Journal of Environmental Chemical Engineering 4 (2016) 11661180

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Journal of Environmental Chemical Engineering

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

Multi-component adsorption of Pb(II), Cd(II), and Ni(II) onto Egyptian

Na-activated bentonite; equilibrium, kinetics, thermodynamics, and
application for seawater desalination
A.A. Tahaa,* , Mohamed A. Shreadahb , A.M. Ahmeda , Hany Fathy Heibab,**
a
Alexandria University, Faculty of Science, Chemistry Department, Egypt
b
National Institute of Oceanography and Fisheries (NIOF), Environmental Division, Alexandria Branch, Egypt

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

Article history: The adsorption potential of the Egyptian Na-activated bentonite (Na-AB) to remove Pb(II), Cd(II), and Ni
Received 18 November 2015 (II) from synthetic ternary-ion solutions and contaminated seawater, was investigated for the rst time.
Received in revised form 28 December 2015 In this study, natural Egyptian Ca-bentonite was activated to Na-AB, which then was characterized using
Accepted 19 January 2016
XRF, XRD, FT-IR, and BET. The adsorption process was strongly inuenced by pH, contact time, adsorbent
Available online 21 January 2016
dose, metal concentration, agitation speed, and temperature. The isotherm equations due to Langmuir
and Freundlich isotherm models showed good ts with the experimental data. Na-AB has a Langmuir
Keywords:
monolayer capacity in a decreasing order of; Pb(II) (5.43 mg/g) > Cd(II) (3.14 mg/g) > Ni(II) (2.77 mg/g),
Egyptian bentonite
Heavy metals
these are considered high capacity values relative to the initial concentration (10 mg/L of each metal). The
Adsorption Thermodynamics adsorption selectivity was interpreted by means of atomic radii, charge density and hydration enthalpy.
Ternary Component The multi-component adsorption kinetics was more accurately described by pseudo-second-order
Adsorption selectivity model. The intraparticle diffusion model gave multi-linear curves, so more than one-step controlled the
Seawater adsorption process. Activation energy was calculated as 17.54, 13.73, and 28.66 kJ mol
1 for Pb(II), Cd(II),
and Ni(II) respectively, suggesting physical adsorption. Thermodynamic parameters at different
temperatures (290328) K showed that (i) Pb(II) adsorption was spontaneous and exothermic, (ii) Cd
(II) adsorption was non-spontaneous and endothermic, (iii) Ni(II) adsorption was non-spontaneous and
exothermic. Application study on polluted seawater, showed removal efciency within range of 92100%
not only for Pb(II), Cd(II), and Ni(II) but also for other co-existing metals like Cu(II), Mn(II), Cr(III), and Zn
(II).
2016 Elsevier Ltd. All rights reserved.

1. Introduction
Contamination of the aquatic environments by heavy metals is
a severe public health problem and an important environmental
issue. Heavy metals are toxic, non-biodegradable and can
bioaccumulate in living cells [1], so the existence of heavy metals
in high concentrations in the aquatic system is detrimental to a
variety of living species [2]. In living organisms, heavy metals
become toxic and non-metabolized when their concentration
* Corresponding author at: University, P.O. Box: 426, Ibrahimia, Alexandria 21321,
Egypt.
** Corresponding author at: National Institute of Oceanography and Fisheries
(NIOF), Alexandria branch, Egypt.
E-mail addresses: asia_152003@yahoo.com, asia_taha@yahoo.com (A.A. Taha),
hanyheiba@gmail.com (H.F. Heiba).
exceeds the tolerance limit, so the metal bioaccumulates in the soft
tissues. Heavy metals can enter the human body through water,
food, air or through skin absorption when they come in direct
contact with humans in agriculture, pharmaceutical industries, or
residential settings [3].
Lead comes from many sources such as electroplating,
manufacturing of batteries, pigments and ammunition; it causes
brain damage, anorexia, loss of appetite, and anemia [4]. Cadmium
is a highly toxic metal, which is released through industrial wastes,
mainly from metallurgical alloying, electroplating, leadzinc
mining, pigment works, photography, and production of alkaline
batteries. Exposure to a high level of Cd causes acute and chronic
disorders of the kidneys, nervous system, liver, and cardiovascular
system [5]. Nickel is widely used in battery manufacturing,
electroplating, mineral processing, paint formulation, nonferrous
metal, and stainless steel. Trace amounts of Ni(II) are useful for
human as an activator for some enzyme systems, but higher

http://dx.doi.org/10.1016/j.jece.2016.01.025
2213-3437/ 2016 Elsevier Ltd. All rights reserved.
 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180
concentrations of Ni(II) can cause severe diseases such as lung
cancer, skin dermatitis, renal edema, chest pain, gastrointestinal
disorder, rapid respiration, cyanosis, and extreme weakness [6].
Conventional technologies for the removal of heavy metals such
as chemical precipitation, ion exchange, electrolysis, and reverse
osmosis are often neither effective nor economical. Among the
physicochemical treatment, adsorption technique is cheap, effec-
tive, and easy to adapt [7]. Clay is a potential good adsorbent
because of its large surface area, high cation exchange capacity,
chemical and mechanical stability, and layered structure. Alumi-
num oxides and clay minerals such as bentonite and kaolin are
widespread minerals of the earth's crust, which are known to be
good adsorbents of various metal ions, inorganic anions, and
organic ligands. The abundance of bentonite and its low cost make
it a strong candidate as an effective adsorbent for the removal of
heavy metals from wastewater [8].
Most previous studies heavily investigated the adsorption of Pb
(II) [9], Cd(II), [10] and Ni(II) [11] from single ion solution however,
the metal of interest in wastewater is usually found to be in a
matrix containing various metal ions. The interaction between
these charged ions can create an electrostatic eld around them,
which further will affect the behavior of heavy metal ions towards
the adsorbent [12] therefore, it is important to study the removal of
metal ions in the presence of other metal ions.
In this study, natural Ca-bentonite was collected from Alamein
area, which is located in the northern part of the western desert of
Egypt where bentonitic clays have a high proportion of montmo-
rillonite content (6090%) with very low amount of impurities [13].
The raw Ca-bentonite was activated to Na-AB, which possesses
better physicochemical properties such as higher cation exchange
capacity, better dispersibility and better thermostability [12].
However, the adsorption of heavy metals on bentonite has been
studied extensively in many countries such as Turkey [7,1417],
Brazil [18,19], Pakistan [20,21], Saudi Arabia [22], China [23,24] and
Greece [25,26]; the investigation of Egyptian bentonite ability to
remove heavy metals is very rare. In addition, there is relatively
less research attention has been paid to the removal of heavy
metals from multi-component systems, especially in thermody-
namics and activation energy of adsorption, and nearly no data
published in the application of adsorption studies on the removal
of heavy metals from seawater. The aims of this study were
therefore to investigate; (a) Adsorption capacities of Egyptian Na-
AB for competitive adsorption of Pb(II), Cd(II), and Ni(II) from a
ternary-ion solution containing equimolar concentrations of each.
(b) The inuence of adsorption parameters, such as time, pH,
agitation speed, adsorbent amount, adsorbate concentration, and
temperature. (c) Removal mechanism, kinetics, adsorption iso-
therms, and thermodynamics. (d) The potential ability of Egyptian
Na-AB to remove metal ions from contaminated areas of seawater.
2. Material and methods
2.1. Preparation of Na-AB
Sodium activated bentonite was prepared in the laboratory by
treatment of Ca-bentonite with 7.5% sodium carbonate [27]
(SigmaAldrich 99.5%). The required quantities of sodium
carbonate and calcium bentonite (Eq. (1)) were boiled in water
for 8 hours to allow the maximum exchange to occur, and then the
solution was cooled and allowed to settle. The settled clay; was
washed several times with deionized water, dried in the oven, and
nally kept in a desiccator until use in the experiments [28].
Ca2
Bentonite Na2 CO3 2Na
Bentonite CaCO3 # 1 (0.125, 0.250, 0.375 and 0.500 g) of adsorbent, pH 3.8, time
1167
2.2. Characterizations of Na-AB
2.2.1. Fourier transform infrared (FTIR) spectrum
Identication of the surface functional groups of Na-AB were
carried out with PerkinElmer Spectrum BX Infrared spectrometer
in the wavenumber range of 4000400 cm
1 using the KBr pellet
technique.
2.2.2. Chemical composition
The chemical composition of Na-AB was determined using X-
Ray Fluorescent Spectrometer (XRF)ALR 9400.
2.2.3. Mineral composition
Mineral composition (non-clay and clay minerals) was charac-
terized using XRD (Philips PW-1010), with CuKa radiation under
target voltage 40 kV and current 30 mA in a scanning rate of 2 (2u )/
min.
2.2.4. Na-AB surface area
The specic surface area of Na-AB was measured by BET method
using Nova 2000 quantachrome. The moisture and gases on the
solid surface or the penetrated in the open pores were removed by
heating at 120  C for 2 h prior to the surface area measurements.
2.3. Adsorbate, chemicals and reagents
All chemicals used were of analytical grade. Stock standard
solution of Pb(NO3)2, Cd(NO3)2 and Ni(NO3)2 (1000 mg/L each in
0.5 Mol/L HNO3) have been purchased from MERK (Germany). The
pH of the system was adjusted using extra pure 0.01 N NaOH (Loba
Chemie) and Analar-R 0.01 N HNO3 [BDH] respectively.
All plastic sample bottles and glassware (pipettes, measuring
asks, conical asks, graduated cylinders and beakers) were
cleaned, rinsed with deionized water and allowed to dry.
2.4. Adsorption experimental procedure
Stock solutions of ternary-ion solution [Pb(II) + Cd(II) + Ni(II)]
were prepared by serial dilution of the standard solutions using
deionized double-distilled water where the appropriate amounts
of each metal standard were added in a concentration ratio 1:1:1 of
each. A blank solution of deionized double-distilled water was
analyzed to ensure that it did not contain any of the investigated
metals.
The following conditions were maintained for the different sets
of batch experiments:
(I) Effect of pH was studied in the pH range from 2.0 to 7.0, Na-
bentonite dose 0.25 g, solution volume 100 mL, concentration
10 ppm of each metal, T = 298 K and agitation speed is
100 rpm. For maintaining the pH of the medium, either
0.01 N HNO3 or 0.01 N NaOH was added in order to set a
specic pH value.
(II) Effect of contact time was conducted through the time
intervals (1, 3, 5, 10, 15, 20, 30, 40, 50 and 60 min), 0.25 g of Na-
AB, 100 mL solution, 10 mg/L concentration for each metal,
298 K, pH 3.8, and 100 rpm agitation speed.
(III) Effect of agitation speed was investigated under 4 different
speeds (50, 100, 150 and 200 rpm), pH 3.8, time 60 min,
concentration 10 mg/L, for each metal, solution volume
100 mL, adsorbent dose 0.25 g, and temperature 298 K.
(IV) Effect of Na-AB dose was examined using different weights
60 min, concentration 10 mg/L for each metal, solution
volume 100 mL, 100 rpm, and temperature 298 K.
1168 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180
(V) The effect of initial concentration was conducted using 5, 10,
15 and 20 mg/L of each metal (thus total concentrations were
15, 30, 45 and 60 mg/L), pH 3.8, time 60 min, adsorbent dose
0.25 g, 100 rpm, and temperature 298 K.
(VI) Effect of temperature was carried out under different
temperatures of 290, 298, 313 and 328 K, pH 3.8, time
60 min, concentration 10 mg/L for each metal, adsorbent dose
0.25 g, solution volume 100 mL, and 100 rpm.
In all experiments; the suspensions were shaken in Thermo
incubated forma orbital shaker (Model 436 [HEPA lter]), then
solutions were ltered with Munktell lter paper and the
remaining unadsorbed metal ions in the ltrate liquid were
analyzed.
2.5. Analytical methods
Trace metal concentrations were measured using ame atomic
absorption spectrophotometer (Shimadzu AAS-6800) equipped
with an ASC-6100 auto-sampler and operating with air/C2H2 ame.
Pb(II), Cd(II) and Ni(II) were measured at wavelengths 283.3, 228.8,
232 nm respectively.
In the application study, due to the very low concentrations of
heavy metals in seawater, the metal concentrations were
measured using the graphite furnace atomizer (Shimadzu AA-
GFA-EX7) under the optimum conditions of measurement.
2.6. Data processing
The amount of metal ions adsorbed was determined by the
difference between the initial and nal concentrations. The
sorption efciency (%) was determined by Eq. (2);
Co
Ce
Adsorption efficiency  100
Co
The adsorption capacity [the amount of metal(II) ions adsorbed
per gram adsorbent (mg/g)] was calculated using Eq. (3);
Co
Ct V
Adsorption capacity qt
m
Fig. 1. Infrared (IR) spectra of Na-AB (abefore and bafter adsorption) at room temperature.
where [Co] is the metal concentration at the initial time, [Ct] is the
metal concentration at time (t = t) and [Ce] is metal concentration
at the equilibrium time, [V] is the volume of the solution in litre (L)
and [m] is the mass of adsorbent in grams (g).
2.7. Quality control
The calibration curve for metal analysis in all measurement
series was constructed with a blank and four or more standards
(Merck Germany). Accuracy and precision of the metal measure-
ment were conrmed using external reference material for trace
metals in water.
The relation between data output was performed by calculating
the standard deviation (SD) and R-values for the measured
variables with origin-8 software
3. Results and discussion
3.1. Characterizations of Na-AB
3.1.1. Fourier transform infrared (FT-IR) spectrum
The infrared spectrum of Na-AB before adsorption is shown in
Fig. 1a. The spectral regions of interest are: (i) The broad absorption
band in the region 34003854 cm
1 can be attributed to the
stretching of lattice OH (SiOH, AlOH) and OH of the physically
adsorbed water [5] and the overtone of the bending vibration of
water observed at 1645 cm
1. (ii) The deep band of about
(1060) cm
1 in the stretching mode region is due to SiOSi
stretching frequencies. (iii) Bands centered around (540
791) cm
1 in the stretching mode are due to SiOAl and SiO
Mg stretching frequency, and SiO bending frequencies [29,30].
After adsorption of an equimolar mixture of Pb(II), Cd(II), and Ni
(II), some bands disappeared (Fig. 1b); such as that bands of SiO
2 Al, SiOMg stretching frequency, and SiO bending frequencies, in
addition, the deep band at 1060 cm
1 of SiOSi stretching
frequencies. This is due to the binding of metal ions into clay
metal oxides which indicates that adsorption of metal ions mainly
located on the clay lattice region, so basically affected the SiO
3 vibrations. FTIR also, indicated the shifting of 1645 cm
1 band to
1660 cm
1. In addition, there was a strong broadening band of
water, which maybe due to moisture after adsorption experiment.
 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180 1169

Table 1
XRF chemical analysis of Na-AB.

Main Constituents SiO2 Al2O3 Fe2O3 Na2O CaO MgO K2O TiO2 P2O5 MnO Cr2O3 L.O.I
Wt (%) 51.18 15.75 8.70 2.91 1.58 2.16 1.17 1.12 0.17 0.07 0.035 15.2

Fig. 2. XRD pattern; (A) bulk Na-AB sample. (B) oriented Na-AB < 2 mm clay fraction. (C) Na-AB < 2 mm clay fraction after glycolation using ethylene glycol. (D) Na-AB < 2 mm
clay fraction heated at 550  C for 2 h. (M: montmorillonite; K: kaolinite; Q: quartz; F: feldspar; Ca: calcite; I: illite).

3.1.2. Chemical composition 3.1.4. Particle size distribution of Na-AB

XRF analysis (Table 1) showed that Na-AB is composed mainly
of silicon dioxide, Aluminum oxide, iron oxide, and enriched with
sodium oxide (due to activation), in addition to calcium,
magnesium and potassium oxides.
3.1.3. Mineral composition
The particle size distribution indicated that the main portion of
the Na-AB is less than 2 mm (82.09) as shown in Table 2.
3.1.5. Na-AB surface area
The determined surface area value was 138.4 m2 g
1, which
indicates a large surface area, and hence more available active sites.

3.1.3.1. Non-clay minerals. The XRD analysis of bulk Na-AB sample
(Fig. 2(A)) indicated that bentonite consists mainly of, quartz
(SiO2), calcite (CaCO3) and Feldspar (KAlSi2O8, NaAlSi2O8,
CaAl2Si2O8) as non-clay minerals (clay mineral impurities).
3.1.3.2. Clay minerals. Clay minerals of Na-AB are represented
mainly by; Na-montmorillonite (Na,Ca)0.33(Al,Mg)2(Si4O10)
(OH)2nH2O as main constituent and kaolinite followed by
traces of illite (K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]
(Fig. 2(B)).
On XRD patterns of ethylene glycol solvated specimen,
diffractograms revealed three main clay minerals, montmorillon-
ite, kaolinite and illite (Fig. 2(C)). However, in the heated Na-AB
fraction, the characteristic peaks of kaolinite disappeared
(Fig. 2(D)) due to transformation of kaolinite to metakaolinite
which conrms montmorillonite as the main clay mineral.
Table 2
Particle size distribution of Na-AB.
Clay <2 mm Silt 632 mm
82.09% 13.88%
3.2. Parameters affecting adsorption onto Na-AB
3.2.1. Effect of pH
The pH of the aqueous solution is an important variable, which
controls the uptake of the metal at the adsorbent-water interfaces.
The pH effect was investigated in the range of 27 where the
material exhibits chemical stability, and to prevent metal
precipitation in hydroxide form so, maintain their cationic species.
The adsorption % removal of Pb(II), Cd(II), and Ni(II) onto Na-AB
(Fig. 3) increased with increasing pH value from 2 to 7. The reduced
adsorption noticed at lower pH could be attributed to two reasons:
(i) the surface functional groups of Na-AB contain a large number
of binding sites, which become positively charged at lower pH due
to the protonation reaction Eq. (4).

Si
OH H ,
Si
OH
2 4
This creates an electrostatic repulsion between the metal ion
and the edge groups with positive charge (SiOH(II)) and so,
restricts metal ions from access to the surface binding sites, which
nally leads to a lower adsorption efciency [12]. (ii) The positively
Sand >63 mm
charged metal ions face a good competition with the higher
4.03%
concentration of H+ ions present in the reaction mixture. However,
1170 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180

100

90

80
% Removal

70

60 2+
Pb
2+
Cd
2+
50 Ni

40
2 3 4 5 6 7
pH
Fig. 3. Effect of pH on the adsorption % removal of Pb(II), Cd(II) and Ni(II) by Egyptian Na-AB.

at high pH values, the Na-AB surface becomes negatively charged and this study is preferred to be according to the reliable status of
due to the deprotonation process Eq. (5). waste water. (II) Ensuring slow reaction rate to allow investigation
of reaction kinetics, thermodynamics, and isotherms. (III) Avoiding

SiOH OH
,
Si
O
H2 O 5
metals precipitation as metal hydroxides. (IV) Fixed pH value
allows a fair comparison between afnities of the adsorbent
towards each metal.
2
Si
O
MII ,
Si
O2
M 6

The electrostatic repulsion decreases with the increase in OH
due to the reduction of positive charge density on the sorption
edges, which enhances the adsorption of the positively charged Pb
(II), Cd(II) and Ni(II) ions through electrostatic attraction [12] as in
Eq. (6).
The results indicated that the metal ions adsorbed by Na-AB
increased in the order of Pb(II) (96.81%) > Cd(II) (90.63%) > Ni(II)
(86.09%).
It must be highlighted that the choice of pH 3.8 to perform
further experiments was due to several reasons; (I) The worst
conditions of industrial waste water usually lies around this value
3.2.2. Effect of contact time
The effect of contact time on the adsorption of Pb(II), Cd(II) and
Ni(II) from a ternary-ion solution was investigated at different time
intervals in the range of 1 60 min. It can be noticed from Fig. 4 that
the initial 40 min was sufcient for Pb(II) Cd(II) and Ni(II) to reach
equilibrium. The adsorption was fast at the initial stages and
gradually became slower until the equilibrium attained; this could
be attributed to the availability of the Na-AB surface area, the large
number of vacant binding sites, and the well oriented functional
groups during the initial stages so the interaction between the Na-
AB and the free metal ions in solution was feasible. On the other

90

80

70
% Removal

60

50
2+
Pb
40 2+
Cd
2+
Ni
30

0 10 20 30 40 50 60
Contact time (min)

Fig. 4. Effect of contact time on the adsorption % removal of Pb(II), Cd(II) and Ni(II) from a ternary-ion solution.
 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180 1171

90
2+
Pb
85 2+
Cd
2+
80 Ni
75

70
% Removal
65

60

55

50

45

40
50 75 100 125 150 175 200
rpm

Fig. 5. Effect of agitation speed on the adsorption % removal of Pb(II), Cd(II) and Ni(II) from a ternary-ion solution.

hand, with the increase in contact time, the adsorbent surface
gradually became interacted (covered) with the metal ions [31,32]
thus; the occupation of the remaining vacant sites was difcult due
to the repulsive forces between the metal ions in the solid and
liquid phases. This relatively short equilibrium contact time
(40 min) may also provide an economic advantage for the large-
scale application of the adsorption method to real wastewater
treatment systems [33]. Shorter treatment time helps in reduction
of capital and operational costs, because longer shaking time
consumes more energy, and consequently the cost increases, so it
is important to determine the optimal contact time that maximizes
the removal efciency without the unacceptably increasing cost
[34]. Thus, such results are promising by virtue of the economic
viability.
3.2.3. Effect of agitation speed (rpm)
Agitation is an important parameter in adsorption phenomena,
inuencing the distribution of the solute in the bulk solution and
the formation of the external boundary lm [35]. The effect of the
agitation on the adsorption of Pb(II), Cd(II) and Ni(II) on Na-AB was
monitored at low, medium and high- agitation speeds (50, 100, 150,
200 rpm) for 60 min. The results are graphically represented in
Fig. 5, indicating that the removal percentage increased as
agitation speed increased. High agitation speed plays a critical
role, where it causes a decrease in the boundary layer and so
decreases the resistance of transportation. Finally, this enhances
the transfer rate of metal ions to the surface of the adsorbent,
which is called diffusion-controlled mechanism [26].
3.2.4. Effect of Na-AB dose
The effect of adsorbent dose was studied by variation of Na-AB
dose from 0.125 to 0.5 g. From Fig. 6(A) it is clear that the % removal
of Pb(II), Cd(II) and Ni(II) increased with the increase in Na-AB
dosage. This is because, the metal ions were competing for limited
adsorption sites at lower dose, but as the dose increased, there
were a larger surface area and more available vacant sites, which in
turn increases the adsorption percentage [23]. However, the
adsorption capacity (qe) Fig. 6(B) declined as the adsorbent dose
increased. This is attributed to two reasons: (I) the large adsorbent
amount effectively reduces the saturation of the adsorption sites
and correspondingly, the number of covered sites per unit mass
comes down, resulting in a reduced capacity, (II) higher adsorbent
amount creates particle aggregates, which cause a decrease in the
total surface area, and an increase in the divisional path length,
both of which contribute to a decrease in the amount adsorbed per
unit mass [18].

100

90
A 4.0

B
3.5
80
3.0
70
% Removal

qe mg/g

60 2.5

50
2.0
40
2+
Pb 1.5 Pb
2+
2+
30 Cd 2+
2+
Cd
Ni Ni
2+

20 1.0
0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4 0.5
Na-AB dose (g) Na-AB dose (g)

Fig. 6. Effect of Na-AB dose on the % removal (A) and adsorption capacity (B).
1172 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180

100

90
A 5.5

5.0 B
4.5
80
4.0
70
3.5
% Removal

qe mg/g
60 3.0

2.5
50
2.0
40
2+ 1.5
Pb Pb
2+
2+
30 Cd 2+
1.0 Cd
2+
Ni Ni
2+

20 0.5
0 5 10 15 20 0 5 10 15 20
Ci (mg/L) Ci (mg/L)

Fig. 7. Effect of initial concentration on the % removal (A) and adsorption capacity (B).

90
2+
Pb
2+
Cd
80 2+
Ni

70
% Removal

60

50

40

290 300 310 320 330

T (K)
Fig. 8. Temperature effect on the % removal of Pb(II), Cd(II) and Ni(II) by Egyptian Na-AB.

6 A B
0 .2 8 S e p a ra tio n F a c to r R L
Langmuir plot for mixed ion system
2+
Pb (y) = 0.184x + 0.171, R = 0.985, SD=0.1233 2+ 2+ 2+
5 2+ Pb Cd Ni
Cd (y) = 0.318x + 0.409, R = 0.998, SD=0.1027 0 .2 4
2+
Ni (y)= 0.360x + 0.687, R = 0.999, SD=0.0751

4 0 .2 0

0 .1 6
Ce/qe

3
L
R

0 .1 2
2
2+
Pb 0 .0 8
2+
Cd
1 Ni
2+
0 .0 4

0 0 .0 0
0 2 4 6 8 10 12 14 5 10 15 20
Ce(mg/L) C o (m g /L )
Fig. 9. (A) Langmuir plot for adsorption of Pb(II), Cd(II) and Ni(II) onto Na-AB. (B) Effect of concentration on Langmuir separation factor.
 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180
Table 3
Langmuir and Freundlich isotherm constants.
Metal Langmuir isotherm constants Freundlich isotherm constants
qm (mg/g) b (L/ R SD Kf (mg/ n R SD
mg) g)
Pb(II) 5.435 1.076 0.985 0.123 2.831 3.831 0.984 0.04
Cd(II) 3.145 0.778 0.999 0.103 1.524 3.774 0.965 0.04
Ni(II) 2.778 0.525 0.999 0.075 1.153 3.311 0.976 0.03
3.2.5. Effect of initial concentration
The effect of initial concentration on the adsorption was studied
in the concentration range from 5 to 20 ppm (so the total
concentration varied from 15 to 60 mg/L). Fig. 7(A) showed that
with increasing metal ion concentration, the% removal of Pb(II), Cd
(II) and Ni(II) decreased and this is attributed to competition
between metal ions. However, the adsorption capacity (qe)
increased gradually with the increase in concentration
(Fig. 7(B)), where at lower metal concentration, the ratio of the
number of metal ions to the number of available adsorption sites is
small and consequently, adsorption is independent on initial
concentration, but as metal concentration increases, the situation
changes and the competition for adsorption sites becomes erce
due to increasing driving force of the metal ions toward the active
sites on the adsorbents. As a result, the extent of adsorption comes
down considerably, but the amount adsorbed per unit mass of the
adsorbent rises [36,37]. This is in agreement with the previously
reported results for adsorption of Ni(II) by bagasse y ash [38]. The
adsorption capacities of Na-AB towards the studied metals were in
the order of Pb(II) > Cd(II) > Ni(II).
3.2.6. Effect of temperature
The inuence of temperature on the adsorption onto Na-AB was
carried out at 4 different temperatures ranging from 290 to 328 K.
Fig. 8 shows that the removal percentage of Pb(II) and Ni(II)
decreased with the increase in temperature, indicating that the
adsorption process of Pb(II) and Ni(II) was exothermic in nature. In
contrast, it increased with the increase in temperature in case of Cd
(II) indicating endothermic adsorption of Cd(II).
3.3. Adsorption isotherms models
The adsorption isotherm was investigated using Langmuir,
Freundlich isotherm.
3.3.1. Langmuir isotherm
Langmuir isotherm predicts the formation of adsorbed solute
monolayer and is based on the assumptions that metal ions are
adsorbed on a xed number of well-dened sites, each site can
hold one ion, all sites are energetically equivalent and there is no
interaction between the ions [39,40]. This isotherm dictates a
limiting adsorption capacity, once the monolayer coverage is
achieved, the sorption is no longer inuenced signicantly by the
solute transport. Such behavior is characteristic to the Langmuir
type sorption, and a strong afnity of the solute on the solid phase
at low concentration can be shown [34]. Maximum adsorption
occurs when the surface is covered by a monolayer of the
adsorbate. The linear form of Langmuir equation Eq. (7) has been
successfully applied in this adsorption study [41].
Ce 1 Ce
7
qe qm b qm
where, Ce is the equilibrium concentration of metal ions in mg/L, qe
is the equilibrium adsorption adsorption capacity in mg, qm is the
maximum amount of metal adsorbed in mg (metal)/g (adsorbent);
which represents monolayer coverage of sorbent with sorbate, and
1173
b is the constant that refers to the bonding energy of adsorption in
L/mg.
The linear plot of Langmuir isotherm is shown in Fig. 9(A). The
corresponding Langmuir parameters and correlation coefcients
(Table 3), pointed out that the Langmuir model was applicable for
the three studied metals. Using traces of initial concentration
(10 mg/L for each metal), the sequence of adsorption selectivity
appears to be Pb(II) (5.43 mg/g) > Cd(II) (3.14 mg/g) > Ni(II)
(2.77 mg/g), this trend may be explained by assuming differences
in binding constants and the order of stability for metal complexes
[42,43]. Yasemin and Zek [44] reported a similar observation.
To predict the adsorption efciency, the essential character-
istics of Langmuir isotherm model was explained in terms of a
dimensionless constant separation factor or the equilibrium
parameter RL[45]. which is dened by Eq. (8):
1
RL 8
1 bC o
where, b is Langmuir constant (L/mg) and Co is the initial
concentration (mg/L). The separation factor RL value conrms
the adsorption to be unfavorable (RL > 1), linear (RL = 1), favorable
(0 < RL < 1) or irreversible (RL = 0). The RL values for Pb(II), Cd(II)
and Ni(II) for each initial concentration, was greater than zero and
less than unity which indicates a favorable adsorption. In addition,
it can be seen from Fig. 9(B) that RL values decreased as the initial
concentration increased from 5 to 20 mg/L.
3.3.2. Freundlich isotherm
Freundlich isotherm derived from the assumption that the
adsorption sites are distributed exponentially with respect to the
heat of adsorption. It also assumes that the stronger adsorption
sites are occupied rst and the binding strength decreases with the
increase in site occupation. It can be applied for non-ideal
adsorption on heterogeneous surfaces and multilayer sorption.
The linear form of Freundlich model can be represented by Eqs. (9)
and (10) [46,47];
qe K F C e 1=nF 9
1
logqe log K F log C e 10
n
where, Ce is the concentration at equilibrium and (qe) is the
corresponding adsorption capacity. The Freundlich coefcients, Kf
and n, are respectively, related to adsorption capacity and
adsorption intensity of the solid adsorbent. The logarithmic plot
of qe against Ce (Fig. 10) gives the constants Kf, and n for the
adsorption experiments (Table 3). Kf values pointed that the order
of removal follows Pb(II) > Cd(II) > Ni(II) under the same experi-
mental conditions. The values of adsorption intensities (n) were
higher than 1.0 (1/n < 1), this indicates an easy separation of metal
ions from aqueous solution and so favorable adsorption [48].
3.4. Adsorption kinetics models
The kinetics of Pb(II), Cd(II), and Ni(II) adsorption was analyzed
using pseudo-rst-order model (Eq. (11)) and pseudo-second-
order model [49] (Eq. (12)).
lnqe
qt ln qe
k1 t 11
t 1 t
12
qt k2 q2e qe
1174 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180

Freundlich Isotherm for mixed ion system

2+
Pb y = 0.261x + 0.453,
0.7
R = 0.984, SD=0.0404
2+
Cd y = 0.265x + 0.183,
R = 0.965, SD=0.03977 0.6
2+
Ni y = 0.297x + 0.067,
R = 0.976, SD=0.03203

0.5

0.4

Log qe
0.3

0.2
2+
Pb
2+
Cd
2+
0.1 Ni

-0.8 -0.4 0.0 0.4 0.8 1.2

Log Ce

Fig. 10. Freundlich isothermal plot for adsorption of Pb(II), Cd(II), and Ni(II) from ternary-ion solution onto Na-AB.

35 50
A 45
B C
40 45 Ni(II) pseudo-second-order kinetics
Pb(II) pseudo-second-order kinetics Cd(II) pseudo-second-order kinetics
30 Adsorption from ternary ion solution
Adsorption from ternary ion solution Adsorption from ternary ion solution
40
5 ppm 35 5 ppm 5 ppm
25 10 ppm 10 ppm 35 10 ppm
15 ppm 30 15 ppm 15 ppm
20 ppm 20 ppm 30 20 ppm
20 25
25
t/qt

t/qt

20
t/qt

15
20
15
10 15
10
10
5
5 5

0 0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60
Contact time (min) Contact time (min) Contact time (min)

Fig. 11. Pseudo-second-order kinetics plots for adsorption onto Na-AB for Pb(II) (A), Cd(II) (B) and Ni(II) (C).

Table 4
Values of kinetic parameters for pseudo-rst-order and pseudo-second-order models.

Metal Co qe (exp.) Pseudo-rst-order kinetics Pseudo-second-order kinetics

(mg/l) (mg/g) K1 qe(cal.) R SD k2 (g/mg min) qe(cal.) R SD

(min
1) (mg/g) (mg/g)
Pb(II) 5 1.920 0.199 0.904 0.982 0.334 0.660 1.949 0.999 0.207
10 3.116 0.178 1.882 0.988 0.180 0.292 3.215 0.999 0.354
15 4.331 0.207 3.421 0.990 0.249 0.136 4.505 0.999 0.137
20 4.977 0.184 3.957 0.975 0.348 0.092 5.236 0.999 0.147

Cd(II) 5 1.520 0.335 0.493 0.977 0.349 3.633 1.534 0.999 0.188
10 2.444 0.060 0.884 0.937 0.362 0.230 2.506 0.999 0.335
15 2.624 0.082 1.135 0.978 0.340 0.183 2.717 0.999 0.202
20 2.893 0.070 1.201 0.954 0.407 0.148 3.021 0.999 0.236

Ni(II) 5 1.304 0.229 0.392 0.996 0.094 3.431 1.321 0.999 0.359
10 2.050 0.200 1.125 0.999 0.023 0.853 2.092 0.999 0.331
15 2.263 0.200 1.413 0.962 0.374 0.361 2.336 0.999 0.329
20 2.453 0.352 3.302 0.969 0.588 0.234 2.577 0.999 0.338
 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180 1175

5.5 A B C
Pb(II) Intraparticle diffusion plot Ni(II) Intraparticle diffusion plot
5.0 C d(II ) I ntrapa rticle diff usion plot
3.0 2.5
4.5
4.0 2.5
2.0
3.5
qt (mg/g)

qt (m g /g )

qt (mg/g)
2.0
3.0
1.5
2.5
1.5
2.0
5 pp m 1.0 5 ppm
1.5 5 ppm
1.0 10 pp m 10 ppm
10 ppm
15 ppm 15 pp m 15 ppm
1.0 20 pp m 20 ppm
20 ppm
0.5 0.5 0.5
0 1 2 3 4
5 6 7 8 0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8
0.5 0.5
0.5 0.5
t (min ) t 0.5 ( m in 0.5 ) t (min )

Fig. 12. Intraparticle diffusion plot for Pb(II) (A), Cd(II) (B) and Ni(II) (C).

where qe and qt are the values of amount adsorbed per unit mass at was explored by using Weber and Morries Eq. (13) [53,54].
equilibrium and at any time t. k1 and k2 are the equilibrium rate
constants for pseudo-rst and pseudo-second-order adsorption, qt kid t0:5 C 13
respectively. where qt is adsorption capacity at any time t, kid is the
It was found that pseudo-rst-order kinetic model did not well intraparticle diffusion rate constant (mg/g min1/2) and C is the lm
t. Plots of ln(qe
qt) vs. t displayed less-linearity (plots not shown thickness. The greater the value of C, the greater the effect of the
here), the model was found to be suitable only for the initial (15 boundary layer on adsorption process. If the rate limiting step is
20), (1050), (515) min for Pb(II), Cd(II) and Ni(II) respectively and the intra-particle diffusion, the plot of qt against the square root of
did not t for the whole range of contact time. On the other hand, time should be a straight line and pass through the origin. The
the plot of t/qt vs. t for pseudo-second-order model (Fig. 11) is deviation of the plot from the linearity indicates that the rate-
applicable over the whole range of contact time with excellent limiting step should be boundary layer diffusion [55].
linearity. Intraparticle diffusion plots (Fig. 12) show three-linear portions,
The kinetic parameters for pseudo-rst-order and pseudo- which indicates that two or more steps inuenced the adsorption
second-order were calculated and tabulated in Table 4. According process. According to Table 5, it could be observed that the order of
to the results, the adsorption capacities qe (calculated and adsorption rate of the three stages was kid1 > kid2 > kid3. At the
experimental) were found to decrease in the order Pb(II) > Cd beginning, Pb(II), Cd(II) and Ni(II) were adsorbed by the exterior
(II) > Ni(II). The real test for the validity of the kinetic model arises surface of Na-AB, and the rst stage was the instantaneous
from the comparison between the experimentally determined qe diffusion period (kid1). When adsorption on the exterior surface
and the calculated qe [50,51]. It can be noticed that in the pseudo- reached saturation, the metal ions diffused into the pores of Na-AB,
second-order kinetic model, the calculated qe is very close to the and so the diffusion resistance gradually increased, resulting in a
experimental to qe values. In addition, the correlation coefcients decreased diffusion rates (kid2). The nal stage was the equilibrium
R-values for the pseudo-second-order kinetic model were higher period, during which the intraparticle diffusion rate (kid3) slowed
than 0.99 (higher than those obtained in pseudo-rst-order down and reached equilibrium [5].
kinetics). Moreover, in pseudo-second-order a trend was observed The value of the intercept C in the second section provides
with the rate constants, as the initial concentration increases, k2 information related to the thickness of the boundary layer. Larger
generally decreased due to the occupation of active sites, but in intercepts suggest that boundary layer diffusion has a larger role as
pseudo-rst-order no trend was observed for the rate constant k1, a rate-limiting step [56,57].
and this is not logic where for pseudo-rst-order model to be The non-linearity of the plots indicates that the intraparticle
applicable k1 generally decreases with increasing metal concen- diffusion cannot be accepted as the only rate controlling step for
tration [52]. Furthermore, the values of standard deviation (SD) the adsorption of metal ions onto Na-AB surface. Thus, the overall
of pseudo-second-order model were lesser than pseudo-rst- rate of the adsorption process appears to be controlled by more
order model. Therefore, it was reasonable to conclude that the than one-step.
pseudo-second-order model is the obeyed model.
Although the pseudo-second-order model represents an 3.5. Adsorption activation energy
approximation of the overall reaction kinetics, but it does not
provide information about the rate-limiting step. Thus, the rate- The values of the pseudo-second-order rate constant (k2) at
limiting step may be either the boundary layer (lm) or the intra- different temperatures (290, 298, 313 and 328) K were calculated
particle (pore) diffusion of solute from the bulk solution to the using Eq. (12) for adsorption of Pb(II), Cd(II) and Ni(II) onto Na-AB
adsorbent surface. The probability of the intraparticle diffusion and listed in Table 6 (gures not shown here). Then, k2 values were
further applied to Arrhenius equation (Eq. (14)) and the activation
1176 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180

0.8 Arrhenius plot

2+
Pb
2+
0.4 Cd
2+
Ni
0.0

-0.4
ln k2

-0.8

-1.2

-1.6

0.0030 0.0031 0.0032 0.0033 0.0034 0.0035

1/T

Fig. 13. Arrhenius plot for adsorption of Pb(II), Cd(II) and Ni(II) from ternary-ion solution onto Na-AB.

Table 5
Intraparticle diffusion coefcients and intercept values for adsorption of Pb(II), Cd(II) and Ni(II) from ternary ion solution onto Na-AB.

Intraparticle diffusion parameters

Metal Co kid1 C1 R1 kid2 C2 R2 kid3 C3 R3

(mg L
1) (mg g
1 min
0.5) (mg g
1 min
0.5) (mg g
1 min
0.5)
Pb(II) 5 0.35 0.762 1 0.043 1.729 0.613 0.004 1.887 0.396
10 0.744 0.71 0.92 0.508 1.136 0.955
0.034 3.368 0.78
15 0.867 1.126 1 0.476 2.222 0.947
0.015 4.448 0.857
20 0.967 1.046 0.989 0.131 4.3 0.972
0.012 5.07 0.998

Cd(II) 5 0.32 0.764 0.941 0.031 1.405 0.973
0.014 1.62 0.932
10 0.464 0.765 0.977 0.29 1.132 1 0.087 1.796 0.93
15 0.53 0.679 0.997 0.259 1.325 0.997 0.001 2.604 0.036
20 0.939 0.051 0.949 0.288 1.447 0.94
0.007 2.937 0.136

Ni(II) 5 0.161 0.827 0.999 0.084 0.993 0.995
0.01 1.383 0.775
10 0.403 0.733 0.999 0.04 1.958 0.656
0.005 2.093 0.594
15 0.532 0.499 0.953 0.164 1.602 0.882
0.005 2.303 0.594
20 0.628 0.277 0.982 0.163 1.764 0.942
0.022 2.632 0.805

energy (Ea) was estimated. the entropy change (DS ), were calculated using the following
equations:
Ea
ln k2 ln A
14
RT DG
RT ln K d 15
where A is the Arrhenius factor and R is the universal gas constant
(8.314J/mole K), a straight line is obtained by plotting ln k2 against
the reciprocal of the absolute temperature with a slope
Ea/R as
shown in Fig. 13. The activation energies Ea were calculated and
listed in Table 7. Table 6
The apparent activation energies for adsorption were 17.54, Pseudo-second-order kinetic parameters (at different temperatures) for adsorption
13.73, and 28.66 kJ mol
1 for Pb(II), Cd(II) and Ni(II) respectively. of Pb(II), Cd(II) and Ni(II) from ternary ion solution onto Na-AB.

These relatively low activation energy values indicate that the Metal T (K) qe(exp.) (mg/g) Pseudo-second-order kinetic parameters
adsorption process was mainly physisorption process, which
qe(cal) (mg/g) k2 (g/mg min) R SD
normally had activation energy of 540 kJ mol
1, while chemi-
Pb(II) 290 3.244 3.294 0.390 1.000 0.060
sorption had higher activation energy (40800 kJ mol
1) [58].
298 3.116 3.165 0.652 0.998 0.471
Therefore, the afnity of Na-AB for metal ions may be ascribed to 313 2.958 2.986 0.670 1.000 0.161
Van der Waals forces and electrostatic attractions between the clay 328 2.862 2.877 1.040 1.000 0.243
surface and the metal ions. The low activation energy values
(<42 kJ/mol) also indicate that the process is diffusion-controlled Cd(II) 290 2.286 2.394 0.176 0.999 0.213
298 2.444 2.511 0.212 0.999 0.353
more than chemically controlled [59]. 313 2.620 2.680 0.297 0.999 0.178
328 2.794 2.831 0.334 0.999 0.121
3.6. Thermodynamics of adsorption
Ni(II) 290 2.313 2.348 0.433 1.000 0.102
298 2.050 2.078 1.288 1.000 0.380
The thermodynamic parameters for the adsorption process;
313 1.923 1.936 1.509 1.000 0.140
Gibbs free energy change (DG ), the enthalpy change (DH ), and 328 1.788 1.813 2.143 1.000 0.411
 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180 1177

Table 7
Activation energy for adsorption Ni(II) Pb(II), Cd(II) and Ni(II) from ternary ion
solution onto Na-AB.
Parameter Metal
Pb(II) Cd(II)
Ea (kJ/mol) 17.536 13.731
R 0.928 0.982
SD 0.182 0.068
DS  DH 
ln K d
16
R RT
where T is the absolute temperature (K), R the universal gas
constant (8.314 J/mol K) and (Kd, L/g) is thermodynamic distribu-
tion coefcient for the adsorption [59] calculated from Eq. (17);
qe
Kd
Ce
Kd was calculated at the equilibrium time of different temperatures
(290, 298, 313 and 326 K) then, the values of DG was calculated
from Eq. (15) and the values of DH and DS were calculated using
Eq. (16) from the slope and intercept of the plot of ln Kd against 1/T
(Fig. 14) and tabulated in Table 8.
It is obvious that at higher temperatures the adsorption on Na-
AB was unfavorable for Pb(II) and Ni(II), but favorable for Cd(II).
The DG values for Pb(II) are negative at all temperatures and
become less negative with increasing temperature, indicating the
adsorption process is spontaneous and that the degree of
spontaneity decreases with the increase in temperature, mainly
owing to physisorption rather than chemisorption [34]. While in
Cd(II) and Ni(II), DG values are positive which suggest that the
reaction is non-spontaneous and requires small amount of energy.
In case of Cd(II) the positivity decreases with increasing tempera-
ture which reects that degree of non-spontaneity decreases with
increasing temperature. However, in case of Ni(II) the positivity of
DG increases as temperature increases, this suggest that the
degree of the non-spontaneity increases in parallel with increasing
temperature.
The negative values of standard enthalpy change (DH ) both Pb
(II) and Ni(II) states the exothermic nature of the adsorption
process. The low enthalpy values of DH < 20 kJ/mol conrms the
physisorption process [55,60]. Conversely, the positive DH value
for Cd(II) reected the endothermic adsorption, one possible
explanation to this positive enthalpy that Cd(II) ions dissolved well
in water and have to lose a part of its hydration sheaths before
being adsorbed, where the endothermicity of Cd(II) desolvation
consumes energy that exceeds the exothermicity of its attachment
Ni(II) to the surface of Na-AB [61].
28.663
The negative value of DS for both Pb(II) and Ni(II) indicated a
0.882 stable arrangement (low randomness) of Pb(II) and Ni(II) on the
0.398 Na-AB surface. On the contrary, the positive values of DS Cd(II)
reect the increasing randomness at the solid/liquid interface
during the adsorption process [62].
3.7. Adsorption selectivity interpretation
The obtained order of adsorption selectivity was Pb(II) > Cd
(II) > Ni(II). Qi and Aldrich [63] also reported the same order of
adsorption. The adsorption selectivity can be explained in terms of
the relative afnity of the solute towards the liquid and solid
17 phases [49]. This afnity arises from; the nature and distribution of
the active groups on the adsorbent, the way in which the metal ions
interact with the adsorbent, and difference in the ionic size of the
metal ions, which can be deeply explained by the following items
[64]:
1) The ionic radii (Pauling) of the metal ions are 1.20 , 0.97 and
0.69 for Pb(II), Cd(II) and Ni(II) respectively. Pb(II) which has
the biggest ionic size had the highest adsorption capacity, so
adsorption on the surface plays a more vital contribution to the
adsorption capacity than the microporous adsorption (which
prefer smaller ions) and this is more pronounced for Pb(II) ion
than Cd(II) ion than Ni(II) [64].
2) The larger the unhydrated ions, the less charge density, and
since the charge is more dispersed, the hydration water is less
held and so a weaker binding of the metal ion with the water
phase [65].
3) The smaller metal ions has a larger hydration enthalpy (energy
that detach the H2O molecules from metal ions), and so less
interacted with the adsorbent [66].
3.8. Application case: removal of heavy metals from seawater collected
from contaminated areas at Alexandria, Egypt
The practical application of Na-AB to remove Pb(II), Cd(II) and
Ni(II) and other metals contaminant from seawater was

0.8 Plot of ln Kd against 1/T for adorption of Pb , Cd

2+ 2+
and Ni
2+

from mixed ion solution

2+
0.4 Pb
2+
Cd
2+
Ni
0.0
ln Kd

-0.4

-0.8

-1.2

0.0030 0.0031 0.0032 0.0033 0.0034 0.0035

1/T

Fig. 14. Van't Hoff plot for adsorption of Pb(II), Cd(II) and Ni(II) from ternary-ion solution onto Na-AB.
1178 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180

Table 8
Thermodynamic parameters for adsorption of Pb(II), Cd(II) and Ni(II) from ternary ion solution onto Na-AB.

Thermodynamic parameters

Metal T (K) Kd (qe/ce) DG (kJ mol
1) DH (kJ mol
1) DS (kJ mol
1 K
1) R SD
Pb(II) 290 1.715
1.301
10.972
0.034 0.984 0.051
298 1.411
0.852
313 1.135
0.329
328 1.005
0.015

Cd(II) 290 0.533 1.515 11.206 0.034 0.998 0.020

298 0.628 1.153
313 0.759 0.717
328 0.927 0.208

Ni(II) 290 0.548 1.449
10.139
0.041 0.957 0.080

298 0.421 2.145
313 0.370 2.584
328 0.323 3.080

Table 9
Effect of adsorption on pH, salinity and metal concentrations of seawater samples collected from polluted semi-closed areas in Alexandria, Egypt.

Parameter Eastern Harbor El-Mex Bay El-Dekheila Harbor

Raw sample After adsorption Raw sample After adsorption Raw sample After adsorption Raw sample After adsorption
pH 7.29 7.63 6.81 8.01 7.23 7.94
Salinity (g/kg) 37.10 37.00 3.90 3.90 32.30 32.10

Metal (mg/L) Pb(II) 16.86 0.40 23.28 1.93 25.49 1.15

Ni(II) 15.28 1.13 19.76 2.05 11.86 1.08
Cd(II) 0.29 0.00 13.73 0.99 11.01 0.65
Cu(II) 6.54 0.89 7.56 1.22 6.77 1.01
Mn(II) 10.17 1.21 9.62 2.36 14.93 2.10
Cr(total) 4.32 0.55 6.48 0.79 5.51 0.70
Zn(II) 80.74 6.13 66.87 11.21 68.62 7.77

investigated. Samples were collected from some semi-closed
contaminated areas in Alexandria where water is subjected to
several sources of pollution. Seawater samples were collected from
the Eastern Harbour, El-Mex Bay and El-Dekheila harbor. Surface
seawater samples were collected in polyethylene bottles, pH and
salinity were measured in situ. Samples were then transferred to
the laboratory to be analysis for different heavy metals.
The raw initial concentrations of heavy metals in seawater
samples were preconcentrated through complexation with am-
monium pyrrolidine dicarbamide (APDC), then extracted into

Pb
Ni
Cd
Cu
100 Mn
Cr
Zn

80
% Removal

60

40

20

0
Eastern harbour El_Mex Bay El-Dekheila harbour
Studied area
Fig. 15. Adsorption efciency of Na-AB expressed in % removal for different heavy metals in the polluted studied areas.
 A.A. Taha et al. / Journal of Environmental Chemical Engineering 4 (2016) 11661180
methyl isobutyl ketone (MIBK) [67,68] and nally back extracted
into acidic media and measured using atomic absorption graphite
furnace atomizer (AA-GFA).
Batch experiments were performed using 600 mL of raw
seawater samples (without any previous treatments) into an
Erlerimeyer ask and transferred into the incubator shaker
(adjusted at 25  C and agitation speed 200 rpm) then 0.25 g of
Na-AB was added and the run started. After 60 min, the
suspensions were ltered then pH and salinity were measured,
and the nal concentrations of heavy metals were preconcentrated
by APDC, extracted into MIBK, back extracted into acidic media and
measured by graphite furnace atomic absorption.
3.8.1. Effect of adsorption on pH and salinity
The obtained results for pH and salinity are listed in Table 9; it is
obvious that after adsorption, the pH values in all stations
markedly increased, this is attributed to adsorption of hydrogen
ion on Na-AB surface. The salinity values after adsorption show no
signicant changes it decreased 0.1%.0 and 0.2%, 0 for eastern
harbor and El-dekheila harbor respectively, such decrease may be
due to adsorption of some salts into Na-AB surface.
3.8.2. Adsorption of heavy metals from seawater
The analysis results before and after treatment are listed in
Table 9 and the % removal is graphically represented in Fig. 15. The
results indicated that Na-AB is a potential applicable material for
removal of heavy metals from polluted seawater not only for Pb(II),
Cd(II) and Ni(II) (recoveries were in range of 92100%) but also for
other metals such as Cu(II), Mn(II), Cr(total) and Zn(II).
It must be highlighted that the adsorption selectivity between
the studied areas can not be set due to several reasons such as the
differences between areas in surface metal concentrations, pH,
salinity, the extent of the organic matters which may complexes
heavy metals, the interfering ions in each area, and other existing
pollutants so as yet it is difcult to establish a general order for the
adsorption selectivity.
4. Conclusion
The current study revealed that Egyptian Na-AB, can be
employed as an effective adsorbent for removal of Pb(II), Cd(II)
and Ni(II) from waste water and saline solutions. The FT-IR showed
that the adsorption occurred mainly at the clay lattice (SiOSi, Si
OAl and SiOMg groups) in addition to lattice OH (SiOH, Al
OH). XRD analysis indicated that Na-AB is represented mainly by
Na-montmorillonite. The parameters such as contact time, pH,
initial metal concentration, the amount of the adsorbent, the
agitation speed and temperature of the solution, which inuence
the adsorption capacity, were examined. The multi-metal systems
study suggested that Na-AB had a relative selectivity toward Pb
(II) > Cd(II) > Ni(II). The adsorption isotherms of Pb(II), Cd(II) and Ni
(II) onto Na-AB were well described by the Langmuir and
Freundlich model. Adsorption kinetics was investigated using
pseudo-rst and pseudo-second-kinetic models. It was found that
the pseudo-second-order rate model described the kinetic data
more accurately. The intraparticle diffusion model gave multi-
linear curves indicating that adsorption process is controlled by
more than one-step. The data obtained from the thermodynamic
study at different temperatures (290328) K were used to calculate
the thermodynamic quantities. Application of Na-AB for removal of
heavy metals from the contaminated seawater showed excellent
removal efciency. In the view of these results, it can be concluded
that the Na-AB can be utilized as a low cost and effective adsorbent
in removal of Pb(II), Cd(II) and Ni(II) ions from aqueous and saline
solutions.
1179
Acknowledgment
The work was nancially supported from National Institute of
Oceanography and Fishers (NIOF), Alexandria Branch, Egypt.
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