Desalination 210 (2007) 248256

Removal of Pb(II) from aqueous solutions by using

clinoptilolite and bentonite as adsorbents

Vassilis J. Inglezakis, Marinos A. Stylianou*, Despoina Gkantzou,

Maria D. Loizidou
National Technical University of Athens, School of Chemical Engineering, Laboratory of General Chemistry,
Heroon Polytechniou 9, 15773 Zographou Campus, Greece
Tel. +30 (210) 7722334; Fax +30 (210) 7723285; email: marinosstylianou@yahoo.com

Received 3 November 2005; revised 14 March 2006; accepted 11 May 2006

Abstract
In the present study, the ability of natural zeolite clinoptilolite and bentonite (clay) to remove Pb(II) from
aqueous solutions has been investigated in batch reactors with a maximum contact time of 120 min. Adsorption
tests of Pb(II) were carried out using a solution concentration of 1,036 ppm at initial pH = 4, and solid to liquid ratio
of 2 g/100 mL. The effects of agitation speed (0, 100, 200, 500 rpm), temperature (28C, 45C, 60C) and particle
size (2.55.0 mm, dust) of the minerals were examined. The effect of acidity of the aqueous solution was also
examined. Bentonite was found to be more effective for the removal of Pb(II) than clinoptilolite, under the
experimental conditions used. The removal of Pb(II) using bentonite reached 100% at ambient temperature and
mild agitation (100 rpm), while it was approximately 90% at 60C without agitation. On the other hand, the highest
removal level reached by clinoptilolite was 55%. Clinoptilolite dust is found to be more efficient than granular
clinoptilolite. Agitation and temperature affected the uptake of Pb(II), especially in the case of granular clinoptilolite
(2.55.0 mm). Finally, it can be seen that acidity of the aqueous solution influences the removal of lead by the
minerals. The adsorption of lead increases with an increase in pH of the solution from 1 to 4.
Keywords: Ion exchange; Lead; Clinoptilolite; Zeolites; Bentonite

*Corresponding author.

Presented at the 9th Environmental Science and Technology Symposium, September 13, 2005, Rhodes, Greece.
Organized by the Global NEST organization and prepared with the editorial help of the University of Aegean,
Mytilene, Greece and the University of Salerno, Fisciano (SA), Italy.

0011-9164/07/$ See front matter 2007 Published by Elsevier B.V.

doi:10.1016/j.desal.2006.05.049
 V.J. Inglezakis et al. / Desalination 210 (2007) 248256 249

1. Introduction ing on copper, lead, chromium (III, VI), silver etc.

[1013].
Wastewater contaminated with heavy metals This paper presents results on the ability of
is generated in many industrial activities, such as natural zeolite (clinoptilolite) and bentonite (clay)
tanneries, metal plating facilities and mining op- to remove lead from aqueous solutions. Batch
erations. Especially Pb(II), Cu(II), Fe(III), and experiments examine the effect of particle size of
Cr(III) are common metals found in industrial the minerals, agitation speed and temperature.
wastewater. Heavy metals are not biodegradable Furthermore, the optimum pH values of the aque-
and tend to accumulate in organisms, causing ous solution to be treated are investigated.
numerous diseases and disorders.
Lead has been found to be acute toxic to hu-
man beings when present in high amounts (e.g. 2. Materials and methods
>15 g/L in drinking water). Lead is known to 2.1. Materials
damage the kidney, liver and reproductive sys-
Two different minerals were used in order to
tem, basic cellular processes and brain functions.
examine the removal of Pb(II) from aqueous so-
The toxic symptoms are anemia, insomnia, head-
lutions. Natural zeolite (clinoptilolite) and bento-
ache, dizziness, irritability, weakness of muscles,
nite (clay) were supplied from S&B Industrial
hallucination and renal damages [5].
Minerals S.A. Clinoptilolite was ground and then
Various treatment processes are available. Ion
sieved to different fractions of which 2.55.0 mm
exchange constitutes one of them that is consid-
and dust were used in this study. Bentonite was
ered to be cost effective if low-cost ion exchang-
used in dust form. The chemical composition of
ers, such as zeolites and clays, are used [1]. Zeo-
the materials was determined through XRF and
lites and bentonite are naturally occurring struc-
wet chemical analysis (for oxides: XRF on fused
tured and phyllosilicate minerals respectively,
beads containing Li2B4O7 flux, LOI: mass loss
with high cation exchange and ion adsorption ca-
upon firing at 1,100C) (Tables 1 and 2). XRD
pacity. From zeolite species, clinoptilolite has re-
analysis for the two minerals was also checked
ceived extensive attention due to its attractive se-
(Fig. 1). CEC of clinoptilolite is 188.40 meq/100
lectivity for certain heavy metal cations, such as
g and for bentonite 100.19 meq/100 g (NH4AC
Pb(II), Cu(II) and Cd(II) [1,2]. Furthermore, ben-
method). The % concentration of monmorillonite
tonite has been used as an adsorbent for the re-
in bentonite is 75.92%.
moval of Pb(II), Fe(II), Zn(II) and Cr(III) [3,4].
The minerals were used without any chemical
Finally, it is known that natural zeolites tend
pretreatment. The samples were washed and air-
to elevate the solution acidity. Acidity of solu-
dried at 80C and then kept in desiccators. Solu-
tions is expected to change during ion exchange,
tion of [Pb(NO3)2 0.01 N ( 0.005 mol/L or 1,036 ppm
as H+ ions are exchanged with the cations initially
Pb)] was prepared using analytical grade reagents
present in zeolite structure. Therefore, during the
and high-purity deionized water. The pH was ini-
ion-exchange process, acidity is changing due to
tially adjusted to avoid precipitation during all ion
H+ uptake by clinoptilolite, but also due to the
exchange experiments at 4, using nitric acid
uptake of metal cations, which have a tendency
(HNO3).
to give acidic solutions. The acidic range under
which ion exchange takes place should be speci-
2.2. Batch experiments
fied [9]. Several reports have determined the op-
timum pH value of the aqueous solution to be The ion exchange of Pb on clinoptilolite and
treated with natural zeolite and bentonite, focus- bentonite was examined in batch mode experi-
250 V.J. Inglezakis et al. / Desalination 210 (2007) 248256

Table 1 were repeated for each different period of time in

Chemical analysis of zeolite order to avoid sampling during experiment (one
experiment for each time interval). The final pH
Zeolite XRF analysis Wet chemical was recorded in order to check for precipitation.
analysis
In order to check the effect of acidity on lead
SiO2 (%) 70.08 72.34 uptake by the minerals, initial acidity was adjusted
Al2O3 (%) 11.72 14.82
TiO2 (%) 0.00
using HNO3 at 4, 3, 2 and 1. Since the aim of this
0.14
work is to investigate the effects of acidity on the
Fe2O3 (%) 0.67 0.72
MgO (%) 0.71 4.00 ion-exchange process only, lower values are not
CaO (%) 3.18 2.78 used, as clinoptilolite structure breaks down in
Na2O (%) 0.55 0.72 highly acidic solutions. This process known as
K2O (%) 3.50 3.65 dealumination, takes place at acidity values typi-
LOI (%) 9.45 9.45 cally lower than 1 [9,14].
Total 100.00 108.48
The concentrations of metal ions were mea-
sured by atomic absorption spectroscopy (AAS),
using a Perkin Elmer Model 2380 spectrophotom-
Table 2
eter.
Chemical analysis of bentonite

Bentonite
3. Results and discussion
SiO2 (%) 53.72
Al2O3 (%) 19.12 3.1. Effect of particle size of the minerals on the
TiO2 (%) 0.85 uptake of lead
Fe2O3 (%) 4.93
MgO (%) 3.29 The time-dependent behavior of lead adsorp-
CaO (%) 5.28 tion was measured by varying the equilibrium time
Na2O (%) 3.64 between the adsorbate and adsorbent in the range
K2O (%) 0.44
of 1120 min. The percentage removal of lead
LOI (%) 8.75
Total 100.0 [Pb(II)] from aqueous solution as a function of
contact time (without agitation, T = 30C) indi-
cates that higher removal of lead was observed
ments. A measured quantity of mineral (2 g) was for bentonite. Furthermore, clinoptilolite dust is
added to a vessel containing measured volume of found to be more efficient than granular clino-
Pb solution (100 mL). Different parameters were ptilolite (Fig. 2).
tested (Table 3) and the solutions were analyzed Comparisons between materials showed that
after a specified time interval. The experiments % removal of lead from the aqueous solution fol-

Table 3
Various parameters tested on the ion exchange of Pb on clinoptilolite and bentonite in batch mode experiments

Parameters tested Temperature (C) Time interval (min) Agitation (rpm)

Effect of particle size 30 135102045120
Effect of temperature 304560 1045120
Effect of agitation 30 5102045120 0100200400
Effect of acidity 30 1045120
 V.J. Inglezakis et al. / Desalination 210 (2007) 248256 251

Fig. 1. XRD analysis for zeolite and bentonite (m-12.4 : Ca-montmorillonite, calcite CaCO3, quartz SiO2, anatase TiO2,
dolomite CaMg(CO3)2, pyrite FeS2, mica/illite).
252 V.J. Inglezakis et al. / Desalination 210 (2007) 248256
80.0
Clinoptilolite Dust
70.0
60.0 Bentonite Dust
% removal 50.0 Clinoptilolite 2,5-5 mm
40.0
30.0
20.0
10.0
0.0
0 20
Fig. 2. Percentage removal of lead as a function of contact time (T = 30C, without agitation).
lows: bentonite > clinoptilolite dust > clinoptilolite
2.55.0 mm.
Dust form of the minerals is found to be more
efficient than the granular form of mineral and
this is attributed to the increasing surface area of
the mineral, which helps the phenomenon of ion
exchange.
An exchange or an adsorption site is charac-
terized by its availability and its accessibility in
respect to the incoming ion. Availability is
straightforwardly related to the equilibrium be-
havior of the ion exchange system (available is
the site that can be occupied by the incoming ion).
Accessibility is related to the kinetic behavior of
the ion exchange system: it expresses the ease of
movement of the specific cation within the pores
leading to this site. By this point of view, while a
site could be available for the incoming cation,
the movement of the latter to this site is charac-
terized by a degree of difficulty, generally differ-
ent for each site. Thus, the availability and the
accessibility of an exchange site depend not only
on the characteristics of the site, but also on the
specific incoming cation [2].
3.2. Effect of temperature on the uptake of lead
An increase in lead removal from the aqueous
solution with a raise in temperature was observed.
Bentonite was found to be more effective, reach-
40 60 80 100 120
min
ing 70% and 90% removal at 4560C. Clino-
ptilolite dust seems to be more effective than clino-
ptilolite 2.55.0 mm at 45C, but at 60C it seems
to reach the same level of removal (50%) (Fig. 3).
Concerning the effect of temperature on the
adsorption process, the metals uptake is favored
at higher temperatures, since a higher tempera-
ture activates the metal ions for enhancing adsorp-
tion at the coordinating sites of the minerals [8].
Also, it is mentioned that cations move faster with
increasing temperature. Likely explanation for this
is that retarding specific or electrostatic, interac-
tions become weaker and the ions become smaller,
because solvation is reduced [2]. In our experi-
ments the phenomenon can be observed in the
clinoptilolite 2.55.0 mm sample (Fig. 3c).
3.3. Effect of agitation on the uptake of lead
Experimental results for the effect of agitation
speed (0, 100, 200, 400 rpm) are presented in
Fig. 4. It is obvious that agitation is found to be
appropriate for maximum adsorption of lead from
the minerals. The removal of Pb(II) using bento-
nite reaches 100% at 400 rpm. On the other hand,
the higher removal level reached by clinoptilolite
is found to be (for the dust form) at 65%.
Effect of agitation speed was examined at 0
100200400 rpm. Agitation speed above 500 rpm
was not examined, because the suspension was
 V.J. Inglezakis et al. / Desalination 210 (2007) 248256 253

100.0
(a) T=30C
80.0
T=45C

%removal 60.0 T=60C

40.0

20.0

0.0
10 45 120
min
60.0
(b)
50.0
% removal

40.0

30.0
T=30C
20.0
T=45C
10.0 T=60C
0.0
10 45 120

min
60.0
(c) T=30C
50.0
T=45C
% removal

40.0
T=60C
30.0
20.0

10.0
0.0
10 45 120

min
Fig. 3. Percentage removal of lead for (a) bentonite dust, (b) clinoptilolite dust and (c) clinoptilolite 2.55 mm as a
function of temperature.

not homogeneous [6]. It is obvious that agitation
helps lead removal from aqueous solutions. This
is because Pb ions, through their transportation
to the solid phase, meet resistance at the liquid
phase, through the boundary layer. Agitation of
suspensions during experiments has led to a de-
crease of the boundary layer and a decrease to the
resistance of transportation of lead ions. This in-
creases the transfer rate of the ions and the ad-
sorption of the minerals.
The effect of agitation speed can be seen in
the bentonite sample (Fig. 4a).
254 V.J. Inglezakis et al. / Desalination 210 (2007) 248256

100.0 examined in the pH range of 14. It can be seen

(a) that acidity influences the removal of lead by the
80.0
minerals (Fig. 5). The adsorption of lead increases
% removal

60.0 with an increase in pH of the solution from 1 to 4.

40.0
For bentonite, it can be seen that there is a de-
crease for pH 4. This decrease in the adsorption
20.0 0rpm 100rpm of Pb(II) probably reflects a reduction in the quan-
200rpm 400rpm tity of negative surface charges on the clay. At
0.0
5 10 20 45 120 low pH, the silica attracts positively charged ad-
min sorbate ions by coulombic forces. This negative
charge density on the surface of the adsorbent
70.0 decreases as the pH increases and this leads to
60.0 (b)
low adsorption of Pb(II) from water at high pH. It
% remonal

50.0
is therefore evident, that the presence of a nega-
40.0
tive charge on the silica surface sites of the adsor-
30.0
bent over the pH range investigated is the main
20.0 0rpm 100rpm reason for Pb(II) adsorption.
10.0 200rpm 400rpm
H+ cations should be considered as competi-
0.0
tive ones in ion-exchange processes and, conse-
5 10 20 45 120
quently, ion exchange of metals is favoured by
min
high acidity, which should, however, be lower than
50.0 the minimum acidity of precipitation. Similar re-
(c) 0rpm sults have been published elsewhere for ion ex-
40.0
100rpm change of metals on clinoptilolite [9,10]. Accord-
% removal

200rpm
30.0 ing to these studies, there is no significant change
400rpm
in Pb2+ uptake in the range of acidity between 3
20.0
and 12. It has been pointed out that considerably
10.0 lower metal concentrations were used in these
studies and, thus, higher acidity values could be
0.0 used without precipitation risk (150 ppm).
5 10 20 45 120
Acidity, on the other hand, influences the hy-
min
drolysis of the metals. Hydration is followed by
Fig. 4. Percentage removal of lead with agitation for (a)
hydrolysis, according to the following two-ray
bentonite, (b) clinoptilolite dust and (c) clinoptilolite 2.5 reversible reaction, giving acidic properties to
5 mm. heavy metal solutions.
[M(H 2 O) x ]c+ + H 2 O [M(H 2 O) x 1 (OH)](c 1) +
+ H 3O +
3.4. Effect of acidity on the uptake of lead
Consequently, at lower acidity the above equi-
The pH of the aqueous solution is an impor- librium is shifted to the left and more highly
tant variable which controls the adsorption of the charged metal complexes are formed, a fact ben-
metal at the solidwater interfaces. Hence, the eficial for the exchange [9].
influence of pH on the adsorption of Pb(II) on A similar study showed the same results for
bentonite, clinoptilolite (granular and dust) was bentonite. This study also examined the role of
 V.J. Inglezakis et al. / Desalination 210 (2007) 248256 255

35
(a) pH 1 pH 2
30
pH 3 pH 4
25

% removal 20

15

10

0
0 20 40 60 80 100 120

min
45
40 (b)
35
30
% removal

25
20
15
10
5
pH 1 pH 2 pH 3 pH 4
0
0 20 40 60 80 100 120

min
80
pH 1 pH 2
70 (c)
pH 3 pH 4
60
% removal

50

40

30

20

10

0
0 20 40 60 80 100 120
min

Fig. 5. Percentage removal of lead, in the pH range of 14, for (a) clinoptilolite 2.55 mm, (b) clinoptilolite dust and (c)
bentonite dust.

HNO3 as an electrolyte on the adsorption of lead. centration tend to suppress the hydrolysis of
The results showed that by increasing the con- Pb(II). Therefore, very low adsorption of the metal
centration of the electrolyte, the adsorption of takes place from highly acidic solutions [5].
Pb(II) onto bentonite decreases. Higher acid con-
256 V.J. Inglezakis et al. / Desalination 210 (2007) 248256
4. Conclusions
In the present study, the ability of natural zeo-
lite clinoptilolite and bentonite (clay) to remove
Pb(II) from aqueous solutions has been investi-
gated in batch reactors with a maximum contact
time of 120 min. Bentonite was found to be more
effective for the removal of Pb (II) than clino-
ptilolite. The removal of Pb(II) using bentonite
reaches 100% at ambient temperature and mild
agitation (100 rpm), while it is approximately 90%
at 60C without agitation. On the other hand, the
highest removal level reached by clinoptilolite was
55%. Clinoptilolite dust is found to be more effi-
cient than granular clinoptilolite. Agitation and
temperature affected the uptake of Pb(II), espe-
cially in the case of granular clinoptilolite (2.5
5.0 mm). Finally it can be seen that acidity of the
aqueous solution influences the removal of lead
by the minerals.
Acknowledgment
We extend our thanks to the Ministry of Na-
tional Education and Religious Affairs of Greece,
which has been financing a project (EPEAEK II,
Pythagoras) a part of which is presented in this
paper.
We would also like to thank S&B Industrial
Minerals S.A. for supplying the minerals.
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