DESALINATION

Desalination 247 (2009) 636–646

www.elsevier.com/locate/desal

Removal of Cu(II) and Pb(II) ions from aqueous solutions

by adsorption on sawdust of Meranti wood
Anees Ahmada*, Mohd. Rafatullahb, Othman Sulaimanb,
Mahamad Hakimi Ibrahima, Yap Yee Chiia, Bazlul Mobin Siddiquea
a
Environmental Technology Division, School of Industrial Technology, Universiti Sains Malaysia,
11800 Penang, Malaysia
b
Bioresource Paper and Coatings Technology Division, School of Industrial Technology,
Universiti Sains Malaysia, 11800 Penang, Malaysia
Tel.: +604-653-2214, Fax: +604-657-3678; email: anees@usm.my, aneesahmad_ana@yahoo.com

Received 6 August 2007; accepted 19 January 2009

Abstract
Meranti tree sawdust, an inexpensive material, is currently being investigated as an adsorbent for the removal
of Cu(II) and Pb(II) ions from aqueous solutions. In this work, adsorption of Cu(II) and Pb(II) ions on Meranti tree
sawdust has been studied by using batch techniques. The equilibrium adsorption level was determined to be a
function of the solution of pH, contact time, and adsorbent dosage. Adsorption isotherms of Cu(II) and Pb(II)
ions on adsorbents were determined and correlated with common isotherm equations such as Langmuir
and Freundlich models. The thermodynamic parameters like free energy, enthalpy, and entropy changes for
the adsorption of Cu(II) and Pb(II) ions have also been computed and discussed. The heat of adsorption
[DH = 31.47 kJ/mol for Cu(II) and DH = 20.07 kJ/mol for Pb(II)] implied that the adsorption was endothermic
in nature.

Keywords: Heavy metals; Adsorption; Endothermic; Meranti wood; Sawdust

1. Introduction heavy metals are generally refractory and non-

The presence of heavy metal in the aquatic
environment has been of great concern to scien-
tists and engineers because of their increased dis-
charge, toxic nature, and other adverse effects on
receiving waters. Unlike most organic pollutants,
*Corresponding author.
degradable or readily detoxified biologically.
Copper is essential to human life and health,
but like all heavy metals, it is potentially toxic,
especially at high concentrations. Copper and
its compounds are ubiquitous in the environment
and are thus found frequently in surface waters.
Potential sources of copper bearing waste
include plating baths, fertilizer industry, paints

0011-9164/09/$– See front matter Ó 2009 Published by Elsevier B.V.

doi:10.1016/j.desal.2009.01.007
 A. Ahmad et al. / Desalination 247 (2009) 636–646
and pigments, municipal and storm water
run-offs. Intake of excessively large doses of
copper by man leads to severe mucosal irritation
and corrosion, widespread capillary damage,
hepatic and renal damage, and central nervous
system irritation followed by depression. Severe
gastrointestinal irritation and possible necrotic
changes in the liver and kidney could occur.
The maximum recommended concentration for
drinking water that is regulated in Environmen-
tal Quality Act 1974 is 0.2 mg/L [1–3].
Another heavy metal lead has been introduced
into natural waters from a variety of sources such
as storage batteries, lead smelting, tetraethyl lead
manufacturing, mining, plating, ammunition, and
the ceramic glass industries. The permissible limit
of lead in drinking water by Environmental Qual-
ity Act is 0.10 mg/L. The presence of excess lead
in drinking water causes diseases such as anemia,
encephalopathy, and hepatitis. Lead ions have an
affinity for ligands containing thiol and phos-
phatic groups and they inhibit the biosynthesis
of heme, causing damage to both the kidney and
liver. However, lead can remain immobilized
for years, and hence it is difficult to detect the
metabolic disorders it causes [4–6].
In developed countries, removal of heavy
metals in wastewater is normally achieved by
advanced technologies such as ion exchange,
chemical precipitation, ultra filtration, or electro-
chemical deposition [7–9]. But these technologies
do not seem to be economically feasible because
of their relatively high costs and that developing
countries may not afford such technologies.
Therefore, there is a need to look into alternatives
to investigate a low-cost method, which is effec-
tive and economical. To overcome this difficulty
there is a strong need to develop cheap adsorbents
which can be used in developing countries.
Adsorption by natural materials is another
alternative method to solve this kind of problems.
The natural materials form complexes with metal
ions using their ligand or functional groups.
Process for metal removal like adsorption
637
has been suggested as being cheaper and more
effective than the other technologies [10].
Adsorption was first observed by Lowitz in
1785 [11] and was soon applied as a process
for removal of color from sugar during refining.
In the second half of the nineteenth century,
American water treatment plants used inacti-
vated charcoal filters for water purification.
Currently, adsorption on activated carbon is a
recognized method for the removal of heavy
metals from wastewater [12, 13], while the
high cost of activated carbon limits its use in
adsorption. A search for a low-cost and easily
available adsorbent has led to the investigation
of materials of agricultural and biological origin
as potential metal sorbents [14]. Agricultural
by-products, such as sugar beet pulp and
sawdust [15, 16], coconut shell [17], clay [18],
red mud [19], tea leaves [20], and so on,
have received attention in these types of applica-
tion. The sorption of metals by these kinds of
materials might be attributed to their proteins,
carbohydrates, and phenolic compounds that
have carboxyl, hydroxyl, sulfate, phosphate,
and amino groups that can bind metal ions.
Most cases have confirmed that the use of
large quantities of wastes from agricultural
products for the treatment of polluted water is
an attractive and promising option with a double
benefit for the environment [21]:
• It reduces the residues whose disposal
becomes a major, costly problem and
• It converts the wastes into useful and inexpen-
sive sorbents for water purification
The aim of this article is to assess the poten-
tial of Meranti tree sawdust to adsorb Cu(II)
and Pb(II) ions from aqueous solutions. The
effect of the solution pH, temperature, contact
time, and adsorbent doses on the removal of
Cu(II) and Pb(II) ions was studied. The adsorp-
tion isotherm and probable mechanism are
explained. The thermodynamic parameters for
638 A. Ahmad et al. / Desalination 247 (2009) 636–646
the adsorption of Cu(II) and Pb(II) ions have
also been computed and discussed.
2. Experimental
2.1. Apparatus and instrumentation
The concentrations of Cu(II) and Pb(II) in
aqueous solutions were determined using atomic
absorption spectrophotometer (Analyst 100 Perkin
Elmer) operating with an air-acetylene flame. The
pH measurements were done with a pH-meter
(HACH Model SensION-3). The pH-meter was
standardized using buffer solutions with pH values
of 4.0, 7.0, and 10.0. The BET surface area was
determined through N2 gas adsorption by a
Micromeritics PulseChemiSorb 2705 instrument.
Temperature-controlled shaker (Rillins Sains
Sdn Bhd Model IKA KS 260) was used for equi-
librium studies. All filtrations during this work
were carried out using Whatman No. 1 filter paper.
2.2. Adsorbent
Meranti tree sawdust was collected from
Bio-resource, paper and coating (PBC) division
of School of Industrial Technology of USM.
The sawdust was washed with distilled water
and then dried in a dryer at 708C until all the
moisture had evaporated. The material was
ground to a fine powder in a still mill. The result-
ing material was sieved in the size range of
100–150 mm particle size. To immobilize the
color and water-soluble substances, the ground
powder was treated with 2% formaldehyde in
the ratio of 1:4 (sawdust: formaldehyde, w/v)
at room temperature for 4 h. After that, the saw-
dust was filtered out, washed with distilled water
to remove free formaldehyde, and activated at
708C in a dryer for 24 h. The material was placed
in an airtight container for further use.
2.3. Adsorbate solution
The aqueous solutions (1000 mg/L) of Cu(II)
as well as Pb(II) were prepared in distilled water
using Cu(II) sulfate pentahydrate, CuSO4.5H2O
and Pb(II) nitrate, Pb(NO3) respectively. The
solutions of different dilutions (25–250 mg/L)
required for the adsorption studies were pre-
pared by dilution of the stock solutions.
2.4. Batch adsorption studies
Batch adsorption studies were carried out by
shaking 0.25 g of the sawdust with 25 ml of the
aqueous solutions of Cu(II) and Pb(II) ions in
different conical flask at 150 rpm, respectively.
The mixtures were filtered out and analyzed
for its metal ion concentrations using Atomic
Adsorption Spectrometer (AAS) (Analyst 100
Perkin Elmer). All metal solutions were used
at neutral pH and performed at room tempera-
ture unless otherwise stated. The effect of pH
of the initial solution on the equilibrium uptake
of Cu(II) and Pb(II) ions was analyzed over a
pH range from 2.0 to 7.0 and 2.0 to 7.5, respec-
tively. The pH was adjusted using 0.1 M NaOH
and 0.1 M HCI solutions. The adsorption experi-
ments were also conducted to determine the
equilibrium time, the optimum pH, and dosage
of the adsorbent for maximum adsorption.
2.5. Adsorption model
To quantify the adsorption capacity of Mer-
anti tree sawdust for the removal of Cu(II) and
Pb(II) ions from aqueous solution, the Langmuir
and Freundlich models were used.
Langmuir mode: Langmuir proposed the follow-
ing model:
Ce =Am ¼ ð1=KÞð1=bÞ þ ð1=bÞðCe Þ ð1Þ
where Ce is the equilibrium concentration (mg/L)
and Am is the amount adsorbed per specified
amount of adsorbent (mg/g), b is the equilibrium
constant, and K is the amount of adsorbate
required to form a monolayer. Hence, a plot of
Ce/Am versus Ce should be a straight line with a
slope (1/b) and an intercept as 1/Kb.
 A. Ahmad et al. / Desalination 247 (2009) 636–646 639

Freundlich model: According to Freundlich

model:

Am ¼ ðKÞðCe1=n Þ

log Am ¼ log K þ 1=n log Ce ð2Þ

where n is an empirical constant. Thus, a plot of

log Am versus log Ce should be a straight line
with a slope 1/n and an intercept of log K. This
model deals with the multilayer adsorption of
the substance on the adsorbent.
A computer modeling technique has been
applied to fit the Freundlich and Langmuir
equations for the adsorption data. The coeffi- Fig. 1. SEM image (Mag:500) of sawdust of meranti
tree.
cients of determination of least square fitting
to a straight line (r2) were computed for these
3. Results and discussion
two models.
3.1. Characterization of Meranti tree sawdust
A SEM micrograph of Meranti tree sawdust
2.6. Thermodynamic parameters of sorption
is shown in Fig. 1. Meranti tree sawdust is a het-
The Gibbs free energy (DG) is the fundamen- erogeneous material consisting largely of small
tal criterion of spontaneity of a process and can spheres, irregular, porous, coke like particles of
be determined using equilibrium constant as cell wall of plant cells. The surface seems to
below: be rough, and protrusions can be seen through-
out the micrograph. Pores can be seen however,
DG ¼ RT ln K ð3Þ not extending into the matrix. The surface
roughness is indicative of high surface area.
where R is the universal gas constant
(8.314 Jmol1K1) and T is the absolute tem- 3.2. Physical–chemical characteristics
perature (K).
Characteristics of the adsorbent such as sur-
Similarly, the enthalpy was computed from
face area, bulk density, moisture content, ash
the following equation
content, solubility in water (inorganic and
organic matter) were determined. The results
ln K ¼ DS=R  DH=RT ð4Þ
are summarized in Table 1.

DH8 can be obtained from the slope of plot of ln

K versus 1/T. 3.3. The pH of adsorbent surface
The entropy was calculated from the equation, A 25 ml of metal solution of 100 mg/L con-
centration was agitated with 0.25 g of adsorbent
DG ¼ DH  TDS ð5Þ at room temperature for 60 min at 150 rpm to
640 A. Ahmad et al. / Desalination 247 (2009) 636–646

Table 1 percentage removal of Cu(II) and Pb(II) ions is

Various physical parameters for the adsorbent (Meranti initially high which is probably due to the avail-
tree sawdust) ability of larger surface area of the sawdust for
the adsorption of these ions. As the surface adsorp-
Parameters Values tion sites become exhausted, the rate of uptake is
pH (aqueous solution) 7.10 controlled by the rate of transport from the exterior
Particle size (mm) 100–150 to the interior sites of the adsorbent particles. Fur-
Surface area (m2/g) 630.00 ther, the maximum percentage removal of Cu(II)
Bulk density (g/cm3) 0.27 and Pb(II) ions was attained after 60 min of stirring
Moisture contents (%) 6.25 time at different concentrations. Therefore, the
Water soluble components 21.73
contact time of 60 min was sufficient to achieve
(inorganic matter) (%)
equilibrium for both these ions. The adsorption
Insoluble components (organic matter) (%) 76.22
did not change much with further increase in con-
tact time. Therefore, in each experiment, the shak-
reach equilibrium. Then, the pH of the slurry ing time was set to be 60 min. Figure 2 shows that
was measured. The results are shown in Table 1. the percentage adsorption of Pb(II) ions is higher
than Cu(II) ions. The adsorption of Pb(II) ions
3.4. Effect of contact time only slightly increases with the increase in contact
The dependence of adsorption of Cu(II) and time compared to the Cu(II) ions. A similar result
Pb(II) ions with time is presented in (Fig. 2). The has been found by Unlu and Ersoz [22] in adsorp-
data obtained from the adsorption of Cu(II) and tion characteristic of heavy metal ions onto a low-
Pb(II) ions on the Meranti tree sawdust showed cost biopolymeric sorbent from aqueous solutions.
that the adsorption increases with an increasing It is necessary to point out that these tests were
contact time. The plot reveals that the rate of done under a condition without any pH adjust-
ment. However, it is supposed that the pH of the
metal ions solution may affect metal affinity for
80
adsorption on the Meranti tree sawdust and that
70 the process of metal adsorption may change the
pH of an unbuffered solution. Anyway, pH may
60 play an important role in the metals adsorption,
which is an important aspect of our further studies.
% Adsorption

50

40 3.5. Effect of pH
30 The pH is one of the most important environ-
mental factors influencing not only the site dissoci-
20 ation, but also the solution chemistry of the heavy
copper
lead metals: hydrolysis, complexation by organic and/
10
or inorganic ligands, redox reactions, and precipi-
0 tation are strongly influenced by pH and, on the
0 30 60 90 120 150 180 other hand, strongly influence the speciation and
Time (min) adsorption availability of heavy metals.
Fig. 2. Effect of time in the removal of Cu(II) and Pb(II) The effect of pH on the adsorption of Cu(II)
by sawdust. and Pb(II) ions on Meranti tree sawdust has
 A. Ahmad et al. / Desalination 247 (2009) 636–646
been studied by varying it in the ranges of
2.0–7.0 for Cu(II) ions and 2.0–7.5 for Pb(II)
ions as shown in (Fig. 3). As shown in Fig. 3,
the uptake of Cu(II) and Pb(II) ions depends
on pH, it increases with the increase in pH
from 2.0 to 6.6 and 2.0 to 7.0, respectively.
Above this pH range, a decrease in the uptake
of both the metal ions was observed. The peak
percentage adsorptions of Cu(II) as well as
Pb(II) ions were attained at pH 6.6 and 7.0,
respectively.
Based on the behavior of heavy metal adsorp-
tion on sawdust, it is speculated that the ion
exchange and hydrogen bonding may be the
principal mechanism for the removal of heavy
metals [15]. There are a number of parameters
to support this speculation, including the compo-
nents and complexing properties of the sawdust,
the properties of heavy metals and the adsorp-
tion behavior, such as the effect of pH of the
aqueous media leading to change in speciation.
Based on the electron-donating nature of the
O-, S-, N-, and P-containing groups in sawdust
and the electron-accepting nature of heavy
metal ions, the ion exchange mechanism could
100
90
80
70
% Adsorption
60
40
50
30
20
copper
10 lead
0 The influence of adsorbent dosage in the removal
0 1 2 3 4 5 6 7
pH
Fig. 3. Effect of pH in the removal of Cu(II) and Pb(II)
by sawdust.
641
be preferentially considered. For instance, a
divalent heavy metal ion may attach itself to
two adjacent hydroxyl groups and oxyl groups
which can donate two pairs of electrons to the
metal ion, forming four coordination number
compounds and releasing two hydrogen ions
into solution. It is then readily understood that
the equilibrium is quite dependent on pH of
the aqueous solution. At lower pH, the H+ ions
compete with metal cations for the exchange
sites on the sawdust, thereby partially releasing
the latter. The heavy metal cations are com-
pletely released under circumstances of extreme
acidic conditions [23, 24].
At pH value lower than 3, the adsorption
capacities were found to be low due to the com-
petitive adsorption of HO3+ ions and metal ions
for the same active adsorption site. As the pH
increases, the adsorption surface becomes less
positive and therefore electrostatic attraction
between the metal ions and sawdust surface is
likely to be increased. The maximum sorption
efficiency in the range of 2.0–6.6 for Cu(II)
and 2.0–7.0 for Pb(II) ions may be due to the
interaction of M+, M(OH)+, and M(OH)2 with
surface functional groups present in the sawdust.
A decrease in adsorption at high pH is due to the
formation of soluble hydroxyl complexes.
3.6. Effect of adsorbent dosage
Adsorbent dosage is an important parameter
because it determines the capacity of an adsorb-
ent for a given concentration of the adsorbate.
The adsorption studies of Cu(II) and Pb(II) ions
on Meranti tree sawdust were done at room tem-
perature by varying the quantity of adsorbent
from 0.25 to 2.00 g while keeping the volume
of the metal solutions constant at different pH.
8 of Cu(II) and Pb(II) ions is shown in Fig. 4. The
increase in the adsorbent dosage from 0.25 to
2.0 g at pH 6.6 for Cu(II) resulted in an increase
of adsorption from 90% to 97.5%. On the other
642 A. Ahmad et al. / Desalination 247 (2009) 636–646

98 3.7. Adsorption behavior of sawdust

97
(isotherm studies)

96 The related parameters for the fitting of

Freundlich and Langmuir equations at different
% Adsorption

95 temperatures are summarized in Table 2 and iso-

94
93
92
91
90
89
0 0.5 1 1.5
Amount of adsorbent (g)
Fig. 4. Effect of adsorbent dosage in the removal of
Cu(II) and Pb(II) by sawdust.
hand, the percentage for Pb(II) ions adsorption at
pH 7.0 is 90.4% to 93.9% with the adsorbent dos-
age ranging from 0.25 to 2.00 g. The results show
that the adsorption increases with the increase in
the dose of sawdust. This is because of the avail-
ability of more binding sites on the surface at
higher concentration of the adsorbent for com-
plexation of metal ions. From this point of
view, it is easily understandable that the initial
concentration of Cu(II) and Pb(II) ions gave
some effect on its percentage removal (Fig. 4).
therm plots are shown in Figs 5–8 for Cu(II) and
Pb(II) ions, respectively. The adsorption of
Cu(II) and Pb(II) ions on sawdust at pH 6.6 and
7.0, respectively, follow both Freundlich- and
Langmuir-type adsorption isotherms. However,
copper the Freundlich equation is better obeyed by the
lead system than the Langmuir one as is evident
from the values of regression coefficient shown
2 2.5 in Table 2. The Freundlich-type adsorption iso-
therm is an indication of surface heterogeneity
of the adsorbent while Langmuir-type isotherm
hints toward surface homogeneity of the adsorb-
ent. This leads to the conclusion that the surface
of sawdust is made up of small heterogeneous
adsorption patches which are very much similar
to each other with respect to adsorption phenom-
enon. With the increase in concentration at ele-
vated temperature, the activation of adsorption
sites takes place leading to increased adsorption
probably via a surface exchange reaction.
Actually at high temperatures, the aggregation
of Cu(II) ions at the surface of sawdust increases
which results in an exchange reaction with the
already-adsorbed species along with the normal
physio-sorption.

Table 2
The related parameters for the Cu(II) and Pb(II) adsorption on sawdust at different temperatures

Temp (8C) Freundlich constants Langmuir constants

Cu(II) Pb(II) Cu(II) Pb(II)
r2 K 1/n r2 K 1/n r2 b K r2 b K
(mg/g) (mg/g) (mg/g) (L/mg) (mg/g) (L/mg)

30 0.99 2.74 0.70 0.99 1.01 0.76 0.95 37.17 0.07 0.97 37.04 0.02
40 0.99 3.20 0.68 0.99 1.17 0.74 0.96 34.84 0.09 0.99 34.84 0.02
50 0.99 3.83 0.67 0.99 1.28 0.73 0.97 34.13 0.12 0.99 33.90 0.03
60 0.99 5.43 0.59 0.99 1.76 0.68 0.95 30.67 0.22 0.97 31.95 0.04
 A. Ahmad et al. / Desalination 247 (2009) 636–646 643

1.6 1.6

1.4 1.4

1.2
1.2
1
1
log Am

0.8

log Am
0.8
0.6
30°C 0.6
40°C
0.4 50°C
60°C 30°C
40°C
0.4 50°C
0.2 60°C

0 0.2
⫺1 ⫺0.5 0 0.5 1 1.5
log Ce 0
0 0.5 1 1.5 2
Fig. 5. Freundlich plots for the adsorption of Cu(II) by log Ce
sawdust.
Fig. 7. Freundlich plots for the adsorption of Pb(II) by
sawdust.

1.2 3

1 2.5

0.8 2
Ce /Am (mg/L)
Ce /Am (mg/L)

0.6 1.5
30°C
40°C
50°C
0.4 1 60°C

30°C
40°C
0.2 50°C
60°C 0.5

0 0
0 5 10 15 20 25 0 10 20 30 40 50 60
Ce (mg/L) Ce (mg/L)

Fig. 6. Langmuir plots for the adsorption of Cu(II) by Fig. 8. Langmuir plots for the adsorption of Pb(II) by
sawdust. sawdust.

It was reported in our previous study [15] that an excellent adsorbent for copper removal
the efficiency for the removal of copper from from aqueous solution. In 2001, Yu et al. [25]
river water using Mango sawdust was 63%, on the adsorption behavior of maple sawdust
and it was thus concluded that the sawdust is for the removal of heavy metals, such as Cu(II)
644 A. Ahmad et al. / Desalination 247 (2009) 636–646
and Pb(II), presented some guidelines for the
application of sawdust adsorption. In these
studies, it was investigated that the adsorption
behavior, capacity, and other factors, such as
pH and sawdust dose, using untreated maple
sawdust. Under optimized conditions, the per-
centage of metal removal by maple sawdust
adsorption was over 90%; indicating sawdust is
an appealing adsorbent for the removal of
heavy metals.
Raji and Anirudhan reported studies on the
removal of Pb(II) using polyacrylamide grafted
sawdust [26] and polymerized sawdust [27]. In
those studies, adsorption and desorption experi-
ments were conducted, and various affecting
factors tested. Research data showed that the
treated sawdusts might be effectively used as
sorbents for the removal of Pb(II) from aqueous
media. The maximum removal of over 98%
was reported.
By comparison of the results obtained from
this study to the previously reported work on
percentage removal of various low-cost adsorb-
ents in aqueous solution for Cu(II) and Pb(II)
ions, it can be stated that our findings are well.
3.8. Thermodynamic parameter of sorption
The various thermodynamic parameters, that is
free energy (DG), enthalpy (DH), and entropy
(DS), and its values associated with the sorption
Table 3
Thermodynamic parameters for the Cu(II) and Pb(II) adsorption on sawdust at different temperatures
Temp (8C) For Langmuir isotherms
Cu(II)
ln K DG DS DH (30–608C)
30 8.37 21.09 0.17 31.47
40 8.64 22.51 0.17
50 8.92 23.98 0.17
60 9.53 26.40 0.17
DG = kJmole1, DS = kJmole1K1, and DH = kJmole1
of Cu(II) and Pb(II) ions onto the Meranti tree
sawdust are listed in Table 3 which show that
the overall processes for both ions are endother-
mic. The DH for Cu(II) is 31.47 kJ/mol and the
DH for Pb(II) is 20.07 kJ/mol. Besides that, the
K value from Table 2 indicates the affinity
toward the binding of metal ions [28]. The
highest value of K was found at 608C for each
metal ion.
The free energy of adsorption (DG) can be
related with the equilibrium constant K, corre-
sponding to the reciprocal of the Langmuir con-
stant from Eqn (3). The free energy of the
process at all temperature is negative for both
ions and it decreases with an increase in temper-
ature which indicates that the process is sponta-
neous in nature and the spontaneity increases
with the rise in temperature.
Also enthalpy (DH) and entropy (DS)
changes can be estimated by Eqns (4) and (5).
The values of DS were found to be positive
due to the exchange of the metal ions with
more mobile ions present on the exchanger,
which would cause increase in the entropy,
during the adsorption process. Besides that, the
entropy also can be increased in the case of
physisorption which may also contribute to the
total adsorption process. This is due to the
water molecules released from the hydrated
ions or water molecules present on the surface
during the adsorption process [29].
Pb(II)
ln K DG DS DH (30–608C)
8.33 20.99 0.13 120.07
8.55 22.26 0.13
8.69 23.34 0.13
9.08 25.16 0.14
 A. Ahmad et al. / Desalination 247 (2009) 636–646
4. Conclusions
Based on the present study, it is clearly shown
that sawdust obtained from Meranti wood is an
effective adsorbent for the removal of Cu(II)
and Pb(II) ions from aqueous solution. The
adsorption process is strongly affected by
parameters such as time, pH, adsorbent dosage,
and temperature. The equilibrium time for
Cu(II) and Pb(II) ions is determined as 60 min.
The percentage adsorption for Pb(II) seems to
be greater than adsorption of Cu(II) in this equi-
librium time. The plot of pH versus percentage
adsorption shows significant adsorption at pH
6.60 for the Cu(II) ions and at pH 7.00 for the
Pb(II) ions. The removal is almost 100% for
Cu(II) at this pH value being 99.39%. On the
other hand, percentage removal for Pb(II) at
this pH is 94.61%. The percentage adsorption
of Cu(II) and Pb(II) ions was increased with
increasing the adsorbent dosage. The adsorption
of Cu(II) and Pb(II) ions on sawdust at pH 6.60
and 7.00, respectively, follow both Freundlich-
and Langmuir-type adsorption isotherms. Ther-
modynamic constants were also evaluated
using equilibrium constants changing with tem-
perature. The negative value of DG for Cu(II)
and Pb(II) ions indicated the spontaneity of the
process. The positive value of DH showed the
endothermic nature of Cu(II) and Pb(II) sorp-
tion, respectively.
Acknowledgment
The study was funded through USM short-
term grant number 304/ PTEKIND/ 637044.
The authors acknowledge the USM for provid-
ing research facilities.
References
[1] P. King, P. Srinivas, Y. Prasanna Kumar and
V.S.R.K. Prasad, Sorption of copper(II) ion from
aqueous solution by Tectona grandis l.f. (teak
645
leaves powder). Journal of Hazardous Materials,
136 (2006) 560–566.
[2] B. Yu, Y. Zhang, A. Shukla, S. S. Shukla and K. L.
Dorris, The removal of heavy metal from aqueous
solutions by sawdust adsorption-removal of copper.
Journal of Hazardous Materials, B80 (2000) 33–42.
[3] B. Acemioglu and M. H. Alma, Sorption of copper
(II) ions by pine sawdust. Holz als Roh-und
Werkstoff, 62 (2004) 268–272.
[4] U. S. Environmental Protection Agency, Lead:
Identification of dangerous levels of lead; final
rule, 66 (2001) 4, U. S. Government Printing
Office, Washington, DC.
[5] S.H. Frisbie, R. Ortega, D.M. Maynard and B.
Sarkar, The concentrations of arsenic and other
toxic elements in Bangladesh’s drinking water.
Environmental Health Prospect, 110 (2002)
1147–1153.
[6] G.T. Antonio and L. Corredor, Ecotoxicology
Environmental Safety, 57 (2004) 184–189.
[7] P. Kaewsarn and Q. Yu, Binary adsorption of
Cu(II) and Cd(II) from aqueous solutions by bio-
mass of marine alga (Durvillaea potatorum). Sepa-
ration Science Technology, 34 (1999) 1595–1605.
[8] M. Suzuki, Role of adsorption in water environ-
ment processes. Water Science Technology, 35
(1997) 01–11.
[9] K.C. Sekhar, S. Subramanian, J.M. Modak and
K.A. Natarajan, Removal of metal ions using an
industrial biomass with references to environmen-
tal control. International Journal of Miner Proc-
ess, 53 (1998) 107–120.
[10] E. Pehlivan, S. Cetin and B.H. Yank, Equilibrium
studies for the sorption of zinc and copper from
aqueous solutions using sugar beet pulp and fly
ash. Journal of Hazardous Materials, 135 (2006)
193–199.
[11] S. Brunauer, (Ed.), The Adsorption of Gases and
Vapors Vol I - Physical Adsorption, Oxford
Univ. Press, London, 2007, pp 03.
[12] M. Chan-Jun and L. Jung-Heon, Use of curdlan
and activated carbon composed adsorbents for
heavy metal removal. Process Biochemistry, 40
(2005) 1279–1283.
[13] K. Santhy and P. Selvapathy, Removal of heavy
metals from wastewater by adsorption on coir
pith activated carbon. Separation Science and
Technology, 39 (2004) 3331–3351.
[14] D. Mohan and K.P. Singh, Single and multi-com-
ponent adsorption of Cd(II) and Zn(II) using
646 A. Ahmad et al. / Desalination 247 (2009) 636–646
activated carbon desired from bagasse an agricul-
turalwaste. Water Research, 36 (2002) 2304–2318.
[15] M. Ajmal, A.H. Khan, S. Ahmad and A. Ahmad,
Role of sawdust in the removal of copper(II)
from industrial wastes. Water Research, 32
(1998) 3085–3091.
[16] Y.S. Chung, K.W. Lee, Y.S. Yoon, S.H. Kwon and
K.S. Lim, The adsorption behavior of heavy metal
ions on sawdusts. Bulletin of the Korean Chemical
Society, 13 (1992) 212–214.
[17] M. Sekar, V. Sakthi and S. Rengaraj, Kinetics and
equilibrium adsorption study of lead(II) onto acti-
vated aarbon prepared from coconut shell. Journal
of Colloid Interface Science, 279 (2004) 307–313.
[18] D.V. Ladonin, The effect of iron and clay minerals
on the adsorption of copper, zinc, lead, and cad-
mium in the concretion horizon of podzolic soil.
Pochvovedenie, 10 (2003) 1197–1206.
[19] R. Apek, E.Tuten, M. Hugul and M. Hizal, Heavy
metal cations retention by unconventional sorbents
(red muds and fly ashes). Water Research, 32
(1998) 430–440.
[20] T.W. Tee and A.R.M. Khan, Removal of Pb, Cd
and Zn by waste tea leaves. Environmental Tech-
nology Letter, 9 (1988) 1223–1232.
[21] S. Larous, A.H. Meniai and M.B. Lehocine,
Experimental study of the removal of copper
from aqueous solutions by adsorption using saw-
dust. Desalination, 185 (2005) 483–490.
[22] N. Unlu and M. Ersoz, Adsorption characteristic of
heavy metal ions onto low cost biopolymeric sorb-
ent from aqueous solutions. Journal of Hazardous
Material, 136 (2006) 272–280.
[23] U. Forstner and G.T.W. Wittmann, Metal pollution
in the aquatic environment, 2nd edition, Springer,
New York, 1983.
[24] A. Shukla, Y. Zhang, P. Dubey, J.L. Margrave and
S.S. Shukla, The role of sawdust in the removal of
unwanted materials from water. Journal of Haz-
ardous Materials, B95 (2002) 137–152.
[25] B. Yu, Y. Zhang, A. Shukla, S.S. Shukla and K.L.
Dorris, The removal of heavy metals from aqueous
solutions by sawdust adsorption — removal of lead
and comparison of its adsorption with copper.
Journal of Hazardous Material, B84 (2001)
83–94.
[26] C. Raji and T.S. Anirudhan, Kinetics of Pb(II)
adsorption by polyacrylamide grafted sawdust.
Indian Journal of Chemical Technology, 4
(1997) 157.
[27] C. Raji and T.S. Anirudhan, Use of chemically
modified sawdust in the removal of Pb(II) ions
from aqueous media. Indian Journal of Environ-
ment Health, 39 (1997) 230.
[28] A.Y Dursun, A Comparative on determination of
the equilibrium, kinetic and thermodynamic
parameter of biosorption o copper(II) an lead(II)
ions onto pretreated aspergillus niger. Biochemical
Engineering Journal, 28 (2006) 187–195.
[29] G. Uslu and M. Tanyol, Equilibrium and thermo-
dynamic parameters of single and binary mixture
biosorption of lead(II) and copper(II) ions onto
pseudomonas putida: effect of temperature.
Journal of Hazardous Materials, 135 (2006)
87–93.