Journal of Environmental Management 91 (2010) 1634e1640

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Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Green coconut shells applied as adsorbent for removal of toxic metal ions using
xed-bed column technology
Francisco W. Sousa c, Andr G. Oliveira a, Jefferson P. Ribeiro a, Morsyleide F. Rosa b, Denis Keukeleire d,
Ronaldo F. Nascimento a, *
a

Laboratory of Trace Analysis, Department of Analytical and Physical Chemistry, Federal University of Cear e UFC, Fortaleza, CE, Brazil
Embrapa, Tropical Agroindustry, Fortaleza, CE, Brazil
Department of Hydraulic and Environmental Engineering, Federal University of Cear e UFC, Fortaleza, CE, Brazil
d
Ghent University, Faculty of Pharmaceutical Sciences, Harelbekestraat 72, B-9000 Ghent, Belgium
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 25 July 2009
Received in revised form
24 November 2009
Accepted 8 February 2010
Available online 18 April 2010

This study applies green coconut shells as adsorbent for the removal of toxic metal ions from aqueous
efuents using column adsorption. The results show that a ow rate of 2 mL/min and a bed height of
10 cm are most feasible. Furthermore, larger amounts of efuent can be treated for removal of single
ions. The breakthrough curves for multiple elements gave the order of adsorption capacity:
Cu2 > Pb2 > Cd2 > Zn2 > Ni2. Real samples arising from the electroplating industry can be efciently handled.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Adsorption
Green coconut shells
Toxic metal ions
Fixed-bed technology

1. Introduction
The presence of heavy metal ions in industrial discharges has
caused serious environmental problems (Johnson et al., 2002; Gupta
and Ali, 2004; Lodeiro et al., 2006), mainly because of unwanted
bioaccumulation in humans (Bailey et al., 1999; Kumar and
Bandyopadhyay, 2006). Removal of toxic metal ions can be achieved by techniques such as coagulation, occulation, precipitation,
ltration, ozonation and ion exchange. However, these methods
have high operating cost (Bandyopadhyay and Biswas, 1998; Sohail
et al., 1999; Rao et al., 2002), while adsorption proved to be versatile and readily applicable (Gupta and Ali, 2000). Activated charcoal
is the adsorbent of choice, but high costs are a concern (Pollard et al.,
1992; Gupta et al., 2003; Aravindhan et al., 2009). Therefore, cheap
bioderived materials of renewable sources are suitable alternatives
(Saeed et al., 2005; Horsfall et al., 2006; Agarwal et al., 2006; Moreira
et al., 2009; Wang et al., 2009; Sousa et al., 2009).
Thus, agricultural residues seem to be preferred (Pollard et al.,
1992; Nasernejad et al., 2005; Johnson et al., 2002; Horsfall et al.,
* Corresponding author at: Laboratory of Trace Analysis, Department of Analytical and Physical Chemistry, Federal University of Ceara e UFC, Block 939, Campus
do Pici s/n, CEP 60455-760, Fortaleza, CE, Brazil. Tel.: 55 85 3366 99 58; fax: 55
85 3366 99 82.
E-mail address: ronaldo@ufc.br (R.F. Nascimento).
0301-4797/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2010.02.011

2006) and the green coconut shells are a most appropriate

example for the biosorption removal of dissolved metals (Sousa
et al., 2007) and organics (Crisafully et al., 2007).
The majority of adsorption studies have been carried out in the
batch mode (Krishnan and Anirudhan, 2002; Lopez et al., 1998;
Namasivayam and Yamuna, 1995; Gharaibeh et al., 1998), but
a continuous system should be economically most valuable for
wastewater treatment (Cooney, 1999). The elucidation of the
interaction that governs metal uptake by biosorbents (e.g., coconut
shells) constituted principally by lignin and cellulose as major
constituents and functional groups such as alcohol, ketone and
carboxylic groups involve in the ion exchange or complexation
reactions with metallic cations (Pino et al., 2006; Gadd, 2009;
Nurchi and Villaescusa, 2008).
The present work focuses on adsorption of toxic metal ions in
model aqueous solutions as well as in a real efuent using green
coconut (Cocos nucifera) shells in xed-bed technology.
2. Materials and methods
2.1. Materials
Stock solutions of 1 g/L of metal ions were prepared from the
following salts: Cu(NO3)2.4H2O, Zn(NO3)2.6H2O, Cd(NO3)2.4H2O, Pb

F.W. Sousa et al. / Journal of Environmental Management 91 (2010) 1634e1640

(NO3)2 and Ni(NO3)2.6H2O (analytical grade, Merck, So Paulo, SP,

Brazil) in deionized water. A standard solution of the salts at
a concentration of 100 mg/L at pH 5.0 was also prepared. The
concentrations of ions were analyzed by atomic absorption spectroscopy (AAS, GBC 933 plus model) in an air-acetylene ame.
2.2. Pre-treatment of the adsorbent
Green coconut shells were supplied by Embrapa Tropical Agroindustry, CE, Brazil (EMBRAPA/CE). The adsorbent was treated with
NaOH 0,1 mol L1 for 3 h and then washed with deionized water,
buffer solution (pH 5.0) and dried at 50  C. This material was cooled
at room temperature and then sieved to obtain desired particle size
(0246e0074 mm) (Sousa et al., 2007). The material was characterized by infrared spectroscopy using a FTIR Prestige Shimadzu
apparatus and morphological characteristics were obtained by
scanning electron microscopy using a Philips, SEM e XL30 model.
2.3. Flow rates, bed heights and breakthrough curves
A polyethylene column (30 cm  1.1 cm i.d.), lled with a known
mass of adsorbent corresponding to 5.0, 10.0 and 18.0 cm bed
heights was percolated with 150 mL of multi-component model
solution (100 mg/L at pH 5.0) at ow rates of 2.0; 4.0; 6.0 and
15.0 mL/min using a peristaltic pump.
Breakthrough curves of model wastewaters were obtained by
plotting C/Co versus volume. Aliquots of 10.0 mL were collected at
the exit of the column for measuring the ion concentrations.
2.4. Column regeneration
Volumes of 150 mL, containing 100 mg L1 of Cd2, Cu2, Ni2,
Pb2 and Zn2 were passed through the polyethylene column using
the conditions as found for multi-component solution. After
circulation from sample on the column, elution took place with
50 mL of 1.0 mol L1 HCl and HNO3 1.0 mol L1. Aliquots of 10 mL
were collected and the ion concentrations were determined before
and after adsorption.
Thus, after the choice of an eluant, ve cycles were applied and
each cycle used 50 mL of water, 150 mL of multi-component model
solution and 50 mL nitric acid (HNO3 1.0 mol L1).

1635

Table 1
Physical parameters of the column bed containing the adsorbent.
Properties

Green coconut shell

Column diameter (dL) (cm)

Bed height (cm)
Total area of the column (cm2)
Volume of the empty column (VL) (cm3)
Mass of adsorbent in the column (g)
Bulk density (g/cm3)
Packing density (g/cm3)
Particle volume (Vap) (cm3)
Porosity of the bed (%)

1.10
10.0
105.5
28.49
1.620
0.176
0.057
9.20
0.677

2.5. Application in real sample of an efuent

A real efuent of the electroplating industry (Juazeiro do Norte,
CE, Brazil) was examined for Ni2 (2.787 mg/L); Zn2 (98.02 mg/L)
and Cu2 (320.4 mg/L) ions.
2.6. Theory
The system used was a conventional xed bed in a polyethylene
column and the efciency was evaluated by determining breakthrough curves. An ideal breakthrough curve is shown in Fig. 1,
where Co is the adsorbate concentration in the efuent and Ve is the
volume of efuent passed through the column. The breakpoint
chosen arbitrarily as Cb occurs when the concentration of the
efuent reaches 5% of the initial concentration Co. The column
attains complete saturation, when the concentration Cx approaches
Co. The total amount of efuent, Vb, is passed through the column
until the breakpoint is reached (Cooney, 1999).
The part between Cx (exhaustion point) and Cb (breakpoint) is
called the primary adsorption zone (PAZ) and the time needed to
establish PAZ in the column is calculated by Equation (1) (Gupta
et al., 1997, 2000; Kundu and Gupta, 2005):

tx

Vx
Fm

(1)

where, tx is the time to establish PAZ (min), Fm is the ow rate

(mL/min) and Vx is the exhaustion volume (mL).

Fig. 1. Ideal breakthrough curve.

1636

F.W. Sousa et al. / Journal of Environmental Management 91 (2010) 1634e1640

Table 2
Hydraulic detention time (HDT), observed in the system of the column, in different
ows (Initial concentration: 100.0 mg/L of multi-component model solution; pH 5.0;
bed height 10.0 cm).

Table 3
Parameters obtained from breakthrough curves. Condition: single and multicomponent model solution 100 mg/L; pH 5.0; ow 2.0 mL/min; bed height 10 cm at
ambient temperature (28  2  C).

Flow (mL/min)

Hydraulic load (mL/min cm2)

HDT (min)

Metallic on Cb (mg/L) Cx (mg/L) Vb (mL) Vx (mL) Vx  Vb (mL) Fm (mL/min)

2.0
4.0
6.0
15

2.11
4.21
6.32
15.8

9.98
5.00
3.33
1.33

Single-component
5.69
Pb2
4.38
Ni2
Cd2
5.51
4.68
Zn2
2
4.99
Cu

90.94
86.76
81.18
83.44
88.37

470
150
270
120
160

920
280
510
280
320

450
130
240
160
160

2
2
2
2
2

Multi-component
5
Pb2
5
Ni2
5
Cd2
2
5
Zn
2
5
Cu

87.11
75.9
79.6
78.8
95

150
40
40
40
90

270
80
90
90
250

120
40
50
50
160

2
2
2
2
2

The time required for movement of PAZ down the column is

given by Equation (2) (Gupta et al., 1997, 2000; Kundu and Gupta,
2005):

ts

Vx  Vb
Fm

(2)

where, td is the time required for movement of PAZ down the

column (min), Vb is the breakthrough volume (mL), Fm is the ow
rate (mL/min) and V is the exhaustion volume (mL).
Thus, for depth D of the adsorbent, the depth and time ratios are
given by Equation (3) (Gupta et al., 1997, 2000; Kundu and Gupta,
2005):

d
D

td
tx  tf

(4)

where, F is the fractional capacity of adsorbent in the adsorption

zone characterized by removing the solute from the solution under
the limiting conditions.
The fractional capacity of the adsorbent is given by Equation (5)
(Gupta et al., 1997, 2000; Kundu and Gupta, 2005):

R Vx
F

Vb

C0  C$dv

CoVx  Vb

(5)

The percentage of saturation in the column is obtained by

Equation (6) (Gupta et al., 1997, 2000; Kundu and Gupta, 2005):


1

dF  1


 100

(6)

The maximum capacity of removal of toxic metal ions in the

column is given by Equation (7) (Gupta et al., 1997, 2000; Kundu
and Gupta, 2005):

(3)

where, d is the length of PAZ (cm), D is the depth of the adsorbent

(cm), tf is the time of formation of PAZ.
The time required to achieve PAZ is given by Equation (4) (Gupta
et al., 1997, 2000; Kundu and Gupta, 2005):

tf 1  Ftd


%S

C0  V
ms

t x
t 0

1


C
dt
C0

(7)

where, Q is the maximum adsorption capacity (mg/g); C0 and C are

the initial concentration of the solution and the concentration of
the metal ion in a determined volume (mg/L), respectively; ms is
the mass of the adsorbent (g); V is the ow rate (L/min) and the
time is in minutes.
3. Results and discussion
3.1. Characterization of adsorbent bed
Physical properties of the column bed containing the adsorbent
are shown in Table 1. The data show that packing density was below
5.8% and the porosity was above 67%.
3.2. Effects of the hydraulic loading rate
The experiments were carried out at a bed height of 10 cm with
a constant feed concentration of 100 mg/L and a hydraulic loading
rate ranging from 2.11 to 15.8 mL/min cm2. The results shown in
Table 2 indicate that the hydraulic retention time (HRT) increases

Table 4
Parameters tx, tf, td, f, d and saturation in the column for a single and multicomponent solution.
td (min)

tf (min)

d (cm)

Saturation %

Single-component
460
Pb2
140
Ni2
255
Cd2
Zn2
140
160
Cu2

225
65
170
80
80

116.1
32.76
85.00
41.12
41.44

0.484
0.496
0.500
0.486
0.482

6.54
6.06
10.0
8.09
6.75

66.25
69.46
50.00
58.42
65.04

Multi-component
135
Pb2
40
Ni2
45
Cd2
45
Zn2
2
125
Cu

60
20
25
25
80

30.0
13.68
12.49
15.15
40.00

0.500
0.316
0.500
0.394
0.500

5.73
7.59
7.68
8.37
9.41

71.00
48.08
61.60
49.19
52.95

Metallic ion

Fig. 2. Single-component breakthrough curves of Pb2, Ni2, Cd2; Zn2 and Cu2 on
green coconut shell. Condition: single-component model solution 100 mg/L; pH 5.0;
ow 2.0 mL/min; bed height 10 cm at room temperature (28  C).

tx (min)

F.W. Sousa et al. / Journal of Environmental Management 91 (2010) 1634e1640

1637

Table 5
Comparison of the adsorption capacity in the single-component model system of
batch and column. Condition: single-component model solution 100 mg/L; pH 5.0;
room temperature (28  2  C).
Metallic ion

Q (mg/g)
Batch

Column

Single-component
Pb2
Ni2
Cd2
Zn2
Cu2

3.07
2.98
3.63
0.753
5.35

54.62
16.34
37.78
17.08
41.36

Multi-component
Pb2
Ni2
Cd2
Zn2
Cu2

7.61
1.68
4.48
4.16
2.06

17.9
3.12
11.96
7.32
20.26
Fig. 3. Multi-component breakthrough curve on green coconut shell. Condition: multicomponent model solution 100 mg/L; pH 5.0; ow 2.0 mL/min; bed height 10 cm;
room temperature (282  C).

from 1.33 to 9.98 min thereby resulting in a decrease of the time

required to achieve a breakthrough. Han et al. (2006) advocated
that the greater the hydraulic loading is, smaller the adsorption is,
which is due to the short contact time between the adsorbent and
the adsorbate.
3.3. Effects of bed height
The effects of bed height (mass of adsorbent) on the adsorption
of the metal ions were investigated at a constant feed concentration
of 100 mg/L and an optimized hydraulic loading rate of 2.11 mL/
min cm2. Bed heights from 5 to 18 cm were examined showing
a decrease of the minimum efuent concentration with bed height
keeping other parameters constant. The increases in bed height
resulted in a greater adsorption capacity of the column. According
to the literature, the larger the bed height is, the greater the service
time is in the column, which is due to the increase of the supercial
area of the adsorbent and the amount of active sites available for
binding (Han et al., 2006). Furthermore, as the bed height increases,
the maximum adsorption capacity of the column increases (Malkoc
and Nuhoglu, 2006). Thus, a bed height of 10 cm was chosen for
studying breakthrough curves.
3.4. Breakthrough curves for single-components
Breakthrough curves for the adsorption of individual metal ions
on green coconut shells are shown in Fig. 2. The bed height, the
ow rate and the initial concentration were xed at 10 cm,
2.0 mL min1 and 100 mg L1, respectively. The breakthrough and
exhaustion volumes for lead and cadmium ions occurred at 470;
920 mL and 270; 510 mL, respectively. A similar trend was observed
for copper, zinc and nickel ions, however, the breakthrough and

exhaustion volumes occurred faster when compared with

cadmium and lead ions. The results obtained from the breakthrough curves show that an additional quantity can be treated
(VxVb) between breakthrough points for all metal ions (Table 3).
The values obtained from the breakthrough curves were used to
calculate the parameters tx, tf, td, f and the percentage saturation in
the column (Table 4).
The time to establish the primary adsorption zone (tx) is at
maximum for Pb2 (460 min) and at minimum for Ni2 and Zn2
(140 min), with Cu2 and Cd2 at intermediate values. The time
required to move the adsorption zone down in the column (td) is
situated between 65 and 225 min. The time required for initial
formation of the primary adsorption zone (tf), is between 32 and
116 min. The fractional capacities of the column (f) in the adsorption zone at the breakpoint are 0.484; 0.496; 0.500; 0.486 and
0.482 for Pb2, Ni2, Cd2, Zn2 and Cu2, respectively. The
percentage
saturation
is
in
the
following
order:
Ni2 > Pb2 > Cu2 > Zn2 > Cd2.
The mechanisms that govern metal uptake by vegetal biomaterials involve ion exchange, surface adsorption, chemisorption,
complexation, and adsorptionecomplexation processes (Nurchi,
2008). 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
(Carrijo et al., 2002; Pino et al., 2006) which can be involved in
metal binding by ion exchange or complexation mechanism interaction. One of the mechanisms involved in the sorption of positively charged metal species is the ion-exchange process between
protons present in the biomass and metal ions taken up from water.
The adsorption capacity was determined by Equation (7) as
C/Co 0.5. The values of the adsorption capacities in the batch

Table 6
Comparison of adsorption capacity of the metallic ions Pb2, Ni2, Cd2, Zn2 and Cu2 with several agricultural residue and activated charcoal to system of xed bed.
Adsorbent

Green coconut shell sol. single-component

Green coconut shell sol. multi-component
Activated carbon developed from fertilizer waste
Sargassum muticum
Modied activated carbon SDDC
Manganese oxide coated zeolite
Immobilized fungal biomass
Tea waste

Q (mg/g)
Pb2

Ni2

Cd2

Zn2

Cu2

54.62
17.9
1110.6
e
e
1.117
10.05
65

16.34
3.12
e
e
e
e
1.08
e

37.78
11.96
e
88
e
e
3.60
e

17.08
7.32
e
e
9.9
e
e
e

41.36
20.26
e
e
38
0.125
2.89
48

pH

Flow
(mL/min)

Bed
height (cm)

References

5
5
4.0
3.5e4.5
e
5.0
5e7
5e6

2
2
e
5
2
5.45
3
20

10
10
7
13
20
15
24.5
10

Present work
Present work
Gupta et al., 1997
Lodeiro et al., 2006
Monser and Adhoum, 2002
Han et al., 2006
Kappor and Viraraghavan, 1998
Amarasinghe and Williams, 2007

1638

F.W. Sousa et al. / Journal of Environmental Management 91 (2010) 1634e1640

Fig. 4. Percentage of desorption from metallic ions in the column using HNO3
1.0 mol L1 as elutant.

Fig. 6. Efciency of removal of metals in the function of number for cycles of reuse of
the column contained green coconut shell.

system and on column are shown in Table 5. It was found that the
adsorption capacity of the column performs better than that of the
batch system. Gupta et al. (2000) attributed the increased capacity
of the column method to a continuously increasing gradient
concentration in the interface of the adsorption zone, as it passes
through the column, while the gradient concentration decreases
with time in batch experiments.

The breakthrough curves for adsorption of multiple metal ions

on green coconut shells are shown on Fig. 3. The bed height, the
ow rate and the initial concentration were xed at 10 cm,
2.0 mL min1 and 100 mg L1, respectively. The results indicated
that the breakthrough and exhaustion volumes for lead and copper
ions occurred at 150; 270 mL and 90; 250 mL, respectively. A similar
trend was observed for cadmium, zinc and nickel ions, however, the
breakthrough and exhaustion volumes came earlier. The saturation
volumes are smaller than those for single ions, indicating that more
efuent can be treated for single ions and that competition effects
are operating (Table 6).
The values obtained from the breakthrough curves were used to
calculate parameters tx, tf, td, f and the percentages of saturation of
the column, as shown in Table 6.

The total time to establish the primary adsorption zone (tx) is at

maximum for Pb2 (135 min) and at minimum for Ni2 (40 min),
with intermediate values for Cu2, Zn2 and Cd2. The time
required to move the adsorption zone down the column (td) is
situated between 20 and 80 min. The time required for initial
formation of the primary adsorption zone (tf) is between 12 and
40 min. The fractional capacities of the column (f) in the adsorption
zone at breakthrough are 0.500; 0.316; 0.500; 0.394 and 0.500 for
Pb2, Ni2, Cd2, Zn2 and Cu2, respectively. The percentage
saturation follows this order: Pb2 > Cd2 > Cu2 > Zn2 > Ni2.
There is apparently a relationship between the adsorption zone
length (d) and the percentage of saturation at the breakthrough
point, C/Co 0.5. The results reveal that the major percentage of
saturation was obtained for Pb2 with a short length adsorption
zone, while, for the other ions, the presence of a major length
adsorption zone was observed below the saturation values. Gupta
et al. (1997) argued that a small adsorption zone (d) presents the
best percentage of removal, when its fractional (f) is high.
The adsorption capacity of the column was determined by
Equation (7) as C/Co 0,5. The values of the adsorption capacities in
the batch system and on the column are shown in Table 5. The
adsorption capacities of the column perform better than the batch
system. Gupta et al. (2000) reported that a higher capacity of the
column method is established by a continuously increasing
concentration gradient at the interface of the adsorption zone, as it

Fig. 5. Percentage of desorption from metallic ions in the column using HCl 1.0 mol L1
as elutant.

Fig. 7. Breakthrough curve of real sample in the green coconut shell. Condition: pH
1.14; ow 2.0 mL/min; bed height 10 cm; room temperature (28  2  C).

3.5. Breakthrough curves for multi-components

F.W. Sousa et al. / Journal of Environmental Management 91 (2010) 1634e1640

1639

Table 8
Parameters tx, tf, td, f, d, Q and saturation (%S) of the column to real sample in the
efuent of pH 1.14 and 5.0.
Metallic ion

tx (min)

td (min)

pH 1.14
Ni2
Zn2
Cu2

15
15
15

10
10
10

pH 5.0
Ni2
Zn2
Cu2

35
45
100

10
20
60

d (cm)

Q (mg/g)

5.00
5.00
4.99

0.500
0.500
0.500

10.0
10.0
9.99

0.056
1.98
4.92

50.00
50.15
50.05

4.98
10.0
30.36

0.502
0.500
0.494

3.33
5.71
8.62

0.132
5.96
42.50

83.42
71.45
56.40

tf (min)

%S

3.8. Breakthrough curves for a real efuent

Fig. 8. Breakthrough curve of real sample in the green coconut shell. Condition: pH
5.0; ow 2.0 mL/min; bed height 10 cm; room temperature (282  C).

passes through the column, while the concentration gradient

decreases with time in batch experiments.
The adsorption capacities obtained for green coconut shells in
a xed-bed technology were compared with other bioderived
adsorbents that were used for the treatment of aqueous solution
containing toxic metal ions (Table 6). The use of green coconut
shells can be considered as a cheap renewable material for use in
the treatment of industrial efuents. However, a direct comparison
between the adsorbents is difcult due to the use of different
experimental conditions.

3.6. Column regeneration

The recovery (desorption) of the metal ions was carried out by
an acid elution method, using HNO3 1.0 mol L1 and HCl 1.0 mol L1.
The results are shown in Figs. 4 and 5. According to Vijayaraghavan
et al. (2006), an optimal eluent elutes all ions using the smallest
volume. Our results did not differentiate between HNO3 and HCl,
while both acids removed all metal ions with 50 mL solution. HNO3
1.0 mol L1 was chosen for the study of the column regeneration.

3.7. Recycling of the column

After the adsorptionedesorption experiments, tests were
carried out in order to evaluate whether the column could be
recycled. The results (ve cycles) are shown in Fig. 6. It can be
observed that the reuse of the adsorbent decreases the removal
efciency for all metal ions from the rst cycle. Removal capacities
were reduced more than 50% for Pb2, 70% for Ni2; 67% for Cd2;
76% for Zn2 and 75% for Cu2.

Table 7
Parameters obtained from breakthrough curve of real sample from efuent in pH
1.14 and pH 5.0.
Metallic on Cb (mg/L) Cx (mg/L) Vb (mL) Vx (mL) Vx  Vb (mL) Fm (mL/min)
pH 1.14
Ni2
Zn2
Cu2

0.066
0.001
0.096

2.44
89.29
286.44

10
10
10

30
30
30

20
20
20

2
2
2

pH 5.0
Ni2
Zn2
Cu2

0.187
3.65
14.45

2.49
94.7
240.13

50
50
80

70
90
200

20
40
140

2
2
2

The procedure was applied on a real sample from the electroplating industry, containing Ni2 (2.787 mg/L); Zn2 (98.02 mg/L)
and Cu2 (320.4 mg/L). Figs. 7 and 8 show breakthrough curves
derived at pH 1.14 and pH 5.0. The column seems saturated with
a volume of about 30 mL for all metal ions (Ni2, Zn2 and Cu2) at pH
1.14. However, at pH 5.0, saturation occurs at volumes of 70 mL for
Ni2, 90 mL for Zn2 and 200 mL for Cu2 (Table 7). The adsorption
properties are very sensitive to pH. A larger quantity of solution can
be treated, when the pH of the sample is adjusted to 5.0.
The values obtained from the breakthrough curves were used to
calculate parameters tx, tf, td, f and the percentage of saturation of
the column.
The total time to establish the primary adsorption zone (tx) is
15 min at pH 1.14 and between 35 and 100 min at pH 5.0. The time
required to move the adsorption zone down the column (td) and the
time required for the initial formation of the primary adsorption
zone (tf) are from 5 to 10 min at pH 1.14 and from 10 to 60 min at pH
5.0. The adsorption capacities increased to 0.132; 5.96 and
42.50 mg/g for Ni2, Zn2 and Cu2, respectively, at pH 5.0. The
saturation percentage at pH 1.14 was about 50% for all metal ions,
while at pH 5.0, 83.42% saturation was observed for Ni2; 71.45% for
Zn2 and 56.40% for Cu2 (Table 8). It may be that at pH 5.0,
competitive effects of protons for active sites on the adsorbent are
diminished (Han et al., 2006).
4. Conclusion
At a ow rate of 2 mL/min and a bed height of 10 cm, the efciencies of removal of toxic metal ions duly by green coconut shells
are at an optimum.
The breakthrough curves show that larger quantities of efuent
can be treated for individual ions with respect to multiple ions.
Using HNO3 1.0 mol L1, the adsorbent can be reused, but
removal efciencies decrease from the rst cycle. Investigation of
a real sample, containing Ni2 (2.787 mg/L); Zn2 (98.02 mg/L) and
Cu2 (320.4 mg/L), showed that the xed-bed technology can be
applied, provided that the pH of the sample is adjusted to 5.0.
Acknowledgements
The authors would like to thank the Laboratory of Trace Analysis
(LAT) of Federal University of Cear (UFC), FUNCAP (Fundao
Cearense de Pesquisa, Process No.610/07) and CNPq (Conselho
Nacional de Desenvolvimento Cientco e Tenolgico Process No.
576591/2008-4).
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