Chemical Engineering Journal 281 (2015) 345–359

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Chemical Engineering Journal

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

Selective removal of Hg(II) from aqueous solution by functionalized

magnetic-macromolecular hybrid material
Khalid Z. Elwakeel a, Eric Guibal b,⇑
a
Environmental Science Department, Faculty of Science, Port-Said University, Port-Said, Egypt
b
Ecole des mines d’Alès, Centre des Matériaux des Mines d’Alès (C2MA), 6, avenue de Clavières, F-30319 Alès cedex, France

h i g h l i g h t s

 Magnetic hybrid material for mercury recovery from slightly acidic solutions.
 Diethylenetriamine grafting on chitosan for improved sorption performance.
 Pseudo-second order rate equation for modeling uptake kinetics.
 Selectivity for mercury recovery against other base metals.
 Mercury can be easily desorbed from sorbent for efficient recycling.

a r t i c l e i n f o a b s t r a c t

Article history: A new hybrid material was prepared using chitosan, glycidyl methacrylate and magnetite microparticles.
Received 17 April 2015 The concentration of amine groups on the sorbent was increased by grafting diethylenetriamine. These
Received in revised form 28 May 2015 materials were tested for the sorption of Hg(II) metal ions. These materials showed high affinity and
Accepted 29 May 2015
selectivity for Hg(II) uptake from aqueous solutions: maximum sorption capacity reached 2.6 mmol g1
Available online 18 June 2015
at pH 4.0. The influence of pH was tested on the selective separation of Hg(II) from a mixture of Hg(II),
Co(II), Cu(II), Fe(II), Ni(II), Zn(II) and Mg(II). The effect of counter anions was also studied at different
Keywords:
pH values. Sorption may occur by chelation of cationic mercury species on amino groups or by ion
Hg(II) sorption
Magnetic hybrid sorbent
exchange of chloroanionic mercury species on protonated amino groups. Uptake kinetics and sorption
Diethylenetriamine-grafted chitosan isotherms were modeled using the pseudo-second order rate equation and the Langmuir equation,
Uptake kinetics respectively. The distribution coefficient was obtained at different temperatures and the thermodynamic
Sorption isotherms parameters have been calculated: the sorption is endothermic, spontaneous and contributes to increase
Thermodynamics the entropy of the system. Potassium iodide was used for Hg(II) desorption from loaded sorbents: desorp-
tion yields 99%, and the sorbent could be efficiently recycled for a minimum of three sorption/desorption
cycles.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction
The regulations at international level are becoming more and
more drastic concerning the discharge of heavy metal ions into
the environment. Therefore controls on industrial wastewater are
stressed because of their potential threat on human health and
on the biosphere. In addition, due to the rarefaction of some metal
resources (critical, strategic and precious metals, for example)
strongly incentive politics of material reuse and recycling have
been recently elaborated.
⇑ Corresponding author. Tel.: +33 (0)466782734; fax: +33 (0)466782701.
E-mail address: Eric.Guibal@mines-ales.fr (E. Guibal).
The Agency for Toxic Substances and Disease Registry ranked
mercury as the third priority hazardous substance, after arsenic
and lead [1]. Water pollution by Hg(II) is thus a serious environ-
mental issue, though many national or international directives
are recommending as far as possible substituting other metal to
mercury or changing the production processes to avoid using mer-
cury. This metal is non-biodegradable and can threat the ecosys-
tem by being accumulated in the food chain; the dramatic
Minamata intoxication of local population clearly illustrates this
hazardous effect. Hg(II) may be discharged into the environment
through wastewaters issued from different industries such as:
electroplating, leather tanning, metal finishing and petroleum
refining.

http://dx.doi.org/10.1016/j.cej.2015.05.110
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
346 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359
Hg(II) removal from contaminated water is imperative to make
water fit for the human uses (drinking, agriculture, etc.). The
allowed concentrations for discharge into surface water and for
drinking water are 10 and 1 lg/L, respectively [2]. The aforemen-
tioned threats of mercury require developing treatment processes
capable to face, alone or in combination with other processes, the
target levels for discharge into the environment. Generally, metal
ions can be recovered from solutions through conventional
processes such as precipitation, solvent extraction, membrane
techniques, ion-exchange and chelating resins. Frequently these
techniques fail to fit with target regulations (technical limitations),
or economic constraints (solvent extraction is not appropriate for
dilute effluents; membrane processes may be expensive for
large-scale applications) or produce huge amounts of contami-
nated sub-products (with potential complementary hazards for
the environment, as it may occur with precipitation processes).
Sorption is one of the preferred methods for the removal of metal
ions from the wastewater as it is effective as well as cost-effective
[3]. In the field of sorption processes, several alternative materials
have been investigated for the last decades making profit of mate-
rials of biological origin for metal binding: biosorption consists in
using functional groups held on materials of biological origin for
metal recovery with mechanisms similar to those found in
ion-exchange and chelating resins. These materials can be issued
from agriculture, fishing or as by-product of other industries: fun-
gal, algal, bacterial biomass, agriculture or food industry residues,
for example. Chitosan ((1,4)-2-amino-2-deoxy-b-D-glucan) is an
emblematic biopolymer that was abundantly studied for metal
binding. Being produced at the commercial scale from the shells
of crustacean, it is obtained by alkaline deacetylation from chitin
(the primary resource) and bears many hydroxyl groups (which
bring hydrophilic behavior to the biopolymer, and also possible
sites for chemical modification and grafting) and amino groups.
This biopolymer has unique properties among polysaccharide hav-
ing cationic behavior in acid solutions. Amino groups are involved
in metal binding through different mechanisms including (a) metal
cation chelation in near neutral solutions (through the free elec-
tron doublet of nitrogen), and (b) binding of metal complex anion
by ion-exchange/electrostatic attraction on protonated amino
groups (in acidic solutions). With a pKa that depends on the degree
of acetylation (incomplete deacetylation of chitin) and the degree
of neutralization but ranges between 6.3 and 6.7 for most common
commercial samples [4] the protonation of chitosan leads, in most
cases (with the remarkable exception of sulfuric acid) to the dis-
solving of chitosan in acid media. This is the base of the mecha-
nisms used for changing the conditioning of the biopolymer but
this is also a serious drawback for potential applications in the field
of metal sorption. A cross-linking treatment or a chemical modifi-
cation is thus required for extending the pH field of application (for
both sorption and desorption steps). On the other hand, glycidyl
methacrylate (GMA) is an attractive vinyl monomer because of
its low toxicity, lower cost compared with other acrylic monomers,
versatile properties and especially due to the presence of epoxy
group in its molecule [5], which makes it very reactive for chemical
modification or for reacting with other materials. These polymers
are potent sorbents for various transition metals [6,7]. Various
studies on metal sorption on chitosan-based materials have
pointed out the limitations in uptake kinetics due to the resistance
to intraparticle diffusion (which may be explained by the residual
crystallinity of the biopolymer and by poor porous and surface
properties). This drawback was partially solved changing the con-
ditioning of the biopolymer (manufacturing gel beads, membranes
and so on). Another possibility consists in reducing the size of sor-
bent particles but at the expense of serious drawbacks concerning
particle recovery at the end of the process (in batch systems) or
head loss (in fixed-bed applications). Recently, a number of studies
have developed an alternative for solving the problem of filtration
or recovery of fine (micro- or nano) particles: the incorporation of a
magnetic core (or its in situ production, with simultaneous coating
with biopolymer) in the particle makes easier the handling and
recovery of these fine sorbent particles. These methods are cheap
and often highly scalable. Moreover, these techniques employing
external magnetic fields are more amenable to automation [8].
The reactivity of the sorbent can be improved by grafting new
functional groups such as polyamine compounds [9–13]. The
objective may consist in increasing the density of sorption sites,
in improving the sorption selectivity, in changing the sorption
mechanism (ion-exchange vs. chelation or the reciprocal), or in
extending the field of application (especially regarding pH range).
The objective of this work consists in synthesizing a magnetic
composite made of glycidyl methacrylate (GMA) and chitosan
(coating the magnetic Fe3O4 core) that is functionalized by grafting
diethylenetriamine (DETA) through GMA (to increase the density
of sorption sites and their potential selectivity). These composite
materials are being tested for Hg(II) recovery through the study
of pH effect, the investigation of competition effects (composition
of the matrix: competitor metal ions, counter anions), the determi-
nation of sorption isotherms and thermodynamic characteristics
and the identification of controlling steps in uptake kinetics.
Finally the desorption of Hg(II) is studied with the objective of ver-
ifying the possibility to recycle the sorbent.
2. Materials and methods
2.1. Materials
All chemicals used were of analytical grade and demineralized
water was used for the preparation of all aqueous solutions.
Glycidyl methacrylate (GMA) was provided by Riedel-de Haën
(Germany), while N,N0 -methylenebisacrylamide (MBA) and ben-
zoyl peroxide (Bz2O2) were supplied by Fluka AG (Switzerland).
Chitosan, epichlorohydrin (chloromethyloxirane) and diethylene-
triamine (DETA) were obtained from Sigma-Aldrich (Switzerland)
while isopropyl alcohol was provided by Carlo Erba (France).
Chitosan was provided by Aber Technologies (France); the deacety-
lation degree of the biopolymer was 87% and the molecular weight
(MWn) was 125,000 g mol1. All other chemicals were Prolabo
products (France) and were used as received. HgCl2 salt was used
for the preparation of the stock solution, except in the case of the
study of counter anions (for which the relevant salt of mercury
was used).
The principle of the synthesis of Fe3O4 particles consisted in the
co-precipitation of ferric and ferrous salts following a procedure
derived from the so-called Massart method [14].
2.2. Preparation of the magnetic-macromolecular hybrid material
Step 1: Magnetic chitosan particles were prepared by the
co-precipitation method, 4 g chitosan powder was dissolved in a
volume of 150 mL of acetic acid solution (10%, w/v). The magnetite
precursors were mixed with 150 mL of demineralized water (i.e.,
6.479 g of FeCl36H2O and 3.334 g of FeSO47H2O) using a volume
of 2 mL of HCl (concentrated) for improving salt dissolution under
continuous stirring for 30 min. After complete dissolution of iron
salts, the solution was mixed with the chitosan solution. Then
the chemical precipitation of magnetic chitosan material was per-
formed at 30 °C under vigorous stirring by dropwise addition of
20 mL of NaOH solution (50%, v/v) for 30 min. The pH was roughly
controlled around pH 11. The solid product that was recovered by
centrifugation was freeze-dried using a freeze-dryer (Bioblock
 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359
Scientific, Christ) at 223 K and 0.01 mbar; this intermediary pro-
duct was called MC (magnetic chitosan).
Step 2: The magnetic-chitosan-glycidyl-methacrylate macro-
molecular hybrid material was prepared through the polymeriza-
tion of GMA in the presence of MC particles (Step 1). GMA (5.0 g)
corresponding to a mass ratio of 50% (w/w, referred to MC amount)
was used for GMA grafting; 0.2 g of MBA was used as the
cross-linking agent and 0.1 g of Bz2O (acting as the initiator of
the polymerization reaction) was added under agitation before
adding 1.0 g of magnetite. Three milliliter of isopropyl alcohol
and 25 mL of cyclohexane were mixed and added to the former
solution. The solution was then poured into a flask containing
100 mL (1%) polyvinyl alcohol and heated on a water bath at
75–80 °C under continuous stirring for 3 h. The product was fil-
tered off and washed repeatedly with demineralized water and
acetone before being air-dried. The product was called MCGMA.
The preparation and modification of magnetic-macromolecular
hybrid material is described in Scheme 1, and the suggested chem-
ical structure of MCGMA is shown in Scheme 2.
2.3. Chemical modification of MCGMA
2.3.1. Diethylenetriamine grafting – First method
MCGMA was suspended in dioxane (100 mL) and then treated
with 5 mL of diethylenetriamine (DETA). The suspension was stir-
red at 70 °C for 12 h. The product was successively washed with
water and acetone. The product was then air-dried and called
MCGMA-I.
2.3.2. Diethylenetriamine grafting – Second method (via
epichlorhydrin)
MCGMA was suspended in 70 mL of isopropyl alcohol. Then
7 mL of epichlorohydrin (62.5 mmol) dissolved in 100 mL ace-
tone/water mixture (1:1 v/v) was added to the suspension. The
reaction was performed under continuous stirring for 24 h at
60 °C. The solid product was filtered off and washed several times
with water. The obtained product was treated with DETA according
to the method reported in Section 2.3.1. The product was finally
air-dried; it was sieved and the fraction below 1 mm was retained
for experiments. This sorbent was called MCGMA-II.
2.3.3. Estimation of the amine content
The amine content in the obtained resin was estimated using a
volumetric method previously described by Atia et al. [15]. Fifty
milliliter of HCl (0.05 M) was added to 0.5 g of MCGMA-II or
MCGMA-II and conditioned for 15 h on a shaker at 20 °C. The resid-
ual concentration of HCl was measured by the titration against
0.05 M standardized NaOH (using phenolphtalein as the titration
indicator). The number of moles of HCl that reacted with the amino
groups was determined and the concentration of amino group was
calculated by the following equation
Concentration of ðNH2 Þ groups
ðM 1  M 2 Þ  50
¼ ðmmol=g resinÞ
0:5
where M1 and M2 are the initial and final concentrations of HCl.
2.4. Analytical methods
Mercury was analyzed using inductively coupled plasma atomic
emission spectrometer ICP-AES (Jobin-Yvon Activa M, Horiba-Jobin
Yvon, France). The morphology and the elemental distribution of
Hg in the magnetic-macromolecular material were analyzed with
a Scanning Electron Microscope coupled with an Energy
Dispersive X-ray analysis system (SEM-EDX; Environmental
347
Scanning Electron Microscope (ESEM) Quanta FEG 200, equipped
with an OXFORD Inca 350 Energy Dispersive X-ray microanalysis
(EDX) system). The magnetic property of the sorbent was mea-
sured on a vibrating-sample magnetometer (VSM) (Lake Shore
730T, Westerville OH, USA) at room temperature.
2.5. Sorption experiments
Demineralized water was used for the preparation of metal ion
solutions. A stock solution (20 mM) of HgCl2 was prepared in dem-
ineralized water. The other solutions were obtained by dilution of
the stock solution with demineralized water just prior experi-
ments. HCl (0.5 M) and NaOH (0.5 M) were used to control the
pH of the solutions.
Sorption experiments were performed in batch systems using
polyethylene flasks and the temperature was set to 20 ± 1 °C
(unless specified). For the study of pH effect 20 mL of 10 mM
Hg(II) solutions at different pH values (in the range 1–6) were
mixed with 50 mg of sorbent (dried weight) for 5 h, and the stirring
speed was maintained at 100 rpm using a reciprocal agitator
Rotabit, J.P. Selecta (Spain). Samples were collected and filtrated
through 1.0 lm pore size filtration membrane and/or magnetic
separation and the filtrate was analyzed for residual Hg(II) concen-
tration using ICP-AES. The pH was not controlled during the sorp-
tion but the final pH was systematically recorded.
For sorption isotherms 50 mg of sorbent (m) were mixed with
20 mL (V) of Hg(II) solutions at different initial concentrations
(C0, ranging between 3 and 10 mmol Hg L1) for 5 h. The pH of
the solutions was initially set at 4. After solid/liquid separation,
the residual concentration (Ceq, mmol Hg L1) was determined by
ICP-AES and the sorption capacity (qeq, mmol g1) was determined
by the mass balance equation: qeq = (C0  Ceq) V/m.
For uptake kinetics 300 mg of sorbent were mixed with 120 mL
of Hg(II) solutions (C0: 10 mmol Hg L1) at pH 4. Samples (a volume
of 4 mL) were collected (the sorbent was magnetically separated) at
fixed times and the residual concentrations were determined by
ICP-AES. The agitation speed was set at 100 rpm while the temper-
ature was maintained at 20 ± 1 °C. The sorbed amount of Hg(II) per
unit weight of the sorbent at time t (q(t), mmol Hg g1), was calcu-
lated from the mass balance equation (taking into account the
decrement in the volume of the solution) as:
 
X
n CðtÞði1Þ  CðtÞðiÞ  VðtÞði1Þ
qðtÞ ¼ ð2Þ
i¼1
m
where C(t)(i) (mmol Hg L1) is the Hg(II) concentration of the with-
drawn sample number i at time t and C(t)(0) = C0, V(t)(i) (mL) is the
volume of the solution in the flask at sample number i and time t,
and m is the amount of resin added into the flask. Here
V(t)(i)  V(t)(i1) equals 4 mL.
Regeneration experiments were performed by contact of
250 mg of the sorbent with 100 mL of 10 mmol Hg L1 solution
at pH 4 Hg(II) for 5 h. The amount of metal sorbed (and the sorp-
ð1Þ tion capacity) was determined by the mass balance equation. The
solution was magnetically decanted and the sorbent was washed
by distilled water. The loaded sorbent was mixed with 100 mL of
100 mM KI for 50 min. Samples were collected at different time
intervals and the residual concentration of Hg(II) was determined
by ICP-AES after solid/liquid separation. The regenerated sorbent
was carefully washed by distilled water for reuse in the second
run. The regeneration efficiency (RE, %) was calculated according
to the following equation:
Amount of desorbed HgðIIÞðmmolÞat runðnÞ
RE % ¼  100 ð3Þ
Amount of desorbed HgðIIÞðmmolÞat runðn  1Þ
348 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359

O
NH2 NH2
HO HO
OH n polymerization O CH2 CH CH2
O OH O
H2N H2N
OH OH
O
O
(MC) + (GMA) + (magnetite) (MCGMA)
NH
NH2 NH2
CH2
HO CH
NH2
HO
NH
(MCGMA) NH2 NH2 O CH2 CH CH2

H2N OH
OH
HO CH
CH2
NH
NH2 NH2

( M C G MA - I)

CH2 HC CH2
O
NH O
HO

(MCGMA) Cl CH2 HC CH2 O CH2 CH CH2

O OH O
HN
OH
H2C CH CH2 O
O
( M C G M A - E CH )

NH
OH NH2 NH2
NH
NH2 NH H2C CH CH2 HO CH
NH
HO
NH
(MCGMA-ECH) NH2 NH2 O CH2 CH CH2

HN OH O
NH OH
NH2 NH H2C CH CH2
HO CH
OH
CH2
NH
NH2 NH2

(MCGMA-II)

Scheme 1. Scheme for the synthesis and modification of magnetic-macromolecular hybrid material.

3. Results and discussion
3.1. SEM and SEM-EDX analysis
Fig. 1 shows the SEM and SEM-EDX analyses of the sorbents
MCGMA-I and MCGMA-II before and after Hg(II) sorption. The sur-
face of MCGMA-I and MCGMA-II is generally smooth with several
small pores inside and interconnected macropores can be identi-
fied within the sorbents (Fig. 1a and b). However, after Hg(II) sorp-
tion, differences in the surface structure of the sorbents clearly
appear: agglomerated spherical particles are formed on the surface
and the porous structure disappears (Fig. 1c and d). These conclu-
sions are consistent with observations made on SEM-EDX analysis
(Fig. 2): the typical signals of Hg element are appearing at 1.7, 2.2,
2.6 and 10 keV on both MCGMA-I and MCGMA-II sorbents. Though
a quantitative analysis of the Hg load on the sorbent by SEM-EDX
would not be accurate, the levels of Hg are high enough to demon-
strate qualitatively the homogeneous distribution of the metal on
the surface of the sorbent. The mass percentages of Hg element
are found close to 27.5% and 32.9% for MCGMA-I and MCGMA-II,
respectively. This is a first evidence of the good affinity of the sor-
bents for mercury. The presence of Cl element is due to the binding
of mercury under the form of chloroanionic species: the sample
used for analysis was collected after metal sorption at pH 3
(controlled with HCl).
Fig. AM1 (see Additional Material Section) shows the SEM
images of the two sorbents at different magnitudes. There is a
large dispersion in the size of sorbent particles (in the range
10–200 lm) and the particles are characterized as
irregularly-shaped flakes.
 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359 349

H2C CH3 CH3

C H2C CH
CH CH2 C
C O O C
O O C C O
NH
NH O
H2C
CH2
CH2 H2C
HC OH NH
NH HC OH
O C
CH2
O C
H2C CH CH2
O CH2 CH
O O
O O
O O
HO NH2 O
HO NH2

Chitosan-GMA (MBA) Macromolecular hybrid material

(MCGMA)

Scheme 2. Proposed chemical structure of chitosan–glycidyl methacrylate – N,N0 -methylene-bis-acrylamide (macromolecular hybrid material).

(a) (b)

(c) (d)
Fig. 1. Scanning electron micrographs of; (a) unloaded MCGMA-I, (b) unloaded MCGMA-II, (c) Hg(II)-loaded MCGMA-I and (d) Hg(II)-loaded MCGMA-II.

3.2. Amine content
The amine content in MCGMA, MCGMA-I and MCGMA-II (which
was determined by titration) are 3.12, 5.92 and 6.5 mmol g1,
respectively. The chitosan used in this study was characterized
by a deacetylation degree of 87% (this means 6 mmol N g1). The
magnetite fraction in the sorbents was characterized by weight
loss at 700 °C: the materials contain 36% and 34% of magnetite
for MCGMA-I and MCGMA-II, respectively. On the basis of similar
magnetite fraction and chitosan (without chemical modification)
the theoretical nitrogen content would be close to
3.9 mmol N g1. This confirms the efficient grafting of additional
350 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359

(a) (b)

(c) (d)
Fig. 2. Energy dispersive X-ray analysis (EDX) of MCGMA-I and MCGMA-II sorbents: (a) unloaded MCGMA-I, (b) unloaded MCGMA-II, (c) Hg(II)-loaded MCGMA-I and (d)
Hg(II)-loaded MCGMA-II.

amino groups on the reference material (MCMA). The 25

semi-quantitative analysis of nitrogen content obtained by 20 MCGMA-I
SEM-EDX analysis confirms this trend. Indeed, the nitrogen mass
Moment/Mass (emu g-1)

15 MCGMA-II
percentages were close to 8.6% and 9.1% for MCGMA-I and
10
MCGMA-II, respectively (this means 6.15 and 6.5 mmol N g1,
5
respectively). These observations and analyses confirm the suc-
cessful experimental procedure described in Scheme 1 for the 0
grafting of additional amino groups on chitosan backbone. -5
-10
3.3. Magnetic properties
-15

The magnetic properties of the materials were determined -20

using VSM (vibrating sample magnetometry). Fig. 3 shows their
typical magnetization loop. There was no remanence and coerciv-
ity, contrary to certain supported-magnetite materials [16]. This
means that MCGMA sorbents are superparamagnetic. The satura-
tion magnetization of MCGMA-I and MCGMA-II were found to be
about 19.1 and 17.9 emu g1, respectively. These values are much
smaller than the levels reported for bulk phase magnetite (i.e.,
92 emu g1) and also smaller than the values obtained for mag-
netite nanoparticles [17]. The slight decrease in the magnetization
in case of MCGMA-II may be due to the grafting of DETA via
epichlorhydrin, which increases the mass of organic material and
decreases the relative percentage of magnetite in the sorbent.
The reported decrease in saturation magnetization can be
explained by several factors including size effect and particle crys-
tallization [17], and obviously by the fact that only a fraction of the
sorbent (about 65%) is constituted by the magnetic core. Similar
decrease in magnetization was observed for other
chitosan-magnetite composites [18]. Therefore, MCGMA sorbents
-25
-2500 -2000 -1500 -1000 -500 0 500 1000 1500 2000 2500
Field (G)
Fig. 3. Magnetization curves for MCGMA-I and MCGMA-II sorbents.
can be readily separated with the help of an external magnetic
field. This may be very helpful for solid/phase separation or for
handling the material in hazardous environment.
3.4. Infra-red spectrometry
FT-IR spectrometry was used to characterize the structure of the
sorbents (Fig. 4). The two sorbents have very similar FT-IR profiles:
the same bands are appearing on the two spectra, the only small
differences observed are small shifts in some of these bands. The
large band around 3410 cm1 is generally attributed to the
 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359
combination of stretching vibrations of OH and NH2 groups, while
a series of –CH vibrations are reported around 2940 and 2850–
2860 cm1. These bands are present in a wide number of com-
pounds and they are bringing poor information on the specific
properties of the sorbents. More interesting and representative
are the different bands identified in the range 1800–400 cm1.
The bands at 1264, 1162 and 986/990 cm1 are representative of
the saccharide ring. The band at 1653–1657 cm1 is associated to
the CONH2 group [19], while the band at 1561–1573 cm1 is prob-
ably assigned to the in-plane bending vibration of free amine
groups and/or the asymmetric carboxylate stretching vibration
[19,20]. The grafting of diethylenetriamine, via glycidylmethacry-
late, can be identified by the strong peak observed around
1724 cm1 (assigned to C@O stretching vibration) [20,21].
Additional methylene (–CH2–) groups can probably be associated
to the band observed at 1466–1470 cm1 [22]. The band at 586–
596 cm1 was attributed to c-Fe2O3 [23].
3.5. Hg(II) sorption properties
3.5.1. Effect of pH
The pH of the aqueous solution is a key parameter that controls
the sorption of the Hg(II). This effect can be associated to metal
speciation, to chemical properties of the polymer (protona-
tion/deprotonation of amino groups). Fig. 5 shows the effect of
pH on Hg(II) sorption (varying the initial pH from 0.9 to 6), and
the pH variation observed during sorption operation. Fig. 5a con-
firms that the pH influences sorption capacity: the sorption
increases with the pH up to pH 4–4.2 before beginning to stabilize
and even reducing when pH exceeds 5. It is remarkable that the pH
variation during metal sorption is not varying significantly
(Fig. 5b): at low pH (below pH 4) a slight increase of the equilib-
rium (below 0.4 pH unit) is observed, while above pH 4–4.5 the
equilibrium pH tended to slightly decrease (variation being less
than 0.5 pH unit). This is remarkably stable compared to other
chitosan-based systems where a kind of ‘‘buffering effect’’ is
obtained around 5–6 due to the acid-base properties of the
biopolymer (pKa in the range 6.3–6.7) that binds protons. It is sus-
pected that the grafting of new functional groups (including other
amino groups with different acid-base properties, associated to
primary and secondary amino groups) contributes to smooth this
pH variation effect.
As the pH increases the protonation of amine groups decreases,
which, in turn, contributes to make free the amino groups for inter-
acting with metal cations by chelation. For MCGMA-II sorbent the
sorption capacity increases from pH 1 to pH 4 and then tends to
stabilize. At higher pH (above pH 5) the formation of hydrolyzed
species (Hg(OH)+ or soluble Hg(OH)2, before precipitation) that
have less affinity for amino groups, may explain the slight decrease
in sorption capacity (which represents less than 0.2 mmol Hg g1).
This effect is completed by the impact of deprotonation of amine
groups. On the other hand, at low pH (below 2–3), the sorption
capacity remains quite high (up to 1.5 mmol Hg g1), especially
compared to the levels reached with pure chitosan [24]. This can
be explained by either (a) differences in the acid-base properties
of amino groups grafted on chitosan (lower pKa compared to chi-
tosan amino groups), and/or (b) the binding of chloro-anionic mer-
cury species on protonated amino groups. Indeed, in the presence
of HCl, at low pH, metal speciation can be displaced to the forma-
tion of HgCl2 
4 or HgCl3 species which may be bound to protonated
amino groups through an electrostatic attraction mechanism of an
ion-exchange mechanism: chloride ions bound to protonated
amino groups may be exchanged with anionic chloroanions. The
sorbent MCGMA-I has a slightly different behavior: the sorption
capacity tends to increase with pH increasing from 0.9 to 2.5 and
progressively decreases when pH increases: the acid-base
351
properties of the different amino groups present on the sorbent
are different to those on the MCGMA-II sorbent due to differences
in their chemical environment. The decrease in amino group proto-
nation at pH above 2.5 (which contributed to bind anionic mercury
chloroanions) is not compensated by the chelation properties of
amino groups and by the speciation of mercury in solution (metal
speciation is shifted from chloroanions to positively charged mer-
cury species with low affinity for protonated amino groups). The
two sorbents have comparable sorption capacities at pH 2.3: below
this value MCGMA-I is more efficient for Hg(II) binding while
above this value the best results were obtained by MCGMA-II
sorbent.
Above pH 5 the formation of colloidal mercury species
(Hg(OH)2) may occur and their precipitation may overestimate
sorption performance [25]. This phenomenon should be taken into
account. For further experiments the pH was set to 4–4.2.
3.5.2. Kinetics
The uptake kinetics of Hg(II) using MCGMA-I and MCGCMA-II is
shown in Fig. 6. Fig. 6a shows the relative decay of concentration
with time, which allows comparing the two sorbents both in terms
of equilibrium performance and relative decay slopes. Fig. 6b
shows the evolution of the concentration of Hg(II) in the sorbent
(i.e., q(t) vs. time): the approach of equilibrium is another method
for comparing the kinetic profiles. Experimental conditions have
been selected to be able to illustrate the effect of resistance to dif-
fusion. Indeed, an excess of sorbent (compared to metal) would
lead to fast and complete removal of the metal bound on the sorp-
tion sites at the surface of the sorbent and minimizing the impact
of mass transfer mechanisms. Under these conditions, the solu-
tions is not fully decontaminated (Fig. 6a); this issue (complete
metal recovery) is addressed below (see Section 3.5.7).
The kinetic profiles (both in terms of relative concentration
decay; i.e., Fig. 6a, and metal concentration in the sorbent; i.e.,
Fig. 6b) are characterized by two main phases in the uptake: (a) a
first initial step that lasts for about 60 min and counts for more than
60% of total sorption, (a) a second step that takes about 6 h and cor-
responds to a much slower metal accumulation. The initial section
of the curve corresponds to a great availability of reactive groups
(surface coverage is progressively increasing) and a large concentra-
tion gradient between the solution and both the surface and the
internal sorption sites. These two conditions may explain the fast
initial accumulation of Hg(II). The sorption mainly occurs on the
reactive groups covering the surface of the sorbent. The second step,
much slower, is controlled by the decrease of the concentration gra-
dient and by the resistance to intraparticle diffusion and requires
much longer time for reaching the equilibrium (i.e., about 6 h).
Actually the binding kinetics is controlled by a series of mecha-
nisms including: (a) the bulk diffusion, (b) the resistance to film
diffusion (or external diffusion), (c) the resistance to intraparticle
diffusion, and (d) the proper reaction rate (chemical reaction rate)
[26]. Usually a sufficient agitation allows neglecting the resistance
to bulk diffusion and minimizes the resistance to film diffusion
whose contribution in the control of uptake kinetics is mainly sig-
nificant within the first minutes of contact. The modeling of such a
complex system, which is beginning even more complex when the
sorbent is heterogeneous, when the solution is subject to changes
in the speciation of the metal ions, etc., requires complex numeri-
cal tools. Experimental data have been modeled using simplified
conventional equations to fit kinetic profiles and make possible
the comparison of kinetic parameters for the two sorbents.
Hence, the kinetics of Hg(II) sorption on modified MCGMA sorbents
were analyzed using the pseudo-first order rate equation (PFORE)
[27], the pseudo-second order rate equation (PSORE) [28], the sim-
plified resistance to intraparticle diffusion equation [29] and the
Elovich equation [30]. These models and their linear forms are
352 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359

Transmittance

MCGMA-I
MCGMA-II

4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wavenumber (cm-1)

Fig. 4. FT-IR spectra of MCGMA-I and MCGMA-II sorbents.

3.5 0.9

3.0 MCGMA-I

0.8 MCGMA-II
2.5
q e (mmol g-1)

2.0 0.7
C(t)/C0

1.5
0.6
1.0
MCGMA-I
0.5
0.5 MCGMA-II

0.0 0.4
(a) 0 1 2 3 4 5 6 7 8 9 10 (a) 0 50 100 150 200 250 300 350 400
Equilibrium pH t (min)

7 2.1

1.8
6
q (t) (mmol g-1)

1.5
5
1.2
Final pH

4 MCGMA-I
0.9
MCGMA-II
3 0.6 Simulated from PSORE (MCGMA-I)

2 0.3 Simulated from PSORE (MCGMA-II)

MCGMA-I

1 MCGMA-II 0.0
0 50 100 150 200 250 300 350 400 450 500
(b) t (min)
0
0 1 2 3 4 5 6 7
(b) Initial pH
Fig. 6. Hg(II) uptake kinetics using MCGMA-I and MCGMA-II (a: relative concen-
tration decay of Hg(II) in the solution, b: Hg(II) concentration in the sorbent (i.e.,
q(t)) vs. time) (C0: 10 mmol Hg L1; pH 4; T: 20 °C; sorbent dosage, SD: 2.5 g L1).
Fig. 5. pH effect on Hg(II) sorption using MCGMA-I and MCGMA-II: (a) sorption
capacity, (b) pH change (T: 20 °C; C0: 10 mmol Hg L1).

sorption rate (mmol g1 min1) and b the desorption constant

reported in Table 1, where k1 is the pseudo-first order rate constant
(min1) of sorption and qeq and q(t) (mmol Hg g1) are the
amounts of Hg(II) sorbed at equilibrium and time t, respectively,
k2 is the pseudo-second order rate constant (g mmol1 min1), Ki
is the intraparticle diffusion rate (mmol g1 min0.5), a the initial
(g mmol1). The validity of each model is checked by the correla-
tion coefficient associated to the linear fits. Table 2 reports the
parameters of the different models for both MCGMA-I and
MCGMA-II sorbents. Systematically, the best correlation coeffi-
cients were found for the PSORE model; this is confirmed by the
 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359
plot of experimental data according the linearized forms of these
models: Fig. AM2a and AM2b (see Additional Material Section)
for PFORE and PSORE, respectively, show a best fit of kinetic pro-
files by PSORE. In addition, the comparison of equilibrium sorption
capacities for the calculated values and the experimental values
are only consistent for the PSORE model: the equilibrium sorption
capacities are found close to 1.4 and 2.0 mmol Hg(II) g1 for
MCGMA-I and MCGMA-II, respectively. PSORE modeling gave val-
ues of 1.49 and 2.09 mmol Hg(II) g1 closer from experimental val-
ues than PFORE (0.91 and 1.27 mmol Hg g1, respectively). It was
more likely to reflect that the rate-determining step might be
chemical sorption and that the sorption behavior might involve a
chelation mechanism through coordination between Hg(II) ions
and the reactive groups of the sorbents [25]. The Hg(II) ions may
form complexes with amino groups of the modified MCGMA sor-
bents (with possible contribution of hydroxyl groups in the stabi-
lization of metal binding) [31].
However, the PSORE describes kinetics data through a global
approach, and does not take into account the contribution of diffu-
sion mechanisms in the control of the kinetics. Under these condi-
tions, the kinetic parameters should be considered as apparent rate
coefficients. The influence of resistance to intraparticle diffusion
has been approached using a simplified model: the so-called
Weber and Morris plot (Table 1). The intraparticle diffusion model
provides a more comprehensive approach for defining sorption
mechanism, and the plot generally allows identifying different suc-
cessive steps in the global process [32]. The Weber and Morris
shows multi-linear sections (Fig. AM3a, see Additional Material
Section), i.e., three linear sections (on the plot q(t) vs. t0.5) with fast
kinetics in first step followed by the gradual attainment of equilib-
rium for both sorbents, and a pseudo saturation plateau. The
multi-linear plot does not pass through the origin suggesting that
the resistance to intraparticle diffusion is not the sole
rate-limiting step: other steps, e.g., resistance to film diffusion
and/or reaction rate, are probably involved in the control of uptake
kinetics (Table 2, Fig. AM3a, see Additional Material Section). We
can assume that the first linear section corresponds to a regime
controlled by the resistance to film diffusion and that the binding
is limited in this stage at the sorption on external sorption sites
or on the macropores in the first external layers of the material.
The second section is characterized by a much lower kinetic rate
and leads to a slow approach to equilibrium with the control by
the resistance to intraparticle diffusion (into internal macroporous
and mesoporous network). The last step is very slow and repre-
sents only a few percentage of the total sorption: this phase can
be associated to the resistance to diffusion in the microporous net-
work of the sorbent. In addition the progressive saturation of avail-
able and accessible sorption sites influences the local equilibrium
on the surface between surface sorption and desorption. The low
values of intraparticle rate constants (Ki) appearing in Table 2 with
values available in the literature indicates that the sorbents (both
MCGMA-I and MCGAM-II) are significantly affected by the resis-
tance to intraparticle diffusion, at least compared to the fast reac-
tion rate of chemical sorption of Hg(II) ions at the surface of the
sorbent [33]. The analysis of the rate constants for the Weber
and Morris model shows that except for the first step, the param-
eters were systematically higher for MCGMA-II compared with
MCGMA-I. In the initial stage, MCGMA-I seems to be faster in sorp-
tion than MCGMA-II: this first stage corresponds to a kinetic con-
trol by external film diffusion and/or diffusion in the macropores
present at the external surface of sorbent particles. While in the
next steps the uptake kinetics is controlled by the diffusion in
meso- and micro-pores, which appears to be a little more accessi-
ble for MCGMA-II material.
The Elovich equation was developed for modeling chemisorp-
tion processes [30]. Table 1 displays the model equation and its
353
linearization as well the plots to be used for determining the
parameters (which are reported in Table 2). The values of a and
b were determined from the intercept and slope, respectively, of
the linear plot of qt vs. ln t (Fig. AM3b, see Additional Material
Section). The values of a for the sorption of Hg(II) ions on the mod-
ified sorbents are 0.46 and 0.73 (mmol g1 min1) for MCGMA-I
and MCGMA-II, respectively. These values are higher than the val-
ues cited in literature [34,35], which may be attributed to the high
concentration of active sites on the sorbent surface allowed for
reacting with Hg(II) ions. The values of b (desorption constant)
are found to be 4.54 and 3.54 g mmol1 for MCGMA-I and
MCGMA-II, respectively. These values are smaller compared with
the levels cited in the literature [34,35]. This is another confirma-
tion of the high affinity of the sorbents for Hg(II) ions.
3.5.3. Equilibrium sorption isotherm
The sorption isotherms represent the distribution of the sorbate
between the solid phase (sorption capacity or sorbate concentra-
tion in the solid) and liquid phase (residual concentration of the
sorbate in the solution), at equilibrium. This distribution is only
controlled by the temperature and is independent of the size of
sorbent particles, on the experimental procedure (batch,
fixed-bed column) providing a sufficient time has been given to
the process for reaching equilibrium. The distribution of the sor-
bate between the two phases can be modeled using different equa-
tions; however, the models the most frequently used for describing
solid/liquid equilibrium systems have been established by
Langmuir [36], Freundlich [37], and Dubinin–Radushkevich [38].
These models and their linear forms are reported in Table 3, where
qeq the sorbed value of Hg(II) at equilibrium concentration
(mmol Hg g1), qm,L is the maximum sorption capacity (corre-
sponding to the saturation of the monolayer, mmol Hg g1) and
KL is the Langmuir binding constant, which is related to the energy
of sorption (L mmol1), Ceq is the equilibrium concentration of
Hg(II) in solution (mmol Hg L1). KF (mmol g1) (L mmol1)1/n
and n are the Freundlich constants related to the sorption capacity
and intensity, respectively. KDR (J2 mol2) is a constant related to
the sorption energy, QDR (mmol g1) is the theoretical saturation
capacity, e (J2 mol2) is the Polanyi potential.
At low initial concentrations (1.0–3.0 mM) the sorption of Hg(II)
was almost quantitative. Brunauer et al. [39] divided the sorption
isotherms into five types. Type I isotherm represents unimolecular
sorption and applies to non-porous, microporous and sorbents
with small pore sizes (not significantly greater than the molecular
diameter of the sorbate). The isotherm curves (Fig. 7) are following
the typical shape of I-type systems, according to the BET classifica-
tion [39]: they are characterized by a high degree of sorption at low
concentrations. At higher concentrations, the sorption sites becom-
ing progressively occupied the sorption tends to stabilize and
forms the saturation plateau.
The Langmuir model is the simplest theoretical model that is
used for describing monolayer sorption onto a surface with a finite
number of identical sites. It was originally developed to represent
gaz/solid sorption before being extrapolated to liquid/solid sorp-
tion. The values of qm,L and KL were determined from the slope
and intercept, respectively, of the linear plot of Ceq/qeq vs. Ceq
(Fig. AM4a, see Additional Material Section); parameters of the
Langmuir equation are reported in Table 3. The maximum sorption
capacities (qm,L) are in good agreement with the experimental val-
ues. The correlation coefficients reported in Table 4 confirm the
better fit of experimental data by the Langmuir model compared
with the other two models. Though the fact that the mathematical
fit of the sorption equation fits well experimental data does not
necessarily mean that the hypotheses associated to the model
are verified this is indicative of the relative homogeneity of the sur-
face; or at least that the active sites are energetically equivalent.
354 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359

Table 1
Kinetics models and their linear forms.

Kinetic model Non-Linear form Linear form Plot References

 
Pseudo-First order qt ¼ qe ½1  e  k1 t
 logðqe  qt Þ ¼ log qe  K1
t log (qe  qt) vs. t [27]
2:303
 
Pseudo-Second order qt ¼ k2 t t 1 1 (t/qt) vs. t [28]
1 þ k2 qe t q ¼ k q2 þ q t
t 2 e e

Intraparticle diffusion – qt = Kit0.5 + X qt vs. t0.5 [29]

Elovich equation dqt
¼ aebq qt ¼ 1b ln ab þ 1b ln t qt vs. ln t [30]
dt

Table 2
Kinetic parameters for Hg(II) sorption.

PFORE PSORE Weber & Morris model Elovich equation

Sorbent qe,exp k1 qe,calc R2 k2 qe, calc R2 Ki X R2 a b R2
MCGMA-I 1.43 0.0130 0.91 0.942 0.035 1.49 0.9976 Ki1 0.124 0.247 0.953 0.470 4.55 0.993
Ki2 0.042 0.751 0.942
Ki3 0.013 1.178 0.889
MCGMA-II 2.01 0.0095 1.27 0.979 0.017 2.10 0.9899 Ki1 0.091 0.664 0.991 0.736 3.54 0.951
Ki2 0.079 0.689 0.989
Ki3 0.035 1.342 0.996

Units: qe,exp/calc: mmol g1; k1: min1; k2: g mmol1 min1; Ki: mmol g1 min0.5; a: mmol g1 min1; b: g mmol1.

Table 3
Sorption isotherms: equation in their linear and non-linear forms.

Isotherm Non-Linear form Linear form Plot References

Langmuir qeq ¼
qm;L K L C eq Ceq
¼
Ceq
þ 1 Ceq
vs: Ceq [36]
1 þ K L C eq qeq qm;L K L qm;L qeq
Freundlich qeq ¼ K F C 1=n ln qeq ¼ ln K f þ 1n ln C eq ln qeq vs. ln Ceq [37]
eq
Dubinin–Radushkevich qeq ¼ Q DR expK DR e
2
lnqe ¼ lnQ DR  K DR e2 ln qeq vs. e2 [38]

2.4 The Freundlich isotherm model is applicable to highly heteroge-

neous surfaces, and a sorption isotherm lacking to form a satura-
2.1
tion plateau indicates a multi-layer sorption. The values of n and
1.8 KF were determined from the slope and intercept, respectively, of
the linear plot of ln qeq vs. ln Ce (Fig. AM4b, see Additional
q eq (mmol g-1)

1.5 Material Section) and the calculated parameters of the Freundlich

equation are summarized in Table 4. Both the saturation plateau
1.2
formed on Fig. 7 at high residual mercury concentration and the
0.9 MCGMA-I
relatively low correlation coefficients confirm that the Freundlich
MCGMA-II
poorly fit experimental data.
0.6 Another popular equation for the analysis of isotherm was pro-
Simulated Langmuir isotherm (MCGMA-I)
posed by Dubinin and Radushkevich (Table 3). This isotherm was
0.3 Simulated Langmuir isotherm (MCGMA-II)
developed taking into account the effect of the porous structure
0.0 of the sorbent, and the energy involved in the sorption process.
0 1 2 3 4 5 6 7 8 9 10 The Polanyi potent (e) is given by Eq. (5) [38]:
Ceq (mM)  
1
e ¼ RTln 1 þ ð5Þ
Fig. 7. Hg(II) sorption isotherms using MCGMA-I and MCGMA-II (pH 4; T: 20 °C). C eq
R is the universal gas constant (8.314 J mol1 K1) and T is the
absolute temperature (K). The slope of the plot of ln qeq vs. e2
Furthermore, the Langmuir parameters can be used to predict the (Fig. AM4c, see Additional Material Section) gives KDR and the
affinity between the sorbate and sorbent using the dimensionless intercept yields QDR (Table 4). The D–R constant (KDR) can give
separation factor RL valuable information regarding the mean energy of sorption (Ea,
J mol1) by Eq. (6):
1
RL ¼ ð4Þ
1 þ K LCo 1
Ea ¼ ð6Þ
ð2K DR Þ0:5
where KL is the Langmuir equilibrium constant and Co is the initial
concentration of Hg(II) ions. Values of 0 < RL < 1 indicates the ‘‘suit- The results of D–R isotherm are reported in Table 4. Fig. AM4c
ability’’ of the process. In this study, the values of RL for the resin for (see Additional Material Section) shows that the experimental data
the sorption of Hg(II) ions lie between 0.002 and 0.088 for each sor- are poorly fitted to the model (consistently with the low value of
bents and all concentrations at 20 °C. These values confirmed the correlation coefficients): the values of the parameters of the model
affinity of modified MCGMA sorbents for Hg(II) ions. should be taken as indicative values (order of magnitude). The
 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359 355

Table 4
Parameters of the sorption isotherm models.

Sorbent Langmuir model Freundlich model Dubinin–Radushkevich (D–R) model

2 2
qmax,exp qm,L KL R n KF R QDR KDR Ea R2
(mmol g1) (mmol g1) (L mmol1) (mmol g1) (mmol g1) (J2 mol2) (kJ mol1)
(L mmol1)1/n
MCGMA-I 1.43 1.55 27.78 0.999 12.87 1.37 0.965 1.50 4.72  109 10.3 0.892
MCGMA-II 2.02 2.28 16.48 0.999 7.98 1.89 0.945 2.16 6.48  109 8.78 0.894

Table 5
values of the mean energy of sorption range between 8.7 and Effect of temperature on Hg(II) sorption capacity.
10.3 kJ mol1: this is consistent with the proposed mechanism of
chemisorption. Indeed, it is generally admitted that 8 kJ mol1 is Temperature (°C) Sorption capacity (mmol Hg g1)

the limit energy for distinguishing physical (below 8 kJ mol1)
and chemical sorption. A comparison of the correlation coefficient
values obtained from the Langmuir, Freundlich and D–R isotherm
models in Table 4 reveals that the correlation coefficients for the
Langmuir isotherm are somewhat higher than those for the
Freundlich and D–R isotherm. This result suggests that the binding
of Hg(II) may occur as a monolayer on the surface of the sorbent
and that the uptake occurs on a homogenous surface by monolayer
sorption. This should be confirmed by experimental observation
(as reported above the mathematical fit of isotherm curve by a
given model equation does not mean that the relevant hypotheses
of the model are verified). The uptake can be described in terms of
chemisorption as the formation of ionic or covalent bonds between
the sorbent (free mercury species or chloroanionic species,
depending on the pH and the sorption mechanism) and the sorbate
(free amine groups or protonated amino groups depending on the
pH).
The coexistence of different metal species that could be sorbed
in function of the pH as well as the different mechanisms, and the
simultaneous presence of different types of amino groups are not
comforting the hypothesis of homogeneous surface (or homoge-
neous energies of sorption).
3.5.4. Influence of temperature
The sorption performance may be controlled by the tempera-
ture both in terms of kinetics (depending on the activation energy)
and equilibrium: the thermodynamics of the process influences the
instantaneous kinetics of sorption and desorption, and conse-
quently the equilibrium. The sorption capacities were compared
at different stabilized temperatures (under identical experimental
conditions) for both MCGMA-I and MCGMA-II (Table 5): the sorp-
tion capacity increases with temperature and the sorption is an
endothermic process. The sorption equilibrium constant, Kc was
determined (Eq. (7)) and used with the van’t Hoff equation (Eq.
(8)) and conventional thermodynamic equation (Eq. (9)) for evalu-
ating the thermodynamic constants of the sorbents (i.e., the stan-
dard enthalpy change, DH°, the standard free Gibbs energy, DG°,
and the standard entropy change, DS°).
qeq
Kc ¼
C eq
where qeq and Ceq are equilibrium concentrations of Hg(II) on the
sorbent and in the solution, respectively.
DG ¼ RTlnK c
MCGMA-I MCGMA-II
20 1.48 2.12
30 1.74 2.40
40 1.91 2.58
50 2.21 2.65
The values of standard enthalpy change (DH°) and standard
entropy change (DS°) for the sorption process are thus deter-
mined from the slope and intercept of the plot of ln Kc vs. 1/T:
the values of thermodynamic parameters are reported in
Table 6. The positive values of DH° confirm the endothermic nat-
ure of sorption process. The negative values of DG° indicate that
the sorption reaction is spontaneous. The increase in the negativ-
ity of DG° with increasing temperature confirms that the ‘‘favor-
ability’’ increases with temperature. In addition, the values of
standard free energy change for MCGMA-II are more negative
than these of MCGMA-I: Hg(II) sorption is more favorable on
MCGMA-II than on MCGMA-I, especially at low temperature.
The density of sorption sites and the spatial arrangement of func-
tional groups are more favorable for Hg(II) binding on MCGMA-II
sorbent. It is noteworthy that in the case of MCGMA-I, the stan-
dard free Gibbs energy becomes positive only at higher tempera-
ture (i.e., above 40 °C): the spontaneous nature of sorption
process is only possible when the system is ‘‘activated’’ by tem-
perature. With MCGMA-II more amine groups are available; in
addition their distribution along a free long chain makes them
more accessible. This could explain the better ‘‘spontaneity’’ of
sorption process for MCGMA-II compared to MCGMA-I (which
possibly requires an increase in temperature for the enhancement
of metal ion or polymer chains ‘‘mobility’’ that, in turn, improves
sorption performance).
In industry and water purification plants the optimum tem-
perature at which the sorption is highly feasible and sponta-
neous is essential. The sorption of metals onto sorbent surfaces
may be either spontaneous or non-spontaneous in function of
temperature. The limit temperature value corresponding to a
null value of standard free energy can thus be deduced from
Eq. (11). The range of temperature can be predicted from the
value of temperature at which the standard free energy is zero
ð7Þ (T0), and then the minimal temperature for the process to being
spontaneous.

DH
T0 ¼  ð11Þ
ð8Þ DS

Here, the calculated values of zero standard free energy temper-

DG ¼ DH  T DS ð9Þ
ature (T0) are 312.8 and 283.8 for MCGMA-I and MCGMA-II,
Therefore the van’t Hoff equation becomes: respectively. The low T0 for MCGMA-II indicates the feasibility of
  Hg(II) removal at ambient temperature, while MCGMA-I sorbent
DH DS requires a thermal activation: the spontaneous reaction occurs at
lnK C ¼ þ ð10Þ
RT R around 40 °C.
356 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359

Table 6
Standard enthalpy, entropy and free energy changes for Hg(II) sorption.

Adsorbent DH° (kJ mol1) DS° (J mol1 K1) T0 (K) DG° (kJ mol1)
293 K 303 K 313 K 323 K
MCGMA-I 19.2 61.4 312.8 1.22 0.60 0.01 0.62
MCGMA-II 15.3 54.0 283.8 0.50 1.04 1.58 2.12

Table 7
Effect of counter ion on Hg(II) sorption.

Initial pH Sorption capacity (mmol Hg g1)

HgCl2 HgNO3 HgSO4
MCGMA-I MCGMA-II MCGMA-I MCGMA-II MCGMA-I MCGMA-II
0.95 1.51 2.07 0.15 0.16 0.048 0.054
2.12 1.45 2.07 1.00 1.41 0.153 0.164
3.2 1.36 1.95 1.33 2.14 – –

3.5.5. Effect of counter anions and metal speciation
The effect of the counter anion on the uptake of Hg(II) by mod-
ified MCGMA sorbents was investigated at different pH values
using different mercury salts. The pH of the solution was adjusted
using HCl for HgCl2 solution, HNO3 for Hg(NO3)2 solution and
H2SO4 for HgSO4 solution. Table 7 shows that at low pH (i.e.,
0.95) an appreciable sorption was obtained in the case of HgCl2
for both sorbents, while with Hg(NO3)2 and HgSO4 salts the sorp-
tion was negligible. This result can be explained by the possibility
for the sorbents to bind mercury by an ion-exchange between the
counter anions (chloride) bound to amino groups and the Hg(II)
2
chloroanions (HgCl 3 or HgCl4 ) [25]. In the case of other
counter-anions, mercury does not form stable anionic complexes
that could be bound to protonated amine groups by
ion-exchange and the sorption strongly decreases. The limited
uptake in the case of Hg(NO3)2 or HgSO4 salts may be also attribu-
ted to the higher stability of (MCGMA-NH+)NO 3 or the
(MCGMA-NH+)2SO2 4 that retards the ion exchange mechanism.
At pH 2.12 for both MCGMA-I and MCGMA-II Hg(II) was signifi-
cantly sorbed when using HgCl2 or Hg(NO3)2 salts, while the sorp-
tion was negligible with HgSO4 salt. Sulfate salts have more affinity
for protonated amine groups than other mono-anions making
more difficult metal anion exchange. The composition of the solu-
tion may thus have a significant impact on the sorption perfor-
mance, especially at pH where the ion-exchange is the
predominant sorption mechanism.
3.5.6. Selectivity of modified MCGMA for Hg(II) sorption
In order to evaluate the possible selectivity of the sorbents
Hg(II) sorption was carried out in multicomponent solutions
(containing Hg(II), Co(II), Cu(II), Fe(II), Ni(II), Zn(II) and Mg(II)) at
different pH values (0.4–1.6). Table 8 shows that the recovery of
Hg(II) is almost quantitative in the presence of equimolar concen-
trations of other base metal cations, regardless of the pH (at least in
the selected pH range). Whatever the pH, the maximum sorption
capacities of competitor metal ions by the modified MCGMA
sorbents is less than 5.0% of sorbed amounts of Hg(II) ions. The sor-
bents appears to have a selective recognition pattern for Hg(II) ions
against other selected heavy metal ions. The reported negative val-
ues for the uptake of Fe(II) can be attributed to the release of iron
from magnetite at low pH: when the pH increases this release
decreases. The stability of the composite material is an important
issue to take into account and it sounds preferable managing the
hybrid material in solution whose pH is higher than pH 1.5–2.
The selectivity of the sorbents for Hg(II) against other base metals
may be explained by the sorption mechanism which is attributed
to ion-exchange of Hg(II) chloro-anions on protonated amine
groups in acid conditions: the other selected metal ions are not
supposed to form stable chloro-anions under selected experimen-
tal conditions.
3.5.7. Effect of sorbent dose
The sorption of Hg(II) on modified MCGMA sorbents was stud-
ied by changing the sorbent dosage (in the range 1.5–10 g L1),
metal concentration being fixed to 9.8 mM (pH 4 and T: 20 °C).
Fig. AM5a (see Additional Material Section) shows the variation
in sorption capacity with sorbent dosage: the sorption capacity
decreases from 1.52 to 0.97 mmol Hg g1 and from 2.07 to
0.97 mmol Hg g1 for MCGMA-I and MCGMA-II, respectively when
the SD increases from 1.5 to 10 g L1. Fig. AM5b (see Additional

Table 8
Multicomponent sorption – effect of pH on the sorption capacity for Hg(II) Co(II), Cu(II), Fe(II), Ni(II), Zn(II) and Mg(II) (initial concentration of 1.0 mmol metal L1 for each metal
ion).

Adsorbent Initial pH Final pH Uptake (mmol g1)

Metal ion
Hg(II) Co(II) Cu(II) Fe(II)* Ni(II) Zn(II) Mg(II)
MCGMA-I 0.4 0.82 0.280 0.016 0.001 0.209 0.002 0.034 0.000
0.8 1.12 0.342 0.006 0.000 0.118 0.011 0.021 0.001
1.2 1.26 0.350 0.016 0.005 0.008 0.015 0.008 0.004
1.6 1.80 0.301 0.014 0.004 0.005 0.016 0.000 0.000
MCGMA-II 0.4 0.90 0.310 0.014 0.000 0.192 0.004 0.027 0.000
0.8 1.22 0.372 0.000 0.003 0.109 0.005 0.008 0.000
1.2 1.29 0.380 0.001 0.006 0.007 0.000 0.000 0.005
1.6 1.86 0.331 0.000 0.013 0.004 0.000 0.000 0.002
*
Negative values for Fe(II) are associated to metal release due to magnetite partial dissolving.
 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359 357

Table 9
Comparison of sorption capacity for Hg(II) ions with various sorbents.

Adsorbent material Initial Contact time Temperature Initial Sorbent dosage Sorption capacity References
pH (min) (°C) concentration (g L1) (mmol Hg g1)
(mM)
Thiourea modified Hg(II) ion-imprinted 5.00 180 30 1.99 0.30 0.54 [42]
cellulosic cotton fibers
Schiff-base modified guar gum 5.00 120 25 0.24 1.00 0.20 [43]
Hydrolyzed acrylamide-grafted PET films 4.5 40 25 0.49 4.00 0.07 [44]
ZnCl2-MCM-41 6.00 30 20 0.24 0.33 0.43 [45]
Chitosan foam 4.00 2880 20 0.49 0.45 1.74 [40]
Thiol modified activated coke 5.00 480 25 0.49 0.10 2.29 [41]
Glycidylmethacrylate grafted on cellulose 5.00 50 – 0.24 20.00 0.18 [6]
Sheep bone charcoal 3.0 360 25 0.39 4.00 0.06 [46]
MCGMA-I 4.0 300 20 5.00 2.50 1.43 This work
MCGMA-II 4.0 300 20 5.00 2.50 2.02 This work

Material Section) shows the effect of sorbent dosage on the relative 4.0
equilibrium concentration (C/C0). As expected when the sorbent
3.8
dosage increases, the equilibrium concentration of Hg(II)

Released Hg(II) (mM)

decreased. The results shown indicate that the residual concentra- 3.6
tion C/C0 may decrease up to 0.0014 for SD = 10 g L1. At low sor-
bent dosage, all sorption sites are exposed and the can be easily 3.4
saturated. With an increase of sorbent dosage the amount of sorp-
tion sites becomes in excess compared to present metal ions and 3.2
the saturation of the sorption sites is not achieved. According to
3.0 Cycle I
these results, the sorbent dosage of 1.5 g L1 allows achieving the
Cycle II
saturation of the sorbent and makes possible the concentration
2.8
effect and the enrichment of mercury after desorption step. On Cycle III
the opposite hand with a sorbent dosage of 10 g L1 it is possible 2.6
removing about 99.6% of mercury from the solution (achieving
environmental target). The sorbent dosage to be used depends on (a) 0 10 20 30 40 50 60
the target of the sorption process: concentration effect or maxi- t (min)
mum decontamination.
6.0
3.5.8. Comparison of sorption capacity for Hg(II) ions with various 5.8
sorbents
5.6
Released Hg(II) (mM)

Table 9 shows the comparison of maximum sorption capacities

of MCGMA-I and MCGMA-II with a series of values found in the lit- 5.4
erature (together with the best operating conditions reported by 5.2
respective authors). A direct comparison of sorption performance
5.0
is difficult due to different experimental conditions; however, this
is a useful criterion for roughly evaluating the potential of these 4.8 Cycle I
materials. The modified MCGMA sorbents have a sorption capacity 4.6 Cycle II
of the same order of magnitude as other sorbents; although chi-
4.4
tosan foam [40] and thiol-modified activated coke [41] showed Cycle III
better sorption capacity. It is noteworthy that the modified 4.2
MCGMA sorbents have an important advantage related to their fast 4.0
kinetics. The high sorption capacity of the modified MCGMA sor- 0 10 20 30 40 50 60
bents towards Hg(II) ions reveals that sorbents could be promising
(b) t (min)
for practical application in Hg(II) ions removal from wastewater.
Fig. 8. Desorption kinetics for successive sorption/desorption cycles for MCGMA-I
(a) and MCGMA-II (b).
3.5.9. Regeneration
Three successive sorption/desorption cycle runs were per-
formed using 100 mL of 0.1 M KI solutions for 50 min. Samples
were collected at different time intervals and the residual concen- MCGMA-II for the first three sorption/desorption cycles,
tration of Hg(II) was determined. Fig. 8 shows the time course of respectively.
released Hg(II) ions. About 97% of the sorbed Hg(II) ions is released
within 15 min. The desorption is even faster than the sorption.
Though a slight and progressive decrease in the amount of 4. Conclusion
desorbed Hg(II) ions is observed along the successive cycles the
desorption efficiencies remained higher than 90% after three sorp- Novel magnetic macromolecular hybrid materials were
tion/desorption cycles. The sorbent MCGMA-I seems to be slightly prepared by grafting glycidyl methacrylate (synthetic polymer) to
more efficient than MCGMA-II sorbent in terms of desorption with chitosan (biopolymer) and functionalizing the intermediary com-
desorption yield of 97.2, 98.2 for MCGMA-I and 99.6%, 89.0% for pound with diethylenetriamine (directly, or via epichlorhydrin
358 K.Z. Elwakeel, E. Guibal / Chemical Engineering Journal 281 (2015) 345–359
spacer, MCGMA-I and MCGMA-II, respectively). The two sorbents
are characterized by efficient and selective sorption towards
Hg(II) ions from aqueous medium at approximately pH 4. The
uptake kinetics are well fitted by the PSORE, while the distribution
of the metal at equilibrium between the solid and the liquid is
modeled by the Langmuir equation. The maximum capacity
reached 1.43 mmol g1 for MCGMA-I and 2.01 mmol g1 for
MCGMA-II at 20 °C. The tests performed in the presence of other
heavy metals (multicomponent solutions) demonstrated the selec-
tivity of the sorbents for Hg(II). Depending on the pH two sorption
mechanisms can be involved: ion-exchange on protonated amine
groups in acidic solutions, or chelation on amine groups at mild
acidic pH. However, this interpretation of sorption mechanisms is
affected by the composition of the solution and more specifically
the nature of counter-anions present in the solution. The presence
of counter anions that form anionic complexes in acidic solutions
makes possible Hg(II) sorption while those counter anions that
do not form stable complexes with mercury reduce the affinity of
the sorbent for metal ions. The investigation of temperature effect
on Hg(II) sorption isotherm confirms that the sorption mechanism
is endothermic. Mercury ions bound to the sorbents can be suc-
cessfully desorbed using 0.1 M potassium iodide solutions and
the sorbent can be effectively re-used.
Acknowledgements
This study was supported by the French Government through a
fellowship granted from the French Embassy in Egypt (Institut
Français d’Égypte). The authors would like to thank Thierry
Vincent, André Brun and Jean-Marie Taulemesse for their technical
and scientific contributions to this work.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2015.05.110.
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