Adsorption of Pb(II) from Aqueous Solution Using Natural Clay

Linlin Zhang
1,2
, J inli Zhang
1,2,*
and Man Yuan
1,2
1
State Key Laboratory of Coastal and Offshore Engineering, Dalian University of Technology,
Dalian, P.R. China, 116024
2
Institute of Geotechnical Engineering, Dalian University of Technology, Dalian, P.R. China,
116024
*Corresponding author. Tel.: +86 41184708511; fax: +86 41184707609;e-mail:jlzhang@dlut.edu.cn.
Keywords: adsorption, clay, lead, thermodynamic.
Abstract. The adsorption of lead on natural clay (NC) was studied through batch experiments. The
effect of solution pH, adsorbent dosage, Pb(II) initial concentration, temperature and contact time on
the removal of Pb(II) by NC were investigated. The optimum pH
0
for the removal of lead is 4.46. The
removal efficiency increases sharply, while adsorption capacity decreases with the increasing of
adsorbent dosage. Before 15 min, it is very fast adsorption and the following is gradual adsorption
process with rather lower rate. Thermodynamic parameters like free energy change (
0
G ), enthalpy
(
0
H ) and entropy (
0
S ) indicate the spontaneous, exothermic and decreased randomness nature of
Pb(II) adsorption.
1. Introduction
Lead, one of the most toxic heavy metal pollutants from industrial effluents, is becoming a serious
threat to our environment. It is widely used in various industrial processes, such as storage batteries,
mining, metal plating, painting and smelting
[1-3]
. Pb(II) is non-biodegradable and accumulate
throughout food chain in living tissues
[4, 5]
, causing hypertension, nephritis, abdominal pain, cramps,
nausea and vomiting
[6]
. Therefore, Pb(II) should be treated before the effluents are discharged to
receiving environment. Among the physico-chemical treatment processes for heavy metals removal,
adsorption has been proven to be cost effective, because the process is low operating cost, easily
available sources, minimization of production of sludge and regeneration of metals from the loaded
adsorbent. A great number of soil adsorbents have been studied for the removal of heavy metals, such
as Chinese loss
[7-10]
, clay
[11-13]
and bentonite
[3, 14]
.
Montmorillonite is the most important components of the clay and composed of two silica
tetrahedral sheets with an octahedral alumina sheet. It is commonly used as excellent materials for
adsorption by means of the high specific surface area, chemical and mechanical stability, layered
structure and high cation exchange capacity (CEC), etc
[14, 15]
.
The objective of this paper was to investigate natural clay as an adsorbent for Pb(II) removal from
aqueous solution. The study included the evaluation of the effect of various experimental factors,
such as adsorbent dosage, Pb(II) initial concentration, solution pH, temperature and contact time. The
thermodynamic parameters were also studied.
2. Materials and methods
2.1 Preparation of adsorbent
NC was obtained from suburban area of Dalian, China. The samples were collected from areas free of
anthropogenic heavy metal contamination. The NC was ground with wood mill and sieved from
2012 Asia Pacific Conference on Environmental Science and Technology
Advances in Biomedical Engineering, Vol.6
978-1-61275-003-3 /10/$25.00 2012 IERI



APEST2012


55
60-mesh. The sieved sample was dried in electric oven (DHG-9011A, China) at 333K for 24h in order
to avoid removing natural organics at higher temperatures, cooled to room temperature and then
placed in desiccators before further experiment.
2.2 Preparation of lead solutions
Lead nitrate in analytical grade was dissolved in distilled water to prepare the stock solution
(1000mg/L). Experimental Pb(II) solutions of different concentration were prepared by diluting the
stock solution.
2.3 Adsorption experiments
In order to determine the optimum Pb(II) adsorption conditions, adsorption experiments were
performed by batch technique. The equilibrium Pb(II) concentration was analyzed by atomic
absorption spectroscopyAA6000, China).
The removal efficiency (removal, %) and the amount of Pb(II) sorbed on NC (
e
q ) were calculated
using Eqs. 1 and 2, respectively:
removal =
0 e
0
100
c c
c

. (1)
0 e
e
( ) c c V
q
m

= . (2)
Where
0
c and
e
c are initial and equilibrium concentration(mg/L), respectively; V = volume of the
solution(L); m=weight of soil(g)and
e
q (mg/g).
3. Results and discussion
3.1 Effect of adsorbent dosage
Different amounts of NC (from 0.2g to 2g) were mixed with 50mL of different Pb(II) initial
concentration (200 and 300mg/L) for 12h in a shaking box and at 30KSHA-C, China. The removal
efficiency increases sharply from 22.54 and 18.43 to 87.51 and 84.77 (Figure 1) for 200 and
300mg/L, respectively. This could explain that increasing adsorbent dosage would increase active
adsorption sites, resulting in the increase in removal efficiency of Pb(II) onto NC. The amount of
Pb(II) sorbed on NC decreases with the rise of NC dosage. The reason may be higher adsorbent
amount creating particle aggregation, resulting in the decrease in the total surface area, an increase in
diffusion path length
[16]
. The decrease may be also interference between binding sites and higher
adsorbent dosage or insufficiency of Pb(II) in solution with respect to available binding sites
[17]
.
3.2 Effect of Pb(II) concentration
NC was equilibrated with Pb(II) concentration of different initial concentrations (20-300 mg/L) for
12h. As shown in Figure 2, the removal efficiency decreases rapidly, while the amount of Pb(II)
sorbed on NC increases with the increase in initial Pb(II) concentration with fixed temperature.
The removal efficiency may be that surface saturation related with initial Pb(II) concentration. At
lower concentration, Pb(II) ions are adsorbed on the high energy sites; at higher concentration, sites
with higher energy are saturated and adsorption starts to the lower energy sites, resulting in the
decrease in the removal efficiency. However, the increasing amount of Pb(II) sorbed on NC with the
rise of initial concentration may attribute to increase the probability of collision between Pb(II) and
soil particles; the higher Pb(II) gradient can provide an important driving force toward active sites.
The decrease in both removal efficiency and the amount of Pb(II) sorbed on NC with the rise of
temperature indicates that Pb(II) adsorption on NC is exothermic process. It may be explained as a
result of increase in the average kinetic energy of lead ions, thus making the attractive force between
56
lead ions and NC insufficient to retain lead ions at the binding site
[18]
. The effect also suggests that
the adsorption mechanism involves a physical process arising from the electrostatic interaction
[19]
.
3.3 Effect of pH
Figure 3 shows species distribution of Pb(II) calculated using Visual MINTEQ v2.6.1 in aqueous
solution. The species of Pb (II) is mainly Pb
2+
at pH
0
<6.0, followed by a sharp reduction in Pb
2+
at
6.0<pH
0
<8.0. Pb(OH)
+
and Pb
3
(OH)
4
2+
are formed at pH
0
>6.0, while the Pb(OH)
+
reaches the peak at
pH
0
7.5; the Pb
3
(OH)
4
2+
shows steadily increase at pH
0
>7.25 and reaches the peak at pH
0
9.25. The
precipitation of lead Pb(OH)
2
is formed at pH
0
>6.75 and reaches its peak at pH
0
11. At higher pH
0
, it
would be difficult to determine the actual adsorption performance of NC. Thus, the study on the effect
of pH was limited to pH
0
values less than 6.0.
Adsorption of Pb(II) by NC was studied using the initial pH range 1.5-6. The equilibrium pH (PH
e
)
were measured by pH meter (Starter2C, China), as well as removal efficiency and pH
e
are presented
in Figure 4. The removal efficiency is 7.46% at pH
0
1.63, sharply increases 85.76% at pH
0
2.9, finally
keeps almost unchanged at pH
0
3.77-5.57 and reaches a maximum 98.77% at pH
0
4.46. In other
words, it is beneficial to obtain a higher Pb(II) removal efficiency by keeping the pH
0
>3.77, whereas
a lower pH
0
<1.63 could be used to desorbed the immobilized Pb (II) from NC and thus could
regenerate the adsorbent for repeated utilization.
The decrease in removal efficiency at lower pH
0
may be the fact the aluminol and silanol groups
are more protonated. The electrostatic repulsion exists between Pb
2+
ions and the positive surface of
the NC. The high buffering capacity of NC is recognized because of all pH
e
higher than pH
0
in the
acid condition. The phenomenon may be due to the presence of amphoteric groups (like the hydroxyl
groups on the sides and edges of the clay minerals) and alkaline components in NC.

Fig.1. Effect of adsorbent dosage on the Pb(II) Fig.2. Effect of initial concentration on Pb(II)
removal efficiency and adsorption capacity removal efficiency and adsorption capacity

Fig.3. Species distribution of Pb(II) in aqueous Fig.4 Effect of pH on the Pb(II) removal
solution with different pH efficiency and the equilibrium pH
3.4 Effect of contact time
The effect of contact time on the adsorption of Pb(II) by NC was investigate for different time
intervals from 5 to 150min. As shown in Figure 5, adsorption rate is quite fast and 120min adequately
reaches equilibrium. The adsorption trends also demonstrate that the removal Pb(II) from solution has
57
a two-step adsorption process. Before 15min, first rapid adsorption step results from external mass
transfer, leading to most of the Pb
2+
adsorbed on vacant surface of NC. The diffusion into NC
particles has great effect on the rate of adsorption after 15min, which is rather slow.

Fig.5. Effect of contact time on adsorption Fig.6. Linear fit of thermodynamic data on
capacity at different initial concentration NC at different Pb(II) concentration
NC is highly porous material, providing large volume of pore and adequate surface area for
adsorption. However, the existence of diffusion into NC particles may lead to the decrease in the
adsorption rate and the increase in reactive time. It cannot be useful for the treatment of effluents on
an industrial scale.
3.5 Thermodynamic parameters
The thermodynamic parameters of Pb(II) on NC were evaluated with the following equations:
ln
R R
c
S H
K
T

= . (3)
0 0 0
G H T S = . (4)
Where
c
K is the distribution coefficient of solute between adsorbent and solution in equilibrium ( /
e e
q c ,
mL/g), R the ideal gas constant, T the temperature (K),
0
H enthalpy,
0
S entropy and
0
G is the
standard Gibbs free energy.
Linear fit of thermodynamic data on NC shows in Figure 6. It was seen from Table 1, the Gibbs
free energy is negative as expected for a spontaneous and feasible process in the experimental
Table 1. Thermodynamic parameters of Pb(II) adsorption on NC
C
0
(mg/L) Temperature(K) G (kJmol
-1
) H (kJmol
-1
) S (Jmol
-1
K
-1
) R
2

20
303 -12.83
-25.33 -41.29 0.9582
313 -12.42
323 -12.00
333 -11.59
50
303 -12.65
-28.44 -52.10 0.9136
313 -12.13
323 -11.63
333 -11.09
150
303 -11.79
-29.75 -59.54 0.8484
313 -11.11
323 -10.52
333 -9.92
200
303 -11.36
-29.75 -60.71 0.8657
313 -10.75
323 -10.15
333 -9.54
conditions. In addition, the decrease in the magnitude of
0
G to higher temperature showed the
diminishing of the spontaneous in the process, so the adsorption was not favorable at higher
temperatures. Then, the more negative values of free energy suggest a more energetically favorable
58
adsorption at lower initial concentration. Generally, the change in free energy for physisorption is
between -20 and 0 kJmol
-1
, but chemisorption is in the range of -80 to-400 kJ mol
-1 [20]
.
The negative enthalpy indicates exothermic nature in adsorption process. Typically, the enthalpy
of a physisorption process is lower than 40kJmol
-1
, whereas the enthalpy of a chemisorptions process
approaches 100 kJmol
-1 [21]
. The values of Gibbs free energy and enthalpy suggest physisorption
process during the reaction.
The negative entropy indicates that there is a decrease in the randomness in the system
solid/solution interface during the adsorption process. Positive entropy changes mainly attributed to
the ion exchange with surface hydroxyl groups
[22]
, since bivalent lead ions can exchange hydrogen
ions on the electric double layer of NC surfaces with the molar ratio of 1/2.Therefore, the
ion-exchange between Pb(II) and surface hydroxyl groups cannot be dominant in this system.
Physical adsorption has been as the predominant mechanism for Pb(II) on NC; light metal ions
loaded onto NC surface (mainly Ca
2+
) can exchange with Pb(II) from solution due to ion-exchange
mechanism, which were found a slightly increase in the solution (not providing data).
4. Conclusion
The Pb(II) removal efficiency on NC increases steadily with increasing adsorbent dosage and with
decreasing solution concentration. The maximum removal efficiency occurs at pH
0
4.46. Adsorption
rate is quite fast and 120min adequately reaches equilibrium. The thermodynamic study shows that
the adsorption process is spontaneous, exothermic and the system disorder decreased nature in the
experiment. Based on the results, it is concluded that the clay is an attractive candidate for removing
Pb(II) from industrial effluents.
5. Acknowledgement
This research was financially supported by the National Natural Science Foundation of China (Grant
NO. 50979713).
References
[1] M. A. Schneegurt, J. C. Jain, J. J. A. Menicucci, et al, Biomass byproducts for the remediation of
wastewaters contaminated with toxic metals, Environmental Science and Technology, vol. 35,
pp. 3786-3791, 2001.
[2] J. Z. Chen, X. C. Tao, J. Xu, T. Zhang, Z. L. Liu, Biosorption of lead, cadmium and mercury by
immobilized Microcystis aeruginosa in a column, Process Biochemistry, vol. 40, pp. 3675-3679,
2005.
[3] A. Safazcan, Gk, A zcan, Adsorption of lead(II) ions onto 8-hydroxy
quinoline-immobilized bentonite, Journal of Hazardous Materials, vol. 161, pp. 499-509, 2009.
[4] V. C. Srivastava, I. D. Mall and I. M. Mishra, Equilibrium modeling of single and binary
adsorption of cadmium and nickel onto bagasse fly ash, Chemical Engineering Journal, vol. 117,
pp. 79-91, 2006.
[5] H. Chen, J. Zhao, G. L. Dai, J. Y. Wu, H. I. Yan, Adsorption characteristics of Pb(II) from
aqueous solution onto a natural biosorbent, fallen Cinnamomum camphora leaves. Desalination,
vol. 262, pp. 174-182, 2010.
[6] H. Ghassabzadeh, M. T. Mostaedi, A. Mohaddespour, M. G. Maragheh, S. J. Ahmadi, P. Zaheri,
Characterizations of Co(II) and Pb(II) removal process from aqueous solutions using expanded
perlite, Desalination, vol. 262, pp. 73-79, 2010.
59
[7] Z. Z. Li, X. W. Tang, Y. M. Chen, Y. Wang, Sorption Behavior and Mechanism of Pb(II) on
Chinese Loess, Journal of Environmental Engineering, vol. 135, pp. 58-67, 2009.
[8] Y. Wang, W. Tang, Y. M. Chen, L. T. Zhan, Z. Z. Li, Q. Tang, Adsorption behavior and
mechanism of Cd(II) on loess soil from China, Journal of Hazardous Materials, vol. 172, pp.
30-37, 2009.
[9] X. W. Tang, Z. Z. Li, Y. M. Chen, Adsorption behavior of Zn(II) on calcinated Chinese loess,
Journal of Hazardous Materials, vol. 161, pp. 824-834, 2009.
[10] X. W. Tang, Z. Z. Li, Y. M. Chen, Z. Q. Wang, Removal of Zn(II) from aqueous solution with
natural Chinese loess Behaviors and affecting factors, Desalination, vol. 249, pp. 49-57, 2009.
[11] P. Saha, S. Datta, S. K. Sanyal, Application of Natural Clayey Soil as Adsorbent for the Removal
of Copper from Wastewater, Journal of Environmental Engineering, vol. 136, pp. 1409-1417,
2010.
[12] A. Saria, M. Tuzen, M. Soylak, Adsorption of Pb(II) and Cr(III) from aqueous solution on Celtek
clay, Journal of Hazardous Materials, vol. 144, pp. 41-46, 2007.
[13] J. U. K. Oubagaranadin, Z. V. P. Murthy, Adsorption of Divalent Lead on a
Montmorillonite-Illite Type of Clay, Industrial and Engineering Chemistry Research, vol. 48,
pp. 10627-10636, 2009.
[14] A. Mellah, S. Chegrouche, The removal of zinc from aqueous solutions by natural bentonites,
Water Research, vol. 31, pp. 621-629, 1997.
[15] K. G. Bhattacharyya, S. S. Gupta, Adsorption of a few heavy metals on natural and modified
kaolinite and montmorillonite: A review, Advances in Colloid and Interface Science, vol. 140,
pp. 114-131, 2008.
[16] S. Rengaraj, K. H. Yeon, S. Y. Kang, J. U. Lee, K. W. Kim, S. H. Moon, Studies on adsorptive
removal of Co(II), Cr(III) and Ni(II) by IRN77 cation-exchange resin, Journal of Hazardous
Materials, vol. B92, pp. 185-198, 2002.
[17] T. Fan, Y. Liu, B. Feng, G. Zeng, C. Yang, M. Zhou, H. Zhou, Z. Tan, X. Wang, Biosorption of
cadmium(II), zinc(II) and lead(II) by Penicillium simplicissimum: isotherms, kinetics and
thermodynamics, Journal of Hazardous Materials, vol. 160, pp. 655-661, 2008.
[18] E. Atalay, F. Gode, Y. C. Sharma, Removal of Selected Toxic Metals by a Modified Adsorbent,
Journal of Hazardous, Toxic, and Radioactive Waste, vol. 14, pp. 132-138, 2010.
[19] I. Kula, M. Ugurlu, H. Karaoglu, A. Celik, Adsorption of Cd(II) ions from aqueous solutions
using activated carbon prepared from olive stone by ZnCl
2
activation, Bioresource Technology,
vol. 99, pp. 492-501, 2008.
[20] M. J. Jaycock, G. D. Parfitt, Chemistry of Interfaces, Onichester, Ellis Horwood Ltd., 1981.
[21] A. M. Sevim, R. Hojiyev, A. Gl, M. S. elik, An investigation of the kinetics and
thermodynamics of the adsorption of a cationic cobalt porphyrazine onto sepiolite, Dyes and
Pigments, vol. 88, pp. 25-38, 2011.
[22] N. Meunier, J. Laroulandie, J. F. Blais, R. D. Tyagi, Cocoa shells for heavy metal removal from
acidic solutions, Bioresource Technology, vol. 90, pp. 255-263, 2003.
60