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Minerals Engineering 19 (2006) 380387

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Biosorption of cadmium by green coconut shell powder


Gabriela Huaman Pino a, Luciana Maria Souza de Mesquita a,
Mauricio Leonardo Torem a,*, Gustavo Adolfo Saavedra Pinto b
a

Department of Material Science and Metallurgy, Catholic University of Rio de Janeiro, Rua Marques de Sao Vicente, 225-Gavea,
22453-900 Rio de Janeiro-RJ, Brazil
b
Laboratory of Bioprocess, Embrapa Tropical Agroindustry, Rua Dra. Sara Mesquita, 2270-Pici, 60511-110 Fortaleza-CE, Brazil
Received 12 July 2005; accepted 1 December 2005
Available online 23 January 2006

Abstract
The eective removal of heavy metals from aqueous wastes is among the most important issues for many industrialized countries. The
traditional treatment methods used to remove heavy metals from wastewaters have certain disadvantages such as incomplete metal
removal, high reagent and energy requirements, generation of toxic sludge or other waste products that require disposal. The search
for alternative and innovate treatment techniques has focused attention on the use of biological materials for metal removal and recovery
technologies. Biosorption has gained important credibility during recent years because of its good performance and low cost.
In the present study, the biosorption capacity of powder from coconut shell was studied for cadmium. The adsorption capacity of
biomass was investigated by batch experiments. The inuence of metal ion concentration and pH were evaluated and the results were
tted using adsorption isotherm models. The kinetic of cadmium biosorption was also investigated.
 2005 Elsevier Ltd. All rights reserved.
Keywords: Biotechnology; Biosorption; Heavy metals; Cocos nucifera; Adsorption isotherms

1. Introduction
It is well recognized that the presence of heavy metals in
the environment can be detrimental to a variety of living
species, including man. Cadmium is one of the most toxic
metals aecting the environment. Mining and metallurgy
of cadmium, cadmium electroplating, battery and accumulator manufacturing, pigments and ceramic industries
waste waters contain undesired amounts of Cd2+ ions.
The main techniques which have been utilized for treatment Cd2+ bearing waste streams include precipitation,
evaporation, adsorption, ion exchange, membrane processing, solvent extraction, etc. These methods have been
found to be limited, since they often involve high capital
and operational costs and may also be associated with

Corresponding author. Tel.: +55 21 3114 1233; fax: +55 21 3114 1236.
E-mail addresses: mluciana@dcmm.puc-rio.br (L.M. Souza de Mesquita), torem@dcmm.puc-rio.br (M.L. Torem).
0892-6875/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.12.003

the generation of secondary wastes which present treatment problems (Volesky, 2001; Zouboulis et al., 2004).
The uptake of both metal and non-metal species by biomass, whether living or denatured, is commonly termed
biosorption. A variety of microbial and other biomass
types has been shown to have good biosorption potential
and several have been proposed as the basis for treatment
for metal-bearing industrial wastewaters (Volesky, 2004;
Wase and Forster, 1997; Costa et al., 1995; Rubin et al.,
2005; Wilde and Benemann, 1993). Compared to techniques such as precipitation and ion exchange, biosorption
as a polishing or adjunct process oers the advantages of
low cost, good eciency and it does not produce sludge
of high metal content. Furthermore, the potential exists
for metal recovery from loaded biosorbents through elution or incineration treatment (Volesky, 1990).
Several investigations have been carried out to identify
suitable and relatively cheap biosorbents that are capable
of removing signicant quantities of ions. Among the
various resources in biological wastes, both dead and

G.H. Pino et al. / Minerals Engineering 19 (2006) 380387

live biomass, exhibit particularly interesting metal-binding


capacities (Costa et al., 1996; Volesky, 1994). In recent
years, agricultural by-products have been widely studied
for metal removal from water. These include peat, wood,
pine bark, banana pith, soybean and cottonseed hulls, peanut, shells, hazelnut shell, rice husk, sawdust, wool, orange
peel, and compost and leaves (Chandra et al., 2003; Dornellas de barros and Arroyo, 2000; Gaballah et al., 1994
and Schneider et al., 2001). The use of dead biomass eliminates the problem of toxicity and the economics aspects of
nutrient supply and culture maintenance (Gomes et al.,
1995).
The use of the coconut shell as a biosorbent material
presents strong potential due to its high content of lignin,
around 3545%, and cellulose, around 2343% (Carrijo
et al., 2002). As a low cost, powder of coconut shell
Cocos nucifera is an attractive and inexpensive option for
the biosorption removal of dissolved metals. Various
metal-binding mechanisms are thought to be involved in
the biosorption process including ion exchange, surface
adsorption, chemisorption, complexation, and adsorptioncomplexation (Pino, 2005; Matheickal et al., 1999).
Coconut shell is a material composed of several constituents, among them lignin acid and cellulose bear various
polar functional groups including carboxylic and phenolic
acid groups which can be involved in metal binding (Matheickal et al., 1999; Ting et al., 1991). The cellulose and lignin are biopolymers admittedly associate to the removal of
heavy metals (Gaballah and Kilbertus, 1994; Gaballah
et al., 1997; Hunt, 1986).
In the present work the sorption of cadmium from aqueous solution by using powder of coconut shellCocos
nucifera was investigated. The adsorption capacity of biomass was investigated by batch experiments. The inuences
of pH values, size of particle and ion concentration were
investigated and the experimental data obtained were evaluated and tted using adsorption equilibrium modelling
and kinetic models.
2. Material and methods
2.1. Biosorbent material
The powder of green coconut shells used in this work
was supplied by Embrapa Tropical AgroindustryBioprocess Laboratory/Fortaleza, Ceara. The methodology
used in the production of the powder is described in Rosa
et al. (2001a,b).
2.2. Biosorption experiments
Batch experiments of biosorption were performed at
constant temperature (27 C) in Erlenmeyer asks, stirred
in a reciprocal shaker (175 rpm) for 2 h. In all sets of experiments 0.5 g of powder of coconut shells was thoroughly
mixed into 100 ml solution of metallic specie. After shaking
the asks, the reaction mixtures were ltered to remove

381

particulates and the ltrates were analyzed by atomic


absorption spectrophotometer for the concentration of
metallic species.
The stock solution of metal was prepared in deionized
water using CdSO4 8/3H2O. The reagent used was analytical grade supplied by Merck.
A rst series of biosorption experiments were carried out
with Cd2+ with an initial concentration of 20 mg/l. In these
tests the optimal pH value of biosorption was determined
for the metallic specie. After this, the inuence of particle
size was too evaluated. Using HCl and NaOH solutions
made all the pH adjustments.
2.3. MEV and EDS analyses
The morphological characteristics of coconut shell were
evaluated by using DSN 960 Zeiss Scanning Electron
Microscope. The samples of powder of coconut shell were
covered with a thin layer of gold and an electron acceleration voltage of 20 kV was applied. The EDS analyses of
biomass were performed after and before biosorption
experiments in order to identied the presence of metallic
specie.
2.4. Equilibrium modelling
Equilibrium data, commonly known as adsorption isotherms, are basic requirements for the design of adsorption
systems. This set of experiments was performed at dierent
initial concentration of Cd2+, 201000 mg/l.
Classical adsorption models (Langmuir and Freundlich)
were used to describe the equilibrium between adsorbed
metal ions on the coconut shell powder (qeq) and metal ions
in solution (Ceq) at a constant temperature. The Langmuir
equation is valid for monolayer sorption on to a surface
with a nite number of identical sites and is given by Eq.
(1):
qeq

qmax bC eq
1 bC eq

where qmax (mg/g) is the maximum amount of metal ion


per unit weight of coconut powder to form a complete
monolayer on the surface bound at high Ceq, and b (l/
mg) is a constant related to the anity of the binding sites.
The qmax represents a practical limiting adsorption capacity
when the surface is fully covered with metal ions and assists
in the comparison of adsorption performance, particularly in cases where the sorbent did not reach its full saturation in experiments. The qmax and b can be determined
from the linear plot of Ceq/qeq versus Ceq (Veglio and Beolchini, 1997; Donmez et al., 1999; Matheickal et al., 1999;
McKay et al., 1999). The empirical Freundlich equation
based on sorption on a heterogeneous surface is given below by Eq. (2):
1=n
qeq K f C eq

382

G.H. Pino et al. / Minerals Engineering 19 (2006) 380387

where Kf and n are the Freundlich constants characteristic


of the system. Kf and n are indicators of adsorption capacity and adsorption intensity, respectively. Eq. (2) can be linearized in logarithmic form and Freundlich constants can
be determined. The Freundlich isotherm is also more
widely used but provides no information on the monolayer
adsorption capacity, in contrast to the Langmuir model
(Aksu and Kutsal, 1990; Veglio and Beolchini, 1997; Donmez et al., 1999; Matheickal et al., 1999; McKay et al.,
1999).

dq
2
k 2;ad qeq  q
dt

where k2,ad is the rate constant of second-order biosorption


(g mg1 min1). For the boundary conditions t = 0 to t = t
and q = 0 to q = qeq; the integrated form of Eq. (5)
becomes:
1
1

k 2;ad t
qeq  q qeq

In order to investigate the mechanism of biosorption


and potential rate controlling step such as mass transport
and chemical reaction processes, kinetic models have been
used to test experimental data. When the biomass is
employed in a well-agitated batch system, all the material
surface binding sites are made readily available for metal
uptake so the eect of external lm diusion on biosorption rate can be assumed not signicant and ignored in
any engineering analysis (Aksu, 2001). The kinetic models
included the pseudo rst-order and pseudo second-order
equations can be used in this case assuming that measured
concentrations are equal to powder surface concentrations.
The rst-order rate expression of Lagergren (1898) based
on solid capacity is generally expressed as follows:
dq
k 1;ad qeq  q
dt

where qeq and q are the amounts of adsorbed metal ions on


the biosorbent at equilibrium and at time t, respectively
(mg/g) and k1,ad is the rate constant of rst-order biosorption (min1). After integration and applying boundary conditions, t = 0 to t = t and q = 0 to q = qeq; the integrated
form of Eq. (3) becomes
k 1;ad
t
2:303

A straight line of log(qeq  q) versus t suggests the applicability of this kinetic model (Lagergren, 1898; McKay et al.,
1999; Ho and McKay, 1999a,b). In order to t Eq. (4) to
experimental data, the equilibrium sorption capacity, qeq,
must be known. In many cases qeq is unknown and as
adsorption tends to become unmeasurably slow, the
amount sorbed is still signicantly smaller than the equilibrium amount. For this reason it is necessary to obtain the
real equilibrium sorption capacity, qeq, by extrapolating
the experimental data to t = 1 or by using a trial and error
method. Furthermore in most cases the rst-order equation
of Lagergren does not t well for the whole range of contact time and is generally applicable over the initial 20
30 min of the sorption process. The pseudo second-order
equation is also based on the sorption capacity of the solid
phase (Ho and McKay, 1999a). Contrary to the other
model it predicts the behavior over the whole range of
adsorption and is in agreement with an adsorption mecha-

which is the integrated rate law for a second-order reaction.


Eq. (6) can be rearranged to a linear form:
t
1
1

t
q k 2;ad q2eq qeq

If second-order kinetics are applicable, the plot of t/q


against t of Eq. (7) should give a linear relationship, from
which qeq and k2,ad can be determined from the slope and
intercept of the plot and there is no need to know any
parameter beforehand (Ho and McKay, 1999a,b).
The detailed procedure is described elsewhere (Pino,
2005).
3. Results and discussion
3.1. Eect of pH
There is general consensus that pH is a key parameter,
along with metal concentration and solution composition,
in determining biosorption levels. Accordingly the objectives of this work was evaluate the biosorption of Cd2+
by powder of coconut shell from aqueous solution and to
determine the eects of pH (in the range 49) on uptake
levels. The eect of initial pH on biosorption of cadmium
is presented in Fig. 1.
The results presented show excellent removal capacities
for Cd2+ by using coconut powder. The Cd2+ removal
increased from 69%, at pH 4, to 98%, at pH 7. Above
pH value of 7 the removal comes constant until pH 9; at

Removal (%)

2.5. Kinetic modelling

logqeq  q log qeq 

nism being the rate controlling step. If the rate of sorption


is a second-order mechanism, the pseudo second-order
chemisorption kinetic rate equation is expressed as:

100
90
80
70
60
50
40
30
20
10
0
4

pH

Fig. 1. Percentage removal of Cd2+ by coconut shell for dierent pH


values. Initial concentration of metal: 20 mg/l. Biomass concentration:
5 g/l. Particle size: 200297 lm. Contact time: 2 h.

G.H. Pino et al. / Minerals Engineering 19 (2006) 380387

higher values of pH cadmium ions precipitate as Cd(OH)2


(Scorzelli, 1999).
The dependence of metal uptake on pH is related to
both the surface functional groups present on the biomass
and the metal chemistry in solution. At low pH, the surface
ligants are closely associated with the hydronium ions
(H3O+) and restricted the approach of metal cations as a
result of the repulsive force (Aksu, 2001; Sheng et al.,
2004). Furthermore, the pH dependency on the metal ions
uptake by biomasses can also be justied by the associationdissociation of certain functional groups, such as the
carboxyl and hydroxyl groups present on the biomass. In
fact, it is known that a low pH, most of the carboxylic
groups are not dissociated and cannot bind the metal ions
in solution, although they take part in complexation reactions (Chubar et al., 2004). Based on these results, the following experiments were performed at pH 7.
3.2. Eect of particle size
Another important parameter studied was the inuence
of the particle size of coconut shell used for uptake of
Cd2+. This parameter presents an important inuence in
the process cost. The results presented in Fig. 2 show a
reduction in the removal of Cd2+ with the decrease of particle size of the biomass.

100

Removal (%)

80
60
40
20

383

It is important to stress that larger particles with spherical shapes, in general, present higher external mass transfer than smaller particles (Leusch and Volesky, 1995). In
this case, higher metal adsorption from these particles is
attributed to mass transport inside the sorbent particles.
3.3. MEV and EDS analyses
Scanning electron microscope evaluated the morphological characteristics of coconut. The micrographs of coconut
shell powder before metal uptake and the respective EDS
analyses are presented in Figs. 3 and 4, respectively. Figs.
5 and 6 show the same for coconut shell after cadmium
uptake.
Fig. 3 shows a quite irregular and porous material. This
surface characteristic would be substantiating the high
adsorption observed for particles of larger size, through
mass transport inside the sorbent.
The EDS analysis presented in Fig. 4 shows the presence
of Cl, K, Na, Mg and Si as natural species on the coconut
shell, as already expected (Rosa et al., 2001a). The presence
of these elements could inuence on the adsorption mechanism thought ionic exchange interactions.
Fig. 5 shows no signicant dierence between the surface of particles loaded with metal ions and the particles
that does not suer the biosorption process (Fig. 3).
The EDS analysis in the particle loaded with cadmium
presented in Fig. 6, shows the presence of cadmium bands,
and the absence of Cl, K, Na and Mg bands. This could be
indicative of ionic exchange mechanism involvement
between these elements and Cd2+ on the surface of particles. The band of Au appears in the EDS, a time that the
metallizing of the samples was carried through with this
element.
3.4. Adsorption isotherms

0
0.297 - 0.200

0.210 - 0.105

0.105 - 0.074

0.074 - 0.044

Range of Particle Size (mm)


Fig. 2. Percentage removal of Cd2+ by powder of coconut shell for
dierent ranges of particle size. Initial concentration of metal: 100 mg/l.
Biomass concentration: 5 g/l. pH value: 7. Contact time: 2 h.

The linearized Freundlich and Langmuir adsorption isotherms of Cd2+ ions obtained at the temperature of 27 C
are given in Figs. 7 and 8. The Freundlich and Langmuir
adsorption constants evaluated from the isotherms with
the correlation coecients are also presented in Table 1.

Fig. 3. Scanning electron micrograph of coconut shell before Cd2+ uptakes.

384

G.H. Pino et al. / Minerals Engineering 19 (2006) 380387

Fig. 4. EDS diractogram of micrographs of coconut shell before Cd2+ uptake.

Fig. 5. Scanning electron micrograph of coconut shell after Cd2+ biosorption.

Fig. 6. EDS diractogram of micrographs of coconut shell after Cd2+ biosorption.

As seen from Table 1, very high regression correlation


coecients (>0.96) were found for both studied models.
According to these results both the Freundlich and Langmuir models are suitable for describing the biosorption
equilibrium of Cd2+ by the powder of coconut shell in
the studied concentration range.
An adsorption isotherm is characterized by certain constants; the values of which express the surface properties
and anity of the sorbent and can also be used to nd
the biosorptive capacity of biomass. From Table 1, the
magnitude of Kf and n; the Freundlich constants, showed

easy uptake of Cd2+ from aqueous solutions with high


adsorptive capacity of the coconut shell, at 27 C. The
highest Kf and n values were found as 9.915 and 1.797,
respectively, at this temperature value. Table 1 also indicates that n is greater than unity, indicating that Cd2+ ions
are favorably adsorbed by coconut shell at the temperature
studied. Values of qmax and b have been calculated from the
Langmuir plots in Fig. 8 and the results are also tabulated
in Table 1. The maximum capacity qmax determined from
the Langmuir isotherm denes the total capacity of the biosorbent for Cd2+ (285.7 mg/g). A large value of b also

G.H. Pino et al. / Minerals Engineering 19 (2006) 380387


100

Residual Concentration (ppm)

3
2.5

log q

2
1.5
1
0.5
0
-1

-0.5

0.5

1.5

2.5

3.5

2.5

Cf /q

2
1.5
1
0.5
0
200

300

400

500

600

700

800

Cf (ppm)

Fig. 8. The linearized Langmuir adsorption isotherms of Cd2+ by powder


of coconut shell. Experimental conditionstemperature: 27 C; agitation
rate: 175 rpm; biomass concentration: 5 g/l; size particle: 200297 lm; pH:
7.

Table 1
Sorption isotherm coecients of Langmuir and Freundlich models
applied to Cd2+ biosorption by coconut shell powder

Cd+2

Langmuir

40

20

10

20

30

40

50

60

Time (min)

100

60

Fig. 7. The linearized Freundlich adsorption isotherms of Cd2+ by


coconut shell. Experimental conditionstemperature: 27 C; agitation
rate: 175 rpm; biomass concentration: 5 g/l; size particle: 200297 lm; pH:
7.

80

log C f

Metal

385

Freundlich

qmax (mg/g)

R2

Kf

R2

285.7

0.019

0.986

9.915

1.797

0.966

Fig. 9. Residual concentration of Cd2+ after biosorption with powder of


coconut shell in function of contact time (temperature: 27 C; agitation
rate: 175 rpm; biomass concentration: 5 g/l; size particle: 200297 lm; pH:
7).

uted to physicalchemical interactions between the biomass


and metal ions present in solution (Mesquita, 1993).
In order to analyze the biosorption kinetics of Cd2+
ions, the pseudo rst-order and pseudo second-order
kinetic models were applied to data. Fig. 10 shows a plot
of linearized form of the pseudo rst-order model at the
temperature studied at 80 mg/l initial Cd2+ concentration.
The rst-order rate constant (k1,ad) and qeq values determined from Fig. 10 are compared with the correlation coefcient in Table 2. The correlation coecient obtained was
found a reasonable value, although the theoretical qeq
value found from the rst-order kinetic model give a lower
value. This suggests that this biosorption system is not a
rst-order reaction.
Using Eq. (7), t/q was plotted against t at 27 C and second-order biosorption rate constant (k2,ad) and qeq values
were determined from the slope and intercept of the plots
(Fig. 11). The values of the parameters k2,ad and qeq and
of correlation coecients are also presented in Table 2.
The correlation coecient for the second-order kinetic
model obtained was greater than 0.99. The theoretical qeq
value is close to the experimental qeq values in the case of

implied strong bonding of Cd2+ to the powder of coconut


shell at 27 C.

1.00
0.90
0.80

The kinetic parameters are necessary to determine the


best operational conditions in a continue process of ions
removal. In Fig. 9 are presented the results relative to residual concentration of cadmium in solution after contact
with the biomass in dierent times.
The data obtained show a fast uptake of the metal by
the biomass. Starting from an initial concentration of
80 ppm, with 5 min of contact, the cadmium concentration
falls to 5.1 ppm. Similar results were obtained for others
studies of biosorption where the metal removal was attrib-

0.70
log (qe-q)

3.5. Biosorption kinetics

0.60
0.50
0.40
0.30
0.20
0.10
0.00
0

10

20

30
40
Time (min)

50

60

70

Fig. 10. Pseudo rst-order sorption kinetics of Cd2+ onto coconut shell.
Temperature: 27 C; agitation rate: 175 rpm; biomass concentration: 5 g/l;
size particle: 200297 lm; pH: 7.

386

G.H. Pino et al. / Minerals Engineering 19 (2006) 380387

Table 2
The rst-order and the second-order sorption rate constants
Pseudo rst-order
3

qeq Experimental (mg/g)

Pseudo second-order

1

k1,ad (10 ) (min )

qeq (mg/g)

k2,ad (10 ) (g/mg min)

qeq (mg/g)

13.35

4.589

0.318

10.15

15.31

0.999

17.68

Temperature: 27 C; agitation rate: 175 rpm; biomass concentration: 5 g/l; size particle: 200297 lm; pH: 7.

discussed. The pseudo second-order kinetic model provides


the best correlation of the experimental data, whereas the
pseudo rst-order model does not t the experimental data
well.

t/q

Acknowledgment
2

The authors would like to thank nancial assistance


from FAPERJ, CNPq and CAPES.
0
0

10

20

30

40

50

60

70

Time (min)
2+

Fig. 11. Pseudo second-order sorption kinetics of Cd onto coconut


shell. Temperature: 27 C; agitation: 175 rpm; biomass concentration: 5 g/l;
size particle: 200297 lm; pH: 7.

pseudo second-order kinetics. These suggest that the sorption system is the second-order model, based on the
assumption that the rate limiting step may be the biosorption, provides the best correlation of the data.
4. Conclusions
The powder of coconut shell has the potential to remove
cadmium ion to a large range of concentrations (20
1000 mg/l). It was conrmed that coconut shell also has a
high biosorption capacity (285.7 mg/g).
The obtained results showed that initial pH highly
aected the uptake capacity of the biosorbent. For Cd2+
ions the best value of pH for biosorption was 7.
The analyses accomplished by MEV-EDS proved the
presence of cadmium in the biomass particles after biosorption. The absence of Cl, K, Na and Mg bands in the biomass particles after biosorption of Cd2+ ions suggest a
possible involvement of ionic exchange mechanism interaction. The micrographs obtained show a quite irregular and
porous material. This surface characteristic would be substantiating the high adsorption observed for particles of
larger size, through mass transport inside the sorbent.
The Freundlich and Langmuir adsorption models were
used for the mathematical description of the biosorption
equilibrium of Cd2+ ions to coconut shell at 27 C and
the isotherm constants evaluated from the isotherms were
used to compare the biosorptive capacity of the biomass.
The obtained results showed that the adsorption equilibrium data tted very well to both the models at the temperature studied.
The suitability of the rst- and second-order kinetic
models for the sorption of Cd2+ ions onto biomass is also

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