Chemical Engineering Journal 185–186 (2012) 82–90

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Chemical Engineering Journal

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Biosorption potential of the waste biomaterial obtained from Cucumis melo for
the removal of Pb2+ ions from aqueous media: Equilibrium, kinetic,
thermodynamic and mechanism analysis
Sibel Tunali Akar a,∗ , Sercan Arslan b , Tugba Alp b , Derya Arslan b , Tamer Akar a
a
Department of Chemistry, Faculty of Arts and Science, Eskisehir Osmangazi University, Turkey
b
Department of Chemistry, Graduate School of Natural and Applied Sciences, Eskisehir Osmangazi University, 26480 Eskisehir, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: The potential use of a waste biosorbent material obtained from Cucumis melo (C. melo) for the removal
Received 14 November 2011 of Pb2+ ions from aqueous solutions was investigated by considering equilibrium and kinetic aspects.
Received in revised form 2 January 2012 The biosorption showed a pH dependent profile. An increase in biosorbent dosage up to 1.8 g L−1 caused
Accepted 3 January 2012
an increase in the biosorption yield of the biosorbent. The relatively fast biosorption at all studied tem-
peratures follows the pseudo-second-order kinetic model. Biosorption isotherm modeling shows the
Keywords:
equilibrium data fitted to the Langmuir model with a maximum monolayer biosorption capacity of
Biosorption
3.64 × 10−4 mol g−1 . The thermodynamic parameters indicated the biosorption of Pb2+ on the biomass was
Isotherm
Kinetic
a spontaneous and endothermic process. Experiments conducted with multi-metal system demonstrated
Pb2+ that the presence of co-ions slightly reduced the Pb2+ biosorption capacity of the biomass. The possible
Mechanism Pb2+ ion-biomaterial interactions were evaluated by the zeta potential, FTIR, SEM and EDX analysis.
Thermodynamic Results of this work showed the suggested biosorbent could be an effective and eco-friendly alternative
for the removal of Pb2+ ions from contaminated solutions.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Discharge of metal contaminated effluents into aquatic environ-
ment without adequate treatment is one of the significant problems
and must be seriously considered in the water treatment technol-
ogy. Among different organic and inorganic pollutants heavy metal
ions are serious poisons capable of being assimilated and stored in
the tissues of living organisms, causing noticeable health problems.
For example, Pb2+ is a potent metal toxin and common contaminant
found in the industrial effluents [1]. Due to acute toxicity of lead, it
has joined mercury and cadmium in forming “the big three” of met-
als with the serious potential hazard [2]. The amount of lead used
in the 20th century far exceeds the total consumed in all previous
eras [3]. Effluents from production of batteries, gasoline additives,
pigments, alloys and sheets etc. contain often high concentrations
of Pb2+ ions [4]. Therefore, adequate treatment of lead containing
effluents prior to discharge into receiving bodies of water is of great
importance for human health and environmental quality.
The biosorption has considerable amount of attention as an
alternative process to traditional methods in heavy metal removal
from contaminated water. Different kinds of biomaterials interact
∗ Corresponding author. Tel.: +90 222 2393750/2862; fax: +90 222 2393578.
E-mail address: stunali@ogu.edu.tr (S. Tunali Akar).
effectively with toxic metals [5]. Among the commonly available
sorbent materials, plant origin biomasses being economic and
ecofriendly due to their unique chemical composition, availabil-
ity in large quantity, renewable, low cost and more efficient are
seem to be viable option for heavy metal remediation. Hence the
use of plant derived biomaterials in this field has received much
more attention in recent years [6]. Symphoricarpus albus berries
[7], Tamarindus indica seeds [8], olive mill solid and olive stone
[9], castor tree leaves [10], Capsicum annuum seeds [11], golden
shower pods bark [12], peanut shell [13], coffee husks [14], chaff
[15], Ficus religiosa leaves [16] and black gram husk [17] are just a
few examples of these materials.
Cucumis melo (C. melo) is one of the most important fruit crops
grown in many countries. It is easily cultivated in all the temper-
ate regions of the world because of its good adaptation to growing
conditions [18]. It was reported that about 30% of the world melon
production is in Turkey and it is followed by USA, Spain, and Roma-
nia [19]. The fruits are widely consumed as desert and vegetable in
summer period and contain seeds in large quantities [20]. The seeds
of C. melo are a rich protein (53.90%) and oil (37.67%) [21] and are
sometimes used in Chinese folk medicine as antitussive, digestive,
febrifuge and vermifuge [22].
The objective of the present work was to investigate the pos-
sible use of C. melo seeds as a biosorbent for the removal of Pb2+
ions from contaminated solutions since its biosorption potential

1385-8947/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.01.032
 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90
has not been previously reported. The batch biosorption param-
eters such as pH, biosorbent dosage, contact time, temperature
and ionic strength were investigated. Some instrumental analysis
methods were employed to evaluate the possible biosorbent-metal
ion interactions. Kinetic, isotherm and thermodynamic parame-
ters were deduced. The biosorption performance of the biosorbent
material in multi-metal mixtures was also determined in order to
study the co-ion effect. Overall the first comprehensive report on
the biosorption potential of C. melo seeds was presented.
2. Experimental
2.1. Materials used
C. melo fruits were obtained from local markets in Turkey and
seeds were removed from their flesh. Separated seeds were washed
several times with deionized water. They were crushed and ground
using a laboratory mill and dried at 60 ◦ C for 24 h to obtain a con-
stant weight. Dried seeds were screened through a sieve of 300 ␮m
particle size and then stored for further use. Pb2+ ion solutions were
prepared by dissolving Pb(NO3 )2 in deionized water to make a stock
Pb2+ solution of 1 g L−1 . Other concentrations of Pb2+ ion solutions
used in the experiments were obtained by dilution of this stock
solution. The pH adjustments were done by adding small amounts
of 0.1 M NaOH and/or 0.1 M HNO3 solutions.
2.2. Characteristics of material
Zeta potential measurements were done using a zeta potential
analyzer (Malvern zeta sizer) in order to explain the relation-
ship between the pH and surface charge of biosorbent. A 0.1 g of
biosorbent was placed into 50 mL of deionized water or 100 mg L−1
Pb2+ solutions and stirred for 80 min. The pH of the medium was
adjusted to desired value with the pH range of 2.0–5.5. The small
volumes of the mixtures were used to measure of zeta potentials.
All measurements were done at least three times and mean values
were adopted.
Original and Pb2+ -loaded biosorbent (filtered and dried after
contact with 50 mL of 100 mg L−1 Pb2+ at pH 5.5) samples were
used for FTIR, SEM and EDX analysis.
The surface functional groups on the biosorbent material were
identified using FTIR spectroscopic method. About 1 mg biosorbent
sample was ground with about 100 mg of finely divided spectro-
scopic grade KBr powder. The mixture was placed in a die and
pressed under high pressure. Obtained disks were placed into
Bruker Tensor27 FTIR spectrometer and FTIR spectra were recorded
in the region of 400–4000 cm−1 .
The surface microstructure of the biosorbent material were
characterized using scanning electron microscope coupled with
energy dispersive X-ray analysis (Zeiss SUPRA 50 VP), at 20 kV and
1000 times of magnification. Prior to analyze, biosorbent samples
were mounted on a stainless steel stab with a double stick tape.
Then they were coated with a thin layer of gold under vacuum to
improve electron conductivity and image quality.
The BET surface area, total pore volume, average pore size and
micro pore volume of the biosorbent were determined from the
N2 adsorption isotherm with a surface area and pore size analyzer
(Quantachrome Instruments, Autosorb 1).
2.3. Biosorption studies
The batch biosorption experiments were carried out by using
a sample containing 0.1 g of biosorbent and 50 mL of 100 mg L−1
Pb2+ solution in 100 mL beakers and stirring on a magnetic stirrer
at 200 rpm. The original pH of Pb2+ solution was used through-
out all biosorption experiments except when the pH effect on the
83
20
10
Zeta potential (mV)
0
1 2 3 4 5 6
pH
-10
-20
biosorbent in water
biosorbent in Pb 2+ solutions
-30
Fig. 1. Zeta potential trend for C. melo biomass at different pH values.
Pb2+ biosorption was investigated. The biosorbent dosage was opti-
mized by changing the amount of biosorbent from 0.6 to 4.0 g L−1 .
Pb2+ biosorption kinetics was determined with initial Pb2+ con-
centration of 200 mg L−1 at three different temperatures. For the
biosorption isotherms the concentration of Pb2+ solutions was
changed between 50 and 250 mg L−1 .
In order to study the competitive biosorption of Pb2+ ions from
their binary mixtures, the initial concentrations of the competing
metal ions (Cd2+ , Cu2+ and Ni2+ ) were varied between 5, 50 and
100 mg L−1 while the Pb2+ ion concentration in each biosorption
solution was held constant at 100 mg L−1 . Similarly biosorption tri-
als with Pb2+ , (Cd2+ , Cu2+ and Ni2+ ) were carried out using solutions
containing four metals simultaneously.
The equilibrium concentrations (Ce ) of the biosorbate were
determined by an atomic absorption spectrometer FAAS (ATI Uni-
cam929). Equilibrium biosorption capacities (qe ) were calculated
with Eq. (1);
V (Ci − Ce )
qe = (1)
m
where Ci is initial Pb2+ concentration (mg L−1 ), V is the solution
volume (L) and m is the amount of biosorbent (g).
2.4. Statistical analysis
In order to ensure the reproducibility of results, experiments
were replicated three times and data presented were the mean
values from these independent experiments. Experimental errors
were estimated and depicted with error bars and standard devia-
tions are indicated wherever necessary. All statistical analysis was
performed using SPSS 10.0 for Windows.
3. Results and discussion
3.1. Characterization of biosorbent
The BET surface area, total pore volume, average pore diam-
eter and micro pore volume of the biosorbent were found to be
8.407 m2 g−1 , 0.01152 cm3 g−1 , 54.83 Å and 3.94 × 10−6 cm3 g−1 ,
respectively.
The surface charge trend of the biosorbent in water and Pb2+
solutions as a function of pH was shown in Fig. 1. Firstly, the
zeta potential measurements were carried out in deionized water.
According to these results the biosorbent surface was positively
charged at pH 2.0. When the pH was increased to 3.0 the sur-
face charge of the biomass converted to negative. Above pH 3.0
the zeta potential values of the biosorbent stayed almost constant
84 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90

Fig. 2. FTIR spectra for waste biomass obtained from C. melo before (a) and after (b) Pb2+ biosorption.

(p > 0.05). Zero point of charge (ZPC) values provide useful informa-
tion related to net surface charge of the biosorbent as a function of
pH. In this study the ZPC value of the biomass in water was observed
at about pH 2.5. The high negative charge on the biosorbent sur-
face above ZPC makes it useful for metal removal because of the
attraction forces between metal cation and biosorbent surface. Sec-
ondly, biosorbent was mixed with Pb2+ ion solutions at different
pHs and zeta potentials of the mixtures were recorded. At these
conditions, ZPC value shifted to about 3.75. This finding supports
the mechanism of the electrostatic interactions between Pb2+ ions
and negatively charged groups on the biosorbent surface.
The FTIR spectrum pattern of the biosorbent material before and
after biosorption process is shown in Fig. 2. FTIR spectrum of C.
melo biomass displays a number of absorption bands, reflecting the
complex biomass structure (Fig. 2(a)). The broad stretching absorp-
tion peak at about 3400 cm−1 represents NH and bounded OH
groups. The bands at 2925 and 2854 cm−1 are assigned to symmet-
ric and asymmetric stretching vibrations of CH3 and CH2 groups
and their bending vibrations are observed at 1380 and 1462 cm−1 .
The band at 1745 cm−1 corresponds to C O stretching vibration of
carboxyl groups. Other significant band positions of C. melo seeds
are noted at 1654 cm−1 (indicative of C O stretching vibration of
amide II), 1238 cm−1 (indicative of SO3 group), 1163 cm−1 (indica-
tive of P O stretching) and 1099 cm−1 (indicative of C O stretching
of carbonyl groups and the bending vibrations of hydroxyl group).
The FTIR spectrum (Fig. 2(b)) of C. melo seeds exposed to Pb2+ ions
indicated no considerable change or shifts in any of the character-
istic absorbance bands present in unloaded biomass. This current
result implied the possibility that Pb2+ biosorption onto C. melo
biomass could be taken place through other mechanism rather than
complexation.
SEM and EDX analysis have been extensively used to identify
the possible metal–biosorbent interactions. In order to examine
the textural structure of biomass, SEM micrographs were taken Fig. 3. SEM micrographs for C. melo biomass before (a) and after (b) Pb2+ biosorption.
before (Fig. 3(a)) and after (Fig. 3(b)) Pb2+ biosorption onto C. melo
biomass. SEM micrograph of the unloaded biosorbent indicates
 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90 85

Fig. 4. EDX spectra for C. melo biomass before (a) and after (b) Pb2+ biosorption.

rough, irregular and porous structure of surface. SEM micrograph constant (p > 0.05). Hence further biosorption studies were carried
of Pb2+ -loaded biosorbent surface is significantly different from out at the original pH value of Pb2+ solutions (∼5.5) as the opti-
that of unloaded biosorbent. Many new shiny small particles was mum pH value. Biosorption studies were not conducted above pH
observed over the surface of biosorbent after the biosorption pro- 5.5 because the neutral hydrolysis product of Pb2+ (Pb(OH)2 ) was
cess. This observation evidenced the surface coverage of biosorbent formed as a solid phase in the medium.
by Pb2+ ions. EDX spectra of the unloaded and Pb2+ loaded biosor-
bent were included in Fig. 4(a) and (b), respectively. New peaks
3.3. Effect of biosorbent concentration
revealed between 2 and 3 keV (Fig. 4(b)) corresponding to lead ions
confirm the coverage of the biosorbent surface by Pb2+ ions. Dis-
Fig. 6 shows the variation of the biosorption yield of Pb2+ versus
appeared signals of Mg (at about 1.3 keV) and K (between 3 and
various biosorbent dosages ranging from 0.6 to 4.0 g L−1 . From this
4 keV) showed that an ion-exchange mechanism was included in
Pb2+ biosorption process rather than complexation with functional
groups on the biosorbent surface. 50

3.2. pH effect 40

Among the parameters affecting the biosorption of metals, ini-

tial pH is the most important due to the pH-dependent of the
q (mg g−1)

30
surface characteristics of the biosorbent and ionization degree of
the metals in aqueous medium [2]. To understand the pH effect on
the biosorption of Pb2+ ions onto the biosorbent, biosorption per- 20
formance of the biomass was investigated at pH values in the range
of 2.0–5.5. Fig. 5 shows the relationship between pH and biosorp-
tion capacity of biosorbent. The positive charge of the biosorbent 10
surface at pH 2.0 makes it impossible to bind with Pb2+ ions. There-
fore, it was seen that the biosorption of Pb2+ at pH 2.0 was almost
0
negligible while the biosorption capacity of the biosorbent started 1 2 3 4 5 6
to increase above this pH value (p < 0.05). This may be explained by
pH
the competition between H+ and Pb2+ ions caused to decreased
levels of biosorption at low pH values. At pH 4.0 the biosorp- Fig. 5. Biosorption capacities of C. melo biomass at different pH values (m: 0.1 g; V:
tion capacity attained maximum level and above it stayed almost 50 mL; t: 60 min, T: 20 ◦ C). The bars represent the standard error of the mean.
86 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90

4
o 2
20 C y = -0.0487x + 3.6157 r = 0.856
100 o 2
30 C y = -0.0500x + 3.2978 r = 0.648
3 o 2
40 C y = -0.0458x + 3.3205 r = 0.836

80
Biosorption yield (%)

ln (qe-qt)
60

0
40
-1
20
-2

0 -3
0 1 2 3 4 5 0 20 40 60 80 100
m (g L−1) t (min)

Fig. 6. Effect of biosorbent concentration on the biosorption of Pb2+ ions onto C. melo Fig. 8. Pseudo-first-order kinetic plots for the biosorption of Pb2+ ions onto C. melo
biomass (pH: 5.5; V: 50 mL; t: 60 min, T: 20 ◦ C). The bars represent the standard error biomass at different temperatures (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; T: 20 ◦ C).
of the mean.

liquid phases [25,26]. Therefore, the optimum contact time was

figure it was observed that the biosorption yield firstly increased
from 32.94 ± 0.70% to 94.65 ± 1.20% with an increase in the biosor-
bent concentration from 0.6 to 1.8 g L−1 (p < 0.05). This is due to
an increase in the surface area of the biosorbent, which conse-
quently increases the number of binding sites [23]. Further increase
in biosorbent concentration did not cause much increase in the
biosorption yield for Pb2+ (p > 0.05). This can be explained by the
decreased active binding sites on the biosorbent as a result of partial
aggregation at higher amount of biosorbent [24]. Therefore 1.8 g L−1
was selected as optimum biosorbent concentration that would be
required for cost-effective treatment of Pb2+ ions.
3.4. Equilibrium time and temperature effect
selected as 80 min for further experiments. This relatively short
contact time may also provide an advantage for the large-scale
application of the biosorption method to real wastewater treat-
ment systems.
Fig. 7 also describes the temperature effect on the biosorption
capacity of the biomass at various contact times. The tempera-
ture positively affected the biosorption efficiency of biosorbent
for Pb2+ ions. The experimental equilibrium biosorption capacity
increased from 52.09 ± 1.47 to 75.88 ± 0.75 mg g−1 (p < 0.05) when
the temperature was raised from 20 to 40 ◦ C. Therefore, the Pb2+
biosorption occurred endothermically. The similar results for the
metal biosorption onto the various biosorbents were reported in
the literature [27–30].

Fig. 7 shows the equilibrium time profile of the biosorption
capacity of biomass versus contact time at different temperatures.
The biosorption was rapid in the initial stages of the process and
increased with an increase in contact time up to 80 min (p < 0.05).
After this period the biosorption capacity of biomass did not sig-
nificantly change up to 90 min (p > 0.05). This could be attributed
to a large number of vacant binding sites, which are available for
biosorption during the initial stage, and after an increase in contact
time, the occupation of the remaining vacant sites will be difficult
due to the repulsive forces between the Pb2+ ions on the solid and
100
80
qt (mg g )
3.5. Biosorption kinetics
With respect to the kinetic modeling of Pb2+ biosorption, the
pseudo-first-order and the pseudo-second-order rate equations
have been used.
The pseudo first-order model of Lagergren [31] is presented by
the following equation:
ln(qe − qt ) = ln qe − k1 t (2)
The plot of ln(qe − qt ) against t provides a linear relationship from
which k1 , rate constant of pseudo-first-order biosorption (min−1 )
(Fig. 8) and qe , biosorption capacity at equilibrium (mg g−1 ) are
determined from the slope and intercept of the plot, respectively,
given that qt is the biosorption capacity at time t, (mg g−1 ).
The biosorption kinetics can also be described by the pseudo-
second-order rate equation [32];
t

60 1 1
−1

= + t (3)
qt k2 q2e qe
40 The initial biosorption rate, h (mg g min−1 ), is presented by:

h = k2 q2e (4)
20
where k2 is the equilibrium rate constant of pseudo-second-order
biosorption (g mg−1 min−1 ). Values of k2 and qe were calculated
0 from the plot of t/qt against t (Fig. 9).
0 20 40 60 80 100 The pseudo-first-order and the pseudo-second-order kinetic
t (min) models were tested in the temperature range of 20–40 ◦ C and
the results were represented in Table 1. This table indicated the
Fig. 7. Effect of contact time on the biosorption of Pb2+ ions onto C. melo biomass at
different temperatures (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; T: 20 ◦ C). The bars represent
pseudo-first-order kinetic model did not identify the Pb2+ biosorp-
the standard error of the mean. tion in this study. The r2 values of this model were lower than those
 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90 87

Table 1
Kinetic parameters for the biosorption of Pb2+ ions onto C. melo biomass at different temperatures.

T (◦ C) Pseudo-first-order Pseudo-second-order

qe (exp) k1 (min−1 ) qe (mg g−1 ) r12 k2 (g mg−1 min−1 ) qe (mg g−1 ) h (mg g min−1 ) r22

20 52.09 4.87 × 10−2 37.18 0.856 5.07 × 10−4 70.20 2.50 0.997
30 69.55 5.01 × 10−2 27.05 0.648 9.77 × 10−4 81.04 6.42 0.998
40 75.88 4.58 × 10−2 27.68 0.836 1.67 × 10−3 83.61 11.67 0.998

for the pseudo-second-order model. The biosorption of Pb2+ on ‘RL ’, referred to as separation factor or equilibrium parameter and
the biomass follows the pseudo-second-order kinetic model with RL is defined by the following equation:
the higher (>0.996) r2 values for all temperatures. The biosorp-
1
tion of Pb2+ was endothermic since the biosorption capacity values RL = (7)
1 + KL C0
increased with increasing temperature. In addition, temperature
also affected the kinetics of Pb2+ biosorption in such a way that where C0 is the initial solute concentration (mol L−1 ). If the RL values
the rate constant (overall and initial) increased with tempera- lie between 0 and 1, the biosorption process is considered to be
ture. The values of k2 were found to increase from 5.07 × 10−4 to favorable.
1.67 × 10−3 g mg−1 min−1 when the temperature increased from 20 The linear Dubinin–Radushkevich isotherm model can be rep-
to 40 ◦ C. resented as [36]:

3.6. Effect of initial metal concentration ln qe = ln qm − ˇε2 (8)

where ε = RT ln(1 + 1/Ce ) (Polanyi potential), qm is the biosorp-

The effect of initial Pb2+ ion concentration was investigated in tion capacity (mol g−1 ), ˇ is the activity coefficient related to the
the range of 50–250 mg L−1 at predetermined optimum conditions. biosorption energy, R is the gas constant and T is the absolute tem-
Equilibrium data for the biosorption Pb2+ ions were evaluated with perature (K). D–R isotherm constants, ˇ and qm can be calculated
Freundlich, Langmuir and Dubinin–Radushkevich (D–R) isotherm from the slope and intercept of the plot of ln qe against ε2 , respec-
models. tively and the mean free energy (E) can be calculated from the
The linearized form of Freundlich equation [33] is: ˇ-value obtained from the following equation [37–39]:
1 1
ln qe = ln KF + ln Ce (5) E= (9)
n 1/2
(2ˇ)
where KF (L g−1 )
and n (dimensionless) are Freundlich constants
and indicators of the biosorption capacity and biosorption intensity, From the magnitude of E, the type of biosorption such as chemisorp-
respectively. tion or physical sorption can be determined. If E = 8–16 kJ mol−1 ,
The well known expression of the Langmuir model is [34]: then the reaction is due to the chemical ion-exchange; if
  1 E < 8 kJ mol−1 , then biosorption takes place physically.
1 1 1 The Freundlich, Langmuir and D–R isotherms for the
= + (6)
qe qmax qmax KL Ce removal of Pb2+ onto the waste biosorbent were presented in
where qe (mol g−1 ) and Ce (mol L−1 ) are the amount of biosorbed Figs. 10, 11 and 12, respectively. The calculated model constants
Pb2+ per unit weight of biosorbent and residual Pb2+ concentra- and r2 values are included in Table 2. These data indicated that
tion in solution at equilibrium, respectively. qmax (mol g−1 ) is the Langmuir isotherm model well described the experimental data
maximum amount of Pb2+ per unit weight of biosorbent to form a at all studied temperatures, meaning that the surface of the
complete monolayer on the surface and KL (L mol−1 ) is a constant biosorbent is made up of homogeneous biosorption patches. The
related to the energy of biosorption. maximum monolayer biosorption capacity of the biosorbent was
Hall et al. [35] reported that the essential feature of the Langmuir obtained as 3.64 × 10−4 mol g−1 (75.42 mg g−1 ) at 20 ◦ C and found
isotherm can be expressed by means of a dimensionless constant
-7,6
o
20 C y = 0,3211x -5,6729 r ² = 0,872
1,8 o
-7,8 30 C y = 0,2317x - 6,1437 r ² = 0,775
o
1,6 40 C y = 0,2066x - 6,2277 r ² = 0,847
-8,0
1,4
-8,2
t/qt (min g mg -1)

1,2
-8,4
lnqe

1,0
-8,6
0,8
-8,8
0,6
-9,0
0,4
-9,2
0,2
-9,4
0,0 -13 -12 -11 -10 -9 -8 -7
0 20 40 60 80 100 lnCe
t (min)
Fig. 10. Freundlich isotherm plots for the biosorption of Pb2+ ions onto C. melo
Fig. 9. Pseudo-second-order kinetic plots for the biosorption of Pb2+ ions onto C. biomass at different temperatures (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; t: 80 min; T:
melo biomass at different temperatures (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; T: 20 ◦ C). 20 ◦ C).
88 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90

Table 2
Isotherm constants for the biosorption of Pb2+ ions onto C. melo biomass at different temperatures.

T (◦ C) Langmuir Freundlich Dubinin–Radushkevich (D–R)

qmax (mol g−1 ) KL (L mol−1 ) rL2 n KF (L g−1 ) rF2 qmax (mol g−1 ) ˇ (mol2 kJ−2 ) rD2 –R E (kJ mol−1 )

20 3.38 × 10−4 1.32 × 104 0.992 3.11 3.44 × 10−3 0.872 8.79 × 10−4 1.77 × 10−3 0.903 16.80
30 3.63 × 10−4 4.17 × 104 0.992 4.32 2.15 × 10−3 0.775 7.71 × 10−4 1.42 × 10−3 0.824 18.77
40 3.64 × 10−4 9.52 × 104 0.999 4.84 1.97 × 10−3 0.847 7.58 × 10−4 1.27 × 10−3 0.891 19.88

10000 Table 3
Biosorption results of Pb2+ ions by different biosorbents from the literature.
9000
Biosorbent material Biosorption References
8000 capacity (mg g−1 )

Symphoricarpus albus 62.16 [7]

1/qe (g mol )
−1

7000 Chaff 12.50 [15]

Ficus religiosa leaves 37.45 [16]
6000 Cladonia furcata 12.30 [24]
Phaseolus vulgaris L. 42.77 [27]
5000 Seed husk of Calophyllum inophyllum 34.51 [28]
Penicillium simplicissimum 87.72 [29]
4000 Nostoc sp. 93.46 [30]
o
20 C y = 0,2250x + 2959,1387 r ² = 0,992 Aspergillus flavus 13.46 [40]
3000 o
30 C y = 0,0659x + 2749,0200 r ² = 0,992 Bacillus sp. 92.27 [41]
o
40 C y = 0,0288x + 2744,7379 r ² = 0,999
C. melo 75.42 This study
2000
0,0 2,0e+4 4,0e+4 6,0e+4 8,0e+4 1,0e+5 1,2e+5 1,4e+5 1,6e+5 1,8e+5

1/Ce (L mol−1) 0,30

20 C
30 C
Fig. 11. Langmuir isotherm plots for the biosorption of Pb2+ ions onto C. melo
0,25 40 C
biomass at different temperatures (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; t: 80 min; T:
20 ◦ C).
0,20
RL

to be higher than that of and comparable to many biosorbents 0,15

reported in the literature (Table 3). The RL values in this study
were obtained at the range of 0.250–0.059, 0.095–0.020 and 0,10
0.042–0.008 at the temperatures of 20, 30 and 40 ◦ C, respectively
(Fig. 13), indicating that the biosorption process is favorable. In 0,05
addition, RL values decreased as the initial Pb2+ concentration
increased. Therefore, the biosorption of Pb2+ was more favorable
0,00
at higher concentration. 0 50 100 150 200 250 300
In order to determine the type of biosorption, the equilib- -1
Co (mg L )
rium biosorption data were also tested with the D–R model.
The mean free energy of biosorption (E) is found between 16.80
Fig. 13. RL values for the biosorption of Pb2+ ions onto C. melo biomass at different
and 19.88 kJ mol−1 at studied temperature range, which implies temperatures and initial Pb2+ concentrations.
that the removal process of Pb2+ from aqueous solutions is
chemisorption.
3.7. Thermodynamics of biosorption

Pb2+ biosorption may be represented by the following reversible

-7,6 process:
o
20 C y = -3,141e-9x - 7,0366 r ² = 0,903
-7,8 o
30 C y = -2,015e-9x - 7,1689 r ² = 0,824 Pb2+ in solution  Pb2+ -biosorbent
o
40 C y = -1,601e-9x - 7,1846 r ² = 0,891
-8,0
For such equilibrium reactions, KL (Langmuir constant) can be
-8,2 used as equilibrium constant in order to estimate thermodynamic
parameters, such as change in the free energy (G◦ ), enthalpy
-8,4
(H◦ ) and entropy (S◦ ) associated to the biosorption process.
lnqe

-8,6 They were determined by using following equations and repre-

sented in Table 4.
-8,8

-9,0 G◦ = −RT ln KL (10)

-9,2
Table 4
-9,4 Thermodynamic parameters for the biosorption of Pb2+ ions onto C. melo biomass.
2,0e+8 4,0e+8 6,0e+8 8,0e+8 1,0e+9 1,2e+9
T (◦ C) G◦ (kJ mol−1 ) H◦ (kJ mol−1 ) S◦ (kJ K−1 mol−1 )
ε (J mol )
2 -1 2
20 −23.22
30 −26.59 75.67 0.337
Fig. 12. D–R isotherm plots for the biosorption of Pb2+ ions onto C. melo biomass at
40 −29.97
different temperatures (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; t: 80 min; T: 20 ◦ C).
 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90 89

12,0
y = -9101,908x + 40,5755 r ² = 0,994

11,5

11,0
lnKL

10,5

10,0

9,5

9,0
0,00315 0,00320 0,00325 0,00330 0,00335 0,00340 0,00345
1/T (K-1)

Fig. 14. Plot of ln KL versus 1/T for estimation of thermodynamic parameters for the
biosorption of Pb2+ ions onto C. melo biomass.
G◦ H ◦ S ◦
ln KL = − =− + (11)
RT RT R
where R is the universal gas constant, 8.314 J mol−1 K−1 , and T is
the absolute temperature in K. The plot of ln KL as a function of
1/T (Fig. 14) yields a straight line from which H◦ and S◦ were
calculated from the slope and intercept, respectively. The negative
values of G◦ at all temperatures studied indicate the Pb2+ biosorp-
tion is a spontaneous process and the biosorbent has higher affinity
at higher temperatures. A decrease in the magnitude of G◦ values
with an increase in the temperature may be attributed to a reduc-
tion in the spontaneity degree at studied temperatures. The positive
value of H◦ suggests the endothermic nature of biosorption. The
positive S◦ value indicates that randomness at the solid-solute
interface increases with Pb2+ biosorption onto the biosorbent [42],
suggests good affinity of Pb2+ toward the biosorbent and reflects
some structural changes in biosorbate and biosorbent.
3.8. Effect of ionic strength
The effect of ionic strength on the Pb2+ biosorption was inves-
tigated by changing KNO3 concentration from 0.01 mol L−1 from
0.50 mol L−1 at pH 5.5. Fig. 15 shows that the influence of the ionic
strength on the biosorption of Pb2+ is almost negligible at 0.01
and 0.02 mol L−1 of KNO3 concentrations. The biosorption capacity
100
80
Biosorption yield (%)
Fig. 16. Competitive biosorption results for the biosorption of Pb2+ ions onto C. melo
biosorbent in binary and multi metal mixtures (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; t:
80 min; T: 20 ◦ C). The bars represent the standard error of the mean.
sharply decreased from 80.48± to 57.85± mg g−1 (p < 0.05) when
the ionic strength of the biosorption medium was increased from
0.01 to 0.10 mol L−1 . The biosorption potential of the biosorbent
was almost constant up to 0.50 mol L−1 of KNO3 (p > 0.05). This
can be explained by two ways. Firstly, the competition of the K+
ions with Pb2+ ions on the biosorbent surface caused a decrease in
the biosorption performance of the biosorbent. Secondly, the elec-
trostatic interaction between Pb2+ ions and the active biosorption
sites on the biosorbent can be other mechanism for the biosorption
process. This findings also agree with the literature [43,44].
3.9. Competitive biosorption
The biosorption yield of Pb2+ onto the biosorbent in the presence
of (Cd2+ , Co2+ and Ni2+ ) at different concentrations was evaluated.
The experiments were carried out in binary- and multi-metal mix-
ture conditions. The results were presented in Fig. 16 and indicated
that the presence of other metal ions reduced the Pb2+ biosorption
yield of the biomass. The reduction ratio of biosorption yield of the
biosorbent slightly increased when the concentration of co-ions
was increased from 5 to 100 mg L−1 . The presence of (Cd2+ , Co2+ and
Ni2+ ) in binary systems reduced the biosorption performance of the
biosorbent for Pb2+ by 28.05%, 12.13% and 25.25%, respectively. In
the simultaneous presence of all metal ions it decreased by 30.50%.
This observation could be attributed to the competition between
Pb2+ and the other co-ions for the active biosorption sites on the
biosorbent surface. Similar effects of co-cations in the biosorption

medium were reported in the literature [40,41,45–47].

60
4. Conclusions

40
This study reveals:

• pH 5.5 was suitable for the Pb2+ removal onto the waste biosor-
20 bent of C. melo, 1.8 g L−1 of biosorbent was enough for the
maximum biosorption of Pb2+ ,
• The pseudo-second-order rate equation best described the Pb2+
0
0,0 0,1 0,2 0,3 0,4 0,5 0,6
biosorption kinetics. The equilibrium data for Pb2+ biosorption
fitted well to the Langmuir model,
Csalt (mol L−1) • An endothermic process was responsible for the biosorption of
Pb2+ on the biomass,
Fig. 15. Effect of ionic strength on the biosorption of Pb2+ ions onto C. melo biosor- • Competitive conditions indicated that the biosorption yield was
bent (pH: 5.5; V: 50 mL; m: 1.8 g L−1 ; t: 80 min; T: 20 ◦ C). The bars represent the
standard error of the mean.
decreased by 30.50% in multi-metal mixtures,
90 S. Tunali Akar et al. / Chemical Engineering Journal 185–186 (2012) 82–90
• Finally, characterization studies show the Pb2+ biosorption takes
place with mechanisms including especially electrostatic attrac-
tion forces and ion-exchange.
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