ and surface functional groups (e.g., -COOH) on
MWNTs [124]. In the bi-solute systems, the adsorption isotherm of
CBZ (primary adsorbate) did not change towards linearity,
suggesting that CBZ in the presence of BPA is still capable of
interacting with favorable adsorption sites (which are presumably
not available for, or less favorable to, BPA) and/or exhibits
multilayer adsorption, as noted for CBZ with MWNTs [162].
Antiseptics: TCS, a disinfectant, exhibited noticeably stronger
adsorption affinity with three CNTs (SWNTs, MWNTs, MWTNs-O)
than IBU, presumably due to their differences in hydrophobicity
(log KOW = 4.76 for TCS vs. 3.97 for IBU) [130]. In addition to
hydrophobic interaction, OH groups on TCS may have enhanced
TCS sorption. It was observed that the sorption capacity of 2-
naphthol, containing OH groups, was greater than that of
naphthalene by SWNTs [163]. The study proposed two possible
reasons to explain the effect of OH substitution on organic
compound sorption by CNTs [158]: (i) Attraction between the
adsorbed molecules and molecules in aqueous solution and (ii)
hydrogen bonding between the sorbate’s OH groups and the
sorbent’s O-containing groups. It was also observed that sorption
of phenolics onto CNTs was enhanced significantly by OH
substitution [164]. In a separate study, it was clear that the
adsorption amounts of TCS onto MWNTs increased rapidly with
time and initial concentrations [165]. The lower was the initial
concentration, the faster the equilibria were reached as the rate
constant of pseudo second-order adsorption increased, indicating
that there are many available adsorption sites on the surface of the
MWNTs in the initial stages [166]. As described previously, the
adsorption mechanisms of organic chemicals, including EDCs and
PPCPs, on CNTs is related to the molecular morphology and
functional groups of organic chemicals. Organic molecules, such as
TCS, containing C5 5C double bonds or benzene rings, can form p–p
bonds with MWNTs, which contributes to the strong adsorption of
triclosan onto MWNTs. It has also been reported that bigger
molecules, such as TCS, have a much greater adsorption rate than
smaller molecules, because it is necessary for smaller molecules to
diffuse into inner sites of MWNTs, which is time consuming and
results in extremely low diffusivities [166].
5. Conclusions and areas of future study
This review summarized the adsorption applications of various
types of CNTs in the removal of various EDCs and PPCPs from
aqueous solutions. CNTs have shown high potential adsorption
capacities in the removal of a diverse range of EDCs and PPCPs,
presumably due to their fibrous shape with high aspect ratio,
providing a large external surface area that can be accessed readily
by EDCs and PPCPs. The EDC/PPCP sorption process appears to be
influenced primarily by EDC/PPCP properties, solution chemistry,
and CNT surface chemistry/properties. The modification of CNTs
to provide functional groups can also enhance the sorption
capacity of EDCs and PPCPs significantly. CNT cost currently
stands as a major barrier, and continuous production of CNTs
with low-cost sources is necessary before considering CNTs for
9
large-scale water treatment applications. EDC/PPCP removals by
CNTs are compared with other treatment processes in Table 1,
where values were estimated based on literature reports and/or
chemical structure (size, shape, hydrophobicity, pKa, and
functional group composition).
While numerous reports regarding EDC and PPCP removal by
conventional and advanced water treatment processes are
available, much is still unknown as to the transport of these
emerging contaminants in CNTs. Thus, many additional data
are still needed to better understand the EDC and PPCP removal
by CNTs in water. It is important to better understand the
physicochemical properties of both EDCs/PPCPs (shape, size,
charge, and hydrophobicity) and CNTs (surface area, surface
charge, functional groups, and hydrophobicity), and their associa-
tion with background inorganics, pH, and NOM in raw water
supplies. While CNTs have shown significant potential as superior
sorbents to remove selected EDCs and PPCPs from aqueous
solution, the relatively high unit cost currently limits their
practical use [167]. In addition, it is important to gain more
detailed information with regard to the toxicological impact of
CNTs. The toxicity of CNTs remains a debated issue, while
numerous toxicological studies have currently been reported
[168].
Acknowledgments
This research was supported by a grant (code 14IFIP-B087385-
01) from Industrial Facilities & Infrastructure Research Program
funded by Ministry of Land, Infrastructure and Transport of Korean
government. This research was also supported by the International
Research & Development Program of the National Research
Foundation of Korea (NRF), funded by the Ministry of Education,
Science and Technology (MEST) of Korea (no. 2012R1A1A2044172).
References
[1] USEPA, Endocrine Disruptor Screening and Testing Advisory Committee
(EDSTAC) Final Report. hhttp://www.epa.gov/endo/pubs/edspoverview/
finalrpt.htmi, 1997.
[2] E. Stumm-Zollinger, G.M. Fair, J. Water Pollut. Control Fed. 37 (1965) 1506.
[3] H.H. Tabak, R.L. Bunch, Dev. Ind. Microbiol. 11 (1970) 367.
[4] M.J. Benotti, R.A. Trenholm, B.J. Vanderford, J.C. Holady, B.D. Stanford, S.A.
Snyder, Environ. Sci. Technol. 43 (2009) 597.
[5] H.-S. Chang, K.-H. Choo, B. Lee, S.-J. Choi, J. Hazard. Mater. 172 (2009) 1.
[6] T. Heberer, Toxicol. Lett. 131 (2002) 5.
[7] J. Ryu, Y. Yoon, J. Oh, KSCE J. Civil Eng. 15 (2011) 57.
[8] S.A. Snyder, T.L. Keith, D.A. Verbrugge, E.M. Snyder, T.S. Gross, K. Kannan, J.P.
Giesy, Environ. Sci. Technol. 33 (1999) 2814.
[9] S.A. Snyder, D.A. Verbrugge, R. Pearson, O. Quinones, Y. Yoon, Pract. Period.
Hazard. Toxic, Radioact. Waste Manag.—ASCE 7 (2003) 224.
[10] T.A. Ternes, Water Res. 32 (1998) 3245.
[11] Y. Yoon, J. Ryu, J. Oh, B.G. Choi, S.A. Snyder, Sci. Total Environ. 408 (2010) 636.
[12] P.W. Harvey, D.J. Everett, Best Pract. Res. Clin. Endocrinol. Metabol. 20 (2006)
145.
[13] P. Matthiessen, I. Johnson, Environ. Pollut. 146 (2007) 9.
[14] L.N. Vandenberg, T. Colborn, T.B. Hayes, J.J. Heindel, D.R. Jacobs Jr., D.-H. Lee, J.P.
Myers, T. Shioda, A.M. Soto, F.S. vom Saal, W.V. Welshons, R.T. Zoeller, Reprod.
Toxicol. 38 (2013) 1.
[15] R.T. Zoeller, T.R. Brown, L.L. Doan, A.C. Gore, N.E. Skakkebaek, A.M. Soto, T.J.
Woodruff, F.S.V. Saal, Endocrinology 153 (2012) 4097.
[16] S.A. Snyder, P. Westerhoff, Y. Yoon, D.L. Sedlak, Environ. Eng. Sci. 20 (2003) 449.
[17] J. Ryu, J. Oh, S.A. Snyder, Y. Yoon, Environ. Monit. Assess. 186 (2014) 3239.
[18] N. Vieno, M. Sillanpaa, Environ. Int. 69 (2014) 28.
[19] Y. Luo, W. Guo, H.H. Ngo, N. Long Duc, F.I. Hai, J. Zhang, S. Liang, X.C. Wang, Sci.
Total Environ. 473 (2014) 619.
[20] B. Yang, G.-G. Ying, J.-L. Zhao, S. Liu, L.-J. Zhou, F. Chen, Water Res. 46 (2012)
2194.
[21] C. Park, Y. Fang, S.N. Murthy, J.T. Novak, Water Res. 44 (2010) 1335.
[22] Q. Sui, J. Huang, S. Deng, G. Yu, Q. Fan, Water Res. 44 (2010) 417.
[23] K.E. Conn, L.B. Barber, G.K. Brown, R.L. Siegrist, Environ. Sci. Technol. 40 (2006)
7358.
[24] H.W. Chen, C.H. Liang, Z.M. Wu, E.E. Chang, T.F. Lin, P.C. Chiang, G.S. Wang, Sci.
Total Environ. 449 (2013) 20.
[25] Z.-h. Liu, Y. Kanjo, S. Mizutani, Sci. Total Environ. 407 (2009) 731.
[26] Y. Yoon, J. Ryu, J. Oh, B.-G. Choi, S.A. Snyder, Sci. Total Environ. 408 (2010) 636.
10 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11
[27] P. Westerhoff, Y. Yoon, S. Snyder, E. Wert, Environ. Sci. Technol. 39 (2005)
6649.
[28] N. Cai, P. Larese-Casanova, J. Colloid Interface Sci. 426 (2014) 152.
[29] L. Joseph, J. Heo, Y.-G. Park, J.R.V. Flora, Y. Yoon, Desalination 281 (2011) 68.
[30] L. Joseph, Q. Zaib, I.A. Khan, N.D. Berge, Y.-G. Park, N.B. Saleh, Y. Yoon, Water Res.
45 (2011) 4056.
[31] C. Jung, J. Heo, J. Han, N. Her, S.-J. Lee, J. Oh, J. Ryu, Y. Yoon, Sep. Purif. Technol. 106
(2013) 63.
[32] C. Jung, J. Park, K.H. Lim, S. Park, J. Heo, N. Her, J. Oh, S. Yun, Y. Yoon, J. Hazard.
Mater. 263 (2013) 702.
[33] W.T. Tsai, H.C. Hsu, T.Y. Su, K.Y. Lin, C.M. Lin, J. Colloid Interface Sci. 299 (2006)
513.
[34] V. Calisto, C.I.A. Ferreira, S.M. Santos, M. Victoria Gil, M. Otero, V.I. Esteves,
Bioresour. Technol. 166 (2014) 335.
[35] K. Sun, K. Ro, M. Guo, J. Novak, H. Mashayekhi, B. Xing, Bioresour. Technol. 102
(2011) 5757.
[36] R.H. Baughman, A.A. Zakhidov, W.A. de Heer, Science 297 (2002) 787.
[37] M. Valcarcel, B.M. Simonet, S. Cardenas, B. Suarez, Anal. Bioanal. Chem. 382
(2005) 1783.
[38] M.C. Roco, Environ. Sci. Technol. 39 (2005) 106A.
[39] P. Ball, Nature 414 (2001) 142.
[40] Y.H. Li, Z.C. Di, J. Ding, D.H. Wu, Z.K. Luan, Y.Q. Zhu, Water Res. 39 (2005) 605.
[41] Y. Ge, Z. Li, D. Xiao, P. Xiong, N. Ye, J. Ind. Eng. Chem. 20 (2014) 1765.
[42] M.A. Salam, G. Al-Zhrani, S.A. Kosa, J. Ind. Eng. Chem. 20 (2014) 572.
[43] M.S. Derakhshan, O. Moradi, J. Ind. Eng. Chem. 20 (2014) 3186.
[44] M.A. Baghapour, S. Pourfadakari, A.H. Mahvi, J. Ind. Eng. Chem. 20 (2014) 2921.
[45] J.Y. Chen, W. Chen, D. Zhu, Environ. Sci. Technol. 42 (2008) 7225.
[46] K. Yang, L. Zhu, B. Xing, Environ. Sci. Technol. 40 (2006) 1855.
[47] V.K.K. Upadhyayula, S.G. Deng, G.B. Smith, M.C. Mitchell, Water Res. 43 (2009)
148.
[48] G.P. Rao, C. Lu, F. Su, Sep. Purif. Technol. 58 (2007) 224.
[49] X. Ren, C. Chen, M. Nagatsu, X. Wang, Chem. Eng. J. 170 (2011) 395.
[50] USEPA, Environmental Protection Agency—Endocrine Disruptor Screening Pro-
gram. Report to Congress, USEPA, Washington, DC, 2000.
[51] USFDA, Guidance for Industry Environmental Assessment of Human Drug and
Biologics Applications. Food and Drug Administration Report, USA, 1998.
[52] EPA, United States Environmental Protection Agency, Contaminant Candidate
List 3, hhttp://water.epa.gov/scitech/drinkingwater/dws/ccl/ccl3.cfmi, 2009.
[53] NRC, Biosolids Applied to Land: Advancing Standards and Practices. hhttp://
water.epa.gov/scitech/wastetech/biosolids/i, 2002.
[54] M. Ihara, M.O. Ihara, V. Kumar, M. Narumiya, S. Hanamoto, N. Nakada, N.
Yamashita, S. Miyagawa, T. Iguchi, H. Tanaka, Environ. Sci. Technol. 48 (2014)
6366.
[55] K.V. Thomas, K. Langford, K. Petersen, A.J. Smith, K.E. Tollefsen, Environ. Sci.
Technol. 43 (2009) 8066.
[56] C.D. Metcalfe, S. Kleywegt, R.J. Letcher, E. Topp, P. Wagh, V.L. Trudeau, T.W.
Moon, Sci. Total Environ. 454 (2013) 132.
[57] A. Alum, Y. Yoon, P. Westerhoff, M. Abbaszadegan, Environ. Toxicol. 19 (2004)
257.
[58] O. Hohenwarter, A. Waltenberger, H. Katinger, Anal. Biochem. 234 (1996) 56.
[59] L.E. Gray, J. Ostby, V. Wilson, C. Lambright, K. Bobseine, P. Hartig, A. Hotchkiss, C.
Wolf, J. Furr, M. Price, L. Parks, R.L. Cooper, T.E. Stoker, S.C. Laws, S.J. Degitz, K.M.
Jensen, M.D. Kahl, J.J. Korte, E.A. Makynen, J.E. Tietge, G.T. Ankley, Toxicology
181–182 (2002) 371.
[60] K.-S. Yook, S.-M. Hong, J.-H. Kim, J. Anal. Sci. Technol. 7 (1994) 441.
[61] J.V. Holm, K. Rügge, P.J. Bjerg, T.H. Christensen, Environ. Sci. Technol. 29 (1995)
1415.
[62] J. Romero, F. Ventura, M. Gomez, J. Chromatogr. Sci. 40 (2002) 191–197.
[63] D.T. Bennie, C.A. Sullivan, H.B. Lee, T.E. Peart, R.J. Maguire, Sci. Total Environ. 193
(1997) 263.
[64] S.W. Pryor, A.G. Hay, L.P. Walker, Environ. Sci. Technol. 36 (2002) 3678.
[65] O.S. Fatoki, R.O. Awofolu, J. Chromatogr. A 983 (2003) 225.
[66] E. Kubeck, C.G. Naylor, J. Am. Oil Chem. Soc. 67 (1990) 400.
[67] G.G. Ying, B. Williams, R. Kookana, Environ. Int. 28 (2002) 215.
[68] S.A. Snyder, T.L. Keith, C.G. Naylor, C.A. Staples, J.P. Giesy, Environ. Toxicol. Chem.
20 (2001) 1870.
[69] S. Snyder, B. Vanderford, R. Pearson, O. Quinones, Y. Yoon, Pract. Period. Hazard.
Toxic, Radioact. Waste Manag.—ASCE 7 (2003) 224.
[70] P.C. Lindholm, J.S. Knuutinen, H.S.J. Ahkola, S.H. Herve, Bioresources 9 (2014)
3688.
[71] N. Sridhara Chary, S. Herrera, M. Jose Gomez, A.R. Fernandez-Alba, Anal. Bioanal.
Chem. 404 (2012) 1993.
[72] Y. Yoon, P. Westerhoff, S.A. Snyder, E.C. Wert, J. Yoon, Desalination 202 (2007) 16.
[73] Y. Yoon, P. Westerhoff, S.A. Snyder, E.C. Wert, J. Membr. Sci. 270 (2006) 88.
[74] T. Anumol, S. Merel, B.O. Clarke, S.A. Snyder, Chem. Cent. J. 7 (2013) 1.
[75] S.A. Snyder, S. Adham, A.M. Redding, F.S. Cannon, J. DeCarolis, J. Oppenheimer,
E.C. Wert, Y. Yoon, Desalination 202 (2007) 156.
[76] H. Andersen, H. Siegrist, B. Halling-Sorensen, T.A. Ternes, Environ. Sci. Technol.
37 (2003) 4021.
[77] L. Joseph, L.K. Boateng, J.R.V. Flora, Y.-G. Park, A. Son, M. Badawy, Y. Yoon, Sep.
Purif. Technol. 107 (2013) 37.
[78] C.T. Chiou, S.E. McGroddy, D.E. Kile, Environ. Sci. Technol. 32 (1998) 264.
[79] Y.M. Yoon, P. Westerhoff, S.A. Snyder, M. Esparza, Water Res. 37 (2003) 3530.
[80] J.C. Crittenden, S. Sanongraj, J.L. Bulloch, D.W. Hand, T.N. Rogers, T.F. Speth, M.
Ulmer, Environ. Sci. Technol. 33 (1999) 2926.
[81] R. Renner, Environ. Sci. Technol. 36 (2002) 410A.
[82] S.D. Faust, J.V. Hunter, Principles and Applications of Water Chemistry, John
Wiley and Sons, New York, 1967.
[83] H. Gallard, U. Von Gunten, Environ. Sci. Technol. 36 (2002) 884.
[84] C. Ravacha, R. Blits, Water Res. 19 (1985) 1273.
[85] H. Lei, S.A. Snyder, Water Res. 41 (2007) 4051.
[86] J. Hoigne, H. Bader, Water Res. 17 (1983) 173.
[87] M. Huber, S. Canonica, U. von Gunten, Oxidative Treatment of Pharmaceuticals in
Drinking Waters, AWWA EDC Workshop, Cincinnati, OH, 2002.
[88] R. Alexy, T. Kumpel, K. Kummerer, Chemosphere 57 (2004) 505.
[89] A.J. Al-Rajab, L. Sabourin, A. Scott, D.R. Lapen, E. Topp, Sci. Total Environ. 407
(2009) 5978.
[90] K. Bester, D. Schafer, Water Res. 43 (2009) 2639.
[91] B.D. Blair, J.P. Crago, C.J. Hedman, R.J.F. Treguer, C. Magruder, L.S. Royer, R.D.
Klaper, Sci. Total Environ. 444 (2013) 515.
[92] H. Del Rio, J. Suarez, J. Puertas, P. Ures, Sci. Total Environ. 449 (2013) 189.
[93] B. Kasprzyk-Hordern, R.M. Dinsdale, A.J. Guwy, Water Res. 43 (2009) 363.
[94] T. Kistemann, E. Rind, A. Rechenburg, C. Koch, T. Classen, S. Herbst, I. Wienand, M.
Exner, Int. J. Hyg. Environ Health 211 (2008) 534.
[95] J. Meyer, K. Bester, J. Environ. Monit. 6 (2004) 599.
[96] S.K. Maeng, S.K. Sharma, K. Lekkerkerker-Teunissen, G.L. Amy, Water Res. 45
(2011) 3015.
[97] S.A. Snyder, J. Leising, P. Westerhoff, Y. Yoon, H. Mash, B. Vanderford, Ground
Water Monit. Remediat. 24 (2004) 108.
[98] J. Heidler, A. Sapkota, R.U. Halden, Environ. Sci. Technol. 40 (2006) 3634.
[99] K.C. Hyland, E.R.V. Dickenson, J.E. Drewes, C.P. Higgins, Water Res. 46 (2012)
1958.
[100] S. Kim, P. Eichhorn, J.N. Jensen, A.S. Weber, D.S. Aga, Environ. Sci. Technol. 39
(2005) 5816.
[101] H.R. Buser, T. Poiger, M.D. Muller, Environ. Sci. Technol. 32 (1998) 3449.
[102] M. Carballa, G. Fink, F. Omil, J.M. Lema, T. Ternes, Water Res. 42 (2008) 287.
[103] S. Agnihotri, J.P.B. Mota, M. Rostam-Abadi, M.J. Rood, J. Phys. Chem. B 110 (2006)
7640.
[104] S.M. Gatica, M.J. Bojan, G. Stan, M.W. Cole, J. Chem. Phys. 114 (2001) 3765.
[105] S. Agnihotri, J.P.B. Mota, M. Rostam-Abadi, M.J. Rood, Langmuir 21 (2005) 896.
[106] Y. Gogotsi, Carbon Nanomaterials, Taylor & Francis, Boca Raton, London, New
York, 2006.
[107] B. Pan, B. Xing, Environ. Sci. Technol. 42 (2008) 9005.
[108] J.M. Hilding, E.A. Grulke, J. Phys. Chem. B 108 (2004) 13688.
[109] J.J. Zhao, A. Buldum, J. Han, J.P. Lu, Nanotechnology 13 (2002) 195.
[110] J. Bohdziewicz, G. Kaminska, Water Sci. Technol. 68 (2013) 1306.
[111] N.B. Saleh, L.D. Pfefferle, M. Elimelech, Environ. Sci. Technol. 44 (2010) 2412.
[112] L.A. Girifalco, M. Hodak, R.S. Lee, Phys. Rev. B 62 (2000) 13104.
[113] Q. Zaib, I.A. Khan, Y. Yoon, J.R.V. Flora, Y.-G. Park, N.B. Saleh, J. Nanosci.
Nanotechnol. 12 (2012) 3909.
[114] J.K. Im, J. Heo, L.K. Boateng, N. Her, J.R.V. Flora, J. Yoon, K.-D. Zoh, Y. Yoon, J.
Hazard. Mater. 254 (2013) 284.
[115] S. Agnihotri, J.P.B. Mota, M. Rostam-Abadi, M.J. Rood, Carbon 44 (2006) 2376.
[116] A.J. Brooks, H.-n. Lim, J.E. Kilduff, Nanotechnology 23 (2012) 294008.
[117] H. Nishikiori, T. Tanigaki, M. Endo, T. Fujii, Carbon 66 (2014) 560.
[118] E. Shulga, K. Pohako, A. Treshchalov, U. Joost, V. Kisand, I. Kink, Micro Nano Lett. 6
(2011) 704.
[119] Q. Zaib, I.A. Khan, N.B. Saleh, J.R.V. Flora, Y.-G. Park, Y. Yoon, Water Air Soil Pollut.
223 (2012) 3281.
[120] K. Peng, L.-Q. Liu, H. Li, H. Meyer, Z. Zhang, Carbon 49 (2011) 70.
[121] W.-L. Yim, J.K. Johnson, J. Phys. Chem. C 113 (2009) 17636.
[122] D. Kolacyak, J. Ihde, C. Merten, A. Hartwig, U. Lommatzsch, J. Colloid Interface Sci.
359 (2011) 311.
[123] H. Takagi, Y. Soneda, H. Hatori, Z.H. Zhu, G.Q. Lu, Aust. J. Chem. 60 (2007) 519.
[124] L. Piao, Q. Liu, Y. Li, C. Wang, J. Phys. Chem. C 112 (2008) 2857.
[125] G.-C. Chen, X.-Q. Shan, Y.-S. Wang, Z.-G. Pei, X.-E. Shen, B. Wen, G. Owens,
Environ. Sci. Technol. 42 (2008) 8297.
[126] B. Pan, D. Lin, H. Mashayekhi, B. Xing, Environ. Sci. Technol. 42 (2008) 5480.
[127] S. Zhang, T. Shao, S.S.K. Bekaroglu, T. Karanfil, Water Res. 44 (2010) 2067.
[128] W.H. Xie, W.Y. Shiu, D. Mackay, Mar. Environ. Res. 44 (1997) 429.
[129] X. Wang, J. Lu, B. Xing, Environ. Sci. Technol. 42 (2008) 3207.
[130] H.-H. Cho, H. Huang, K. Schwab, Langmuir 27 (2011) 12960.
[131] M.V. Lopez-Ramon, M.A. Fontecha-Camara, M.A. Alvarez-Merino, C. Moreno-
Castilla, Water Res. 41 (2007) 2865.
[132] Y. Feng, Z. Zhang, P. Gao, H. Su, Y. Yu, N. Ren, J. Hazard. Mater. 175 (2010) 970.
[133] G.-C. Chen, X.-Q. Shan, Y.-Q. Zhou, X.-e. Shen, H.-L. Huang, S.U. Khan, J. Hazard.
Mater. 169 (2009) 912.
[134] G.-C. Chen, X.-Q. Shan, Z.-G. Pei, H. Wang, L.-R. Zheng, J. Zhang, Y.-N. Xie,
J. Hazard. Mater. 188 (2011) 156.
[135] B. Shi, X. Zhuang, X. Yan, J. Lu, H. Tang, J. Environ. Sci.—China 22 (2010) 1195.
[136] C. Lu, C. Liu, J. Chem. Technol. Biotechnol. 81 (2006) 1932.
[137] Y.H. Li, S.G. Wang, Z.K. Luan, J. Ding, C.L. Xu, D.H. Wu, Carbon 41 (2003) 1057.
[138] C.Y. Lu, H.S. Chiu, Chem. Eng. Sci. 61 (2006) 1138.
[139] Y.H. Li, Y.Q. Zhu, Y.M. Zhao, D.H. Wu, Z.K. Luan, Diam. Relat. Mater. 15 (2006) 90.
[140] N. Her, H. Jeong, J. Kim, Y. Yoon, Arch. Environ. Contam. Toxicol. 61 (2011) 166.
[141] M. Asami, K. Kosaka, N. Yoshida, J. Health Sci. 55 (2009) 549.
[142] J.V. Dyke, K. Ito, T. Obitsu, Y. Hisamatsu, P.K. Dasgupta, B.C. Blount, Environ. Sci.
Technol. 41 (2007) 88.
[143] A.B. Kirk, P.K. Martinelango, K. Tian, A. Dutta, E.E. Smith, P.K. Dasgupta, Environ.
Sci. Technol. 39 (2005) 2011.
[144] A.B. Kirk, E.E. Smith, K. Tian, T.A. Anderson, P.K. Dasgupta, Environ. Sci. Technol.
37 (2003) 4979.
 C. Jung et al. / Journal of Industrial and Engineering Chemistry 27 (2015) 1–11 11

[145] N. Her, J. Kim, Y. Yoon, Chemosphere 81 (2010) 732. [162] P. Oleszczuk, B. Pan, B. Xing, Environ. Sci. Technol. 43 (2009) 9167.
[146] J.F. Oldi, K. Kannan, Environ. Sci. Technol. 43 (2009) 142. [163] W. Chen, L. Duan, L. Wang, D. Zhu, Environ. Sci. Technol. 42 (2008) 6862.
[147] D.-H. Kim, Y. Yoon, K. Baek, J. Han, N. Her, Environ. Sci. Pollut. Res. 21 (2014) [164] D. Lin, B. Xing, Environ. Sci. Technol. 42 (2008) 7254.
1251. [165] S. Zhou, Y. Shao, N. Gao, J. Deng, C. Tan, Clean-Soil Air Water 41 (2013) 539.
[148] C.A. Sanchez, K.S. Crump, R.I. Krieger, N.R. Khandaker, J.P. Gibbs, Environ. Sci. [166] I.I. Fasfous, E.S. Radwan, J.N. Dawoud, Appl. Surface Sci. 256 (2010) 7246.
Technol. 39 (2005) 9391. [167] Y.H. Li, J. Ding, Z.K. Luan, Z.C. Di, Y.F. Zhu, C.L. Xu, D.H. Wu, B.Q. Wei, Carbon 41
[149] M. Yang, N. Her, J. Ryu, Y. Yoon, Int. J. Environ. Sci. Technol. 11 (2014) 565. (2003) 2787.
[150] O. Quinones, J.E. Oh, B. Vanderford, J.H. Kim, J. Cho, S.A. Snyder, Environ. Toxicol. [168] Y. Zhang, D. Petibone, Y. Xu, M. Mahmood, A. Karmakar, D. Casciano, S. Ali, A.S.
Chem. 26 (2007) 1349. Biris, Drug Metab. Rev. 46 (2014) 232.
[151] Q. Fang, B. Chen, Carbon 50 (2012) 2209. [169] M. Xia, A. Li, Z. Zhu, Q. Zhou, W. Yang, J. Environ. Sci.—China 25 (2013) 1291.
[152] J.C. Lou, Y.S. Hsu, K.L. Hsu, M.S. Chou, J.Y. Han, J. Environ. Sci. Health Part A— [170] Y. Lu, M. Jiang, C. Wang, Y. Wang, W. Yang, Water Air Soil Pollut. 224 (2013)
Toxic/Hazard. Subst. Environ. Eng. 49 (2014) 503. 1536.
[153] R. Mahmudov, C.P. Huang, Sep. Purif. Technol. 70 (2010) 329. [171] I. Lerman, Y. Chen, B. Xing, B. Chefetz, Environ. Pollut. 182 (2013) 169.
[154] Y.S. Ho, G. McKay, J. Int. Adsorpt. Soc. 5 (1999) 409. [172] H. Wei, S. Deng, Q. Huang, Y. Nie, B. Wang, J. Huang, G. Yu, Water Res. 47 (2013)
[155] J.L. Sotelo, A.R. Rodriguez, M.M. Mateos, S.D. Hernandez, S.A. Torrellas, J.G. 4139.
Rodriguez, J. Environ. Sci. Health Part B—Pestic. Food Contam. Agric. Wastes [173] L. Zhang, P. Fang, L. Yang, J. Zhang, X. Wang, Langmuir 29 (2013) 3968.
47 (2012) 640. [174] L.A. Al-Khateeb, A.Y. Obaid, N.A. Asiri, M.A. Salam, J. Ind. Eng. Chem. 20 (2014)
[156] C. Hepplewhite, G. Newcombe, D.R.U. Knappe, Water Sci. Technol. 49 (2004) 257. 916.
[157] L. Ji, W. Chen, S. Zheng, Z. Xu, D. Zhu, Langmuir 25 (2009) 11608. [175] N. Rambabu, C.A. Guzman, J. Soltan, V. Himabindu, Chem. Eng. Technol. 35
[158] W. Chen, L. Duan, D. Zhu, Environ. Sci. Technol. 41 (2007) 8295. (2012) 272.
[159] L. Ji, Y. Shao, Z. Xu, S. Zheng, D. Zhu, Environ. Sci. Technol. 44 (2010) 6429. [176] W.-W. Tang, G.-M. Zeng, J.-L. Gong, Y. Liu, X.-Y. Wang, Y.-Y. Liu, Z.-F. Liu, L. Chen,
[160] L. Ji, F. Liu, Z. Xu, S. Zheng, D. Zhu, Environ. Sci. Technol. 44 (2010) 3116. X.-R. Zhang, D.-Z. Tu, Chem. Eng. J. 211 (2012) 470.
[161] L.N. Nguyen, F.I. Hai, J. Kang, W.E. Price, L.D. Nghiem, J. Environ. Manag. 119 [177] X.M. Yan, B.Y. Shi, J.J. Lu, C.H. Feng, D.S. Wang, H.X. Tang, J. Colloid Interface Sci.
(2013) 173. 321 (2008) 30.