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Karbala International Journal of Modern Science 2 (2016) 20e28
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Abstract
The prime conditions for the removal of Cu (II) and Pb (II) onto defatted papaya seeds (DPS) from aqueous solution were
studied. The effects of three adsorption variables (adsorbent dosage, shaking speed as well as initial concentrations) were investigated using central composite design (CCD) which is a subset of response surface methodology (RSM). Quadratic models were
developed for both Cu (II) and Pb (II) percentage removals. The optimum adsorption conditions obtained were adsorbent dosage of
0.30 g, shaking speed of 180 rpm as well as initial concentration of 150 mg/L with desirability of 0.987. The predicted and
experimental values obtained were 96.65% and 97.55% for Cu (II) as well as 98.07 and 99.96% for Pb (II), showing good agreement
between the experimental values and those predicted from the models with relatively small errors which were only 0.89 and 1.89,
respectively. Langmuir isotherm model was found to be the best fit for the equilibrium adsorption data of both Cu (II) and Pb (II) on
DPS giving rise to monolayer adsorption capacities of 17.29 and 53.02 mg/g respectively.
2015 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Keywords: Defatted papaya seed; Adsorption; Central composite design; Response surface methodology; Cu (II) and Pb (II)
1. Introduction
The presence of heavy metals in waste stream and
ground water pose a very serious environmental
concern since these metal ions are reported to be toxic
* Corresponding author. School of Chemical Sciences, Universiti
Sains Malaysia, 11800, Penang, Malaysia. Tel.: 60 1126116051;
fax: 60 46574854.
E-mail address: dinigetso2000@gmail.com (Z.N. Garba).
Peer review under responsibility of University of Kerbala.
http://dx.doi.org/10.1016/j.kijoms.2015.12.002
2405-609X/ 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Z.N. Garba et al. / Karbala International Journal of Modern Science 2 (2016) 20e28
21
defatted before use as biosorbent [24]. Response surface methodology (RSM) is a mathematical model that
was reported to be a very useful tool in optimizing the
preparation conditions of activated carbons [25] but not
much was reported on its application in optimizing
adsorption process parameters.
The continuation of our interest in exploring safer
and cheaper alternative methods for the treatment of
wastewater and textile effluents [17,18,26] lead us to
report the optimization of the paramount parameters
for an effective adsorption of Cu (II) and Pb (II) onto
DPS from aqueous solution using CCD. CCD was
chosen to evaluate the interaction of the crucial
adsorption parameters such as adsorbent dosage,
shaking speed as well as initial concentrations.
2. Materials and methods
2.1. Preparation of adsorbent material
Table 1
Experimental design matrix using central composite design.
Run
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Level
1
1
1
1
1
1
1
1
1.682
1.682
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
0
0
1.682
1.682
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
0
0
0
0
1.682
1.682
0
0
0
0
0
0
Cu (II) removal
Pb (II) removal
Adsorbent
dosage (g)
Shaking speed
(rpm)
Initial concentration
(mg/L)
YCu (%)
YPb (%)
0.30
0.80
0.30
0.80
0.30
0.80
0.30
0.80
0.10
1.00
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
120
120
180
180
120
120
180
180
150
150
100
200
150
150
150
150
150
150
150
150
56
56
56
56
149
149
149
149
103
103
103
103
25
180
103
103
103
103
103
103
55.43
63.27
93.62
44.01
54.33
40.00
86.44
54.54
70.34
34.65
43.27
74.82
89.44
98.24
69.44
68.55
70.58
67.77
68.43
69.94
54.19
78.03
89.32
45.66
55.73
45.78
80.64
90.65
57.26
51.57
46.59
96.82
44.33
88.82
38.05
37.10
38.19
37.76
38.29
36.46
22
Z.N. Garba et al. / Karbala International Journal of Modern Science 2 (2016) 20e28
Table 2
Independent variables and their coded levels using central composite
design.
Ce
1
Ce
0
KL $Q0a
qe
Qa
Variables
Adsorbent dosage x1
Shaking speed
x2
Initial concentration x3
a 1
0
1
g
0.10
0.30
0.60
0.80
rpm 100 120
150
180
mg/L 25
56
103
149
a
1.00
200
180
Co Ce
100
Co
Co Ce V
W
RL
1
1 KL Co
Freundlich model on the other hand assumes heterogeneous surface energies. Its linear form is given by
the following equation [29]:
1
logqe logKF logCe
n
In this work, a subset of response surface methodology (RSM) known as central composite design
(CCD) was applied to study the Cu (II) and Pb (II)
adsorption parameters (adsorbent dosage, shaking
speed as well as initial concentrations). The detailed
CCD process was described in our previously published paper [17]. Design expert statistical software
(version 6.0.8 Stat Ease, Inc., Minneapolis, MN 55413,
USA) was used for the model fitting and significance
for the Cu (II) and Pb (II) adsorption efficiencies.
3. Results and discussion
3.1. Development of regression model equations
using CCD
The design matrix incorporating the preparation
variables, their ranges and the responses which are
percentage removal of both Cu (II) and Pb (II) (YCu
and YPb) respectively were displayed in Table 1. The
Cu (II) and Pb (II) percentage removals ranged between 34.65 and 98.24% and 36.46.17e96.82%
respectively. For the sake of comparing and correlating
Z.N. Garba et al. / Karbala International Journal of Modern Science 2 (2016) 20e28
23
Table 3
The ANOVA for response surface quadratic model of Cu (II) by DPS.
Table 4
The ANOVA for response surface quadratic model of Pb (II) by DPS.
Source
Sum of
squares
Degree of
freedom
Mean
square
F value
Prob > F
Source
Sum of
squares
Degree of
freedom
Mean
square
F value
Prob > F
Model
x1
x2
x3
x21
x22
x23
x1 x2
x1 x3
x2 x3
Residual
5519.81
1604.39
1030.66
2.83
777.91
364.80
761.81
703.50
2.49
96.05
455.52
9
1
1
1
1
1
1
1
1
1
10
613.31
1604.39
1030.66
2.83
777.91
364.80
761.81
703.50
2.49
96.05
45.55
13.46
35.22
22.63
0.062
17.08
8.01
16.72
15.44
0.055
2.11
e
0.0002
0.0001
0.0008
0.8081
0.0020
0.0179
0.0022
0.0028
0.8200
0.1771
e
Model
x1
x2
x3
x21
x22
x23
x1 x2
x1 x3
x2 x3
Residual
6989.09
62.99
1809.13
474.79
567.20
2217.40
1614.20
282.51
49.40
561.46
1605.88
9
1
1
1
1
1
1
1
1
1
10
776.57
62.99
1809.13
474.79
567.20
2217.40
1614.20
282.51
49.40
561.46
160.59
4.84
0.39
11.27
2.96
3.53
13.81
10.05
1.76
0.31
3.50
e
0.0108
0.5452
0.0073
0.1163
0.0896
0.0040
0.0100
0.2142
0.5913
0.0910
e
24
Z.N. Garba et al. / Karbala International Journal of Modern Science 2 (2016) 20e28
Z.N. Garba et al. / Karbala International Journal of Modern Science 2 (2016) 20e28
25
Fig. 3. The combined effect of shaking speed and adsorbent dosage on the removal of Cu (II) with initial concentration fixed at zero level
(Co 103 mg/L).
Fig. 4. The combined effect of initial concentration and shaking speed on the removal of Pb (II) with adsorbent dosage fixed at zero level
(W 0.6 g).
26
Z.N. Garba et al. / Karbala International Journal of Modern Science 2 (2016) 20e28
Table 5
The model validation.
Model
desirability
Adsorbent
dosage, x1 (g)
Shaking
speed, x2 (rpm)
Initial
concentration,
x3 (mg/L)
Predicted
Error
Experimental
Predicted
Error
0.987
0.30
180
150
97.54
96.65
0.89
99.96
98.07
1.89
Table 6
Langmuir and Freundlich isotherm model parameters for Cu (II) and
Pb (II) adsorption onto DPS at 30 C.
Isotherms
Parameters
Cu (II)
Pb (II)
Langmuir
Q0a
17.29
0.265
0.073
0.9923
10.713
1.951
2.315
0.8996
13.361
53.02
0.238
0.061
0.9779
7.252
8.382
3.080
0.8080
19.311
Freundlich
(mg/g)
KL (L/mg)
RL
R2
c2
KF (mg/g (L/mg)
n
R2
c2
Table 7
Comparison of adsorption capacity of metal ions onto different
adsorbents.
Adsorbates
Adsorbents
Q0a (mg/g)
References
Cu (II)
Pb (II)
Cu (II)
Cu (II)
Pb (II)
Pb (II)
Ni (II)
Ni (II)
17.29
53.02
8.78
17.83
31.32
22.37
5.41
58.82
This work
This work
[10]
[33]
[10]
[33]
[12]
[22]
Z.N. Garba et al. / Karbala International Journal of Modern Science 2 (2016) 20e28
[11]
[12]
[13]
[14]
[15]
Acknowledgement
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
27
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