ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. (2017)

Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI: 10.1002/apj.2072

Research article
Validity of Egyptian Na-montmorillonite for adsorption of
Pb2+, Cd2+ and Ni2+ under acidic conditions: characterization,
isotherm, kinetics, thermodynamics and application study
A.A. Taha,1 M.A. Shreadah,2 Hany Fathy Heiba2* and A.M. Ahmed1
1
Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
2
Marine Chemistry Department, National Institute of Oceanography and Fisheries (NIOF), Alexandria, Egypt

Received 17 May 2016; Revised 26 December 2016; Accepted 19 January 2017

ABSTRACT: This study investigated the applicability of natural Egyptian Na-montmorillonite (Na-MMT) to remove
Pb2+, Cd2+ and Ni2+ under acidic conditions that mimic industrial wastewater acidity. Cation exchange capacity of
Na-MMT was found 91 meq/100 g and the specic surface area 42 m2 g
1. The adsorbent was characterized using
X-ray uorescence, scanning electron micrograph that showed signicant morphological changes after adsorption and
Fourier transform infrared spectroscopy, which conrmed that the adsorption occurred mainly in the lattice region.
Removal efciency was evaluated as a function of pH, contact time, initial concentration, and adsorbent mass. Acidic
pH value was chosen for the following experiments. Langmuir and Freundlich isotherm models were applied. Freundlich
model showed better tting suggesting heterogeneous adsorption scenario. Freundlich capacity values decreased in the
order of Pb2+ (3.71 mg g
1) > Cd2+ (2.45 mg g
1) > Ni2+ (1.76 mg g
1). Kinetic data were accurately tted to
pseudo-second-order, indicating the adsorption occurrence in the interior surface of Na-MMT and the contribution of
internal diffusion mechanism was signicant. Intraparticle diffusion model gave multi-linear curves so more than one-
step controlled the adsorption process. Under temperature range 290328 K, thermodynamic parameters revealed that
adsorption of Pb2+ and Cd2+ was spontaneous but Ni2+ non-spontaneous. Adsorption was exothermic for Pb2+ and
Ni2+ but endothermic for Cd2+. Arrhenius activation energy values were 5.78, 8.51 and 11.45 kJ mol
1 for Pb2+,
Cd2+ and Ni2+ respectively stating the physical adsorption. Na-MMT reusability was conrmed by regeneration
experiments. Application study showed excellent efciency of Na-MMT within range (23.481.2%) removal for Pb2+,
Cd2+ and Ni2+ from textile dyeing and tannery wastewater. Copyright 2017 Curtin University of Technology and John
Wiley & Sons, Ltd.

KEYWORDS: adsorption; acidic media; montmorillonite; isotherm; kinetics; thermodynamics

INTRODUCTION discharging. Heavy metals are considered as a serious

Industrial activities have generated tons of heavy
metals that contaminate water routes all over the
world[1]; for example, the Egyptian Mediterranean is
subjected to heavy metals pollution owing to the
continuing and increasing release of a great number
of industrial, agricultural, commercial and domestic
waste efuents that affect the characteristics of water,
sediments, and sh.[2] Heavy metals are a class of
pollutants that require extensive treatment before being
discharged into water streams owing to their severe
harmful effect on the living organisms.[3] Therefore,
there is a great deal of research in recent years to
remove heavy metals from wastewater before
*Correspondence to: Hany Fathy Heiba, National Institute of Oceanography
and Fisheries (NIOF), PO Box: 21556, Qayet-Bey, Al-Anfoushy,
Alexandria, Egypt. E-mail: hanyheiba@gmail.com
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Curtin University is a trademark of Curtin University of Technology
threat owing to their toxicity and non-
biocompatibility.[4]
Excessive levels of heavy metals in the environment
can be detrimental to a variety of living organisms and
humans. Metals are not biodegradable and can be
accumulated through the food chain even at lower
concentration in living tissues, causing many diseases
and disorders.[5] Lead (Pb), cadmium (Cd) and nickel
(Ni) are released into natural waters by industrial and
domestic wastewater dischargers. The elevated level
of these heavy metals in water poses a serious threat
to human health[6] (Table 1), animals and ecological
systems.
Common removal technologies of heavy metals are
membrane separation, ion exchange, electro
deposition, and chemical precipitation. These methods
proved to be costly and inept, especially in removing
trace amounts of heavy metals. Another disadvantage
2 A. A. TAHA ET AL.
Table 1. The maximum contaminant levels (MCL) for the most common heavy metals.
Heavy metal
Lead (Pb) Damage the fetal brain and diseases of the kidneys, circulatory
system and nervous system
Cadmium (Cd) Kidney damage, renal disorder and human carcinogen
Nickel (Ni) Dermatitis, nausea, chronic asthma, coughing and human carcinogen
is the production of sludge or mud, which requires
proper disposal and connement. On the other hand,
adsorption effectively removes contaminants in
wastewater with high solute loadings and even at dilute
concentrations (<100 mg L
1).[7]
Recently, many materials have been utilized as
adsorbents for removal toxic metals like agricultural
by-products[6] and nanomaterials that attracted a
growing attention as metal adsorbents owing to their
functionality and large surface area.[8] Among
adsorbents, there is the abundant low-cost clay
minerals that is considered a strong candidate for
removal of heavy metal from wastewater. Montmo-
rillonite is a smectitic clay, {[Na,Ca]0.33[Al,
Mg]2[Si4O10]-[OH]2nH2O} that has specic surface
chemical properties[9] such as that permanent negative
structural charge, which generated largely in the
octahedral sheet through isomorphous substitution of
Al3+ with Mg2+.[10] This negative charge plays a vital
role in attracting the positively charged pollutants. In
industry, montmorillonite is generally classied as
Na-montmorillonite or Ca-montmorillonite, depending
on which exchangeable ion is dominant.[11]
Montmorillonite has interesting properties like high
cation exchange capacity, swelling properties and large
surface area, and it is found in abundant amounts,
which is an economic advantage: such advantages
make it an effective adsorbent for metal removal.
Few studies investigated the ability of natural
Egyptian Na-montmorillonite (Na-MMT) to remove
toxic metals, and it is difcult to nd studies to remove
metals from acidic media. The basic targets of this
study are (1) the use of natural Egyptian Na-MMT
without any pre-treatment to reduce treatment cost,
then evaluation of its adsorption afnity towards toxic,
Pb2+, Cd2+ and Ni2+ under acidic conditions; (2)
characterization of Na-MMT to investigate its surface
and physicochemical properties; (3) isothermal,
kinetics, mechanism and thermodynamic modeling of
the adsorption data; (4) effect of different operating
parameters inuencing the adsorption behavior, such
as time, pH, temperature, adsorbent mass and meal
concentration, was investigated through kinetic,
equilibrium and thermodynamic studies; and (5)
application case to evaluate the Na-MMT ability to
remove metals from wastewater of textile dyeing and
tannery factories.
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacic Journal of Chemical Engineering
Toxicity MCL (mg L
1)
0.006
0.010
0.200
MATERIALS AND METHODS
Na-montmorillonite
Egyptian Na-MMT was obtained from the Egyptian
Bentonite and Derivatives Co. (Alexandria, Egypt).
Batch adsorption experiments
Standard stock solution of Pb2+ (1000 mg L
1), Cd2+
(1000 mg L
1) and Ni2+ (1000 mg L
1) were
purchased from MERK-Germany. The specied
concentrations (ranging from 5 to 20 mg L
1) were
prepared by sequential dilution using deionized water.
The required pH of each solution was adjusted by
adding 0.1 M NaOH or 0.1 M HNO3. The metal
solution was added to the certain weights of the
Na-MMT and was shacked to the required time.
Finally, after adsorption experiments, the remaining
unadsorbed metal concentrations of Pb2+, Cd2+ and
Ni2+ in solutions were determined by ame atomic
adsorption spectrometry. The adsorption parameters
were studied under the conditions listed in Table 2.
Instruments and apparatus
Na-montmorillonite was characterized using scanning
electron micrograph (SEM) with a Jeol-JSM-5300
apparatus. Fourier transform infrared spectroscopy
(FTIR) (PerkinElmer Spectrum BX) was employed to
investigate surface active sites. The chemical
composition was examined using X-ray uorescence
ALR 9400the specic surface area was measured
by N2, BrunauerEmmettTeller method. During
adsorption experiments, the pH values were adjusted
using (JENWAY 3505 pH Meter). Sartorius digital
balance was used for weighing. Incubated forma orbital
shaker (Thermo 436HEPA Filter) was used for
shaking in batch experiments. The metal concen-
trations were analyzed using ame atomic adsorption
spectrometry (Shimadzu AAS 6800).
Analytical calculations
Percentage removal of metals by Na-MMT was
calculated using Eqn (1):
Asia-Pac. J. Chem. Eng. (2017)
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Asia-Pacic Journal of Chemical Engineering ADSORPTION OF HEAVY METALS UNDER ACIDIC CONDITIONS 3
Table 2. Experimental conditions for the adsorption experiments.

Reaction conditions
Time Co Adsorbent mass Temperature Agitation speed
Studied parameters pH (min) (mg L
1) (g) (K) (rpm)
pH 27* 60 10 0.25 298 100
Time (min) 3.8 160 10 0.25 298 100
Metal concentration, Co (mg L
1) 3.8 60 520 0.25 298 100
Adsorbent mass (g) 3.8 60 10 0.1250.500 298 100
Temperature (K) 3.8 60 10 0.25 290328 100
*Effect of pH was studied in the pH range 27 while keeping other parameters constant at t = 60 min; Co = 10 mg L
1; adsorbent
mass = 0.25 g; agitation speed = 100 rpm and T = 298 K.

Co
Ce
Adsorption efficiency % 100 (1) Table 3. Physicochemical analysis for Na-MMT.
Co
Component Value
The adsorption capacity (qt) the amount of metal (II)
adsorbed per gram adsorbent (mg/g) was calculated XRF SiO2 55.78%
Al2O3 16.69%
using Eqn (2) Fe2O3 3.82%
Na2O 3.41%
C o
C t v CaO 1.21%
Adsorption capacity qt (2) MgO 2.56%
m K2O 0.94%
TiO2 0.67%
(Co), (Ce) and (Ct) represent the metal concentration P2O5 0.09%
at the beginning, equilibrium and at time (t), L.O.I 14.85%
respectively. (v) is the volume of the solution in liters CEC 91 (meq/100 g)
Specic surface area 42 (m2 g
1)
(L), and (m) is the mass of adsorbent in grams (g).
The data obtained were applied to the isotherm,
kinetics and thermodynamic equations.

Experimental statistics adsorption are shown in Fig. 1. The 5000

Three replicates were measured for each sample during
the aforementioned assays. Statistical analysis of data
was conducted using ORIGIN 8 software. All
experimental data were presented as mean
values standard deviations.
RESULTS AND DISCUSSION
Characterization of Na-montmorillonite
Physicochemical parameters
The chemical analysis presented in Table 3 reveals that
the major constituents are SiO2 and Al2O3. The
obtained high cation exchange capacity (91 meq/
100 g) and the high specic surface (42 m2 g
1) are
very important factors in metal removal in both ways
of ion exchange and physical adsorption on the more
available binding sites.
Scanning electron micrograph
The SEM images obtained for Na-MMT (before any
adsorption with the metal ions) reveal the surface
texture and morphology of the adsorbent. Selected
SEM micrographs of the Na-MMT (M) and after
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
magnication shows that the starting Na-MMT (M)
consists of particle aggregates of lamellar particles
smaller than 20 m (Fig. 1a), with irregular edges
suggesting a heterogeneous surface with almost non-
compact structure. The extremely thin lamellar particles
forming the montmorillonitic tactoids,[12] are featured
under a higher magnication (20 000) as shown in
(Fig. 1b). Signicant morphological changes are
observed after the treatments experiments, where Na-
MMT shows a rougher irregular surface with multiple
smaller particles (ake-like) deposited on it, and the
tactoid sheets become sharper. These changes are due
to interaction of the clay surface with the metal ions.
Fourier transform infrared spectroscopy
The surface functional groups were identied using
FTIR as shown in Fig. 2. The spectra shows vibration
peaks near 422793 cm
1 due to SiOAl and SiO
Mg stretching frequency and SiO bending frequencies,
the band near 914
1 is due to (A1OH vibration). The
deep band of about 1034 cm
1 in the stretching mode
region is due to SiOSi stretching frequencies.
Overtone of the bending vibration of water is observed
at 1644 cm
1.[13] The broad absorption band in the
region 34003854 cm
1 can be ascribed to the
stretching of lattice OH (SiOH, AlOH) and OH of
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4 A. A. TAHA ET AL. Asia-Pacic Journal of Chemical Engineering

Figure 1. SEM images for A and B raw sample, C and D after Pb adsorption, E and F after Cd adsorption and G and H
after Ni adsorption, where A, C, E and G represent 5000 and B, D, F and H represent the 20 000.

Figure 2. FTIR spectra of (a) starting Na-MMT, (b) after Pb2+ adsorption, (c) after Cd2+ adsorption and (d) after Ni2+
adsorption.

the physically adsorbed water.[14] After adsorption of bands of 692 and 793 of SiOAl, SiOMg stretching
Pb2+, Cd2+ and Ni2+ as shown in Fig. 2bd frequency; also, there was a decrease in the intensity of
consequently, the intensity of the peaks was reduced SiOSi stretching band, in addition broadening in OH
with a little drift. Some bands disappeared such as band attributed to the moisture after adsorption. Such
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering
changes in FTIR spectra adsorption conrm that
adsorption mainly occurred in the clay lattice region.
Effects of operating parameters
Metal removal as a function of pH
The solution pH plays an important role in adsorption
process,[15] affecting not only metal species in the
solution but also the surface properties of the
adsorbents. pH effect on the adsorption of Pb2+, Cd2+
and Ni2+ was studied by evaluating the performance
of Na-MMT at pH values of 2, 3.8, 5.5 and 7. As
shown in Fig. 3, adsorption increases with increasing
pH, when the pH value is 2 and the percentage removal
are 85.60, 75.59 and 62.34 for Pb2+, Cd2+ and Ni2+,
respectively, and then this percentage gradually
increased with pH till reaching 97.75%, 95.11% and
92.72% for Pb2+, Cd2+ and Ni2+, respectively, at
pH 7. The reduced removal efciency at lower pH is
due to protonation of the surface functional groups
and the availability of excess H3O+ ions that compete
with metal ions to bind to the surface binding sites
which in turn result in reducing the total number of
the binding sites available for metal uptake.[16] In
addition, the adsorbent surface functional groups
became positively charged at lower pH that exert an
extra electrostatic repulsion with the positively charged
Pb2+, Cd2+ and Ni2+, which prevents the attachment
between the adsorbent and the adsorbate.[17] However,
by raising the pH from 2.0 to 7.0, the sorption
efciency was increased owing to (1) the decrease in
H3O+ ions on the adsorbent surface.[16] (2) The surface
functional groups became negatively charged, and
there was an electrostatic attractive force between the
positive metal cation and negatively charged
surface.[18] The optimum pH was found to be 7;
however, further removal experiments were performed
Figure 3. Metal removal as a function of pH pH range (27),
t = 60 min, Co = 10 mg/L, adsorbent mass = 0.25 g, agitation
speed = 100 rpm and T = 298 K.
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
ADSORPTION OF HEAVY METALS UNDER ACIDIC CONDITIONS 5
under acidic condition (pH 3.8) where one aim of the
present study is to evaluate the potential of the
Egyptian Na-MMT to remove the toxic metals under
the acidic conditions of wastewater (e.g. wastewater
of battery factories that normally has pH less than
4[19,20]).
Effect of contact time
It is evident from Fig. 4 that contact time has signicant
inuence on the rate of metal uptake. Adsorption was
very fast within the rst 30 min as a result of the
exuberant number of available active sites on adsorbent
surfaces, and then decreased until equilibrium was
reached.[21] As the active sites gradually became
occupied, the adsorption slowed down where metal
ion migrate from the surface to the micropores. Finally,
when the adsorbent surface and the micropores became
saturated with respective metal, the removal efciency
becomes almost constant.[18] The optimum contact
time for adsorption was found to be 30 for Cd2+ and
Ni2+ and 50 min for Pb2+. However, stirring time of
60 min was used in all further sorption experiments to
ensure complete adsorption equilibrium.
Effect of metal concentration
The effect of Pb2+, Cd2+ and Ni2+ concentration on the
adsorption is shown in Fig. 5. As the metal
concentration increased, the percentage removal
decreased because the metal ratio greatly exceeds the
active sites and so high competition between ions to
bind to the unoccupied sites. However, the qe rapidly
increased until it reached a maximum value of 6.15,
4.47 and 3.89 mg g
1 for Pb2+, Cd2+ and Ni2+,
respectively. At high concentrations, more ions are
adsorbed onto the pores because of the adsorption
desorption equilibrium, resulting in an increase
in qe.[13]
Figure 4. Effect of contact time time range (160) min,
pH = 3.8, Co = 10 mg/L, adsorbent mass = 0.25 g, agitation
speed = 100 rpm and T = 298 K.
Asia-Pac. J. Chem. Eng. (2017)
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6 A. A. TAHA ET AL. Asia-Pacic Journal of Chemical Engineering

Figure 5. Effect of metal concentration Co = (520) mg/L, t = 60 min, pH = 3.8,

adsorbent mass = 0.25 g, agitation speed = 100 rpm and T = 298 K.

Effect of adsorbent mass
The effect of adsorbent mass on adsorption of heavy
metal ions was investigated for single-ion system.
The uptake of metal ions was observed to increase as
the adsorbent mass increased up to 0.5 g as shown in
Fig. 6. This can be explained with the increase of
surface area and the availability of the binding sites.
At higher adsorbent dosage, increased number of
adsorption sites enhances the uptake of Pb2+, Cd2+
and Ni2+. On the other hand, the adsorption capacity
decreased with the increase in adsorbent mass, this
behavior could be explained by the high ratio of the
active sites relative to the metal ions, which decreases
the saturation of the active sites. In addition, the
agglomeration and sedimentation of the sorbent
particles (because of London interaction) at high
dosage of Na-MMT might also have a negative effect
on the adsorption capacity.[18]
Adsorption isotherm
Adsorption isotherms draw the relationships between
the adsorbate concentration in the solution and the
amount adsorbed at the interface. Langmuir and
Freundlich are the most commonly used solid/liquid
phase isotherms and were used to describe the

Figure 6. Effect of adsorbent mass adsorbent mass (0.120.500) g, t = 60 min,

pH = 3.8, Co = 10 mg/L, agitation speed = 100 rpm and T = 298 K.
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering ADSORPTION OF HEAVY METALS UNDER ACIDIC CONDITIONS 7

relationship between the adsorbed metal ions in this
study. The Langmuir model is applicable in cases
where monolayer of adsorbate is formed at the
adsorbent surface. The linearized form of Langmuir
adsorption isotherm models is dened by the following
equations (3 (3)).[22]
Ce 1 Ce
qe qm b qm
where Ce is the equilibrium concentration of adsorbate
(mg L
1), qe is the amount of material adsorbed at
equilibrium (mg g
1), qm is the adsorption capacity of
adsorbent (mg g
1) and b a Langmuir constant related
to energy.
Freundlich equation shows the best ttings to the
adsorption data for natural heterogeneous adsorbents.
Freundlich adsorption isotherm equation and its linear
form can be written as follows in Eqn (4).
1
log qe log K f log C e
n Adsorption kinetics
where qe is the amount of the solute adsorbed per
unit weight of adsorbent (mg g
1); Ce is the
equilibrium concentration of the solute in the bulk
solution (mg L
1); Kf is Freundlich constant, which
is a comparative measure of the adsorption capacity
for the adsorbent, and nf is an empirical constant
related to the heterogeneity of the adsorbent
surface.[23]
Linearized Langmuir and Freundlich plot is shown in
Fig. 7. The related isotherm parameters are calculated
and tabulated in Table 4. Freundlich model shows
better tting with the Pb2+, Cd2+ and Ni2+ adsorption
onto Na-MMT, suggesting heterogeneous adsorption
scenario. Freundlich capacity constant values were
found to decrease in the order of Pb2+
(3.71 mg g
1) > Cd2+ (2.45 mg g
1) > Ni2+
(3) (1.76 mg g
1).
Favorable adsorption is normally indicated by a
Freundlich constant (n) of between 1 and 10. A higher
value of n (smaller value of 1/n) implies strong
interaction between adsorbate and adsorbent, while n
equal to 1 indicates a linear adsorption process, with
constant energy on the entire surface. Application of
the linear Freundlich model gave values of n equal to
5.65, 3.31 and 2.92 for Pb2+, Cd2+ and Ni2+,
respectively, reecting a favorable adsorption process
and satisfying the condition of heterogeneity (1 < n < 10
and 0 < 1/ n < 1), as required by the model.[24]
(4)
Adsorption kinetics describes the metal uptake rate at
the solidsolution interface. Thus, it is important to
understand the reaction mechanism and design
appropriate sorption treatment plants. Rapid adsorption
of the metal is desirable and benecial for practical
applications. The pseudo-rst-order Eqn (5) and
pseudo-second-order kinetic models Eqn (6) were used
to predict the adsorption kinetics behavior.[17]

Figure 7. Linearized isotherm models (a) Langmuir model and (b) Freundlich model.
Co = (530) mg/L, t = 60 min, pH = 3.8, adsorbent mass = 0.25 g, agitation
speed = 100 rpm and T = 298 K.
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
8 A. A. TAHA ET AL. Asia-Pacic Journal of Chemical Engineering
Table 4. The calculated Langmuir and Freundlich isotherm constants.

Langmuir isotherm parameters Freundlich isotherm constants

Metals qm (mg g
1) b (L mg
1) R SD Kf (mg g
1) n R SD
Pb2+ 7.52 1.51 0.977 0.091 3.71 5.65 0.981 0.0289
Cd2+ 6.35 0.44 0.943 0.219 2.45 3.31 0.973 0.0305
Ni2+ 5.32 0.33 0.978 0.179 1.76 2.92 0.999 0.008

lnqe
qt ln qe
k 1 t (5) experimental data. The pseudo-second-order kinetic

t 1 t concentration but pseudo-rst-order kinetic rate (k1)
2
(6)
qt k 2 qe qe
where qe is the equilibrium adsorption capacity, qt is
the adsorption capacity at time t (min), k1 and k2 are
the adsorption rate constants for pseudo-rst-order
and pseudo-second-order model, respectively. The
linear plot of the pseudo-second-order model is shown
in Fig. 8 Plots of pseudo-rst-order model are not
shown here. The calculated kinetic parameters for both
models are listed in Table 5. The results indicated that
the experimental data are well described by the
pseudo-second-order kinetic model owing to the
following reasons; by comparing the calculated qe with
the experimental qe, it was found that the experimental
qe values are closer to the values of qe calculated using
the pseudo-second-order kinetics model.
Pseudo-rst-order model was unable to cover the
whole time range, while the pseudo-second-order
model can give a well description of the whole
rate (k2) decreased with the increase in the initial
showed no trend with concentration. Correlation
coefcients in case of pseudo-second-order model
(R > 0.997 for all cases) are higher than those obtained
in case of pseudo-rst-order model. In addition, the
standard deviation (SD) values are lower in case of
pseudo-second-order model than in pseudo-rst-order
model. Therefore, it is logic to conclude that pseudo-
second-order kinetic model provides the best t for
the removal of Pb+, Cd2+ and Ni2+ ions by Na-MMT.
In exploring the adsorption mechanism, and the rate
controlling step in the removal of metal ions by Na-
MMT, Weber and Morris intraparticle diffusion model
Eqn (7)[25] was applied.
qt k id t 0:5 C (7)
where kid is the intraparticle diffusion rate constant
(mg g
1 min
0.5) and C is the thickness of the boundary
layer. Linear plots of qt vs t0.5 for the different initial

Figure 8. The linear plots of the pseudo-second-order model for (a) Pb+2, (b) Cd+2 and (c) Ni+2.
Co = (520) mg/L, t = (160) min, pH = 3.8, adsorbent mass = 0.25 g, agitation speed = 100 rpm
and T = 298 K.
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering ADSORPTION OF HEAVY METALS UNDER ACIDIC CONDITIONS 9
Table 5. Pseudo-rst-order and second-order kinetics parameters.

qe, Pseudo-rst-order kinetics Pseudo-second-order kinetics

experimental qe, calculated. k1 qe, calculated. k2
Metal Co (mg g
1) (mg g
1) (min
1) R SD (mg g
1) (g mg
1min
1) R SD
2+
Pb 5 1.997 0.574 0.070 0.980 0.264 2.033 0.339 0.999 0.362
10 3.800 1.076 0.041 0.976 0.172 3.817 0.144 0.998 0.320
15 4.997 2.696 0.074 0.990 0.195 5.208 0.063 0.998 0.234
20 6.151 4.168 0.077 0.967 0.373 6.667 0.030 0.997 0.238
Cd2+ 5 1.850 0.478 0.157 0.974 0.415 1.887 0.936 0.999 0.268
10 3.170 0.575 0.106 0.978 0.334 3.205 0.594 0.999 0.068
15 3.762 1.669 0.178 0.885 1.394 3.861 0.206 0.999 0.133
20 4.467 2.114 0.117 0.962 0.616 4.608 0.131 0.999 0.102
Ni2+ 5 1.667 0.881 0.117 0.988 0.339 1.733 0.277 0.999 0.453
10 2.646 1.380 0.146 0.971 0.665 2.725 0.259 0.999 0.194
15 3.320 1.470 0.136 0.901 1.206 3.401 0.225 0.999 0.183
20 3.894 1.345 0.102 0.850 1.231 4.049 0.135 0.998 0.289

concentrations. If the plot of qt vs t0.5 is linear and passes
through the origin, then, the adsorption process was
controlled by intraparticle diffusion. However, for the
current study, the obtained curves are multi-linear and
do not pass through the origin as shown in Fig. 9, so
intraparticle diffusion step was not the only controlling
step during adsorption process.[25]
The multi-linearity curves indicated that the
adsorption mechanism was controlled by three stages:
(1) lm or surface diffusion where the metals is
transported from the bulk solution to the external
surface of Na-MMT. (2) Transport of metal ions into
the internal part Na-MMT (intraparticle diffusion).
(3) Adsorption of metal ions onto the interior pores
of the Na-MMT (adsorption), the obtained multi-
linearity curves, establishing that the removal of
Pb2+, Cd2+ and Ni2+ was controlled by three processes.
The intercept value C is a constant related to the
thickness of the boundary layer (Table 6), where larger
intercepts suggest that surface diffusion has an
important role as the rate-limiting step. This
phenomenon was pronounced, owing to the
heterogeneity of surface groups (Si-OH, Al-OH and
Fe-OH).[26]
Adsorption thermodynamics
The effect of the temperature on adsorption of Pb2+,
Cd2+ and Ni2+ was investigated in the temperature
range of 290328 K. The adsorption thermodynamic

Figure 9. Intraparticle diffusion plots for (a) Pb+2, (b) Cd+2, and (c) Ni+2. Co = (520) mg/L, t = (1
60) min, pH = 3.8, adsorbent mass = 0.25 g, agitation speed = 100 rpm and T = 298 K.
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
10 A. A. TAHA ET AL. Asia-Pacic Journal of Chemical Engineering

0.982

0.922

0.964

0.453
0.946
0.882
0.805
0.295
parameters of Gibbs energy, G0 (kJmol
1),

1.00
1.00

0.88

0.52
R3
standard entropy change, S0 (Jmol
1K
1) and
standard enthalpy change, H0 (kJmol
1) were
determined using the Vant Hoff equations [Eqns

1.776
2.494
4.483
4.829

3.127
3.747
4.433
1.603
2.585
2.973
(8) and (9)][27]:

2.19

3.83
C3

G 0
RT lnK d (8)

(mg g
1 min
0.5

S 0 H 0
)

ln K d
(9)
0.029
0.169
0.065

0.045
0.006
0.002
0.004
0.008
0.008
0.048
0.007
0.17
R RT
kid3

where Kd is the thermodynamic distribution coefcient

and was calculated using Eqn (10), R is the universal
gas constant, 8.314 (Jmol
1 K
1), and T is the
absolute temperature (K).
0.867
0.993
0.999
0.943
0.939
0.966
0.901
0.958
0.992
0.985
0.879
0.986
R2

qe
Kd (10)
Ce
Intraparticle diffusion parameters (single-ion system)

1.412

2.077
3.059
1.541
2.711
2.677
2.864
0.561
1.206
1.927
2.698
2.89
C2

The values obtained for thermodynamic parameters

shown in (Table 7) were H0 and S0 were calculated
from the slope and intercept of lnK2 against 1/T
(Fig. 10).
(mg g
1 min
0.5

The negative value of G0 in case of Pb2+ and Cd2+

)

indicates that the adsorption of Pb2+ and Cd2+ on the

0.092
0.093
0.484
0.519
0.059
0.084
0.209
0.281
0.233
0.318
0.283
0.255
kid2

Na-MMT was feasible and spontaneous. The increase

in temperature, the degree of spontaneity decreased in
case of Pb2+ but increased for Cd2+. On the other hand,
the positive G0 values in Ni2+ adsorption indicates
that Ni2+ adsorption was non-spontaneous and
favorable at higher temperatures. H values were
0.673
0.942
0.995
0.984
0.949
0.996
0.958
0.944

0.973
Table 6. Calculated parameters for intraparticle diffusion model.

negative for Pb2+ and Ni2+ indicating that the nature

1.00

1.00
1.00
R1

of adsorption was exothermic; however, positive H0

values conclude endothermic adsorption of Cd2+. S0
values were negative for Pb2+ and Ni2+ but positive
1.485
2.291
2.206
1.069
1.164

1.114
0.773
1.247
1.982
1.697

for Cd2+, this reveals that the ordered arrangement of

1.94
2.00
C1

Pb2+ and Ni2+ at the solidsolution interface during

the adsorption process, however, positive S0 values
in case of Cd2+ indicates the increased randomness
(mg g
1 min
0.5

during its adsorption.

)
0.058
0.329
0.471
0.845
0.249
0.467
0.377
0.994
0.161
0.335
0.311
0.402

Adsorption activation energy

kid1

The Arrhenius equation to calculate adsorption

activation energy[28] is given in Eqn (11).

Ea
ln K 2 lnA
(11)
Co (mg L)

RT
10
15
20

10
15
20

10
15
20
5

where K2 is the pseudo-second-order kinetic rate. Ea

values were calculated from the slope of ln K2 versus
1 T
1 plot (Fig. 11), the magnitude of the activation
energy differentiates between physical and chemical
Metal

Cd2+

adsorption. Physical adsorption are readily reversible,

Pb2+

Ni2+

equilibrium attained rapidly and thus requires small

Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering ADSORPTION OF HEAVY METALS UNDER ACIDIC CONDITIONS 11
Table 7. Calculated thermodynamic parameters.

Metal T (K) Kd (qe/Ce) G H S R SD

Pb 2+
290 12.715
6.131
32.325
0.091 0.912 0.306
298 7.597
5.024
313 3.428
3.206
328 2.785
2.793
Cd2+ 290 1.296
0.626 13.801 0.05 0.995 0.037
298 1.528
1.05
313 1.881
1.643
328 2.567
2.571
Ni2+ 290 0.965 0.087
8.818
0.031 0.969 0.058
298 0.782 0.61
313 0.717 0.866
328 0.606 1.365

(e.g. 40800 kJmol
1).[29] The activation energy

values were found to be 5.78, 8.51 and 11.45 kJmol
1
for Pb2+, Cd2+ and Ni2+, respectively, suggesting that
the studied metal ions was physically adsorbed.

Application case

In order to evaluate the practical application of

Figure 10. Vant Hoff plot for Pb2+, Cd2+ and Ni2+.
T = (290328) K, Co = 10 mg/L, t = 60 min, pH = 3.8,
adsorbent mass = 0.25 g and agitation speed = 100 rpm.
Na-MMT in metal treatment, it was available to collect
two industrial wastewater samples from textile dyeing
company and a tannery factory; unfortunately, we
could not obtain wastewater samples from the batteries
factory at Alexandria. The two collected wastewater
samples are complicated systems where the appearance
of Pb2+, Cd2+ and Ni2+ always accompanies lots of
co-existing ions, dyes and other pollutants. As these
may affect the adsorption process and inuence the
application of adsorption materials in the wastewater
treatment to some extent. The negative effects of such

Table 8. The measured parameters before and after

adsorption for the wastewater samples from textile
dyeing company and tannery.

Textile dyeing Tannery

Parameters Untreated Treated Untreated Treated
Physicochemical parameters
pH 7.900 8.600 6.300 8.100
TDS 3.830 3.790 12.520 12.350
(mg/100 mL)
Tubidity 112.000 94.000 369.000 358.000
EC (S) 948.000 776.000 3080.000 2686.000
Metals under investigation (mg L
1)
Figure 11. Arrhenius plot for adsorption of Pb2+, Cd2+ and Pb 0.847 0.214 0.887 0.343
Ni2+ onto Na-MMT. T = (290328) K, Co = 10 mg/L, Cd 0.101 0.052 0.111 0.085
t = 60 min, pH = 3.8, adsorbent mass = 0.25 g and agitation Ni 0.042 0.006 0.064 0.012
speed = 100 rpm. Competing metals (mg L
1)
Cr 0.023 0.000 5.560 3.459
Zn 0.169 0.094 0.277 0.210
Mn 0.465 0.113 0.837 0.212
energy quantities, ranging from 5 to 40 kJmol
1. Cu 0.045 0.000 0.094 0.000
Chemical adsorption is specic, involves stronger
forces and thus requires larger activation energies
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
12 A. A. TAHA ET AL.
Figure 12. The obtained metal percentage removal after
application of Na-MMT to remove metals from industrial
wastewater.
complex matrix can be explained in two ways:
competing in adsorption or acting as counter ions.
Table 8 summarizes the measured data before and after
the adsorption experiments. Obviously, the pH values
increased owing to hydrogen ions adsorption. The
electron conductivity decreased owing to the
immobilization of the metal ions and other co-existing
cations. However, there was signicant decrease in
percentage uptake of the studied metals compared with
the puried water as shown in Fig. 12. This is because
the competition[30] of the other existing pollutants for
the binding active sites. It is difcult to set the
selectivity order in this application owing to the wide
differences in initial metal concentrations. A general
trend was noted that the percentage removal was
greater in case of the textile dyeing company than in
the tannery, this can be attributed to the lower initial
Figure 13. Regeneration study for the reusability of the adsorbent in four cycles.
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacic Journal of Chemical Engineering
metal concentrations and the lower concentrations of
the competing pollutants. The 100% removal for Cu2+
ions is mainly attributed to the extreme low
concentration in the untreated wastewater (less than
0.09 mg L
1) and the remained unadsorbed Cu2+
concentrations maybe lower than the instrument
detection limit for Cu2+ (0.008 mg L
1). This
application further reafrms the efcient use of Na-
MMT in the metal treatment of industrial wastewater.
Regeneration of the adsorbent
Regeneration of the adsorbent has an important value
in the industrial practical application because the cost-
effective nature depends on the regeneration of the
adsorbents.[8] Regeneration of the clay adsorbent was
performed using acidic eluent of 3 M HNO3. Then
the adsorbent was repeatedly washed with distilled
water for several times followed by vacuum drying.
Finally, the efciency of the regeneration experiment
was tested using further cycles of adsorption
experiment. It is clear from Fig. 13 that the percentage
removal did not change signicantly, conrming the
potential value of Na-MMT application under the
acidic conditions of the industrial wastewater.
Comparative study
Table 9 presents some data on the adsorption capacities
for the removal of the studied metal ions by different
clays. The adsorption capacity of the different clay
materials is highly variable, which can be attributed
to the difference in clay compositions and the reaction
conditions.
Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacic Journal of Chemical Engineering ADSORPTION OF HEAVY METALS UNDER ACIDIC CONDITIONS 13
Table 9. Comparison of maximum adsorption capacity with those of previous removal studies conducted on clays.

Metal Adsorbent qe (mg g
1) Reference

Pb Egyptian Na-montmorillonite 3.71 Current study
[31]
Smectite 3.13
[32]
Ehandiagu clay 0.45
[33]
Jordanian kaolinite 13.32
[34]
Agbani clay 0.82
[35]
Beidellite 24.40
[36]
Polyphosphate-modied kaolinite clay 25.13
Cd Egyptian Na-montmorillonite 2.45 Current study
[37]
Bentonite 11.20
[37]
Montmorillonite 6.30
[38]
Sepiolite 5.69
[38]
Attapulgite 10.57
[39]
Turkish illitic clay 11.25
[40]
Loess modied clay 7.08
[41]
Clinoptilolite 4.88
[42]
Unmodied kaolinite 12.58
[43]
Pure smectite 3.87
[44]
Kaolin 1.46
[45]
Kaolin 3.00
Ni Egyptian Na-montmorillonite 1.76 Current study
[46]
Ca-montmorillonite 4.84
[47]
Smectite 6.68
[48]
Ca-bentonite 6.30
[49]
Montmorillonite K10 0.90
[50]
Clinoptilolite 1.69
[51]
Sepiolite 2.23
[52]
Bofe bentonite 1.91
[53]
Humic acid immobilized amine 2.80
polyacrylamide bentonite
[54]
ZrO-kaolinite 8.40
[55]
Raw kaolinite 2.80

CONCLUSION Cd2+ on the Na-MMT was feasible and spontaneous,

Different sorption batch tests were performed to
characterize the retention behavior of Pb, Cd and Ni
onto low-cost Na-MMT under acidic conditions
(pH 3.8). Na-MMT was characterized using X-ray
uorescence, which indicated the predominance of
Na2O over CaO also the SEM scans showed signicant
changes in surface morphology after adsorption; in
addition, FTIR stated that adsorption mainly localized
in the lattice region. The batch method employed the
effect of operating parameters such as pH, contact time,
adsorbent mass and metal concentrations. The pH was
adjusted to acidic value 3.8. Cadmium and nickel ions
were adsorbed very rapidly within the rst 30 min,
while equilibrium was attained within 50 min for lead.
The equilibrium adsorption data are satisfactorily tted
with Freundlich isotherm model, which conrms the
multilayer adsorption of Pb, Cd and Ni onto
Na-MMT. The percentage removal was in this order
Pb2+ > Cd2+ > Ni2+. Pseudo-second-order model was
most suitable for describing the kinetic data. The
mechanism was investigated using intraparticle
diffusion model stating more than one-step control the
adsorption process. Vant Hoff thermodynamic
parameters suggest that the adsorption of Pb2+ and
Copyright 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
but Ni2+ adsorption was non-spontaneous and
favorable at higher temperatures. Pb2+ and Ni2+
adsorption was exothermic; however, adsorption of
Cd2+ was endothermic. Arrhenius activation energy
values were found to be 5.78, 8.51 and 11.45 kJmol
1
for Pb2+, Cd2+ and Ni2+, respectively, suggesting that
the studied metal ions was physically adsorbed.
Application study showed excellent efciency of
Na-MMT with 74.7%, 48.5% and 80.9% removal for
Pb2+, Cd2+ and Ni2+, respectively, from textile dyeing
and 61.3%, 23.4% and 81.2% for Pb2+, Cd2+ and
Ni2+, respectively, from tannery wastewater.
Regeneration studies conrmed the possibility of Na-
MMT reuse without signicant decrease in the removal
percent. The results indicate that Na-MMT may be
treated as an alternative adsorbent for the treatment of
wastewater containing Pb2+, Cd2+ and Ni2+ ions.
Acknowledgements
This study was nancially supported by the National
Institute of Oceanography and Fishers (NIOF),
Alexandria Branch, Egypt.
Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
14 A. A. TAHA ET AL.
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