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Adsorption of emerging pollutants on activated carbon

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DOI: 10.1515/revce-2016-0027

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 Rev Chem Eng 2017; 33(5): 491–522

Zahra Jeirani, Catherine Hui Niu and Jafar Soltan*

Adsorption of emerging pollutants on activated

carbon
DOI 10.1515/revce-2016-0027
Received June 15, 2016; accepted September 30, 2016; previously
1 Introduction
published online December 9, 2016

1.1 Emerging pollutants

Abstract: Many emerging pollutants (also known as micro-
pollutants) including pesticides, pharmaceutical and per-
The emerging contaminants in the aquatic environment
sonal care products (PPCPs), and endocrine disrupting
are products and chemicals without regulatory status,
chemicals (EDCs) have frequently been detected in surface,
which possibly impact the environment and human
ground, and drinking water at alarming concentrations.
health (Bell et al. 2011, Deblonde et al. 2011). The emerg-
The emission and accumulation of these anthropogenic
ing environmental contaminants of interest in water
chemicals in nature is a potential threat to human health
mainly include pesticides, pharmaceuticals and personal
and aquatic environment. Therefore, it is essential to
care products (PPCPs), and endocrine disrupting chemi-
devise an effective and feasible technology to remove the
cals (EDCs). The presence of pesticides, PPCPs, and EDCs
micro-pollutants from water. Activated carbon adsorption
in the aquatic environment as well as in finished drinking
has been introduced and utilized as a promising treatment
water has raised concerns about their potential effect on
to reduce the concentration of the emerging pollutants
the environment and public health (Holtz 2006, Hua et al.
in water. A summary of research on the removal of pesti-
2006, Jasim et al. 2006, Waiser et al. 2011).
cides, PPCPs, and EDCs by activated carbon adsorption
process is presented in this report. The effects of carbon
characteristics, adsorptive properties, and environmental
1.1.1 Pesticides
factors on the adsorption capacity of activated carbon are
reviewed. In addition, the mechanisms of the adsorption
The pesticide pollution of surface water and ground water
including hydrophobicity and the nature of the functional
supplies has been recognized as a major concern world-
groups of activated carbon and organic compounds are
wide due to their persistence in aquatic environment and
discussed. Furthermore, the applied equilibrium adsorp-
potential adverse public and environmental health effects
tion isotherms (Langmuir, Freundlich, BET, Sips, Dubinin-
(Palma et al. 2004, Ikehata and Gamal El–Din 2005, Hua
Astakhov, Dubinin-Radushkevich, and Toth) and the most
et al. 2006). Based on their application, the different types
common kinetic models (pseudo-first- and second-order
of pesticides include herbicides, insecticides, fungicides,
models, film and intra-particle diffusion models, and
rodenticides, nematicides, microbiocides, and plant as
adsorption-desorption model) are also included for further
well as insect growth regulators. Pesticide contamination
investigation. This comprehensive review report aims to
in drinking water has been mainly caused by agricultural
identify the knowledge deficiencies regarding emerging
and urban runoffs, direct application to control aquatic
pollutant treatment via activated carbon adsorption pro-
insects and vegetation, domestic usage, leaching from
cess and open new horizons for the future research on the
pesticide wastes, and industrial scale pest control opera-
adsorption of emerging pollutants on activated carbon.
tions (Ikehata and Gamal El–Din 2005, Arbuckle et  al.
Keywords: activated carbon adsorption; endocrine dis- 2006, Hua et al. 2006).
rupting chemicals; pesticides; pharmaceutical and per-
sonal care products.
1.1.2 Pharmaceuticals and PPCPs

*Corresponding author: Jafar Soltan, Department of Chemical and
Biological Engineering, University of Saskatchewan, 57 Campus
Drive, Saskatoon, SK S7N 5A9, Canada, e-mail: j.soltan@usask.ca
Zahra Jeirani and Catherine Hui Niu: Department of Chemical and
Biological Engineering, University of Saskatchewan, 57 Campus
Drive, Saskatoon, SK S7N 5A9, Canada
The first possible source of pharmaceutical pollution
includes the partially metabolized and excreted consumed
drugs in the urine and feces, which go into wastewater col-
lection system (Heberer et al. 2002, Jones et al. 2005b). The
second probable source is the unused, surplus, or expired
492      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
drugs, which may be disposed into toilets (Heberer et al.
2002, Jones et al. 2005b). Some of these drugs are practi-
cally non-biodegradable and may be released to surface
water or be subjected to ground water, and as a result,
they enter the aquatic environment. Some of the adverse
effects caused by the PPCPs pollution in the aquatic envi-
ronment include aquatic toxicity, resistance development
in pathogenic bacteria, genotoxicity, and endocrine dis-
ruption (Arcand-Hoy et  al. 1998, Halling-Sørensen et  al.
1998, Sumpter 1998, Kümmerer 2004). In addition, the
presence of trace PPCPs in finished drinking water is
another public health concern, as little is known about
potential chronic health effects associated with long-term
ingestion of mixtures of these compounds through drink-
ing water (Kümmerer 2001, Stackelberg et al. 2004).
1.1.3 Endocrine disrupting chemicals (EDCs)
EDCs are generally classified into two groups. The first
group of EDCs is the excreted steroids, which are inten-
tionally made to cause endocrine disruption, and they
possess the highest estrogenicity. The natural estrogens
estrone, 17α-estradiol, and 17β-estradiol and the exog-
enous 17α-ethinylestradiol and the active ingredients in
oral contraceptive pills (i.e. estrogen and progesterone)
are examples of this group. The second group of EDCs is
the xenoestrogens, which present estrogenic potentials.
For instance, alkylphenols (such as 4-tert-octylphenol),
the technical isomer mixture of 4-nonylphenols (NP), and
bisphenol A (BPA) belong to this group. Most of the EDCs
consumed end up in aquatic environments via discharge
from municipal and industrial wastewater treatment
plants (Kuch and Ballschmiter 2001, Vethaak et al. 2005,
Mohapatra et  al. 2010). The release of EDCs to drinking
water sources is a great public health concern (Welshons
et al. 2006, Chang et al. 2009, Rahman et al. 2009). The
consumptions of EDCs can interfere with human reproduc-
tive systems and block the activity of natural hormones.
There are even some reports that long-term consumption
of EDCs causes deleterious effects in wildlife and humans
such as an increase in hormone-dependent cancers and a
decrease in sperm count owing to estrogenic activity (Safe
et al. 2001, Vandenberg et al. 2007, Soto et al. 2010).
As the presence of emerging pollutants in both the
aquatic environment and in finished drinking water
has various harmful effects on environment and human
beings, it is important to eliminate them from water by the
utilization of a feasible technology.
In the past decades, several physical, chemical, and
biological treatment methods have been applied to fully
or partly remove the unwanted organic contaminants of
water. Different research groups have demonstrated the
efficiency of activated carbon (AC) for removal of several
organic micro-pollutants from water (Fuerhacker et  al.
2001, Tanghe and Verstraete 2001, Ternes et  al. 2002,
Yoon et al. 2003, Choi et al. 2005, Westerhoff et al. 2005,
Snyder et  al. 2007). Applicability at very low concentra-
tions (i.e. ppm and ppb), being suitable both for batch
and continuous processes, possibility of regeneration
and reuse for granular carbons, and low capital cost are
the four distinctive advantages of AC adsorption process,
compared to other technologies (e.g. precipitation,
­coagulation-flocculation, sedimentation, flotation, filtra-
tion, membrane technologies, electrochemical methods,
biological processes, advanced oxidation treatments, and
ion exchange) for removal of micro-pollutants (Mohanty
et al. 2006, Liangliang et al. 2010).
1.2 Activated carbon (AC)
AC as a common adsorbent has been widely used in
various industries such as water and wastewater treat-
ment (Altmann et al. 2015, Islam et al. 2015) as well as in
several gas separation and purification processes (Ramos
et al. 2010, Lemus et al. 2012). ACs are highly porous, and
they present a broad range of pore sizes, from visible
cracks to crevices and slits of molecular dimensions.
ACs have been prepared from various raw materi-
als such as sludge, coconut shells, wood char, lignin,
petroleum coke, bone char, peat, sawdust, carbon black,
rice hulls, sugar, peach pits, fish residues, fertilizer
waste, waste rubber tire, etc. (Mohan and Pittman 2006,
­Al-Qodah and Shawabkah 2009). ACs have also been pro-
duced from waste materials, which are produced from
human activities due to the surge of industrialization and
urbanization (Hadi et al. 2015). Granular activated carbon
(GAC) (Westerhoff et al. 2005, Kim et al. 2010, Islam et al.
2015) and powdered activated carbon (PAC) (Yoon et  al.
2005, Kim et al. 2010, Altmann et al. 2015) are two forms of
ACs, which have been used in adsorption processes.
The surface of AC consists of basal planes, hetero-
geneous superficial groups (mainly oxygen containing
functional groups such as hydroxyl, carboxyl, phenol,
lactone, lactol, and quinone), and inorganic ash. For
simple aromatic compounds, most of the adsorption sites
are found on the basal planes, which correspond to about
90% of the carbon (Franz et al. 2000) surface. Heteroge-
neous groups also contribute towards activity and define
the chemical characteristics of the carbon surface (Franz
et  al. 2000, Delgado et  al. 2012). The heteroatoms are

located at the edges or in the defects of the basal planes
of carbon atoms. The surface functional groups of ACs
strongly depend on the raw material as well as the activa-
tion method (Yin et al. 2007, Vázquez-Santos et al. 2012).
Comparison of the infrared (FTIR) spectra of the raw mate-
rials and the prepared AC samples pertained to the effect
of chemical activation and raw materials on the surface
chemical structure and functional moieties (Djilani et al.
2012, 2015).
Different activation techniques are often used to
modify the adsorption of targeted organic contaminant
species from aqueous solutions on AC (Yin et  al. 2007).
These techniques involve physical, chemical, and electro-
chemical treatments to improve the nature of the surface
groups on AC (Yin et  al. 2007). The porous structure of
AC can be optimized with the alteration of the activation
parameters such as the type of activation (physical, chem-
ical, and electrochemical), choice of activating agent,
pyrolysis or activation temperature, impregnation ratio,
and activation sequence (Hadi et al. 2015). It is also dem-
onstrated that the surface area of AC increases with acti-
vation time because longer activation time provides more
opportunity for the carbon to react with the activating
agent (Fung et al. 2012). Therefore, the optimization of the
activation parameters yields the desired physicochemical
properties and consequently the highest uptake of certain
pollutants.
1.3 A
 pplication of AC for the adsorption
of emerging pollutants
AC adsorption technology has been applied successfully
for the removal of pesticides, PPCPs, and EDCs in water.
Tables 1–3 present a summary of research works on the
removal of pesticides, PPCPs, and EDCs using AC adsorp-
tion treatment.
1.3.1 Removal of pesticides
As for pesticide pollution, several physical treatment
processes such as nanofiltration and reverse osmosis
(­Agbekodo et  al. 1996, Berg et  al. 1997, Van der Bruggen
et  al. 1998, Boussahel et  al. 2000), slow sand filtration
(Lambert and Graham 1995), and AC adsorption (Baldauf
1993, Gicquel et  al. 1997, Thacker et  al. 1997), as well as
chemical oxidation technologies (Reynolds et  al. 1989,
Camel and Bermond 1998) have led to partial removal of
pesticides residues during water treatment. AC adsorption
is considered as one of the most promising technologies
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      493
and has been applied for decades to reduce/eliminate
the aqueous pesticides in water treatment process (Foo
and Hameed 2009, Nam et  al. 2014, Lladó et  al. 2015)
and recently in wastewater treatment process (Altmann
et  al. 2015, Mailler et  al. 2016). Among different studied
adsorbents, AC has generally been found to exhibit
higher adsorption capacity for target pesticides (benta-
zon, clopyralid, and isoproturon) although zeolites and
metal-organic frameworks could adsorb the pesticides
more rapidly (Smedt et al. 2015). Table 1 includes pesticide
compounds, type of AC, maximum removal, maximum
adsorption capacity, isotherms, and kinetic models
reported in the literature.
1.3.2 Removal of PPCPs and EDCs
As for PPCPs pollution, several studies showed that the
conventional water and wastewater treatment processes
(e.g. biodegradation) are unable to act as a reliable barrier
towards some of the prescription and non-prescription
drugs (Ternes et  al. 2002, Stackelberg et  al. 2004, Jones
et al. 2005a, Jasim et al. 2006). In addition, the disinfec-
tion methods such as UV or chlorine are inadequate to
eliminate most polar pharmaceuticals in water (Ikehata
et al. 2006). However, AC adsorption has been introduced
and utilized as one of the promising treatment technolo-
gies (e.g. ozone, membrane filtration, and AC adsorp-
tion) to reduce the concentration of the PPCPs in water
(Redding et  al. 2009, Sotelo et  al. 2012, Nam et  al. 2014,
Rakić et al. 2015).
Adsorption on AC has been also widely considered as
a highly effective treatment technology to remove EDCs
from wastewater (Yu et al. 2007, Nam et al. 2014). Tables
2 and 3 provide information on PPCPs/EDCs compounds,
type of AC, maximum removal, maximum adsorption
capacity, isotherms, and kinetic models available in the
literature.
Despite numerous research studies on the application
of AC for the adsorption of emerging pollutants, there are
a limited number of review manuscripts on this topic in
the literature (Foo and Hameed 2010, Delgado et al. 2012,
Rivera-Utrilla et al. 2013, Hadi et al. 2015). Application of
AC for the adsorption and detoxification of pesticide waste
was presented in a review in 2010 (Foo and Hameed 2010).
Although it was a great contribution in environmental
pollution control, PPCP and EDCs were not included. The
removal of PPCP, EDCs, and cyanobacterial toxins from
water was reviewed in 2012 (Delgado et al. 2012). However,
no information on the pesticide adsorption was provided,
and the adsorption mechanisms, isotherms, and kinetic
Table 1: Summary of research works for pesticides treatment by AC adsorption.

Pesticide compounds   Activated carbon   Experimental conditions   Maximum   Maximum adsorption  Isotherm model(s)   Kinetic model(s)   Reference
removal (%) capacity (mg/g)

Atrazine,   11 Commercial PAC: PB   Wastewater with average   40,   –   –   –   Mailler et al.

Diuron 170, PB 170–400, PC DOC (5.6 ± 0.9 mgC/l), 75 2016
1000, WP 235, Carbsorb C0 (6 and 57 ng/l), AC
28, Cyclecarb 305, doses (10 mg/l)
W 35, SA Super, LP 39,
MP 25 and Hydro XP 17
Bentazon,   GCN-1240, GAC-1240,   Distilled water,   100,   –   Freundlich   –   Smedt et al.
Clopyralid, C-GRAN, ORGANOSORB C0 (10 mg/l) 100, 2015
Isoproturon 10 (commercial GACs); 100
DARCO-KB-WJ, DARCO-
KB-G (commercial PAC)
Atrazine   Filtrasorb 400   Ultra-pure water (Milli-   –   170   Langmuir; Freundlich   Pseudo second   Lladó et al. 2015
(commercial GAC); Norit Q), C0 (40 mg/l), AC order, intra-particle
PK 1-3 (commercial GAC); doses (200 mg/l), 25°C diffusion, diffusion-
SBC (synthesized GAC) reaction model
Atrazine   Three GACs: HD4000,   Two raw waters, anionic   90   –   Freundlich;   –   Hu et al. 2014
UC830 exchange resin treated SEBC
494      Z. Jeirani et al.: Adsorption of emerging pollutants on AC

and F-400 Water and demineralized

water, C0 (5 μg/l), AC
doses (1–20 mg/l), AC
particle size (0.1 mm),
25°C
Fenoprop,   PAC-1000 (commercial)   C0 (5 μg/l), AC doses   98 ± 2%   40–250   –   –   Nguyen et al.
Pentachloro-phenol (0.1–0.5 g/l) 2014
Atrazine,   Coconut shell-based PAC   Distilled water, C0 (100   90,   –   Freundlich   –   Nam et al. 2014
2,4-diclorophenoxyacetic (commercial) ng/l), AC doses (1 g/l) 90
acid (2,4-D)
Chlordecone   GAC (synthesized)   C0 (50–2800 μg/l), AC   –   70   Fowler–Guggenheim;   –   Durimel et al.
doses (0.05 g/l), AC Jovanovic–Freundlic 2013
particle size (0.4–1 mm),
25°C
Phthalic acid   Sorbo Norit (commercial   Ultra-pure water, C0   –   175.7 for PA; 203.3   Prausnitz–Radke   Pseudo-second   Ocampo-Pérez
(PA), diphenolic acid (DPA), GAC); Ceca AC40 (100 mg/l), AC doses for DPA; 20.66 for order; PVSDM et al. 2012
2,4-dichlorophenoxy-acetic (commercial GAC) (25, 50 or 100 mg/ 2,4-D; 14.76 for
acid (2,4-D), and 4-chloro- 100 ml solution), particle MCPA
2-methylphenoxyacetic acid size (0.45–1.00 mm), pH
(MCPA) (3 for PA and 2,4-D and
MCPA, 5 for DPA), 298 K
Table 1 (continued)

Pesticide compounds   Activated carbon   Experimental conditions   Maximum   Maximum adsorption  Isotherm model(s)   Kinetic model(s)   Reference
removal (%) capacity (mg/g)

Alachlor (ALA),   Filtrasorb 400   Ultra-pure water, C0   –   90   Freundlich   –   Hnatukova et al.

Terbuthylazine (TBA) (commercial GAC); Norit (10 mg/l), AC doses 20 2011
1240 (commercial GAC) (1–100 mg/l), AC
particle size (0.8–1 mm),
pH (5 and 8.5)
Fluroxypyr   Chemviron 208C; Norit;   C0 (5–90 mg/l), AC doses   –   720   Langmuir   Pseudo-first order;   Pastrana-
ACF; ACC (commercial (0.1 g/l), AC particle size pseudo-second Martínez et al.
GACs) (0.5 mm for Chemviron order 2010
208C; diameter of
0.7–0.8 mm and length
of 4.0–4.5 mm for Norit;
diameter of 9 μm and
length of 3 mm for ACF;
thickness of 0.45 mm for
ACC), 288 and 308 K
Bromacil   Norit SA-UF (commercial   Buffered reverse osmosis  –   25   Langmuir; Temkin   Pseudo-second   Mardini and
PAC) water (3–10 MΩcm−1, order Legube 2010
DOC < 0.1 mgl−1), pH of
7.8, final ionic strength
of 1.75 × 10−3 M, three
kinds of NOM, AC doses
(1–4 mg/l)
Metribuzin   NFEN 1291 (commercial   Distilled water, C0   –   210.00   –   –   Kitous et al.
GAC) (50–450 mg/dm3), AC 2009
doses (5g/l)
2,4-D   Date stone   C0 (50–400 mg/l), AC   91.83   238.10   Langmuir   Pseudo-first order   Hameed et al.
doses (1 g/l), 30°C, pH 2009
(2–11)
Triadimenol   GAC from sewage sludge   Milli-Q water, C0   –   111.80   Brunauer, Emmett   –   Al-Qodah and
(15–55 mg/l), AC doses and Shawabkah
(0.4 g/l), 22°C, AC particle Teller (BET) 2009
size (45 μm), pH (3, 5, 9)
2,4-D, 2-methyl-4-   Filtrasorb 400   Distilled water, C0   –   1.94, 1.86, 2.77   Langmuir; Sips   PVSDM; HSDM   Kim et al. 2008
chlorophenoxyacetic (commercial GAC) (0.45 mol/m3), AC doses
acid (MCPA), (0.005–1.25 g/l), AC
chlorophenoxyacetic acid particle size (0.37–
(CPA) 0.54 mm), 298 K, pH
(3.5, 7.0, and 10.0)
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      495
Table 1 (continued)

Pesticide compounds   Activated carbon   Experimental conditions   Maximum   Maximum adsorption  Isotherm model(s)   Kinetic model(s)   Reference
removal (%) capacity (mg/g)

Atrazine, Propoxur,   GAC (commercial)   Highly purified (doubly   –   0.356,0.240, 0.456   –   –   El-Sheikh et al.
Methidathion distilled de-ionized) 2008
water and three types
of environmental water
samples (tap water,
reservoir water and
stream water), C0 (10–
100 ng/ml), AC doses
(0.2 g), AC particle size
(20–60 mesh), pH (5)
Isoproturon   Powdered activated   Distilled water and a   –   104.21   Langmuir; Freundlich   –   Sarkar et al.
charcoal treated surface water 2007
(Mula river water), C0
(1–12 mg/l), AC doses
(20–1000 mg/l)
Atrazine   NORIT SA-UF PAC   Distilled deionized water   100   –   Freundlich   HSDM   Li et al. 2006
(commercial)
496      Z. Jeirani et al.: Adsorption of emerging pollutants on AC

and ground water, C0 (10

μg/l), AC doses (2 mg/l)
Ametryn,   Spectracarb 2225 carbon   Deionized water, C0   –   354.61, 421.58,   Freundlich;   Pseudo-first order;   Ayranci and
Aldicarb, cloth (commercial AC) (103.84, 103.96, 22.38 301.84, 213.06 Langmuir Pseudo-second Hoda 2005
Dinoseb, and 32.27 mg/l), 25°C, order
Diuron AC doses (18.0 mg)
Atrazine,   AC fiber (commercial)   Deionized water and   –   238.1, 370.4   Freundlich   –   Faur et al. 2005
Simazine a natural water with
DOC = 18.2 mg/l and pH
of 7.5, C0 (0.23 × 10−6–
9.5 × 10−6 mol/l), AC
doses (2 mg/l), 20°C
Carbofuran   Commercial PAC   Distilled water, C0   –   190   Freundlich   –   Fernndez-Prez
(2–234 mg/l), AC doses et al. 2005
(0.2 g/l), 25°C
Bentazon,   Spectracarb 2225 carbon   Deionized water, C0   –   151,   Langmuir; Freundlich   Pseudo-first order   Ayranci and
Propanil cloth (commercial AC) (20.90 and 23.52 mg/l), 114 Hoda 2004
25°C, AC doses
(18.0 mg)
Paraquat dichloride   Filtrasorb 400   C0 (10–40 mg/l),   –   68.0,   Langmuir   Pseudo-second   Hamadi et al.
(commercial GAC); 25–45°C, AC doses 27.8 order 2004
Used tires (0.5–10 g/l), AC particle
size (0.11, 0.38, and
0.9 mm), pH (5, 7, and 9)
Table 1 (continued)

Pesticide compounds   Activated carbon   Experimental conditions   Maximum   Maximum adsorption  Isotherm model(s)   Kinetic model(s)   Reference
removal (%) capacity (mg/g)

Bromoxynil,   Darco G-60 (commercial   C0 (35.6 and 42.8 mg/l),   –   500,   –   –   Yang et al. 2004
Diuron AC) AC doses (g/l), AC 300
particle size (100 mesh),
pH (2.19–7.20)
Asulam,   Wood-based PAC   Diluted natural water (or   80,   –   –   –   Matsui et al.
Simazine, (commercial) raw water with TOC of 90, 2002
Simetryin 8.3) with ultrapure water, 100
C0 (30 and 10 μg/l), AC
particle size (22–26 μm)
Lindane   Filtrasorb 400   Milli-Q water, C0   –   181   Dubinin-   PVSDM   Sotelo et al.
(commercial GAC) (10 mg/l), AC doses Radushkevich 2002a
(62 mg/l), AC particle
size (0.84–1 mm), 25°C
Lindane,   Filtrasorb 400   Milli-Q water, C0 (0.046–   –   183,   Freundlich   PVDM   Sotelo et al.
Alachlor (commercial GAC) 10 mg/l), AC doses 151 2002b
(62 mg/l), AC particle
size (0.84–1 mm), 25°C
4-(4-Chloro-o-tolyloxy)   Charcoal based PAC   C0 (500 μg/l), AC doses   –   125.77, 208.03   Freundlich   –   Hu et al. 1998
butyric acid, Imazalil (commercial) (0.5–30 mg/l), AC
particle size (300 mesh),
pH (3–8.7), 25°C
2,4-D,   Nuchar C-190   Double-distilled water,   –   334,   Freundlich;   –   Schwartz, 1967,
isopropyl-N-(3-chlorophenyl) (commercial PAC); PAC C0 (5–10 mg/l), AC 412.0 Langmuir Kouras et al.
carbamate (CIPC) 313W (commercial) doses (25, 50, 100 and 1998
250 mg/l), AC particle
size (1.65 μm), pH (4.8,
6.9, 9.3), 20°C
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      497
Table 2: Summary of research works for PPCPs treatment by AC adsorption.

PPCP compounds   Activated carbon   Experimental conditions   Maximum   Maximum adsorption  Isotherm   Kinetic model(s)   Reference
removal (%) capacity (mg/g) model(s)

Atenolol,   11 Commercial PAC: PB 170,  Wastewater with average   54,   –   –   –   Mailler et al.
Carbamazepine, PB 170–400, PC 1000, WP DOC (5.6 ± 0.9 mgC/l), C0 63, 2016
Ciprofloxacin, 235, Carbsorb 28, Cyclecarb (435, 267, 425, 303, 585, 77,
Diclofenac, 305, 61, 33, 197, 1632, 206, 32,
Erythromycin, W 35, SA Super, LP 39, MP 68, 186, 355 ng/l), AC 26,
Ketoprofen, 25 and Hydro XP 17 doses (10 mg/l) 31,
Metronidazole, 16,
Norfloxacin, 79,
Ofloxacin, 79,
Propranolol, 81,
Roxithromycin, 43,
Sulfamethoxazole, 60,
Trimethoprim 46
Carbamazepine, diclofenac,  Carbopal AP (commercial   Three different wastewater,  98,   –   –   –   Altmann et al.
and sulfamethoxazole PAC) DOC (13–15.8, 13–15.4, 95, 2015
11.9–12.3 mg/l), C0 WWA 70
(1.3–1.9, 3.1–6.5, 0.27–
498      Z. Jeirani et al.: Adsorption of emerging pollutants on AC

0.33 μg/l), C0 WWB (2.1–

Ciprofloxacin (CIP)   A commercial PAC  
Paracetamol   Filtrasorb 400 (commercial   Ultra-pure water (Milli-Q),   –
GAC); Norit PK 1-3
(commercial GAC); SBC
(synthesized GAC)
Ranitidine hydrochloride   Superheated steam AC  
(RH) prepared from mung bean
husk
(MBH), an agricultural waste
Salicylic acid,   C-1 (commercial GAC); C-2   Deionized water, C0
Acetylsalicylic acid, (commercial PAC);
Atenolol, C-3 (commercial PAC)
Diclofenac-Na
2.3, 5.4–8.1, 0.25–0.38
μg/l), C0 WWC (1.2–5.9,
2.9–5.5, 0.28–0.35 μg/l),
AC doses (5–100 mg/l), AC
particle size (d70 < 40 μm),
pH (7.2–7.6)
C0 (0.5–20 mg/l), AC doses   40   –   Langmuir;   Pseudo-second order,   Li et al. 2015
(50 mg/l), pH (6.2), 25°C Freundlich pseudo-first order
  170   Langmuir;   Pseudo second   Lladó et al.
C0 (40 mg/l), AC doses Freundlich order, intra-particle 2015
(200 mg/l), 25°C diffusion, diffusion-
reaction
Distilled water, C0   99.16   13.5   Sips   Avrami fractionary   Mondal et al.
(100 mg/l), AC dosage 2015
(0.010–1 g), pH (2–12),
temperature (303–318 K)
  –   –   Freundlich   –   Rakić et al.
(0.02 m), AC doses 2015
(50 mg), pH (2.82, 3.09,
10.15, 7.98), 303 K
Table 2 (continued)
PPCP compounds   Activated carbon  
Acetaminophen, Caffeine,   Coconut shell-based PAC  
Diclofenac-Na, Naproxen, (commercial)
Sulfamethoxazole,
Sulfamethazine
Diclofenac,   Pulverized coal-based GAC;   Ultra-pure water, C0 (10
Caffeine Filtrasorb 400 (commercial
GAC)
Sulfamethoxazole,   PS1000 (commercial PAC)   Synthetic wastewater,
Carbamazepine
Triclosan   Charcoal-based GAC  
(commercial)
Trimethoprim   Wood-based PAC and GAC  
Acetaminophen   Cork waste-based PAC  
(paracetamol) (synthesized); Peach stone-
based PAC (synthesized);
PET waste based PAC
(synthesized); coal-based
PAC (synthesized)
Clofibric acid   Pulverized coal-based  
GAC; cork waste-based
PAC (synthesized);
coconut shell-based PAC
(synthesized)
Levodopa   Pulverized coal-based GAC   Deionized water, C0
Experimental conditions   Maximum   Maximum adsorption  Isotherm   Kinetic model(s)   Reference
removal (%) capacity (mg/g) model(s)
Surface water and   85, 85, 95,   –   Freundlich,   –   Nam et al. 2014
deionized water, C0 (100 90, 85, 85 Linear
ng/l), AC doses (1, 2, and
20 mg), pH (5, 7, 9 or 12)
  95,   330,   Freundlich   –   Sotelo et al.
and 15 mg/l), particle size 95 255 2012
(0.5–0.589 mm), 25°C
  82,   –   Freundlich   –   Li et al. 2011
C0 (30 mg/l), AC doses 92
(10–30 mg), 25°C
Ultra-pure water, C0   31.4   –   Freundlich,   –   Behera et al.
(60 mg/l), AC doses (1 Langmuir 2010
g/l), average particle size
(1.5 mm), pH (3–10), 25°C
Distilled water, C0   97   –   Freundlich,   HSDM   Kim et al. 2010
(50 mg/l), AC doses (0.1, Langmuir,
0.2, 0.5, 1.0 and 2.0 g/l), Toth
average particle size
(0.3 mm), pH (4, 6 and 10),
25°C
Ultra-pure water, C0   –   255   Freundlich,   Pseudo-second order   Cabrita et al.
(120 mg/l), AC doses Langmuir 2010
(10 mg/15 cm3 of
solution), pH (5.8), 30°C
Ultra-pure water, C0   –   250,   Freundlich,   Pseudo-second order   Mestre et al.
(90 mg/l), AC doses 260, Dubinin- 2010
(10 mg/15 cm3 solution), 140 Astakhov
pH (2.0, 3.6 and 5.0), 30°C
  –   450   Freundlich,   –   Quesada-Peñate
(0.031–1.281 g/l), AC Redlich- et al. 2009
doses (0.1, 0.05), average Peterson
particle size (0.2–0.4 mm),
25°C
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      499
 500      Z. Jeirani et al.: Adsorption of emerging pollutants on AC

models were not classified. An exhaustive review on phar-

maceutical class of emerging pollutants and their removal

Yu et al. 2009
Mestre et al.

Mestre et al.

Ternes et al.
from water by different technologies was conducted
Reference

(Rivera-Utrilla et  al. 2013), but the adsorption topic was

2009

2007

2002
very brief. The preparation, characterization, and appli-
cation of porous sludge-based AC for water and wastewa-
 

Pseudo-second order  

Pseudo-second order  

 
ter treatment were recently reviewed (Hadi et  al. 2015).
However, it was mostly focused on the removal of metals
Kinetic model(s)

Film diffusion

and dyes from aqueous media. Therefore, sequestration of

emerging pollutants by AC has been mainly untouched.
This paper presents a comprehensive review on the
adsorption of emerging pollutants by AC. In this work, the

–
literature reports on the utilization of AC for the elimina-
Isotherm  

Freundlich,  

Freundlich  

Langmuir  

Freundlich  
Langmuir
model(s)

tion of emerging pollutants including pesticides, PPCPs,

and EDCs from water are compiled and organized in
Tables 1–3. The main objective of this review is to present
the current status of knowledge on this subject by detailed
Maximum adsorption 

investigations of the information (i.e. adsorption capacity

capacity (mg/g)

of AC, mechanism of adsorption, equilibrium isotherms,

and kinetic models) given in Tables 1–3. Therefore, the
parameters that could affect the adsorption capacity
360

of AC (i.e. carbon characteristics, adsorptive proper-

–

ties, and environmental factors) are explained in detail.

Maximum  

 
removal (%)

Furthermore, hydrophobic interactions, π-π dispersion

interactions, hydrogen bonding formation, and electron
100

donor-acceptor complex formation as the four kinds of

80,
20,
90

75
7,
–

adsorption mechanisms are described. In addition, the

 

pros and cons of Langmuir and Freundlich models, the

40 and 60 mg/l), AC doses
(10 mg/15 cm3 solution),

(10 mg/15 cm3 solution),
(1000 mg/l), AC capacity
Experimental conditions

Ultra-pure water, C0 (20,

two most widely used equilibrium adsorption isotherms,

(100 μg/l), AC doses
Deionized water and
(90 mg/l), AC doses
Ultra-pure water, C0

Ultra-pure water, C0

as well as other rarely used isotherm models (BET, Sips,

ground water, C0

Dubinin-Astakhov, Dubinin-Radushkevich, and Toth), are

pH (4), 30°C

pH (4), 30°C

discussed. Finally, pseudo-first- and second-order film

(100 mg/g)

(0.2 g/l)

and intra-particle diffusion kinetic models are included in

this review paper for the sake of completeness of the topic
of emerging pollutant adsorption on AC.
 

 
(synthesized); wood-based
Filtrasorb 400 (commercial

Filtrasorb 400 (commercial

pulverized coal-based GAC

(synthesized); PET waste-
based PAC (synthesized)

CTIF (commercial GAC);

CTIF (commercial GAC);

2 Adsorption capacity of AC
GAC); commercial PAC;
Cork waste-based PAC

PAC (synthesized)
Activated carbon

Coal-based PAC

Maximum adsorption capacity and maximum removal of

pollutants are two parameters indicating the performance
of used ACs in the adsorption processes. These parameters
GAC)

are included in Tables 1–3 for the adsorption of various

organic pollutants on different AC samples. Some of the
 

Naproxen, Carbamazepine  

Carbamazepine, Diclofenac

most notable data presented in Tables 1–3 are discussed

below.
Table 2 (continued)

A PAC sample with adsorption capacity of 104.21 mg/g

PPCP compounds

was determined to be a more favorable adsorbent for the

Clofibric acid,
Bezafibrate,

sequestration of isoproturon than bentonite and chitosan

Ibuprofen

Ibuprofen

(Sarkar et  al. 2007). In addition, it was reported that a

commercial AC (i.e. NS) exhibited not only the largest
Table 3: Summary of research works for EDCs treatment by AC adsorption.

EDC compounds   Activated carbon   Experimental conditions   Maximum  Maximum adsorption  Isotherm   Kinetic   References
removal (%) capacity (mg/g) model(s) model(s)

Bisphenol A (BPA)   Iron nanoparticle  
impregnated PAC (Norit
DARCO A-51, commercial)
Triclocarban   Coconut shell-based PAC  
(commercial)
bisphenol A (BPA)   Sorbo Norit (commercial  
GAC); Ceca AC40
(commercial GAC)
Nonylphenol   CTIF (commercial GAC);  
Filtrasorb 400 (commercial
GAC)
Amitrol, Nonylphenol,   Filtrasorb 400 (commercial   Treated water, C0 (200 μg/l for
Bisphenol-A GAC); CB-0 (commercial
GAC); WB-0 (commercial
GAC)
17-β-Estradiol   AC800 (commercial PAC);   Ultra-pure water, river water
Hydrodarco-B (commercial
PAC); WPM (commercial
PAC)
Deionized water, C0 (10 ppb), AC   –  0.6   Freundlich   –   Park et al. 2015
doses (1.0 g/l), pH (7), 25°C
Surface water and Deionized   95  –   Linear   –   Nam et al. 2014
water, C0 (100 ng/l), AC doses (1,
2, and 20 mg), pH (5, 7, 9, or 12)
Ultra-pure water, C0 (100 mg/l), AC   –  256.5 for BPA   Prausnitz–Radke  Pseudo-second  Ocampo-Pérez
doses (25, 50, or 100 mg/100 ml order; PVSDM et al. 2012
solution), particle size (0.45–
1.00 mm), pH (5), 298 K
Ultra-pure water, C0 (1000 mg/l),   –  –   Freundlich   film diffusion   Yu et al. 2009
AC capacity (100 mg/g)
  13; 45; 35  –   Langmuir;   –   Choi et al. 2005
amitrol and bisphenol-A, and 500 Freundlich
μg/l for nonylphenol), particle size
(200 mesh), pH (7.0– 7.2), 25°C
  95  –   Freundlich   –   Yoon et al. 2005
and reverse osmosis water, C0
(6.8–1362 ng/l for ultrapure
water, 27 ng/l for the river water
and reverse osmosis water), AC
doses (0.01–25 mg/l), pH (8.2)
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      501
502      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
uptake of acetaminophen (maximum adsorption capacity
of 255 mg/g) but also the fastest adsorption rate (pseudo-
second-order rate constant of 17.6 × 10−4 g mg−1 min−1),
compared to other kinds of AC prepared from biomass
residues (Cabrita et al. 2010). However, the NS carbon pre-
sented about half the affinity for acetaminophen (Cabrita
et al. 2010). It was then concluded that the adsorption of
acetaminophen strongly depends on the characteristics of
the adsorbent in terms of porosity and chemical composi-
tion (Cabrita et al. 2010).
It was also found that the AC with more developed
super-microporous structure presented higher initial
ibuprofen adsorption rate and maximum adsorption
capacity than did the other AC (Mestre et  al. 2007).
However, it was suggested that the adsorption capacity
of the higher surface area AC was considerably lower
than that of the lower surface area AC due to the ultra-
micropore characteristics of the latter, which is favored
for the formation of stronger van der Waals forces (Hadi
et al. 2015).
The investigation on the adsorption of phthalic
acid (PA); bisphenol A (BPA); diphenolic acid (DPA);
2,4-dichlorophenoxy-acetic acid (2,4-D); and 4-chloro-
2-methylphenoxyacetic acid (MCPA) in aqueous solution
on two commercial ACs showed that the highest adsorp-
tion capacities of the used commercial GAC samples were
175.7, 203.3, 20.7, and 14.8 for PA; DPA; 2,4-D; and MCPA,
respectively (Ocampo-Pérez et  al. 2012). The consider-
able difference in the maximum adsorption capacities
was attributed to the differences in molecular size and
shape of these pollutant compounds, species distribution
of the adsorbates, and shape and distribution of carbon
pores (Ocampo-Pérez et  al. 2012). It was found that the
adsorption capacity for the studied phenoxy herbicides
is strongly pH dependent, and the highest adsorption
capacity was in the order of CPA (2.77  mol/kg) > 2,4-D
(1.94 mol/kg) > MCPA (1.86 mol/kg) at pH of 3.5 (Kim et al.
2008).
Experimental equilibrium data for the adsorption of
caffeine and diclofenac on GAC samples showed L1-type
isotherms with the maximum adsorption capacities of 255
and 330 mg/g, respectively (Sotelo et al. 2012). It was con-
sidered as an indicator of high affinity of adsorbent and
adsorbate, and therefore, it was suggested that aromatic
rings of caffeine and diclofenac molecules are adsorbed
in parallel to the carbon surface and that there is no major
competition between adsorbate and water molecules for
the active adsorption sites on the AC (Sotelo et al. 2012).
The experimental results of adsorption of chlorde-
cone on two AC samples reinforced the phenomenon that
the maximum adsorption capacity of chlordecone on both
carbons (i.e. 70  mg/g) occurs where the solution pH is
close to the point of zero charge of the AC, and the charge
surface is neutral (Durimel et al. 2013). The experimental
results on the adsorption of atrazine and paracetamol on
three different ACs indicated that hydrophobic character-
istic of the compounds does not have an impact on the
sorption capacity of the ACs (170  mg/g) but does affect
the uptake rate (Lladó et al. 2015). In a recent AC adsorp-
tion study for the removal of emerging micropollutants
from wastewater, it was found that the efficiency of PACs
was closely related to their specific surface (BET), which
could be obtained by bulk density (Mailler et al. 2016). For
instance, the application of PB 170 (bulk density of 0.30 g/
cm3) led to highest removals for 15 of the 19 studied micro-
pollutants, while PC 1000 (bulk density of 0.54  g/cm3)
was the least efficient AC (Mailler et al. 2016). The highest
removals achieved foratrazine, diuron, atenolol, car-
bamazepine, ciprofloxacin, diclofenac, erythromycin,
ketoprofen, metronidazole, norfloxacin, ofloxacin, pro-
pranolol, roxithromycin, sulfamethoxazole, and trimeth-
oprim were 40%, 75%, 54%, 63%, 77%, 32%, 26%, 31%,
16%, 79%, 79%, 81%, 43%, 60%, and 46%, respectively
(Mailler et al. 2016).
The systematic development of adsorbents with
optimal properties for certain applications requires a
clear aspect of the governing factors. Therefore, the role
of several factors, which affect the adsorption capacity of
AC, is frequently elucidated in the literature. These factors
are classified below.
2.1 T
 he effects of carbon (adsorbent)
characteristics
Texture (surface area and pore size distributions), surface
chemistry (surface functional groups), and ash content
(Haghseresht et al. 2002, Hnatukova et al. 2011, Yan et al.
2013, Nam et al. 2014) are often important characteristics
of carbon, which have a noticeable effect on the adsorp-
tion capacity of AC.
a. Texture of AC
Some conflicting results have been observed in the
literature regarding the effect of surface area of AC
on its adsorption capacity for organic and inor-
ganic compounds. On the one hand, the adsorp-
tion of organics on AC is considered as a surface
phenomenon (McGuire and Suffet 1978, Lakdawala
and Lakdawala 2013). It was reported that the rate
of adsorption increases with the reduction in par-
ticle size of GAC, and it is inversely proportional to
the square of the carbon particle diameter (McGuire

and Suffet 1978, Lakdawala and Lakdawala 2013). On
the other hand, there are reports indicating that the
adsorption capacity increased insignificantly with
increasing surface area of AC. For instance, Zou et al.
(2013) found that there was a slight change in the
Rhodamine-B adsorption capacity of an AC by tripli-
cating the surface area from 121.3 to 346.5 m2/g (Zou
et  al. 2013). Therefore, it is concluded that specific
surface area is not the sole key factor for the removal
of organic compounds by ACs.
In addition, the adsorption process is highly
influenced by the pore size distribution of the
adsorbent (Lorenc-Grabowska 2016). As the pore
width approaches the adsorbate dimensions, mul-
tiple contact points develop between the adsorbate
molecule and the surface of the adsorbent. Over-
lap of the resulting surface forces leads to stronger
adsorption or higher adsorption energy, which
consequently enhances the adsorption of organic
compounds by the microporous ACs (Dimotakis
et  al. 1995). The adsorption energy is greater in
micropores, and hence, increasing the microporos-
ity would increase the adsorption of low molecular
weight organic molecules (Cal et  al. 1994). It was
also demonstrated that the adsorption of trichloro-
ethylene by ACs increased as the pore volume in the
micropore region of <10 Å increased (Karanfil and
Dasgtheib 2004). It was indicated that the trichlo-
roethylene molecule was able to diffuse into the
deep regions of the carbon micropore due to the flat
orientation of the molecule (Karanfil and Dasgtheib
2004). In addition, it was reported that the uptake
of the organic compounds by microporous carbons
occurred only in pores about 1.7 times larger than
the second widest dimensions of the adsorbate mol-
ecules (Kasaoka et al. 1989).
Pore size distribution of AC relative to the molec-
ular weight of adsorbates is also an important fac-
tor when the adsorption of organic molecules is
governed by non-specific dispersive interactions
(van der Waals interactions, hydrophobic inter-
actions, hydrogen bonds) (Moreno-Castilla 2004,
Newcombe 2006). It was suggested that the mecha-
nism of adsorption of organics (benzene, phenol,
p-nitrophenol, paracetamol, acetanilide, and ani-
line) from dilute aqueous solutions is micropore
filling, combined with adsorption on “active” sites
(Terzyk 2004). Adsorption was particularly signifi-
cant for carbons containing the smallest micropo-
res, with diameters in the range of 0.35–0.7 nm, and
the behavior of adsorbed molecules was found to
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      503
be dependent on the pore width and the size of the
adsorbate molecule (Gauden et al. 2014).
b. Surface chemistry
The AC-water interaction depends on the polarity of
the carbon surface, which is controlled by the hydro-
philic surface sites. Water molecules tend to adsorb
on these hydrophilic sites to form clusters, which
can effectively reduce the accessibility and affinity of
organic molecules to the inner pore where the major-
ity of the carbon surface area is located. Therefore, the
overall adsorption capacity is reduced due to the pres-
ence of hydrophilic surface sites. Water cluster forma-
tion is particularly noticeable in the adsorption of
organic compounds in dilute solutions. For instance,
it was showed that the increase of surface acidity (i.e.
polarity of the AC) reduced the adsorption of hydro-
phobic organic compound (single solute trichloroeth-
ylene and trichlorobenzene) onto AC (Karanfil and
Kilduff 1999). Abundant surface functional groups
(i.e. oxygen-containing groups including hydroxyl
and epoxide) on the surface of AC are found to be
favorable for organic contaminant removal from
wastewater (Zou et al. 2013).
2.2 The effects of adsorbates properties
Molecular weight, polarity, pKa, molecular size, and
functional groups of adsorbates are the properties that
can alter the adsorption capability of AC (Hnatukova
et  al. 2011, Yan et  al. 2013, Nam et  al. 2014). The effects
of molecular weight and molecular size of adsorbate were
discussed in relation to pore size and pore size distribu-
tion of adsorbent in the previous section.
Depending on the adsorbates acid dissociation con-
stants (pKa) and pH in solution, some of ionizable organic
chemicals are converted to either cations or anions while
some of them (e.g. 2, 4-D) are converted to either anionic
or non-ionic (protonated) species. The pKa of organic pol-
lutants depends on their molecular structure. Hydrophilic
compounds easily interact with water by polar-polar inter-
action, which consequently leads to the enhancement in
the adsorption of the ionized micropollutants on the AC
surface due to electrostatic interactions. It was found that
the adsorption of hydrophobic organic compounds was
not affected by pH while the adsorption of hydrophilic
organic compounds (with the exception of caffeine) was
significantly affected by pH (Nam et al. 2014). Electrostatic
and specific sorbate-sorbent interactions between micro-
pollutants and AC surfaces may affect the adsorption of
hydrophilic compounds.
504      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
2.3 T
 he effects of operating conditions
Temperature, pH, water matrix [i.e. presence of dissolved
organic matter (DOM)], dosage of AC, and contact time are
the operating conditions, which are recognized to have a
significant impact on the adsorption capacity of carbon.
2.3.1 Temperature
The effect of temperature on the adsorption process on
AC is still controversial. It was initially believed that the
uptake of organic molecules increases with a decrease in
temperature because adsorption is a spontaneous process
(Moreno-Castilla 2004). However, there are some con-
tradictory reports. For instance, it was reported that the
adsorption of paracetamol from diluted aqueous solu-
tion increased with adsorption temperature due to phase
changes in the crystal form of the adsorbate (Terzyk et al.
2003). It was also observed recently that the adsorption
removal of micropollutants is reduced with a decrease in
the temperature of environment (Nam et  al. 2014). This
effect was found to be more noticeable for hydrophobic
micropollutants than hydrophilic compounds because the
diffusion of lipophilic pollutants during the hydrophobic
interaction with the adsorbent is reduced at low tempera-
tures (Nam et al. 2014).
2.3.1.1 pH
As pH affects the charge of the AC surface groups as well
as the dissociation of organic molecule, pH plays a criti-
cal role in the capacity of adsorption process (Mestre et al.
2007, 2009). pH values higher than point of zero charge
(pHPZC) make the surface of AC negatively charged. Mean-
while, the organic pollutant is simultaneously deproto-
nated once the solution pH values exceeded its pKa.
For example, in the specific case of ibuprofen (log
Kow 3.8 and pKa 4.91), it was found that the adsorption
was less favorable at pH values above pKa of the organic
component due to the electrostatic repulsion between
the adsorptive anion and the surface of the AC (Mestre
et  al. 2007, 2009). In contrast, at acidic pH levels (solu-
tion pH < pKa), adsorption was enhanced because the AC
surface was neutral and organic pollutant (i.e. ibuprofen)
was non-dissociated, and therefore, repulsive electrostatic
interactions were minimized (Mestre et al. 2007, 2009).
For chlordecone, it was recently observed that its
adsorption capacity reaches a maximum where the solu-
tion pH is close to the pHpzc of the AC, where the surface
charge is neutral (Durimel et al. 2013). At this pH, chlorde-
cone would mainly bind to the AC surface by hydrophobic
interactions (Durimel et  al. 2013). Fewer chlordecone
molecules were adsorbed at solution pH both higher and
lower than pHpzc. At the solution pH lower than pHpzc,
the solvent molecules (i.e. water) presented higher affin-
ity than the chlordecone molecules for the oxygenated
functional groups on AC surface. Thus the hydrophilic
characteristics of AC were increased due to interactions of
water molecules in solution with the oxygenated function-
alities on AC surface, which subsequently led to a reduc-
tion in the chlordecone uptake. Therefore, the adsorption
of water molecules would induce a steric hindrance and
lower the affinity of the chlordecone molecules for adsorp-
tion on the surface (Durimel et  al. 2013). In contrast, at
the solution pH above pHpzc, the electrostatic repulsion
between the negative surface of the AC and the molecule
would occur leading to a reduction in adsorption capacity
(Durimel et al. 2013).
2.3.2 Presence of DOM
The literature highlighted that the matrix where the
adsorption is taking place plays a crucial role in the fate
of adsorbate molecules, particularly when other pos-
sible adsorbates such as natural organic matters (NOM)
are present in the environment. Substantial investiga-
tions have been undertaken to examine the role of NOM
in assessing an AC adsorption process in water treatment
plants. The presence of NOM (e.g. humic substances, pro-
teins, and polysaccharides) in real water can considerably
reduce the adsorption capacity of AC due to competitive
inhibition of NOM with micropollutants on surface of AC
(Kilduff and Karanfil 2002, Mardini and Legube 2010). The
NOM preloads the carbon ahead of the trace organic pol-
lutant leading to a reduction in adsorption of trace organic
compounds due to direct competition for adsorption sites
or pore blockage by NOM (Newcombe et  al. 2002). The
main factors, which determine the competitive adsorption
of NOM and micropollutants on AC, are pore size distri-
bution of AC relative to the molecular weight of adsorb-
ates (trace organic compounds and NOM) (Quinlivan et al.
2005), chemical composition of NOM, surface functional
group composition, surface charge of adsorbent (New-
combe and Drikas 1997, Kilduff and Karanfil 2002), solution
pH (Bjelopavlic et al. 1999), and ionic strength (Moreno-
Castilla 2004, Campinas and Rosa 2006). The details of
their effects are elucidated in the literature (Hnatukova
et al. 2011). It was also reported that the decline in the AC
adsorptive removal in the presence of NOM is more sig-
nificant for hydrophobic than hydrophilic micropollut-
ants (Nam et al. 2014). Furthermore, the results of a recent

research on the adsorption of 30 common micropollut-
ants in four surface waters in GAC pilot columns showed
that an increase in background DOM resulted in more and
earlier micropollutant breakthrough (Kennedy et al. 2015).
Recently, it was found that not only the quantity of the
DOM but also the composition (i.e. distribution of the dif-
ferent molecular components) of the DOM should be con-
sidered in the study of the adsorption of emerging organic
pollutants on AC in wastewater (Mailler et  al. 2016). For
instance, protein-like fluorophores were identified as the
most problematic for adsorption competition in wastewa-
ter, while a high humification index (HIX) was deduced to
be favorable to micropollutants adsorption (Mailler et al.
2016).
2.3.3 D
 ose of AC
Removal of organic pollutants due to adsorption was
enhanced with an increase in dosage of AC. The relation-
ship was a logarithmic pattern yielding a plateau when
increasing the AC dose (Mailler et al. 2016).
2.3.4 Contact time
The adsorption of trace organic compounds was usually
increased with an increase in contact time (Nam et  al.
2014). However, the change could be significant or neg-
ligible depending on the kinetics of adsorption. It was
observed that the increase of contact time led to limited
increase in the elimination of low molecular weight
organic pollutants (e.g. atrazine, norfloxacin, ofloxacin,
and sulfamethoxazole) due to fast adsorption kinetic
(Mailler et  al. 2016). In contrast, the removals notably
increased with the contact time for other organic pollut-
ants (ciprofloxacin, diclofenac, erythromycin, and rox-
ithromycin) with high molecular weight due to slower
adsorption kinetics (Mailler et al. 2016).
3 M
 echanism of the adsorption of
emerging pollutants on AC
In general, AC’s surface is predominantly hydrophobic
but may also contain functional groups (such as oxygen
and hydrogen heteroatoms) formed during the activation
process. The mechanisms by which AC adsorbs organic
compounds differ depending to the properties of the
compound of interest, the origin of carbon material, the
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      505
differences in location, and type of surface functionalities
(inside pores or located at the edge of the graphite sheets).
The adsorption of organic compounds is generally influ-
enced by different molecular features such as the hydro-
phobicity and the nature of the functional groups. These
mechanisms are elucidated below.
3.1 Hydrophobicity
Adsorption of organic molecules from dilute aqueous
solution onto AC was initially assumed to be driven
by hydrophobic interactions. Westerhoff et  al. (2005)
observed that the trend in the removal efficiency of micro-
pollutants by AC can be predicted from log Kow values. The
term Kow is called octanol-water partition coefficient, and
it is defined by the ratio of a chemical’s concentration in
octanol phase to its concentration in the aqueous phase
of a two-phase octanol-water system. Therefore, Kow indi-
cates the lipophilicity of a chemical. It was suggested that
log Kow served as a reasonable indicator of removal of a
compound under controlled test conditions (Westerhoff
et al. 2005) because log Kow maintained a positive corre-
lation for hydrophobic compounds and a negative cor-
relation for hydrophilic compounds (Nam et  al. 2014).
However, N-heterocyclic compounds (e.g. pentoxifylline
and trimethoprim) and compounds with carboxyl groups
(e.g. clofibric acid, ibuprofen, and diclofenac) are recog-
nized as exceptions of this correlation. It was rationalized
that removal efficiencies of N-heterocyclic compounds
were higher than might be expected from their log Kow
values due to specific interactions of the protonated
compounds with AC. In contrast, removal efficiencies for
compounds with carboxyl groups were much lower than
that expected from their log Kow values, because in water,
they are dissociated to some extent, and therefore, they
are negatively charged.
There are extensive debates in the literature on the
involvement of the hydrophobic interactions on the
removal of organic contaminants from water. Strictly
speaking, the type of adsorption is called hydrophobic
interactions when a sorbate expels water molecules from
a sorbent surface. In this case, the interactions between
hydrophobic parts of the sorbate and the sorbent mole-
cules are van der Waals interactions. However, it is
obvious that the presence of polar functional groups on
both sorbate and polar sorbent influences the adsorp-
tion of polar contaminants more significantly than the
interactions of hydrophobic parts of the sorbate and
sorbent molecules. The reason is that polar interactions
are essentially stronger than van der Waals interactions.
506      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
For instance, in the studies of the adsorption of four sub-
stituted phenols and other simple aromatic compounds
on AC, it was concluded that the compound’s hydropho-
bicity is the main factor determining a higher adsorption
capacity (Li et  al. 2009, Mohamed et  al. 2011, Durimel
et al. 2013). The key point is that both the adsorbates (i.e.
the four substituted phenols and other simple aromatic
compounds) and adsorbent (AC samples) are non-polar.
Therefore, there is no doubt that the hydrophobic inter-
actions control the mechanism of adsorption. In another
recent research, it was proposed that the hydrophobic
character of the organic compounds does not have an
impact on the sorption capacity of the tested carbons but
does affect the uptake rate (Lladó et al. 2015). The emerg-
ing water contaminants of interest were atrazine and
paracetamol, which are considered polar compounds. As
both the adsorbates and adsorbents had polar functional
groups, the van der Waals interactions were more domi-
nant than the hydrophobic interactions. Therefore, the
adsorption capacity was not affected by the hydrophobic-
ity of the compounds.
Overall, it is concluded that Kow is not always a deter-
mining factor in adsorption, and the hydrophobic inter-
actions are not the dominant removal mechanism of
adsorption when polar functional groups are present on
the AC surface and organic pollutant(s).
3.2 N
 ature of the functional groups
Nature of the functional groups also determines the
interaction between the adsorbent and adsorbates,
and consequently, it affects the adsorption mechanism
(Moreno-Castilla 2004). For instance, increasing the
amount of oxygen-containing functional groups on the
AC surface decreases the adsorption of organic solutes,
indicating preferential adsorption of water molecules over
organic solutes at these sites (Li et al. 2002, Cabrita et al.
2010). In another research on the adsorption of levodopa
(a PPCP used to treat symptoms of Parkinson’s disease) by
three ACs derived from different materials, it was observed
that the adsorption of levodopa was clearly disfavored
by the presence of acidic surface groups whereas basic
surface groups in AC had a positive impact on adsorption
(Quesada-Peñate et al. 2009).
Although the role of the nature of the AC functional
groups is still not well established, the three different
mechanisms of π-π dispersion interactions, hydrogen
bonding formation, and electron donor-acceptor complex
formation have been often addressed in the literature
for the adsorption of organics from aqueous solutions
on carbons (Terzyk 2000, Moreno-Castilla 2004, Li et al.
2009, Lladó et al. 2015).
3.2.1 E
 lectron donor-acceptor complex formation
Electron donor-acceptor complex formation mechanism
is one of the first mechanisms given for the adsorption of
organic aromatic pollutants on AC (Mattson et  al. 1969).
In this mechanism, the carbonyl oxygen of the carbon
surface acts as the electron donor while the aromatic com-
pounds (i.e. phenols) act as the acceptor (Mattson et  al.
1969). As the carbonyl groups on AC were oxidized to car-
boxyl groups during the process, the rate of the forma-
tion of electron donor-acceptor complexes was decreased
leading to a reduction in phenol uptake (Mattson et  al.
1969). However, this decrease after the incorporation of
surface groups depends on the polarity of functionalities
and the difference between the polarity of the solute and
solvent (Gauden et  al. 2014). As the carbonyl groups on
AC are oxidized to carboxyl groups in the electron donor-
acceptor complex formation mechanism, the concentra-
tion of carbonyl groups is expected to decrease with time
during the process. However, there are some contrasting
experimental data indicating that although the concen-
tration of carboxyl groups increased, the concentration
of carbonyl groups increased or remained essentially
unchanged during the process (Moreno-Castilla 2004).
It was explained later that once the carbonyl groups are
exhausted, the aromatic compounds form π-π dispersion
interactions complexes with the rings of the basal plane
(Moreno-Castilla 2004).
3.2.2 π-π Dispersion interactions
It was successively reported that organic aromatic com-
pounds can be adsorbed on ACs by dispersion interac-
tions between the electrons of the aromatic ring and those
of the graphene layers (Moreno-Castilla 2004, Li et  al.
2009, Cotoruelo et al. 2011). Therefore, if the organic com-
pound of interest contains aromatic rings in its molecu-
lar structure, functionalization of AC profoundly affects
these dispersion interactions. This effect is not necessar-
ily positive for all organic compounds, and it brings about
an interesting topic of enhancement of AC selectivity
for the adsorption of specific pollutants from a solution
by the functionalization of AC surface. For instance, the
introduction of oxygen onto the carbon surface causes a
decrease in the concentration of π electrons of the basal
planes and, therefore, a weakening of the interactions

of these planes with the π electrons of the benzene ring
(Gauden et al. 2014).
The charge distribution within aromatic molecules
depends on the inductive and resonance effects of the
substituents. For instance, the presence of constituents
such as -NHR and -OH groups adds an electron density
to the aromatic ring, which makes the organic aromatic
compound act as a π-donor. Conversely, the presence of
a -Cl substituent makes the aromatic molecule act as a
π-acceptor compound.
AC is mostly a π-donor surface due to the presence of
-OH aromatic groups, which increase the electron density
of the AC graphitic planes. Therefore, a π-electron accep-
tor organic compound has more affinity for the AC than
a π-donor aromatic compound. However, there are some
recent experimental data in the literature, which contra-
dict the theory of π-π dispersion interactions mechanism
by providing a comparison between the adsorption of
atrazine and paracetamol on two different ACs (Lladó
et  al. 2015). Paracetamol acts as a π-donor compound
due to the presence of -NHR and -OH groups in its aro-
matic structure while atrazine is a π-acceptor compound
due to the presence of -Cl substituent as well as being a
π-deficient N-heterocyclic compound. Based on the theory
of π-π dispersion interactions mechanism, it was expected
to observe higher adsorption for atrazine than paraceta-
mol on the ACs. However, the reported experimental data
did not support this theory (Lladó et al. 2015). It was pro-
posed that the adsorption process followed hydrogen
bonding mechanism. Hydrogen bonding could be estab-
lished between O-H groups on the surface of the ACs with
N-H in atrazine and O-H in paracetamol. It was rational-
ized that paracetamol was adsorbed more than atrazine
because OH-OH interactions are more intense than OH-NH
interactions. In addition, the steric effect of side-chains in
atrazine structure might hinder the formation of hydrogen
bonds between the molecule and the functional groups of
the ACs.
3.2.3 H
 ydrogen bonding formation
Hydrogen bonding can also contribute to the adsorption
of organic aromatic compounds on AC when they have
hydrogen-bonding functional groups (e.g. N-H in atra-
zine and O-H in paracetamol) in their molecular structure
(Terzyk 2000, Moreno-Castilla 2004, De Ridder et al. 2010,
Villaescusa et al. 2011). In this mechanism, the O-H groups
present on the surface of the ACs get involved in the for-
mation of hydrogen bonds with the functional groups of
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      507
organic adsorbates, and the intensity of the net interac-
tions (hydrogen bonds and the steric effect of side chains)
determines the extent of adsorption (Terzyk 2004, Lladó
et al. 2015). In this mechanism, some complexes between
solvent molecules and surface oxides are formed, which
could block the migration of the solute molecules from
the outside to the micropore structure of active carbon
(Gauden et  al. 2014). It was also shown that this effect
vanishes with the rise in temperature due to the increase
in the kinetic energy of the adsorbed molecules (Gauden
et al. 2014).
However, in practice, several mechanisms may
act simultaneously and some competitions among the
micro-pollutants may also occur (Najm et al. 1991), which
make the adsorption mechanism more complicated. For
instance, the mechanism of paracetamol removal by AC
produced from vegetable wastes involves the contribution
of π-π interactions, hydrogen bonding, and hydrophobic
effect (Villaescusa et al. 2011).
4 Adsorption isotherms
For the effective design and operation of adsorption
processes, it is important as a starting point to quantify
adsorption capacity, which is typically expressed as an
isotherm (Yu et  al. 2007). Various adsorption isotherm
models have been developed and used in the literature
to correlate the amount of different adsorbates uptaken
by a specific adsorbent as a function of its concentration
in the solution at equilibrium. A thorough review on the
adsorption isotherms with emphasis on their modeling,
characteristics, and mathematical derivations was pre-
sented (Foo and Hameed 2010). However, the application
of only a few adsorption isotherm models (i.e. Langmuir,
Freundlich, BET, Sips, Dubinin-Astakhov, Dubinin-
Radushkevich, and Toth) is reported for the adsorption
of emerging pollutants (pesticides, PPCPs, and EDCs) on
AC, as shown in Tables 1–3. A review of the equilibrium
adsorption isotherms reported in Tables 1–3 manifested
that Langmuir and Freundlich models are the two most
common adsorption isotherms, which are frequently
used to establish a correlation between the amount of
uptaken organic adsorbate by AC and its concentration
in the solution in equilibrium state. However, in this
review, an effort was made to discuss all the applied
adsorption isotherm models briefly and compare their
applications in the specific case of emerging pollutant
adsorption on AC.
508      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
4.1 L angmuir isotherm model
In the formulation of Langmuir isotherm model, several
assumptions were made (Al-Qodah and Shawabkah 2009,
Foo and Hameed 2010) such as monolayer homogenous
adsorption occurring at specific localized sites, which are
identical and equivalent with no lateral interaction and
steric hindrance between the sorbed molecules.
The Langmuir model in terms of organic pollutant
concentration in solution, Ce (mg/l) in equilibrium with
that on the solid surface, qe (mg/g) is given by (Langmuir
1918) the following:
QbCe
qe = , (1)
1 + bCe
 cates the adsorption affinity of the sorbent and favorabil-
where Q (mg/g) is the maximum amount of adsorbate per
unit mass of AC required to form a complete monolayer
and b (l/mg) is the Langmuir constant related to the affin-
ity of the binding sites. One of the linear expressions of
the Langmuir model is (Foo and Hameed 2010) as follows:
Ce 1  1
= + C.
qe Qb  Q  e

The constants Q and b can be determined by plot-
C 
ting ­ specific adsorption  e  against the equilibrium
 qe 
­concentration (Ce).
The strength of the Langmuir isotherm model is that at
low sorbate concentration, it effectively reduces to linear
isotherm and thus obeys Henry’s law. However, Langmuir
isotherm model is only valid for single-layer adsorption,
assuming maximum adsorption corresponds to a satu-
rated monolayer of organic molecules on the surface of
the AC. Thus it could be invalid for a multilayer adsorption
system occurring due to high adsorbate concentration or
non-uniform distribution of adsorption heat and affini-
ties over the heterogeneous surface. For instance, it was
reported that the Langmuir model did not fit the experi-
mental data adequately particularly when the pesticide
concentration exceeded 40  mg/l where the second layer
started to adsorb (Al-Qodah and Shawabkah 2009). In
addition, as the model parameters are obtained at a spe-
cific condition (e.g. temperature), application of the Lang-
muir isotherm model to extended conditions is limited.
4.2 F reundlich isotherm model
Freundlich isotherm model is the earliest empirical model
developed for non-ideal, reversible, multilayer adsorption
with non-uniform distribution of adsorption heat and
affinities over the heterogeneous surface (Sarkar et  al.
2007, Foo and Hameed 2010). The Freundlich model is
presented in the following form (Freundlich 1907):
 1
qe = K F C
 
 nF  (3)
e

The linear form of the Freundlich model is (Hameed et al.
2009) as follows:
 1
ln qe = ln K F +   ln Ce , (4)
 nF 

where the Freundlich constant KF [mg/g (l/mg)1/n] indi-
ity of adsorption process. The constant KF is the adsorption
capacity at the equilibrium concentration (Ce) of 1  mg/l,
and therefore, it does not necessarily indicate the
maximum adsorption capacity. The Freundlich constants
can be determined from the intercept and slope of the log-
plot of qe against Ce. It was mentioned that the strength
of the Freundlich isotherm is that it assumes unlimited
(2)
sorption sites with heterogeneous surfaces, which cor-
related better with a heterogeneous soil medium having
different chemical and physical properties (Gregory et al.
2005). Therefore, the Freundlich isotherm is a heteroge-
neous binding model, which can provide adjustment and
assess the heterogeneity (Gregory et al. 2005). The slope
 1
of the line in the Freundlich model   is a measure of
 nF 
 1
surface heterogeneity. If the slope   is high, the con-
 nF 
centration of the organic pollutant on the solid surface (qe)
will increase rapidly with a slight increase in the concen-
tration of organic pollutant in solution (Ce). This is clearly
a characteristic of surface heterogeneity. It was mentioned
 1
that the slope   approaches unity in a more homoge-
 nF 
neous system, whereas it approaches zero in a more het-
erogeneous system (Gregory et al. 2005).
As the surface of AC is heterogeneous and Freundlich
isotherm model is applicable to both homogeneous and
heterogeneous systems, it is possibly the most appropriate
isotherm model. Tables 1–3 confirm that Freundlich iso-
therm model is the most widely applied isotherm model in
the applications of AC as an adsorbent for the removal of
emerging pollutants.
However, there are three general deficiencies regard-
ing the use of the Freundlich isotherm model:
1. Unlike the Langmuir isotherm, the Freundlich iso-
therm does not indicate a maximum adsorption

capacity. Therefore, Freundlich isotherm equation
might fail at high adsorbate concentrations (Pastrana-
Martínez et al. 2010). For instance, it was reported that
Freundlich isotherm model was not valid when the
pesticide concentration exceeded 40 mg/l (Al-Qodah
and Shawabkah 2009).
2. It does not obey Henry’s law at low pollutant concen-
trations, and therefore, it has been criticized for the
lack of a strong basis in thermodynamics (Foo and
Hameed 2010).
3. Like Langmuir equation, the parameters in Freun-
dlich isotherm do not give information on the adsorp-
tion mechanism (Inglezakis 2007).
4.3 O
 ther isotherm models
BET, Sips, Dubinin-Astakhov, Dubinin-Radushkevich,
and Toth are other equilibrium isotherm models, which
were seldom fitted to the isotherm data of adsorption of
emerging pollutant on AC.
4.3.1 Brunauer, Emmett, and Teller (BET) isotherm model
The Brunauer, Emmett, and Teller (BET) isotherm model
assumes that several layers of organic adsorbate mol-
ecules form at the surface of the adsorbent and that the
Langmuir equation is applicable to each layer of adsorp-
tion (Al-Qodah and Shawabkah 2009). Therefore, the BET
isotherm model takes the following form (Brunauer et al.
1938):
Qk1Ce
qe = , (5)
(1 − kmCe )[1 + (k1 − km )Ce ]

where k1 and km are the equilibrium constants for the
first and subsequent layers, respectively.
A distinct advantage of the model is the ability to
estimate the maximum adsorption capacity in multilayer
physical adsorption.
4.3.2 S
 ips isotherm model
The Sips isotherm is a combination of the Langmuir and
Freundlich isotherms, and it is given in the following form
(Sips 1948):
1
QK C
ns
qe = s e
(6)
1 qe = Q exp − 
n   E
1 + K LCe s

Z. Jeirani et al.: Adsorption of emerging pollutants on AC      509
It was reported that the Sips equation is the most appro-
priate isotherm model for predicting the single-compo-
nent adsorption of three herbicides (i.e. CPA, 2,4-D, and
MPCA) on the AC (Kim et al. 2008). Fitting of the adsorp-
tion experimental data to Langmuir and Freundlich iso-
therm models exhibited larger fitting error than the Sips
isotherm model (Kim et al. 2008).
Among four isotherm models, namely, Langmuir, Fre-
undlich, Sips, and Redlich-Peterson used for fitting of the
experimental adsorption data of a pharmaceutical com-
pound (i.e. ranitidine hydrochloride) on AC in the temper-
ature range of 303–318 K, the Sips model gave the lowest
error and the highest R2 values (Mondal et al. 2015).
The main advantage of the Sips model is that it can
be reduced to the Freundlich isotherm at low pressures,
and it approaches the monolayer capacity at high pres-
sure similar to the Langmuir isotherm. The Sips isotherm
has also the benefit of estimation of the thermodynamic
parameters of adsorption from the constant value of
Ks (i.e. Sips equilibrium constant) (Calvete et  al. 2009,
Cardoso et al. 2011).
The disadvantage of Sips isotherm model is that it has
three parameters, compared to the Langmuir and Freun-
dlich equations with two parameters. Therefore, a statis-
tical method or a pattern search algorithm (e.g. NMEAD)
is required to be used to fit the Sips isotherm model and
determine its three parameters.
4.3.3 Dubinin-Astakhov (DA) and Dubinin-Radushkevich
(DR) isotherm models
DR adsorption isotherm is one of the most common and
useful models for predicting and describing equilibrium
adsorption capacities of organic vapors on ordinary com-
mercial ACs (Inglezakis 2007). It is generally expressed in
the following form:
  2

RT  Cs  
qe = Q exp −  ln    , (7)
  E  Ce   
  
where E (J/mol), Ce (mg/ml), and Cs (mg/ml) are the
adsorption energy, equilibrium solute concentration, and
its solubility, respectively.
For specialized carbons, the more general DA equa-
tion with an additional parameter can be used, namely,
the heterogeneity parameter (n):
  n

 RT  Cs   
ln    . (8)
 Ce   
  
510      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
The heterogeneity parameter (n) increases as the micropo-
rous structure of AC becomes more homogeneous.
The DA and DR equations have the advantages of
including carbon property parameters (heterogene-
ity parameter), solute property parameters (adsorption
energy), and temperature.
Although the DA and DR adsorption isotherms have
been extensively used for the adsorption of organic vapor
on AC, their applications have been extended to cover the
cases of the adsorption of organic compounds (e.g. clofi-
bric acid and lindane) from aqueous solutions (Sotelo
et al. 2002a, Mestre et al. 2010). For instance, the best fit to
equilibrium data obtained for the adsorption of aqueous
lindane onto GAC were given by the DR equation (Sotelo
et al. 2002a). It was also remarked that DA equation usually
gives good fittings to S-type isotherms (Mestre et al. 2010).
The S-type isotherms indicate that the adsorption of the
organic compound from aqueous phase is a cooperative
process such as capillary condensation or multilayer
adsorption, which involves interactions between adsorb-
ate molecules (Mestre et al. 2010).
4.3.4 T
 oth isotherm model
Toth isotherm is derived from the potential theory and
is applicable to heterogeneous adsorption. This is a
Langmuir-based isotherm assuming a quasi-Gaussian
energy distribution (Toth 1971). In this model, most sites
have adsorption energy lower than the peak or maximum
adsorption energy (Toth 1971). The Toth isotherm model
has the following form:
QCe
qe = 1/m
, fusion of adsorbate molecule across the liquid film sur-
1 m
(9)
 K + Ce 
 adsorbents (i.e. external diffusion), (2) diffusion of adsorb-
where Q (mg/g), K, and m are the maximum monolayer
adsorption capacity parameter, Toth isotherm constant,
and a dimensionless constant, respectively.
The Toth model provides the best fitted isotherm
model in an equilibrium study of the adsorption of an
antibiotic (i.e. trimethoprim) on both powdered and gran-
ular ACs (Kim et al. 2010).
4.3.5 Adsorption-desorption isotherm and hysteresis
Understanding of the sorption mechanism and the
development of improved techniques of water purifica-
tion require the investigation of molecular modeling of
adsorption and hysteresis. Statistical thermodynam-
ics could be used to elucidate the effect of porous mate-
rial microstructure on the properties of confined fluids
(i.e. liquid, gas) and facilitate the development of a suf-
ficiently realistic model of the microstructure (Monson
2005). Therefore, adsorption hysteresis deals with the
transport of fluid in porous materials such as AC. The
phenomenon of adsorption-desorption hysteresis can be
simply described in terms of a pore geometry consisting of
a larger pore space in contact with a bulk vapor through
one or more necks (Libby and Monson 2004). The pore
blocking concept is included in theories of hysteresis, in
which the properties of networks and percolation theory
were used (Libby and Monson 2004).
Despite the importance of the hysteresis phenom-
enon, it has rarely been studied for the adsorption of
emerging pollutants on the AC. This phenomenon was
only applied in the specific case of adsorption of paraceta-
mol on AC at different temperatures and pH levels (Terzyk
et  al. 2003). New correlations were established between
the composition of carbon surface and its physicochemi-
cal properties. Based on that, the mechanism of adsorp-
tion was explained (Terzyk et al. 2003).
5 Adsorption kinetic models
Kinetic analysis of an adsorption process provides infor-
mation on the solute uptake rate, which determines the
residence time required for the completion of adsorption
reaction and, consequently, the scale up of an adsorption
apparatus. An adsorption process generally involves three
consecutive steps (Lazaridis and Asouhidou 2003): (1) dif-
rounding the adsorbent particles to reach the surface of
ate molecule in the liquid in the adsorbent pores from the
surface to sites of internal surface (i.e. internal diffusion),
(3) adsorption and desorption between the adsorbate mol-
ecule and adsorbent active sites (i.e. reaction). Depending
on the rate-limiting step of an adsorption process, differ-
ent kinetic models have been developed and applied. If the
rate-limiting step of an adsorption process is the external
diffusion, the film diffusion model is applicable. In con-
trast, if the rate-limiting step of an adsorption process is
the internal mass transfer, intra-particle diffusion models
such as homogeneous surface diffusion model (HSDM)
are more likely to be appropriate. Finally, pseudo-first-
and pseudo-second-order models are the most suitable
kinetic model if the interaction between the adsorbate
molecule and adsorbent active sites is the rate-limiting

step. Therefore, these models may provide information to
assist in elucidation of the mechanism of the adsorption
process. However, there are some researches available
in the literature, in which the pseudo-first- and pseudo-
second-order models were used for kinetic analysis due
to simplicity although the diffusional steps were the rate-
limiting steps (Ocampo-Pérez et  al. 2012). In such cases,
it is essential to combine other analytical approaches in
order to explore the actual mechanism (Ocampo-Pérez
et al. 2012). Based on the literature, the adsorption kinet-
ics models used for the adsorption of pesticides, PPCPs,
and EDCs on AC are presented in Tables 1–3, respectively.
5.1 Pseudo-first-order model
The pseudo-first-order model is believed to be the earli-
est model pertaining to the adsorption rate based on
the adsorption capacity. It was initially presented to
describe the kinetic process of liquid-solid phase adsorp-
tion of oxalic acid and malonic acid onto charcoal
(­Lagergren  1898). However, it later proved to be appro-
priate for kinetic analysis of various adsorption applica-
tions such as adsorption of pollutants from wastewater in
different fields (Hameed and El-Khaiary 2008, Tan et  al.
2008). As Tables 1–3 show, the pseudo-first-order model
has often been used to describe the kinetics of adsorption
of emerging pollutants on AC, and its wide application is
attributed to its simplicity. The pseudo-first-order kinetic
model can be presented as (Lagergren 1898) follows:
dqt
= k1 (qe − qt ) (10)
dt

The linear form of the pseudo-first-order kinetic model is
as follows:
k1
log(qe − qt ) = log qe −  t , (11)
2.303
 pseudo-second-order rate constant. In this model, Vi can
where qe and qt (mg/g) are the adsorption capacities (i.e.
the amounts of the organic pollutant adsorbed) at equilib-
rium and time t (min), respectively. k1 (min−1) is the pseudo-
first order rate constant, and it can be obtained from
the slope of the regression line on the plot of log(qe − qt)
against time.
In the study of kinetics of adsorption of a herbicide
species (i.e. fluroxypyr) on different kinds of AC, the
values of k1 for AC fiber, AC cloth, and granular AC were
obtained as 6.2 × 10−3, 3.8 × 10−5, and 1.8 × 10−5 g/mg min,
respectively (Pastrana-Martínez et  al. 2010). The results
showed that adsorption kinetics on AC fiber was much
Z. Jeirani et al.: Adsorption of emerging pollutants on AC      511
faster than on granular AC due to the much smaller size
of the fiber and its different micropore network. It was
mentioned that micropores are more easily reached in AC
fiber than in granular AC because they are perpendicular
to the fiber axis and directly open to the external surface
(Pastrana-Martínez et  al. 2010). The adsorption kinetics
was slower on AC cloth due to the increase in size from
the weaving of the fibers, but it was still faster than on
granular AC (Fontecha-Cámara et  al. 2008). The adsorp-
tion of another herbicide [i.e. 2,4-dichlorophenoxy-acetic
acid (2,4-D)] on AC was also found to follow pseudo-first-
order kinetics with the values of k1 about 0.9 h−1 (Hameed
et al. 2009).
Kinetics study of adsorption of some pesticides,
namely, bentazon, propanil, ametryn, aldicarb, dinoseb,
and diuron, from aqueous uni-solute solutions onto an
AC cloth showed that the pseudo first-order rate constants
are 0.011, 0.012, 0.0156, 0.0035, 0.0163, and 0.0051  min−1
(Ayranci and Hoda 2004, 2005). The results prove similar
adsorption behavior for bentazon and propanil (Ayranci
and Hoda 2004) as well as ametryn and dinoseb (Ayranci
and Hoda 2005) on the AC cloth.
5.2 Pseudo second-order model
Pseudo-second-order model can be expressed as (Ho
2006) follows:
dqt
= k2 (qe − qt )2 (12)
dt

or in its linear form of
t 1 1
= + t ,  (13)
qt Vi qe

where Vi [mg/(g min)] is the initial adsorption rate, and
it equals to k2 qe2 . The parameter k2 (g/mg min) is the
be first obtained from the intercept of the regression line
t
on the plot of against time, and k2 can be subsequently
qt
determined from Vi.
As Tables 1–3 present, the pseudo-second-order
model was the favorable model in most research studies
on the adsorption of emerging pollutants on AC. As afore-
mentioned, the pseudo-second-order model is likely
valid when the rate-limiting step is the surface reaction
(adsorption or desorption) involving either chemisorption
or physisorption.
In a mini-review, the suitability of application of
pseudo-second-order kinetic model for adsorption of
512      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
some organic pollutants [i.e. phenol, 4-chlorophenol
(4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophe-
nol (2,4,6-TCP), and methylene blue (MB)] from water
on AC was investigated (Wu et al. 2009). It was deduced
that the pseudo-second-order model was appropriate for
the adsorption of lower molecular-weight adsorbates on
smaller adsorbent particles (with particle size less than
505 microns) (Wu et al. 2009). Furthermore, the rate index
(k2qe) defined as the inverse of the half-life of adsorption
process could provide the relationship between the static
and dynamic behavior of adsorption processes (Wu et al.
2009). As the rate index is a key parameter affecting the
fractional adsorption at any time, it can be used as an
indicator of kinetic performance in engineering applica-
tions (Wu et al. 2009).
The pseudo-second-order model also provides the
best correlation for the adsorption kinetics of a kind of
herbicide (Paraquat dichloride) on AC (Hamadi et  al.
2004). Almost 90% of the maximum possible adsorption
of the organic pollutant onto AC took place in the first
5  min, which indicates a high rate of sorption (Hamadi
et al. 2004).
The k2 for the adsorption of a pharmaceutical com-
pound (i.e. acetaminophen or paracetamol) on five dif-
ferent AC (labeled PP, B, CP, CC, NS) showed an increase
in the order of PP < B  CP  CC  NS (Cabrita et  al.
2010). The five AC samples of PP, B, CP, CC, NS were
prepared from the wastes of plastic, coal, peach stones,
cork powder, and wood, respectively. The largest k2 value
(17.6 × 10−4 g mg−1 min−1) was obtained for NS, and there-
fore, not only the largest uptake (173 mg g−1) but also the
fastest adsorption rate was achieved in the application
of this kind of AC material (Cabrita et  al. 2010). Among
other AC samples, CC presented a relatively high k2 value
(14.7 × 10−4 g mg−1 min−1), which was twice that of sample
CP (6.7 × 10−4 g mg−1 min−1) despite the fact that both mate-
rials had similar adsorption uptakes (159 and 150 mg g−1
for CC and CP, respectively) at equilibrium conditions
(Cabrita et al. 2010). The sample PP showed the smallest
rate constant (1.9 × 10−4 g mg−1 min−1) (Cabrita et al. 2010).
The same trends were obtained for initial adsorption rate
(h, mg g−1 min−1) and half-life time (t1/2, min) parameters
(Cabrita et al. 2010).
In the case of adsorption of ibuprofen on differ-
ent ACs, it was found that there is a linear relation-
ship between mesopores volume and the k2 constant
(Mestre et  al. 2009). The slowest adsorption kinetic (k2:
0.07 g mg−1 h−1) was found for the AC possessing negligible
mesoporous volume, while the fastest adsorption rate (k2:
0.58 g mg−1 h−1) took place in the AC with the most devel-
oped mesoporous network (Mestre et al. 2009). In contrast
to ibuprofen, the adsorption rates of clofibric acid at dif-
ferent pH values presented distinct behaviors of the ACs.
The highest values of k2 were achieved at pH 3.6 and 5.0 for
VP (1.54 g mg−1 h−1) and CPAC (1.65 g mg−1 h−1) AC samples,
respectively (Mestre et al. 2010). The justification for this
behavior was related to both the volume of mesopores and
the dissociation of the clofibric acid at different pH values
(Mestre et al. 2010).
The pseudo-second-order surface-reaction model was
well fitted to the kinetic data of Bromacil adsorption on
AC, even in the presence of NOM (Mardini and Legube
2010). However, the k2 values determined in the presence
of NOM were found to be independent of the Bromacil
equilibrium concentration, contrary to that observed in
pure water (Mardini and Legube 2010). The kinetic data
also confirmed the blockage of high-reactivity sites on the
studied PAC by NOM (Mardini and Legube 2010).
The experimental kinetic data for adsorption of some
emerging pollutants [i.e. phthalic acid (PA), bisphenol A
(BPA), diphenolic acid (DPA), 2,4-dichlorophenoxy-acetic
acid (2,4-D), and 4-chloro-2-methylphenoxyacetic acid
(MCPA)] on two commercial ACs were well described by
the pseudo-second-order kinetic model (Ocampo-Pérez
et  al. 2012). However, no clear relationship was found
between the k2 values and pollutant molecular size or
pore size of the ACs. It was therefore suggested that other
parameters (e.g. molecular shape, pollutant deprotonated
species, and surface groups of ACs) should play an impor-
tant role on the adsorption kinetics (Ocampo-Pérez et al.
2012).
5.3 Film diffusion model
Assuming that the rate of solute accumulation in the solid
phase equals the rate of solute transfer across the liquid
film, the linear form of the film diffusion model is (Boyd
et al. 1947) as follows:
 q
ln  1 − t  = − Rlt (14)
 qe 

in which, Rl (min−1) is the liquid film diffusion constant
and is expressed by the following:
3 Del
Rl = , (15)
r0 ∆r0k ′

where Del (cm2/min), r0 (cm), ∆ r0 (cm), and k′ are the effec-
tive liquid film diffusion coefficient, radius of adsorbent
beads, thickness of liquid film, and equilibrium constant,
 Z. Jeirani et al.: Adsorption of emerging pollutants on AC      513

respectively. In this model, −Rl can be first obtained from Assuming that the spherical adsorbent particle is initially
q free of solute and the concentrations of the solute at the
the intercept of the regression line on the log-plot of 1 − t
qe surface and center remain constant (qs) and zero, respec-
against time, and Del can be subsequently determined tively, the following boundary conditions were used to
from Rl. solve the HSDM equation (Crank 1956):
The experimentally estimated external diffusion coef-
q = 0,  t = 0, 0 < r < R (17)
ficients of two emerging pollutants (i.e. naproxen and
carbamazepine) in their removal by adsorption on AC (Yu q = qs r = R, t > 0 (18)

et  al. 2009) were consistent with those estimated by the
Gnielinski correlation (Sontheimer et al. 1988). Therefore, q = 0 r = 0, t > 0 (19)
it was deduced that the initial phase of the adsorption
process (about 11 h) was controlled by external diffusion The exact solution for the HSDM equation was finally
(Yu et al. 2009). found to be (Crank 1956) as follows:
Overall, the validity of the film diffusion model indi-
q 2 R ∞ ( −1)n nπr  − D n2 π2 t 
cates the existence of external mass transfer as the rate-
qs
=1+ ∑
πr n = 1 n
sin
R
exp  s 2
 R
.

(20)
limiting step. However, film diffusion model has seldom 
been used in the literature to describe the adsorption
kinetics of emerging pollutants on AC. This is likely due to Mathematical calculation of the above equation is rela-
the porous structure of AC, which makes the dominating tively complicated. Therefore, it was solved in two specific
effect of external mass transfer on overall adsorption rate cases, as follows:
negligible for the removal of emerging pollutants from For a short adsorption time (Habib et  al. 2010,
water. Askalany and Saha 2015),
1/2
q  D 
= 6 2s  t 1/2 , (21)
5.4 Intra-particle diffusion models
q∞  R π


Intra-particle diffusion models are classified into three where q̅ (mg/g), q∞ (mg/g), Ds (cm2/min), and R (cm) are
categories depending on the mechanism of diffusion. If the average of adsorption capacity in the spherical par-
surface diffusion is the mechanism, homogenous surface ticle at any particular time, average concentration in the
diffusion model (HSDM) could be applied (Faur et al. 2005, solid at infinite time, intra-particle diffusion coefficient,
1/2
Li et  al. 2006, Kim et  al. 2008, Kim et  al. 2010). If pore  D 
and particle radius, respectively. 6  2 s  can be found
volume diffusion represents the mechanism, pore volume  R π
q
diffusion model (PVDM) is the most appropriate diffusion from the slope of the regression line on the plot of
q∞
model to be used (Sotelo et al. 2002b). If both mechanisms against t1/2, and therefore Ds can be estimated.
(i.e. surface and pore volume) are involved in the diffu- For a long adsorption time (Habib et al. 2010, Askalany
sion mechanism, the general diffusional model, which and Saha 2015),
is called pore volume-surface diffusion model (PVSDM),
q  − Ds π
2
 6
could satisfactorily be fitted to the adsorption experimen- ln  1 −  = t + ln 2 (22)
 q∞  R 2
tal data (Kim et al. 2008, Ocampo-Pérez et al. 2012). π

− Ds π 2
  can be determined from the slope of the regres-
R2 q
5.4.1 Homogenous surface diffusion model (HSDM) sion line on the log-plot of 1 − against time, and subse-
q∞
quently, Ds can be calculated.
The HSDM describes the adsorption processes, where The HSDM was sometimes used for the description of
the rate of adsorption in an amorphous and homoge- the kinetics of adsorption of emerging pollutants on AC.
nous spherical adsorbent depends on the speed at which The HSDM accurately predicted the rate of approaching
adsorbate diffuses towards adsorbent: equilibrium in the adsorption of a trace organic contami-
nant in the presence of NOM (i.e. Atrazine and two model
∂q Ds ∂  2 ∂q  compounds representing the strongly competing (SC) and
= r . (16)
∂t r 2 ∂r  ∂r  pore blocking (PB) fractions of NOM) on AC (Li et al.  2006).

514      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
The Ds values of the three components of atrazine, the
SC fraction, and the PB fraction were determined to be
1.70 × 10−11, 1.70 × 10−11, and 2.11 × 10−10 cm2/min, respec-
tively (Li et al. 2006). However, the HSDM could not accu-
rately predict the distribution of the PB fraction within a
carbon particle. It was noticed that the Ds of the PB frac-
tion is higher than that of atrazine despite the PB fraction
having a larger molecular size (Li et  al. 2006). Based on
the HSDM assumption of homogeneity inside carbon par-
ticles, it was explained that the PB fraction diffuses to the
center of the AC particle reaching a uniform concentration
inside the carbon (Li et al. 2006). However, the PB fraction
may access only large pores, which are most likely close to
the outer surface of a carbon particle (Li et al. 2006). Thus,
the PB fraction may only need to travel a short distance
to reach adsorption sites on the outer part of an AC parti-
cle, and therefore, it rapidly induces pore blockage effects
(Li et al. 2006).
The intra-particle diffusion coefficients were obtained
as 4.8 × 10−12 m2/s and 2.8 × 10−13 m2/s for the removal of tri-
methoprim in a batch adsorber using powdered and gran-
ular ACs, respectively (Kim et al. 2010). It was also found
that the intra-particle diffusion coefficient is usually
independent of the flow rate in a fixed-bed operation
(Kim et al. 2010).
As mentioned earlier, the HSDM is mostly valid in
cases in which internal mass transfer is the rate-limiting
step of an adsorption process due to reasons such as large
particle size of granular AC.
5.4.2 Pore volume-surface diffusion model (PVSDM)
The PVSDM considers external mass transport, intra-
particle diffusion, and adsorption on an active site. Three
specific assumptions were made in the derivation of the
model (Ocampo-Pérez et al. 2012):
1. Intra-particle diffusion takes place by pore volume
diffusion (Fick diffusion) and surface diffusion.
2. The rate of adsorption on the active sites on the sur-
face is instantaneous.
3. The GAC particles are spherical.
The PVSDM consists of the following model equations
(coupled partial and ordinary differential equations) as
well as boundary conditions (Ocampo-Pérez et al. 2012):
dC A
V = −mSkL , exp  C A − C Ar 
 (23)
dt  r = Rp 
 volume diffusion contributed more than 92% to intra-par-
t = 0 ,  C A = C A0 (24)
∂C Ar ∂q 1 ∂  2  ∂C ∂q  
εp + ρp = 2 r  Dep Ar − Ds ρ p   (25)
∂t ∂t r ∂r   ∂r ∂r  

C Ar = 0 , t = 0 , 0 ≤ r ≤ Rp (26)
∂C Ar
=0 (27)
∂t
r =0

∂C Ar ∂q  
Dep + Ds ρ p = kL , exp  C A − C Ar , (28)
∂r ∂r  r = Rp 
r =R

where kL,exp (m/s), Ds (m2/s), and Dep (m2/s) are the experi-
ment external transport coefficient, surface diffusion
coefficient, and effective diffusion coefficient in the pore
volume, respectively.
PVSDM satisfactorily fitted the experimental data
of adsorption rate for three emerging pollutants (i.e.
2,4-dichlorophenoxy-acetic acid (2,4-D), chlorophenoxy-
acetic acid (CPA), and 4-chloro-2-methylphenoxyacetic
acid (MCPA) on AC (Kim et  al. 2008). The values of kL,exp
for CPA, 2,4-D, and MPCA were calculated to be 8.01 × 10−5
m/s, 5.82 × 10−5 m/s, and 3.62 × 10−5 m/s, respectively
(Kim et  al. 2008). The values of Dep for CPA, 2,4-D, and
MPCA were also obtained as 4.99 × 10−11, 2.09 × 10−11, and
1.99 × 10−11 m2/s, respectively (Kim et al. 2008). In addition,
the values of Ds for CPA, 2,4-D, and MPCA were also esti-
mated to be 6.58 × 10−14, 5.01 × 10−14, and 4.63 × 10−14 m2/s,
respectively (Kim et  al. 2008). Therefore, intra-particle
diffusion (particularly surface diffusion) was recognized
as the rate-controlling step in the adsorption process
(Kim et al. 2008).
The PVSDM was also applied for the adsorption of both
pesticides [phthalic acid (PA), 2,4-dichlorophenoxy-acetic
acid (2,4-D), diphenolic acid (DPA), and 4-chloro-2-methyl­
phenoxyacetic acid (MCPA)] and an EDC [bisphenol A
(BPA)] on AC (Ocampo-Pérez et al. 2012). The values of kL, exp
were obtained to be in the ranges of 0.57–2.10 × 10−3  cm/s
for PA, 1.08–5.67 × 10−3 cm/s for BPA, 2.35–9.25 × 10−3
cm/s for DPA, 0.23–0.73 × 10−3 cm/s for 2,4-D, and 0.07–
0.85 × 10−3 cm/s for MCPA (Ocampo-Pérez et al. 2012). The
values of Dep were evaluated to be in the ranges of 9.61–
13.10 × 10−7 cm2/s for PA, 3.36–12.32 × 10−7  cm2/s for BPA,
6.98–10.70 × 10−7 cm2/s for DPA, 4.48–22.40 × 10−7 cm2/s
for 2,4-D, and 5.17–14.80 × 10−7 cm2/s for MCPA (Ocampo-
Pérez et al. 2012). The optimal value of Ds was estimated
to be in the range of 2.80–8.74 × 10−11 cm2/s (Ocampo-Pérez
et  al. 2012). The experimental data indicated that pore
ticle diffusion (Ocampo-Pérez et al. 2012). Therefore, pore
volume diffusion was the controlling mechanism of the
 Z. Jeirani et al.: Adsorption of emerging pollutants on AC      515

overall rate of adsorption and surface diffusion could be significantly. It has been found that adsorption would
neglected (Ocampo-Pérez et al. 2012). dominate at lower temperatures while desorption would
dominate at higher temperatures (Lu et al. 2006, Su and
Lu 2007).
5.4.3 Pore volume diffusion model (PVDM) The adsorption-desorption model is one of the
advanced kinetic models that consider both the adsorp-
The PVDM is a simplified model of PVSDM considering tion and desorption phenomena. The governing equa-
the assumption that the molecular diffusion in the pore tions developed to describe the transport of an organic
volume is the only intra-particle diffusion mechanism compound in the packed zone of an adsorption column
(Sotelo et  al. 2002b, Ocampo-Pérez et  al. 2012). In other are expressed as (Chuang et  al. 2003a, Agnihotri et  al.
words, there is no surface diffusion (i.e. Ds = 0). There- 2004) follows:
fore, the PVDM includes the following model equations ∂C A ∂C 1 − ε ∂q
(coupled partial and ordinary differential equations) and = − uz A − ρ (35)
∂t ∂z ε ∂t
boundary conditions: 

dC A
V = −mSkL , exp  C A − C Ar 
 (29) ∂q
= ka (qm − q )C A − kd q (36)
dt  r = Rp 
∂t
 

t = 0 ,               C A = C A0 (30) ka
= b, (37)
kd

∂C Ar ∂q 1 ∂  2  ∂C  
εp + ρp = 2 r  Dep Ar   (31)
∂t ∂t r ∂r   ∂r  
 where CA (mg/l), uz (cm/min), z (cm), ε, ρ (g/cm3), q (mg/g),
ka (l/(mg·min)), kd (min−1), and b are the concentration of
C Ar = 0 ,  t = 0 ,  0 ≤ r ≤ Rp (32) organic compound, velocity of fluid flow, the position
along the adsorption bed, the bed void fraction, density of
∂C Ar adsorbent, adsorption capacity, adsorption rate constant,
=0 (33)
∂t desorption rate constant, and the Langmuir adsorption
r =0
 constant, respectively. The associated boundary condi-
tions are as follows:
∂C Ar  
Dep = kL , exp  C A − C Ar  (34) C A = q = 0,  t = 0, 0 ≤ z ≤ H   (38)
∂r  r = Rp 
r =R

C A = Cin ,  z = 0,  t ≥ 0 (39)
The PVDM was applied for the removal of pesticides by AC
adsorption (Sotelo et al. 2002b). Like PVSDM, the PVDM is
dC A
an advanced model, and its solution requires the knowl- = 0,  z = H , t ≥ 0 (40)
dz
edge of numerical mathematics. It would also be more 
complicated if the GAC particle is considered bi-porous
This model has been widely used for the adsorption of
containing macro-pores and micro-pores (Sotelo et  al.
organic vapors in airstream (Chuang et al. 2003b, Das et al.
2002b).
2004, Hsu and Lu 2009) as well as some specific cases of
adsorption of organic pollutants from aqueous phase (Lu
et al. 2006, Su and Lu 2007). However, it has seldom been
5.5 Adsorption-desorption model
applied for the adsorption of emerging organic pollutants
in water on AC.
The application of all the aforementioned kinetic models
is limited to a specific range of temperature because in
developing these models, it was simply assumed that
adsorption is the only process occurring on the surface of 6 Conclusions
an adsorbent. However, in reality, some of the adsorbed
molecules could desorb. The desorption rate of organic Based on this review, the following conclusions were
molecules depends on the operating temperature derived:
516      Z. Jeirani et al.: Adsorption of emerging pollutants on AC
–– Adsorption on AC is an effective removal process for
emerging pollutants from water without generating
transformation products. However, the success of the
process strongly depends on many parameters such
as operating conditions, texture of AC, and adsorptive
properties of the pollutants.
–– The presence of NOM can significantly reduce the
adsorption capacity of AC for the removal of emerging
pollutants due to direct competition for adsorption
sites or pore blockage by NOM.
–– Adsorption onto AC could be driven either by one or
combinations of the mechanisms (i.e. hydrophobic
interactions, π-π dispersion interactions, hydrogen
bonding formation, and electron donor-acceptor com-
plex formation).
–– Langmuir and Freundlich isotherm models are the
widely used equilibrium adsorption isotherm mod-
els to establish a correlation between the amount of
uptaken organic adsorbate by AC and its concentra-
tion in the solution in equilibrium state.
–– Although there are a couple of reports on the appli-
cation of intra-particle and film diffusion models,
pseudo-first- and pseudo-second-order models have
been frequently utilized and have been found to be
effective in describing the kinetics of adsorption of
emerging pollutants on AC. This indicates that in most
studies, the adsorption reaction was the rate-limiting
step of the process. However, this inference could not
be generalized to all emerging pollutant adsorption
process on AC because several factors (e.g. operating
conditions, texture of AC, and adsorptive properties
of the pollutants) determine the rate-limiting step of
the process (i.e. surface reaction, external or internal
mass transfers).
7 R
 ecommendations and future
prospects
The following knowledge deficiencies on the adsorption
of emerging pollutants on AC were identified:
–– Despite the efforts to elucidate the mechanism of
adsorption, it is believed that more comprehen-
sive characterization studies are required to further
explain and confirm the mechanism of adsorption,
particularly in complex matrices.
–– The number of reported adsorption isotherms (and
adsorption kinetics) for emerging pollutants at
low concentration (μg/l, ng/l) is very limited. As
the parameters of isotherm models depend on the
concentration range, further isotherm tests should be
performed at equilibrium concentration levels similar
to those experienced in practice.
–– Uncertainties still remain regarding organic com-
pound removal by AC at low initial concentrations
from natural waters containing NOM. Some modifica-
tion on the enlargement of the AC pore size diameter
could possibly reduce the probability of pore blockage
by NOM. The adsorption of trace organic compounds
in the presence of NOM would probably be enhanced if
the competition for adsorption sites can be eliminated
by improvement of the AC surface towards selective
adsorption. These studies would be worthwhile.
–– There is almost no report on the comparison of kinetic
and isotherm models for the application of AC for the
removal of emerging pollutants from wastewater.
–– Some attempts have been recently made to produce
value-added AC from abundant and inexpensive
waste materials. These environmentally friendly prep-
aration methods are encouraged to be continued.
–– Although some of the activation techniques for the
improvement of the nature of the surface groups on
AC are effective, they are costly. It is believed that the
application of these techniques in large industrial
scale will impose huge expenses. Therefore, there are
still some knowledge gaps on tuning or modifying
the AC activation techniques towards energy-saving
prospects.
–– Viability, accuracy, and simplicity are the main
parameters required to be considered in the devel-
opment of isotherms (both linear and nonlinear) in
various applications. This evolution will be a great
contribution leading to the superior improvement in
the area of adsorption science.
–– It is suggested to determine the rate-limiting step of
adsorption prior to the application of a kinetic model.
–– Application of adsorption-desorption model for the
study of kinetics of the process is encouraged.
–– There are some recently published works presenting
the differences of micropollutants adsorption in vari-
ous wastewater matrices. However, more research is
required to elucidate the mechanism, equilibrium
isotherms, and kinetic models in such complicated
matrices.
–– It is suggested to conduct more investigations on the
adsorption hysteresis to achieve a clearer understand-
ing of the mechanism of adsorption of emerging pol-
lutants on AC.
It is hoped that continuing research will shed more light
on the above knowledge gaps, and this review assists

the future developments in the adsorption of emerging
­pollutants on AC.
Acknowledgments: The authors are grateful for the finan-
cial support provided by the Natural Sciences and Engi-
neering Research Council of Canada (NSERC) and the
University of Saskatchewan.
References
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522      Z. Jeirani et al.: Adsorption of emerging pollutants on AC

carbon. I. Adsorption capacity and kinetics. Environ Sci Technol Jafar Soltan
2009; 43: 1467–1473. Department of Chemical and Biological
Zou J, Dai Y, Wang X, Ren Z, Tian C, Pan K, Li S, Abuobeidah M, Fu H. Engineering, University of Saskatchewan,
Structure and adsorption properties of sewage sludge-derived 57 Campus Drive, Saskatoon, SK S7N 5A9,
carbon with removal of inorganic impurities and high porosity. Canada
Bioresource Technol 2013; 142: 209–217. j.soltan@usask.ca

Bionotes Jafar Soltan is a professor of chemical engineering at the University

of Saskatchewan (Saskatoon SK, Canada). He has obtained his
Zahra Jeirani BSc (Petroleum University of Technology, Iran, 1987), MSc (Shiraz
Department of Chemical and Biological University, Iran, 1992), and PhD (University of British Columbia,
Engineering, University of Saskatchewan, Canada, 1998) in chemical engineering. He has worked in industry
57 Campus Drive, Saskatoon, SK S7N 5A9, and academia on methane conversion processes, natural gas utiliza-
Canada tion, and environmental catalysis. His current research involves
developing catalysts and processes for degradation of emerging
pollutants in water and wastewater, adsorption of CO2, and low tem-
perature oxidation of volatile organic compounds in air. He has been
awarded two patents on multiphase reactors and contactors. He has
published two book chapters, 60 journal papers, and more than 130
Zahra Jeirani received her BSc (Shiraz University, Iran, 2003) and conference presentations.
MSc (Shahid Bahonar University of Kerman, Iran, 2005) in chemi-
cal engineering. She earned her first PhD in petroleum engineering
from the University of Malaya, Malaysia, in 2013. She is currently
pursuing her second PhD in chemical engineering at the University
of Saskatchewan, Canada. Her current research involves investiga-
tions of advanced oxidation techniques for removal of emerging pol-
lutants in water. She has numerous research accomplishments (e.g.
a book, a patent, two rewards, several awards, two gold medals,
more than 20 journal papers, and 10 conference presentations).

Catherine Hui Niu

Department of Chemical and Biological
Engineering, University of Saskatchewan,
57 Campus Drive, Saskatoon, SK S7N 5A9,
Canada

Catherine Hui Niu received her Bachelor’s and Master’s degrees in

chemical engineering from Sichuan University in P. R. China in 1989
and 1992, respectively. She received her PhD in chemical engineer-
ing from McGill University in 2002 and began her position at the
University of Saskatchewan in 2004, where she now serves as an
associate professor of chemical engineering. Her research areas
focus on adsorption and biosorption with applications in waste-
water treatment, gas dehydration and purification, and chemical
separation.
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