Journal of Environmental Science and Health Part A, 41:2587–2606, 2006
C Taylor & Francis Group, LLC
Copyright
ISSN: 1093-4529 (Print); 1532-4117 (Online)
DOI: 10.1080/10934520600927989
Biosorption Potential of the
Macrofungus Ganoderma
carnosum for Removal of
Lead(II) Ions from Aqueous
Solutions
Tamer Akar,1 Ahmet Cabuk,2 Sibel Tunali,1
and Mustafa Yamac2
1
Department of Chemistry, Faculty of Arts and Science, Eskişehir Osmangazi University, Eskişehir, Turkey
2
Department of Biology, Faculty of Arts and Science, Eskişehir Osmangazi University,
Eskişehir, Turkey
This paper reports the utilization of a macro-fungus Ganoderma carnosum as a biosorbent material for the removal of lead(II) ions from aqueous solutions. The biosorption potential of G. carnosum was investigated by batch experiments. The influences
of physico-chemical parameters like pH, biosorbent dosage, contact time and initial
metal ion concentration were evaluated. The biosorption equilibrium was attained in
10 minutes. Equilibrium biosorption data were analyzed by the Freundlich, Langmuir
and Dubinin–Radushkevich (D–R) isotherm models. Maximum biosorption capacity of
biosorbent was found to be 22.79 mg g−1 (1.10 × 10−4 mol g−1 ) at the pH value of 5.0. The
biosorbent was regenerated using 10 mM HCl solution, with up to 96% recovery, and
reused four times in biosorption-desorption cycles successively. Biosorption efficiency of
G. carnosum was also examined in a real effluent. The mechanism of the biosorption was
investigated with FTIR, SEM and EDAX analysis and the findings suggested that the
biosorption process involved in ion exchange as dominant mechanism as well as complexation. The ion exchange mechanism was also confirmed by the mean free energy
value obtained from D–R isotherm model.
Key Words: Biosorption, Equilibrium, Ganoderma carnosum, Ion-exchange, Isotherm.
Received March 30, 2006.
Address correspondence to Tamer Akar, Eskişehir Osmangazi University, Faculty of
Arts and Science, Department of Chemistry, 26480, Eskişehir, Turkey; E-mail: takar@
ogu.edu.tr
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INTRODUCTION
Heavy metals are hazardous contaminants because they cannot be broken into
simpler, less toxic forms and they persist unchanged in the environment for
many years.[1] The presence of heavy metal ions in the aquatic systems has
been of great concern because of their toxicity even at lower concentrations.[2]
Toxic metals enter waterways from two main sources: industrial waste discharges and particulates in the atmosphere that settle and are carried in
runoff.[1]
One of the significant toxic metal ions for human health is lead. It is the
most widely distributed in the environment and the one that the average person is the most likely to encounter. The hazardous effects of lead are on central
and peripheral nervous systems, haematopoietic, renal, gastrointestinal, cardiovascular and reproductive systems. The other damaging effects of lead are
anaemia, tenderness, loss of cognitive abilities, nausea[1,2] and suppression of
the mental capacity of children.[3] Studies have shown that infants exposed to
lead have IQ scores that are 5% lower by age 7 than the scores of unexposed
children; the children are six times more likely to have reading disabilities and
seven times more likely to drop out of school.[1] Therefore, there is significant
interest regarding lead removal from contaminated water systems.
Biosorption technology has emerged as a promising alternative method over
conventional treatment methods with the advantages of low operating cost,
minimization of the chemical and/or biological sludge volume, high efficiency
in detoxifying very dilute effluents, no nutrient requirements and regeneration
of sorbent material and possibility of metal recovery. It is based on the property
of microbial biomass to sequester heavy metals through interactions between
toxic metal ions and the metal binding functional groups present on the cell wall
structure of the microbial origin sorbents composed mainly of polysaccharides,
proteins and lipids.[4,5]
The most of the earlier reports in the literature indicates the potential
use of different types of biomass in heavy metal removal. Those include microfungi,[6−11] bacteria,[12−16] yeast[17,18] and algae[19,20] whereas there is still very
little information about the use of the biomass of the macro-fungi[21−23] as a
biosorbent for heavy metal removal.
In the present study macro-fungi Ganoderma carnosum, was identified
as a promising biosorbent for the removal of lead(II) ions from aqueous solution. To our knowledge, it has not been used for the sorption of heavy metals
from aqueous solutions. The influence of initial pH, biosorbent dosage, contact
time, initial lead(II) ion concentration and co-ions on biosorption was studied.
Biosorption-desorption cycles were performed to determine the reusability potential of biosorbent. The biosorption equilibrium data at 20◦ C were modelled
by using the Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm
models. The mechanism of the process was investigated by Fourier transform
Ganoderma carnosum as Biosorbent for Lead Removal
2589
infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energydispersive X-ray analysis (EDAX).
MATERIALS AND METHODS
Preparation of the Biosorbent Material
The macro-fungus used in the present study was G. carnosum, provided
from fungi culture laboratory of Biology Department of Eskisehir Osmangazi
University. The fungal biomass was washed with deionised water for several
times in order to remove dust, cut into small pieces and then dried in an oven at
70◦ C until constant weight. The biomass was then grounded and sieved to select
particle size of less than 300 µm and subsequently was used for biosorption
experiments.
Batch Biosorption Experiments
Batch experiments were performed with a magnetic stirrer at 200 rpm and
20◦ C using 100 mL beakers containing test solutions. The stock lead(II) ion
solution (1 g L−1 ) was prepared by dissolving of Pb(NO3 )2 of analytical grade in
deionised water. Other concentrations were prepared by dilution of this stock
solution and fresh dilutions were used in each experiment.
To study the effect of initial pH on lead(II) biosorption onto G. carnosum
biomass, 50 mL of 100 mg L−1 lead(II) solution was used and then the initial pH
values of the contact solutions were adjusted to a value in the range of 1.0–5.0
by adding 0.1 M HCl or 0.1 M NaOH. Then 0.1 g of biomass was added to each
beaker and the biosorption mixtures were stirred for 1 h, which is sufficiently
long enough for biosorption equilibrium. The effect of biosorbent dosage was
studied by using different dose of biomass (0.2–12 g L−1 ). The optimum pH and
biosorbent concentration were determined as 5.0 and 4.0 g L−1 , respectively and
used throughout all biosorption experiments. The period of contact time was
varied from 5 to 120 min by using the same sorption mixture described above
to determine the optimum biosorption time. The effect of the initial lead(II)
concentration on the biosorption was studied at optimum conditions determined
above except that the concentration of lead(II) in the biosorption mixture was
varied between 30 and 300 mg L−1 . The co-ion effect on the biosorption of
lead(II) was also investigated in multiple metal ion mixture containing Pb2+ ,
Ni2+ , Cd2+ and Mn2+ ions. The medium containing 100 mg L−1 of each metal
ion was incubated with 0.2 g of biosorbent at pH 5.0 for 10 min.
After biosorption, the contents of the beakers were centrifuged at 4500 rpm
for 3 min and the biomass was successfully separated from aqueous solution. The supernatants were analyzed for residual lead(II) concentration using an atomic absorption spectrophotometer (Hitachi 180-70, Japan). The
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measurements were performed under the following conditions: air-acetylene
flame, 7.5 mA lamp current, 1.3 nm spectral slit width and 283.3 nm wavelength.
The instrument calibration was checked using a known lead standard solution in every 10 readings. The biosorption capacity, (qe ), per g of biomass, was
calculated from the general mass-balance equation (Eq. 1) as follows:
qe = [(Ci − Ce )]·V/M
(1)
where, Ci (mg L−1 ) and Ce (mg L−1 ) are the initial and equilibrium lead(II) ion
concentrations of the solution; V: volume of the lead(II) solution (L); M: weight
of the biomass added into reaction mixture (g).
Reusability Tests of Biomass
The recovery and reusability of biosorbent material are important parameters related to the application potential of biosorption technology.[24] In this
work consecutive biosorption and desorption cycles were repeated for four times
using the same biomass in order to determine the reusability potential of G.
carnosum. Following the batch biosorption process, lead(II)-loaded biomass was
separated by centrifugation and suspended into 50 mL of the eluent solution
(10 mM HCl). Each biosorption and desorption cycles were allowed 10 min of
contact time in the solutions containing biosorbent—lead (II) ions or biosorbentdesorbent agent for achieving sorption or desorption equilibrium. The concentrations of the lead(II) ion released into eluent solutions were determined as
described above. The eluted biosorbent was thoroughly washed with deionised
water and placed into metal solution for the next biosorption and desorption
cycles. Desorption efficiency was calculated by using the following equation.
Desorption efficiency =
Amount of lead(II) desorbed
× 100
Amount of lead(II) biosorbed
(2)
Real Industrial Wastewater
The industrial wastewater was collected from the main drain of the casting
unit of metal processing industry from Eskişehir, Turkey. Wastewater sample
was placed into a sterile container and transferred to laboratory and stored at
5◦ C. The various characteristics of wastewater were presented in Table 1. Furthermore, real wastewater sample was spiked with lead(II) and the proposed
biosorption method was applied to with and without spiked samples.
Statistical Analysis
Data presented are the mean values from three independent experiments.
Standard deviation and error bars are indicated wherever necessary. All
Ganoderma carnosum as Biosorbent for Lead Removal
2591
Table 1: Chemical characteristics of wastewater sample.
Parameters
pH
Temperature (◦ C)
Suspended solid (mg L−1 )
Lead (mg L−1 )
Copper (mg L−1 )
Nickel (mg L−1 )
Cadmium (mg L−1 )
Sodium (mg L−1 )
Potassium (mg L−1 )
Calcium (mg L−1 )
Magnesium (mg L−1 )
Effluent quality
3.16
27
26
1.9
137.3
22.3
5.8
66.2
7.0
243.0
112.0
statistical analysis was done using SPSS 9.05 for Windows where it is possible to evaluate whether the effect and the interaction among the investigated
factors are significant with respect to the experimental error.
FTIR Spectral Analysis
In an effort to find out the binding functional groups on the biomass surface
that are responsible from the lead(II) biosorption, infrared analysis of unloaded
and lead(II)-loaded biomass samples were carried out with a Bruker Tensor 27
FTIR spectrophotometer within the range of 400–4000 cm−1 .
SEM and EDAX Analysis
The porosity of biosorbent surface and possible metal-biosorbent interactions were examined with SEM and EDAX analysis. The morphological analysis of unloaded and lead(II) loaded biomass were carried out by means of a
Cam Scan Oxford Link scanning electron microscope coupled with an energy
dispersive X-ray analyzer.
RESULTS AND DISCUSSION
Effect of Initial pH
The pH dependency of the biosorption of lead(II) ions was studied at a
pH range of 1.0–5.0 and the results are represented in Figure 1. It was observed that biosorption was negligible at the initial pH below 2.0. When the
initial pH values were increased from 3.0 to 5.0 the biosorption capacity of G.
carnosum biomass was increased as much as about five fold (from 4.11 ± 0.75
to 18.79 ± 1.19 mg g−1 , P < 0.05). The higher pH values (pH > 5.5) were not
used due to precipitation of lead(II) ions. The low lead(II) biosorption at highly
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Akar et al.
Figure 1: pH effect on the lead(II) biosorption onto G. carnosum.
acidic conditions may be explained by competition between lead(II) ions and
protons for occupancy in the same biosorption sites. This competition creates a
repulsive ionic environment, less favorable to further binding of lead(II) ions,
resulting in the reduced lead(II) biosorption.[25] However, as the pH increases
the concentration of H+ ions decreases and the binding groups on the biosorbent
surface become negative as a result of deprotonation. Thus more negative binding sites for lead(II) ions are provided. The maximum lead(II) biosorption by G.
carnosum was observed at pH 5.0 and the further experiments were performed
at optimal pH. Similar pH trends for different biosorbents were reported in the
literature.[7,26]
Effect of Biosorbent Concentration
The effect of the biosorbent concentration on the lead(II) biosorption yield
was investigated by varying the biosorbent concentration between 0.2–12 g
L−1 at pH 5.0 and the results are presented in Figure 2. From the figure it
was observed that the biosorbent concentration played an important role in the
biosorption yield of G. carnosum for lead(II) ions. The increase in the biosorbent
dosage from 0.2 to 4.0 g L−1 leads to a significantly increase in the percentage
of lead(II) biosorption from 5.6 ± 1.12 to 75.16 ± 1.13% (P < 0.05). So, 4.0 g
Ganoderma carnosum as Biosorbent for Lead Removal
2593
Figure 2: Biosorbent dosage effect on the lead(II) biosorption onto G. carnosum.
L−1 biosorbent dosage was chosen for the next experiments. The increase in
the lead(II) biosorption with the biosorbent concentration can be explained by
increased surface area of the biosorbent and availability of more binding sites
for lead(II) ions.
Effect of Contact Time
To determine the appropriate contact time the biosorption experiments
were conducted with 100 mg L−1 of lead(II) ion concentration and various contact time between 5–120 minutes at pH 5.0. The results are plotted in Figure 3.
It can be seen that the biosorption rate of lead(II) ions was very fast initially
(5 minutes) and the equilibrium was established rapidly within the short period
of 10 min. The amount of sorbed lead(II) ions was increased from 15.49 ± 0.84
to 17.82 ± 1.62 mg g−1 (P < 0.05) during this period. After the sorption equilibrium, the lead(II) uptake values did not significantly change with the further
increase in the contact time (P > 0.05). Therefore, 10 minutes was maintained
as the equilibrium time for the following experiments. Saeed and co-workers
reported that the rate of biosorption process in metal removal is of greatest
significance for developing a biosorbent-based water-treatment technology.[27]
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Akar et al.
Figure 3: Contact time effect on the lead(II) biosorption onto G. carnosum.
Effect of Initial Lead(II) Concentrations
To determine the effect of the initial metal ion concentration on the biosorption capacity of biomass the initial concentrations of lead(II) ions were varied
between 30 and 300 mg L−1 at optimum conditions. The results are plotted in
Figure 4 which clearly indicate that the lead(II) biosorption by G. carnosum
biomass was highly depend on the initial lead(II) concentration. According to
Figure 4, biosorption capacity of G. carnosum biomass increased first with
increasing of the initial concentrations of lead(II) ions in the solution up to
150 mg L−1 (P < 0.05) and then did not significantly change (P > 0.05) with
further increase in the initial lead(II) concentrations. The maximum lead(II)
removal capacity of G. carnosum biomass was found as 22.81 ± 2.03 mg g−1 at
150 mg L−1 of initial lead(II) concentration. This trend is agreement with the
previous reports in the literature.[7,8,28] An increase observed in the biosorption capacity of the biomass from beginning to the saturation value could be
attributed to increase in the driving force the concentration gradient, as an
increase in the initial metal ion concentrations.[29] The reason of observed constant biosorption capacity after the saturation value can be explained by the
completely occupancy of binding sites on the biosorbent surface by metal ions.[6]
The lead(II) ion concentration in industrial wastewaters can vary between 200
Ganoderma carnosum as Biosorbent for Lead Removal
2595
Figure 4: Initial metal ion concentration effect on the lead(II) biosorption onto
G. carnosum.
and 500 mg L−1 .[30] Therefore, this study can provide practical benefits on such
applications when the studied range of lead(II) ion concentration was taken
into account.
Desorption and Reusability Studies
For the more economically biosorption system in water treatment process
the reusability potential of biosorbents after regeneration is very important.
The results of desorption experiments of lead(II) ions by 10 mM of HCl solution are shown in Figure 5. It can be seen that desorption of lead(II) from
metal-loaded biosorbent was resulted with more than 95% recovery of lead(II)
ions. The biosorption efficiency did not significantly change (P > 0.05) and only
a maximum 13% decrease was observed after four consecutive biosorptiondesorption cycles. These results showed that the G. carnosum biomass has a
good potential for the removal of lead(II) ions repeatedly from aqueous solutions
without any detectable loss in the total biosorption capacity.
Co-ion Effect
The co-ion effect on the biosorption of lead (II) ions by G. carnosum biomass
was studied for multi-metal containing solution. Lead(II) biosorption capacity
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Figure 5: Regeneration and reusability of G. carnosum for the lead(II) biosorption.
of biomass was slightly reduced from 18.79 ± 1.34 to 15.03 ± 1.15 mg g−1 by the
presence of nickel(II), cadmium(II) and manganese(II) ions in the same sorption mixture. The slightly decrease in the lead(II) biosorption capacity of the
biomass could be explained by the competition between metal ions for the same
biosorption sites on the biomass surface. This small decrease in the biosorption
capacity of the biomass in multi-metal containing systems could be an advantage for specific lead(II) sorption.
Biosorption Isotherms
The equilibrium sorption isotherms are one of the most important data to
understand the mechanism of the sorption[31] and to evaluate the applicability
of sorption process as a unit operation.[32] In the present study Langmuir
(Fig. 6), Freundlich (Fig. 7) and Dubinin–Radushkevich (D–R) (Fig. 8) isotherm
models were used to describe the equilibrium biosorption data. The Langmuir
isotherm model assumes homogeneous type of sorption onto surface containing
a finite number of binding sites. Once a metal occupies a site, no further sorption can take place at that site. The linearized Langmuir isotherm equation is
represented by the following expression:[33]
1
1
1
1
=
+
(3)
qe
qmax
qmax KL Ce
Ganoderma carnosum as Biosorbent for Lead Removal
2597
Figure 6: The Langmuir isotherm plot for the lead(II) biosorption onto G. carnosum.
where qe and Ce are the amount of sorbed lead(II) ions per unit weight of biosorbent (mol g−1 ), and the equilibrium lead(II) concentration in the solution (mol
L−1 ), respectively. qmax is the monolayer biosorption capacity of the biosorbent
(mol g−1 ), and KL is the Langmuir constant (L mol−1 ) and is related to the
free energy of biosorption which reflects quantitatively the affinity between the
sorbent and sorbate.
The Freundlich isotherm model assumes that the sorption process takes
place on heterogeneous surfaces and sorption capacity is related to the concentration of lead(II) ions at equilibrium. The linearized Freundlich equation is
expressed as follows:[34]
ln qe = ln K F +
1
ln Ce
n
(4)
where K F (L g−1 ) and n are Freundlich isotherm constants, related to the
biosorption capacity and the degree of nonlinearity between solution concentration and biosorption, respectively.
Langmuir isotherm parameters can be used to predict the affinity between
the sorbate and sorbent using the separation factor or dimensionless equilibrium parameter, ‘RL,’ expressed as following equation:[35]
RL =
1
1 + KLCo
(5)
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Akar et al.
Figure 7: The Freundlich isotherm plot for the lead(II) biosorption onto G. carnosum.
Figure 8: The D–R isotherm plot for the lead(II) biosorption onto G. carnosum.
Ganoderma carnosum as Biosorbent for Lead Removal
2599
where KL is the Langmuir constant as described above,Co is the initial lead(II)
ion concentration in solution (mol L−1 ). The value of RL between 0 and 1 represents favorable and >1 represents unfavorable biosorption.[35,36] In this study
the value of RL was found as 6.30 × 10−3 , which indicates that the biosorption
process is favorable. Furthermore, the numerical value of Freundlich constant
of n was 4.30.
The Dubinin–Radushkevich (D–R) isotherm is more general than the Langmuir isotherm since it does not assume a homogeneous surface or constant
biosorption potential. It was applied to distinguish between the physical and
chemical biosorption of lead(II) ions. (D–R) isotherm model is expressed by the
following equation:[37]
ln qe = ln qm − βε 2
(6)
where ε is the Polanyi potential, equal to RT ln(1 + C1e ), qe ,is the amount of lead
(II) ions sorbed at equilibrium per unit weight of biosorbent (mol g−1 ), β is a
constant related to the biosorption energy (mol2 kJ−2 ), qm is the theoretical saturation capacity (mol g−1 ), Ce is the equilibrium concentration of lead(II) ions
in solution (mol L−1 ), R is the gas constant (J mol−1 K−1 ), and T is the absolute
temperature (K). The slope of the plot of lnqe versus ε 2 (Fig. 8) gives the value
of β (mol2 kJ−2 ) and the intercept yields the value of qm (mol g−1 ). The Polanyi
sorption theory assumes that the sorbent surface closed by fixed volume of sorption site and sorption potential exists over these sites. The sorption potential
is related to an excess of sorption energy over the condensation energy and is
independent of temperature.[38,39]
The constant β gives an idea about the mean free energy E, (kJ mol−1 ),
of biosorption per mole of the biosorbate when it is transferred to the surface of the solid from infinity in the solution and can be calculated using the
relationship:[40−42]
1
E=
(7)
(2β)1/2
The value of E gives information about the biosorption mechanism as chemical ion-exchange or physical biosorption. If its value is in the range of 8–16 kJ
mol−1 the biosorption process follows chemical ion-exchange mechanism,[43]
while for the values of E < 8 kJ mol−1 the biosorption process is of a physical nature.[44] The numerical value of the mean free energy of biosorption was
found as 15.62 kJ mol−1 indicating that the biosorption may be occur via a
chemical ion-exchange process.
The Langmuir, Freundlich and D–R isotherm model parameters calculated from the corresponding plots with the regression coefficients are listed
in Table 2. As shown in this table, the experimental data fitted well to all the
isotherm models investigated because of high regression coefficients. This finding implies that the surface of G. carnosum is made up of homogeneous and
heterogeneous biosorption patches.
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Akar et al.
Table 2: Biosorption isotherm constants for the biosorption of lead(II) onto G.
carnosum at 20◦ C.
Langmuir Isotherm
Freundlich Isotherm
D–R Isotherm
qmax
(mol g−1 )
1.10 × 10−4
n
4.30
qmax
(mol g−1 )
2.38 × 10−4
KL
(L mol−1 )
1.09 × 105
KF
(L g−1 )
6.89 × 10−4
β
(mol2 kJ−2 )
4.53 × 10−5
r L2
RL
0.972
r F2
6.30 × 10−3
0.962
2
r D−R
0.987
E
(kJ mol−1 )
15.62
Application of Biosorbent to Real Wastewater
To evaluate the potential performance of G. carnosum biomass for the removal of lead(II) ions from real wastewater, optimized biosorption procedure
was tested with model wastewater samples with and without spikes at optimum experimental conditions. The results are shown in Table 3. As can be
seen from the table the lead(II) removal yields of biomass were varied from
28.99 to 75.29% for real and spiked wastewater samples, respectively. The results showed that the proposed method could be successively applied for the
treatment of real wastewater for the removal of lead(II) ions.
Mechanism of the Biosorption
The SEM microscopic photos of G. carnosum biomass at magnifications
of 70x, 200x and 500x were given in Figure 9. As shown in these pictures,
irregular cavities in fibrous network were observed on the biomass surface,
which is considered helpful for the accessibility of heavy metals to the biosorbent surface. The mechanism of the lead(II) biosorption by G. carnosum biosorbent was elucidated on the basis of FTIR and EDAX analysis. To identify the
type of possible lead(II) binding sites of G. carnosum, the FTIR spectra were
recorded before and after biosorption and presented in Figure 10. The spectrum of the biomass is complex due to many functional groups existed in the
surface of the biomass. The broad stretching absorption peak at 3383 cm−1 represents bonded –OH and –NH groups. The band observed at 2922 cm−1 could
Table 3: The application of the proposed method in wastewater sample.
Sample
Real wastewater
Spiked sample
Spiked sample
Concentration of
added lead(II)
(mg L−1 )
qe
(mg g−1 )
Biosorption
yield
(%)
0
5.0
10.0
0.14 ± 0.03
1.22 ± 0.31
2.25 ± 0.20
28.99
70.19
75.29
Ganoderma carnosum as Biosorbent for Lead Removal
Figure 9: Typical SEM micrographs of G. carnosum, at magnifications of 70× (a), 200× (b)
and 500× (c).
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Akar et al.
Figure 10: FTIR spectra of G.carnosum before (a) and after (b) lead(II) biosorption.
be assigned to symmetric and asymmetric stretching vibrations of the –CH3
and –CH2 groups. The band at 1642 cm−1 corresponds to carbonyl stretching
vibrations of amide considered to be due to the combined effect of double bond
stretching vibrations.[45] The 1042 cm−1 band is caused by C OH stretching
[46]
and the band 569 cm−1 can be assigned to P O vibrations.[47] After the
interaction of biomass with lead(II) ions the spectrum exhibits changes of the
peaks at 3383 and 569 cm−1 , which shift to 3393 and 574 cm−1 , respectively.
This changes may suggest that the involvement of OH, NH and P O groups
in biosorption process.
Figure 11 shows the typical EDAX patterns for G. carnosum biomass before
and after biosorption. The EDAX pattern (a) for unloaded biomass did not show
the characteristic signal of lead and for lead(II) loaded biomass (b) showed
clearly the signals of lead at about 2.4, 10.5, and 12.7 keV. Also the intensity of
the peak at about 2.1 keV corresponding to phosphorus, significantly reduced
after biosorption process. This could be indicated the involvement of phosphate
group in biosorption process. Furthermore, potassium, which is capable of ion
exchange with metal ions, was observed at about 3.2 keV in the spectra of
unloaded biomass and disappeared after the biosorption process. These findings
indicated that the biosorption process also included ion exchange mechanism
for the removal of lead(II) ions by this strain, which is confirmed by the E value
obtained by the D–R isotherm model.
Ganoderma carnosum as Biosorbent for Lead Removal
2603
Figure 11: Typical EDAX spectra of G.carnosum before (a) and after (b) lead(II)
biosorption.
CONCLUSION
The experimental results show that G. carnosum, a macrofungus, can be effectively used as a promising biosorbent for the removal of lead(II) ions from
aqueous solution with the advantage of short biosorption time. The maximum
biosorption capacity was obtained at pH value of 5.0 and 4.0 g L−1 of biosorbent concentration. The experimental data could be well modelled with the
Langmuir, Freundlich and D–R sorption isotherm equations. The desorption
and reusability studies showed that the biosorbent has the potential to be
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Akar et al.
used as an alternative and economic biosorbent material for the removal and
recovery of lead(II) ions from aqueous solutions. The G. carnosum biomass for
lead(II) removal from real wastewater can obtain much better treatment efficiency. The interactions between lead(II) ions and the functional groups on the
surface of the biomass were confirmed by FTIR and EDAX analysis and the
mechanism of the lead(II) biosorption by G. carnosum could be a combination
of ion-exchange and complexation with the functional groups present on the
biosorbent surface.
REFERENCES
1. Girard, J.E. Principles of Environmental Chemistry. Sudbury, Jones and Bartlett,
Canada, 2005; 677.
2. Gupta, V.K.; Ali, I. Removal of lead and chromium from wastewater using bagasse
fly ash-a sugar industry waste. J. Coll. Interf. Sci. 2004, 271, 321–328.
3. Ikeda, M.; Zhang, Z.W.; Shimbo, S.; Watanabe, T.; Nakatsuka, H.; Moon, C.S.;
Inoguchi, N.M.; Higashikawa, K. Urban population exposure to lead and cadmium in
east and south-east Asia. Sci. Total Environ. 2000, 249, 373–384.
4. Veglió, F.; Beolchini, F. Removal of metals by biosorption: A review. Hydrometallurgy.
1997, 44, 301–316.
5. Gadd, G.M.; White, C. Copper uptake by Penicillium ochrochloron: influence of pH
on toxicity and demonstration of energy-dependent copper influx using protoplast. J.
Gen. Microbiol. 1985, 131, 1875–1879.
6. Akar, T.; Tunali, S. Biosorption performance of Botrytis cinerea fungal by-products
for removal of Cd(II) and Cu(II) ions from aqueous solutions. Miner. Eng. 2005, 18,
1099–1109.
7. Kiran, I.; Akar, T.; Tunali, S. Biosorption of Pb(II) and Cu(II) from aqueous solutions by pretreated biomass of Neurospora crassa. Process Biochem. 2005, 40, 3550–
3558.
8. Akar, T; Tunali, S. Biosorption characteristics of Aspergillus flavus biomass for removal of Pb(II) and Cu(II) ions from an aqueous solution. Bioresour. Technol. 2006, 97,
1780–1787.
9. Tunali, S.; Akar, T.; Özcan, A.S.; Kiran, I.; Özcan, A. Equilibrium and kinetics of
biosorption of lead(II) from aqueous solutions by Cephalosporium aphidicola. Sep. Purif.
Technol. 2006, 47, 105–112.
10. Tunali, S.; Akar, T. Zn(II) biosorption properties of Botrytis cinerea biomass. J.
Hazard. Mater. 2006, 131, 137–145.
11. Yan, G.; Viraraghavan, T. Heavy-metal removal from aqueous solution by fungus
Mucor rouxii. Water Res. 2003, 37, 4486–4496.
12. Sar, P.; Kazy, S.K.; Asthana R.K.; Singh S.P. Metal adsorption and desorption by
lyophilized Pseudomonas aeruginosa. Int. Biodet. Biodegr. 1999, 44, 101–110.
13. Tunali, S.; Çabuk, A.; Akar, T.; Removal of lead and copper ions from aqueous
solutions by bacterial strain isolated from soil. Chem. Eng. J. 2006, 115, 203–211.
14. Şahin, Y.; Öztürk, A. Biosorption of chromium(VI) ions from aqueous solution by
the bacterium Bacillus thuringiensis. Process Biochem. 2005, 40, 1895–1901.
Ganoderma carnosum as Biosorbent for Lead Removal
2605
15. Selatnia, A.; Boukazoula, A.; Kechid, N.; Bakhti, M.Z.; Chergui, A.; Kerchich, Y.
Biosorption of lead (II) from aqueous solution by a bacterial dead Streptomyces rimosus
biomass. Biochem. Eng. J. 2004, 19, 127–135.
16. Öztürk, A.; Artan, T.; Ayar, A. Biosorption of nickel(II) and copper(II) ions from
aqueous solution by Streptomyces coelicolor A3(2). Coll. Surf. B 2004, 34, 105–111.
17. Jianlong, W. Biosorption of copper(II) by chemically modified biomass of Saccharomyces cerevisiae. Process Biochem. 2002, 37, 847–850.
18. Seki, H.; Suzuki, A.; Maruyama, H. Biosorption of chromium(VI) and arsenic(V)
onto methylated yeast biomass. J. Coll. Interface Sci. 2005, 281, 261–266.
19. Vijayaraghavan, K.; Jegan, J.; Palanivelu, K.; Velan, M. Batch and column removal
of copper from aqueous solution using a brown marine alga Turbinaria ornata. Chem.
Eng. J. 2005, 106, 177–184.
20. Matheickal, J.T.; Yu, Q. Biosorption of lead(II) and copper(II) from aqueous solutions by pre-treated biomass of Australian marine algae. Bioresour. Technol. 1999, 69,
223–229.
21. Muraleedharan, T.R.; Iyengar, L.; Venkobachar, C. Insight into the mechanism of
biosorption of heavy metals by Ganoderma lucidum. Environ. Technol. 1994, 15, 1015–
1027.
22. Matheickal, J.T.; Yu, Q. Biosorption of lead(II) from aqueous solutions by Phellinus
badius. Miner. Eng. 1997, 10, 947–957.
23. Xiangliang, P.; Jianlong, W.; Daoyong, Z. Biosorption of Pb(II) by Pleurotus ostreatus
immobilized in calcium alginate gel. Process Biochem. 2005, 40, 2799–2803.
24. Iqbal, M.; Edyvean, R.G.J. Biosorption of lead, copper and zinc ions on loofa sponge
immobilized biomass of Phanerochaete chrysosporium. Miner. Eng. 2004, 17, 217–223.
25. Sannasi, P.; Kader, J.; Ismail, B.S.; Salmijah, S. Sorption of Cr(VI), Cu(II) and Pb(II)
by growing and non-growing cells of a bacterial consortium. Bioresour. Technol. 2006,
97, 740–747.
26. Dursun, A.Y. A comparative study on determination of the equilibrium, kinetic and
thermodynamic parameters of biosorption of copper(II) and lead(II) ions onto pretreated
Aspergillus niger. Biochem. Eng. J. 2006, 28, 187–195.
27. Saeed, A.; Iqbal, M.; Akhtar, M.W. Removal and recovery of lead(II) from single
and multimetal (Cd, Cu, Ni, Zn) solutions by crop milling waste (black gram husk). J.
Hazard. Mater. 2005, 117, 65–73.
28. Tewari, N.; Vasudevan, P.; Guha, B.K. Study on biosorption of Cr(VI) by Mucor
hiemalis. Biochem. Eng. J. 2005, 23, 185–192.
29. Özer, A.; Özer, D.; Özer, A. The adsorption of copper(II) ions on to dehydrated wheat
bran (DWB): determination of the equilibrium and thermodynamic parameters. Process
Biochem. 2004, 39, 2183–2191.
30. Ucun, H.; Bayhan, Y.K.; Kaya, Y.; Cakici, A.; Algur, O.F. Biosorption of lead(II)
from aqueous solution by cone biomass of Pinus sylvestris. Desalination 154, 233–
238.
31. Özcan, A.; Özcan, A.S.; Tunali, S.; Akar, T.; Kiran, I. Determination of the equilibrium, kinetic and thermodynamic parameters of adsorption of copper(II) ions onto seeds
of Capsicum annuum. J. Hazard. Mater. 2005, 124, 200–208.
32. Ashraf, S.S.; Rauf, M.A.; Alhadrami, S. Degradation of Methyl Red using Fenton’s
reagent and the effect of various salts. Dyes Pigments 2006, 69, 74–78.
2606
Akar et al.
33. Langmuir, I. The adsorption of gases on plane surfaces of glass, mica and platinum.
J. Am. Chem. Soc. 1918, 40, 1361–1403.
34. Freundlich, H.M.F. Über die adsorption in lösungen. Z. Phys. Chem. 1906, 57,
385–470.
35. Hall, K.R.; Eagleton, L.C.; Acrivos, A.; Vermeulen, T. Pore- and solid-diffusion kinetics in fixed–bed adsorption under constant-pattern conditions. Ind. Eng. Chem. Fundam.
1966, 5, 212–223.
36. Weber, T.W.; Chakravorti, R.K. Pore and solid diffusion models for fixed-bed adsorbers. J. Am. Inst. Chem. Eng. 1974, 20, 228–238.
37. Dubinin, M.M.; Radushkevich, L.V. Proc. Acad. Sci. U.S.S.R. Phys. Chem. Sect.
1947, 55, 331–333.
38. Polanyi, M. Theories of the adsorption of gases. A general survey and some additional remarks. Trans. Faraday Soc. 1932, 28, 316.
39. Malik, U.R.; Hasany, S.M.; Subhani, M.S. Sorptive potential of sunflower stem for
Cr(III) ions from aqueous solutions and its kinetic and thermodynamic profile. Talanta.
2005, 66, 166–173.
40. Hobson, J.P. Physical adsorption isotherms extending from ultrahigh vacuum to
vapor pressure. J. Phys. Chem. 1969, 73, 2720–2727.
41. Hasany, S.M.; Chaudhary, M.H. Sorption potential of Hare River sand for the removal of antimony from acidic aqueous solution. Appl. Radiat. Isot. 1996, 47, 467–471.
42. Dubey, S.S.; Gupta, R.K. Removal behavior of Babool bark (Acacia nilotica) for
submicro concentrations of Hg2+ from aqueous solutions: a radiotracer study. Sep. Purif.
Technol. 2005, 41, 21–28.
43.
Helfferich, F. Ion Exchange. McGraw-Hill, New York, 1962.
44. Onyango, M.S.; Kojima, Y.; Aoyi, O.; Bernardo, E.C.; Matsuda, H. Adsorption equilibrium modeling and solution chemistry dependence of fluoride removal from water by
trivalent-cation-exchanged zeolite F-9. J. Coll. Interf. Sci. 2004, 279, 341–350.
45. Kuyucak, N.; Volesky, B. The mechanism of cobalt biosorption. Biotechnol Bioeng.
1989, 33, 823–831.
46. Lin, Z.; Wu, J.; Xue, R.; Yang, Y. Spectroscopic characterization of Au3+ biosorption
by waste biomass of Saccharomyces cerevisiae. Spect. Chim. Acta Part A. 2005, 61, 761–
765.
47. Santhiya, D.; Subramanian, S.; Natarajan, K.A. Surface chemical studies on sphalerite and galena using Bacillus polymyxa: II. Mechanisms of microbe–mineral interactions. J. Coll. Interf. Sci. 2001, 235, 298–309.