AC 2011 Banana Stalk
AC 2011 Banana Stalk
AC 2011 Banana Stalk
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
Department of Chemistry, Faculty of Science, Imo State University, P.M.B. 2000 Owerri, Nigeria
a r t i c l e
i n f o
Article history:
Received 24 May 2011
Received in revised form 8 August 2011
Accepted 9 August 2011
Keywords:
2,4-Dichlorophenoxyacetic acid
Bentazon
Isotherm
Kinetic
Thermodynamic
a b s t r a c t
Activated carbon was prepared from banana stalk by potassium hydroxide (KOH) and carbon dioxide
(CO2 ) activation and its ability to remove the pesticides, 2,4-dichlorophenoxyacetic acid (2,4-D) and
bentazon was explored. The banana stalk activated carbon (BSAC) was characterized by Fourier transform infrared spectroscopy (FT-IR) analysis. The adsorption kinetic data were analyzed using two kinetic
models: the pseudo-rst-order and pseudo-second-order models. The adsorption kinetics was better
represented by the pseudo-second-order model. The equilibrium adsorption data obtained at 30, 40 and
50 C were analyzed by Langmuir and Freundlich isotherm models and results showed that it was better
described by the Freundlich model. Higher adsorption capacity observed for 2,4-D than bentazon were
attributed to the presence of electron-withdrawing Cl groups on the aromatic ring and smaller molecular
size of 2,4-D. The thermodynamic parameters, G , H and S determined, showed that the adsorption of 2,4-D and bentazon onto BSAC was feasible, spontaneous and exothermic. The results showed that
BSAC is an efcient adsorbent for the adsorptive removal of 2,4-D and bentazon from aqueous solutions.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The contamination of surface and ground water by pesticides
has become a serious environmental problem in recent years
due to the extensive application of these agrochemicals in crop
farms, orchards, elds and forest lands. This contamination arises
from surface runoff, leaching, wind erosion, deposition from aerial
applications, industrial discharges and various other sources. Consequently, pesticides have frequently been detected in water bodies
in different countries of the world [13]. Pesticides are harmful to
life because of their toxicity, carcinogenicity and mutagenicity [4].
The harmful inuence of pesticides on human health and the environment has resulted to the imposition of stringent legislation on
drinking water quality in many countries [5].
2,4-Dichlorophenoxyacetic acid (2,4-D) and bentazon are two
widely used anionic herbicides usually applied for the control
of broad-leaf weeds [6]. 2,4-D is moderately toxic but weakly
adsorbed by soil particles and therefore has high mobility and persistence in aqueous media [7,8]. Exposure to 2,4-D causes serious
eye and skin irritation, nausea, weakness, fatigue and in some cases
neurotoxic effects including inammation of nerve endings [9].
Bentazon is a contact post-emergence herbicide that can provide
42
Table 1
Some of properties and chemical structures of pesticides used.
Molecule weight (g mol1 )
Solubility in water (g L1 )
C8 H6 Cl2 O3
221.04
0.90
C10 H12 N2 O3 S
240.3
0.50
Pesticide
Formula
2,4-D
Bentazon
Chemical structure
no known industrial or commercial importance but rather constitutes a serious environmental problem. The use of banana stalk BS
as a precursor for AC will provide solution to environmental problems caused by this waste as well as produce a value-added product
from a low-cost material. In our previous study, AC prepared from
BS was found to be a good adsorbent for the removal of carbofuran
[32].
The purpose of this study is to determine the removal efciencies of AC prepared from BS for the pesticides, 2,4-D and bentazon
from articially contaminated solutions. The inuences of contact
time, initial concentration of pesticide, pH and temperature on the
adsorption capacities of BSAC for the pesticides were investigated.
In addition, kinetic modeling was carried out to understand the
mechanisms involved in the adsorption system. Isotherm models were also utilized in tting the equilibrium adsorption data
and adsorption performance of BSAC with respect to the two
pesticides were compared. Thermodynamic parameters were also
determined and the adsorption mechanisms further elucidated.
2. Materials and methods
2.1. Adsorbates
2,4-D and bentazon were obtained from SigmaAldrich (M) Sdn.
Bhd., Malaysia and were used separately as adsorbates. They were
of analytical grade and were used without further purication. Distilled water was used in the preparation of all solutions. Some
properties and chemical structures of the pesticides are given in
Table 1.
2.2. Preparation of activated carbon
Banana stalks were collected as wastes from local markets,
cut into small pieces of about 2 cm 2 cm, washed with water to
remove surface dirt and then dried to constant weight at 105 C.
The sample was carbonized and activated following the same
procedure described by Salman and Hameed [32]. The sample was
crushed, sieved to mesh size of 14 mm and carbonized in a stainless steel vertical tubular reactor placed in a tubular furnace under
puried nitrogen (99.995%) ow of 150 cm3 min1 at 600 C, with
a heating rate of 10 C min1 . The carbonization temperature was
maintained for 2 h before cooling still under nitrogen ow. The
carbonized material was soaked in potassium hydroxide (KOH)
solution with an impregnation ratio (KOH:char) of 2.5:1 (w/w) for
12 h and then dehydrated in an oven overnight at 105 C. The sample was then activated under the same conditions as carbonization
but to a nal temperature of 700 C. Once the nal temperature was
reached, the gas ow was switched from nitrogen to carbon dioxide
and this temperature was maintained for 2 h to achieve activation
[32]. The resulting AC was washed with 0.1 M HCl after cooling to
dissolve and remove any residual ash. This was followed by washing with hot distilled water until the pH of the supernatant solution
reached 6.57.0. This was followed by drying of the AC overnight
in an oven at 105 C.
2.3. Characterization of activated carbon
The surface functional groups of BSAC were determined using
Fourier transform infrared (FT-IR) spectroscopy (Perkin Elmer,
Model 2000 FT-IR, USA). FT-IR technique is an important technique
used in identifying characteristic surface functional groups on the
adsorbent, which in some cases are responsible for the binding of
the adsorbate molecules. The spectrum was recorded from 4000 to
400 cm1 adopting the KBr pellet method of sample handling.
2.4. Adsorption experiments
Stock solutions of 500 mg L1 2,4-D and bentazon were prepared
by dissolving appropriate amounts in distilled water. Solutions of
different initial concentrations of the pesticides were prepared by
serial dilution of the stock solutions. The kinetic and equilibrium
studies were undertaken at the pH of 3.5 and temperature of 30,
40 and 50 C. Batch adsorption studies were performed by shaking
200 mL of known initial concentrations of pesticide with 0.3 g BSAC
of 0.52.0 mm particle size in 250 mL conical asks. The effect of
solution initial pH on the adsorption of the pesticides by BSAC was
investigated by contacting 200 mL of 100 mg L1 2,4-D and bentazon solutions with 0.3 g BSAC in various asks of varying pH values
in the range 212 and at temperature of 30 C. The initial solution
pH was adjusted by drop-wise addition of 1.0 M HCl or 0.1 M NaOH
and solution pH was measured using a pH meter (EUTECH Instruments, Model Ecoscan, Singapore). The conical asks were then
covered with glass stoppers and placed inside a water-bath shaker
at shaking speed of 120 rpm. The samples were then withdrawn
at appropriate time intervals using glass syringes to determine the
residual concentrations of the adsorbates. The concentrations of
2,4-D and bentazon in the solutions before and after adsorption
were determined using a double beam UVvis spectrophotometer (Shimadzu UV-1700, Japan) at their maximum wavelength of
284 and 232 nm, respectively. The amounts of pesticide adsorbed
at time t, qt (mg g1 ) and at equilibrium, qe (mg g1 ) were calculated
using Eqs. (1) and (2).
qt =
(C0 Ct )V
W
(1)
qe =
(C0 Ce )V
W
(2)
43
781.72
Transmittance (%)
1160.25
2360.83
2929.75
1402.08
1320.04
1644.41
706.34
832.60
3446.38
1007.92
1621.99
617.85
1053.06
1406.16
2361.26
3736.10
3854.43
1053.07
1537.20
2376.70
4000.0
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
600
400.0
Wavenumber (cm-1)
Fig. 1. FT-IR spectra of BS precursor, BS char and BSAC.
(a)
350
300
250
-1
Ct (mg L )
-1
200
150
100
50
0
0
10
15
20
25
Time, t (h)
(b)
280
240
-1
200
-1
Ct (mg L )
Fig. 2(a) and (b) shows the effect of contact time and initial
concentration of pesticide on the removal of 2,4-D and bentazon by BSAC. The results show that the residual concentration of
pesticides decrease with time, hence, the removal of 2,4-D and bentazon increase with time. Initially, adsorption increased sharply and
slowed gradually until equilibrium was attained in approximately
3 h for all initial concentrations of both pesticides studied. At this
point, the amount of pesticide desorbing from BSAC is in a state of
dynamic equilibrium with the amount of pesticide being adsorbed
on BSAC. This could be attributed to the larger number of vacant surface sites available for adsorption at the initial than the later stages
and the repulsive forces existing between pesticide molecules on
the BSAC surface and those in solution at the later stages.
Adsorption studies were conducted in the pesticide initial concentration ranges of 50300 and 25250 mg L1 for 2,4-D and
bentazon, respectively. Fig. 2(a) and (b) also shows the important
role of initial concentration of pesticide on the adsorption of 2,4D and bentazon onto BSAC. Increasing the initial concentration of
160
120
80
40
0
0
10
15
20
25
Time, t (h)
Fig. 2. Effect of contact time and pesticide initial concentration on adsorption onto
BSAC of (a) 2,4-D and (b) bentazon (30 C; agitation rate, 120 rpm; BSAC dose,
1000 mg L1 ).
44
60
(a)
240
-1
200
50
-1
-1
50 mg g
100 mg g
-1
-1
200 mg g
250 mg g
Pseudo-first-order fit
Pseudo-second-order fit
150 mg g
-1
300 mg g
160
qe (mg/g)
-1
qt (mg g )
40
30
2,4-D
Bentazon
120
80
20
40
10
10
10
12
14
pH
(b)
The effect of solution initial pH on 2,4-D and bentazon adsorption by BSAC was examined and the result is presented in Fig. 3. The
equilibrium adsorption of both pesticides decreased with increase
in initial pH of solution and this is attributable to the increased electrostatic repulsion between the pesticide ions and BSAC surface.
Both 2,4-D and bentazon are weak acids with pKa of 2.63.0 and 3.3,
respectively [8,37]. The FT-IR analysis revealed the presence of negatively charged functional groups on the BSAC surface. At pH above
the pKa values, the pesticides exist predominantly in the anionic
forms and as pH is increased, the extent of dissociation of these
molecules increased and they became more negatively charged.
This resulted to increased electrostatic repulsion or dispersion
between the pesticide ions and the BSAC surface and subsequently
decreased equilibrium adsorption as was observed in the pH range
studied. Similar observations were reported for the adsorption of
2,4-D using fertilizer and steel industry wastes and for the adsorption of bentazon onto AC cloth [11,37].
3.4. Adsorption kinetics
The modeling of adsorption kinetics was investigated using
two models, namely, the pseudo-rst-order (PFO) and the pseudosecond-order (PSO) models. The non-linear form of the PFO
equation [38] is expressed as Eq. (3).
(3)
where k1 (h1 ) is the PFO rate constant and t (h) the contact time.
The non-linear form of the PSO kinetic equation [39] is given by Eq.
(4):
qt =
q2e k2 t
1 + qe k2 t
25
-1
-1
25 mg L
50 mg L
-1
-1
150 mg L
200 mg L
Pseudo-first-order fit
Pseudo-second-order fit
-1
100 mg L
-1
250 mg L
100
-1
80
60
40
20
qt = qe (1 ek1 t )
20
140
120
qt (mg g )
of pesticide is increased [36]. However, the percent removal efciency of 2,4-D decreased from 98.4 to 85.4% as the 2,4-D initial
concentration increased from 50 to 300 mg L1 while for bentazon, the percent removal efciency decreased from 96.5 to 61.6% as
the bentazon initial concentration increased from 25 to 250 mg L1 .
Therefore, the adsorption of 2,4-D and bentazon by BSAC has strong
dependence on the initial concentration of the pesticides.
15
Time, t (h)
(4)
10
15
20
25
Time, t (h)
Fig. 4. Fit of pseudo-rst-order and pseudo-second-order kinetic models for the
adsorption onto BSAC of (a) 2,4-D and (b) bentazon (30 C; agitation rate, 120 rpm;
BSAC dose, 1000 mg L1 ).
45
Table 2
Kinetics parameters for the adsorption of 2,4-D and bentazon onto BSAC at 30 C.
C0 (mg L1 )
2,4-D
50
100
150
200
250
300
Bentazon
25
50
100
150
200
250
qe,exp (mg g1 )
Pseudo-rst-order
Pseudo-second-order
k1 (h1 )
qe (mg g1 )
2
Radj
RMSE
k2 (g mg1 h1 )
qe (mg g1 )
2
Radj
RMSE
32.62
64.61
95.07
122.28
145.45
168.03
2.105
2.483
2.692
2.523
2.626
2.216
32.14
63.11
92.43
118.42
141.81
164.10
0.995
0.994
0.990
0.992
0.988
0.992
0.734
1.631
2.987
3.591
5.232
5.005
0.121
0.078
0.059
0.042
0.037
0.025
33.54
65.54
95.89
123.00
147.21
171.32
0.996
0.996
0.997
0.997
0.999
0.998
0.683
1.334
1.732
2.209
0.752
2.397
15.47
30.10
50.63
67.99
81.59
100.95
1.210
1.447
1.658
2.038
2.065
1.928
15.50
29.33
48.98
66.53
79.91
95.09
0.988
0.978
0.984
0.992
0.991
0.966
0.600
1.515
2.090
2.020
2.495
5.904
0.116
0.074
0.055
0.053
0.046
0.033
16.51
31.16
51.84
69.60
83.58
100.64
0.996
0.989
0.998
0.998
0.998
0.995
0.319
1.048
0.718
0.936
1.002
2.184
qm KL Ce
1 + KL Ce
(5)
(a)
200
180
160
140
-1
120
100
Experimental data
Langmuir fit
Freundlich fit
80
60
40
20
0
0
10
20
30
40
50
80
100
-1
Ce (mg L )
(b)
100
80
-1
qe (mg g )
(6)
qe (mg g )
1/n
qe = KF Ce
60
Experimental data
Langmuir fit
Freundlich fit
40
20
0
0
20
40
60
-1
Ce (mg L )
Fig. 5. Adsorption isotherm tting for adsorption onto BSAC at 30 C of (a) 2,4-D
and (b) bentazon.
46
Table 3
Langmuir and Freundlich isotherm model parameters and correlation coefcients for adsorption of 2,4-D and bentazon onto BSAC at 30 C.
Pesticide
Isotherm model
Parameter
2,4-D
Langmuir
qm (mg g1 )
KL (L mg1 )
2
Radj
Temperature ( C)
RMSE
Freundlich
n
KF (L g1 )
2
Radj
RMSE
Bentazon
Langmuir
qm (mg g1 )
KL (L mg1 )
2
Radj
Freundlich
n
KF (L g1 )
2
Radj
RMSE
RMSE
30
40
50
196.33
0.279
0.961
178.60
0.158
0.978
166.7
0.135
0.973
7.815
4.236
4.310
2.60
42.01
0.979
2.77
40.85
0.998
3.13
40.05
0.998
2.632
1.104
1.218
115.07
0.067
0.943
92.60
0.067
0.972
90.90
0.098
0.975
6.952
4.384
4.065
2.44
14.94
0.961
2.87
16.36
0.997
2.97
18.14
0.977
4.908
2.540
2.856
Table 4
Comparison of 2,4-D and bentazon Langmuir adsorption capacities of various activated carbons.
Pesticide
Reference
2,4-D
8.1310.48
11.7616.25
181.82
238.10
196.33
[41]
[41]
[45]
[46]
This study
Bentazon
17
86.26
115
151
115.07
[37]
[42]
[37]
[47]
This study
H
S
R
RT
(7)
G = H TS
Table 5
Thermodynamic parameters of the adsorption of 2,4-D and bentazon onto BSAC.
H (kJ mol1 )
Kd =
Cad,e
Ce
(9)
S (J mol1 K1 )
30 C
40 C
50 C
5.48
7.12
7.18
7.23
2.88
1.98
2.01
2.04
(8)
where
Cad,e
(mg L1 )
is
the
equilibrium
concentration of pesticide on BSAC and Ce (mg L1 ) is the
2,4-D
5.46
Bentazon
1.11
G (kJ mol1 )
47
48