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INTRODUCTION
Organic pesticides including insecticides and herbicides
used in agriculture have become a real environmental
problem since part of them were identied in surface and
ground waters (1), fruit, vegetables (2), and even in animal
bodies (3). Also, this environment persistence of pesticides
as non-biodegradable or harmful metabolites constitutes a
danger to human health (1,46).
From pesticide class, alpha-cypermethrin (Fig. 1) is a
common pyrethroid chemical used as insecticide and acaricide for control of certain insect pests in crops of cereals,
rice, cotton, sunower, sweet corn, maize, soy, navy and
mung beans, sorghum, and tomatoes. According to the
Received 31 August 2012; accepted 13 May 2013.
Address correspondence to Andrada Maicaneanu, Faculty of
Chemistry and Chemical Engineering, Babes-Bolyai University,
11 Arany Janos st., Cluj-Napoca, RO-400028, Romania. E-mail:
andrada@chem.ubbcluj.ro
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ET AL.
Microscopy Investigations
Scanning electron microscopy (SEM) image was obtained
with a SEM-Quanta 200F microscope for CA. Transmission
electron microscopy (TEM) of CA was performed with a
Hitachi H-7000 microscope operating at 125 keV. Atomic
force microscopy (AFM) investigation was performed for
CA in toping mode with an Agilent-5100 apparatus.
X-Ray Diffraction
Crystalline phase evaluations of CA and CX were performed by analyzing the X-ray diffraction patterns
recorded in a h2h BraggBretano geometry with a
Siemens D5000 powder diffractometer with Cu-Ka incident
).
radiation (k 1.5406 A
Adsorption Experiments
Chemicals
Alpha-cypermethrin (chemical formula C22H19Cl2NO3,
molecular weight 416.30 g=mol), with molecular structure
presented in Fig. 1, active substance in FASTAC pesticide,
was used as adsorbate. Stock solution containing 4 mg=mL
was prepared by dissolving two vials (2 mL) of commercial
available FASTAC 10EC (Bayer) in distilled water. Stock
solution was stored in dark bottles at 4 C. Solutions used
in adsorption experiments were obtained by diluting
the stock solution to the desired concentrations, in
1070 mg=L range.
Batch Adsorption Experiments
Adsorption experiments were conducted in batch
conditions under magnetic stirring (500 rpm) in a 50 mL
Berzelius ask by mixing 10 mL adsorbate solution with
the desired quantity of the adsorbent. Experiments were
realized in thermostatic conditions. Adsorbent quantity
(0.01 0.05 g) and grain size (<0.250 mm, 0.250
0.315 mm, 0.315 0.400 mm), temperature (25, 35, 45 C),
and alpha-cypermethrin concentration (1070 mg=L)
inuence over the adsorption process were considered.
CA reusability was studied as follows: after the rst usage,
adsorbent sample was dried in air for 24 h, subjected to
pyrolysis at 550 C for 2 h, and reused in the same conditions (Ci 55 mg=L, 0.01 g, d < 0.25 mm, 25 C, 5.88
pH, 500 rpm). The procedure was repeated twice (named
1st and 2nd regeneration).
The exact concentration of alpha-cypermethrin in solution was determined at different time intervals up to 180
minutes using an UV=VIS spectrophotometer T70 (PG
Instruments Ltd.), kmax 276 nm. Evolution of the adsorption process was followed using concentration evolution in
time, adsorption capacity, Qe (mg=g), and adsorption
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Qe
Ci Ce V
1000
m
Ci Ce
100
Ci
present two large peaks at about 2h 24o and 44o characteristic for these material types.
Alpha-Cypermethrin Adsorption
Effect of Adsorbent Quantity and Grain Size
CA and CX quantity inuence over the alphacypermethrin removal presented in Figs. 5a and 5b indicated
that as the adsorbent quantity increases, adsorption capacity
will decrease (reduced unsaturation which will lead to a
decrease in the number of occupied sites per unit mass, difcult access to the adsorption sites, particle agglomeration
which will increase diffusion path length, (24)). In terms of
removal efciencies an increase was observed (Fig. 5b) as a
higher quantity of adsorbent is added; due to the fact that
for the same initial concentration a higher surface (increased
number of adsorption sites) will be available for adsorption
(24). Therefore, in case of CA, for example, the adsorption
capacity decreases from 28.44 to 6.27 mg=g for 0.01 and
0.05 g, respectively, while the removal efciency increased
from 69.46 to 78.26%. Another important observation is that
CA is a better adsorbent than CX (the adsorption capacity
values were 28.44 mg=g and 27.20 mg=g, respectively, in the
same conditions and an initial concentration of 40 mg=L).
When grain size was considered as an adsorption parameter (Fig. 6), a decrease in adsorption capacity was
observed as the adsorbent grain size increased. An average
decrease of 6.45% in the adsorption capacity values with
the increase of the grain size was observed. This might suggest a degree of internal diffusion limitation as the grain
size increases. The difference between adsorption capacity
for CA and CX, which is in favor of CA, was also observed. This difference between CA and CX, is due to the distinction that arises from their porous structure. In case of
CA where its structure is formed mainly from mesopores,
an increase in grain size will lead to an increase of pore
length, and therefore, a longer path for molecules to reach
adsorption sites, while in case of CX presence of micropores will lead from the beginning to lower adsorption
capacity and an increase in grain size will further increase
diffusional limitations.
Effect of Temperature
The alpha-cypermethrin removal process on CA and CX
was also studied at different temperatures, results that can
TABLE 1
Physical and textural characteristics of CA and CX samples
Adsorbent
CA
CX
qa (g=cm3)
SBET (m2=g)
VHK (cm3=g)
SHK (m2=g)
VBJH (cm3=g)
SBJH (m2=g)
0.73
1.37
637
79
0.28
0.053
659
86
0.37
331
apparent density was estimated by measuring the dimensions and mass of each monolithic sample.
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L. C. COTET
ET AL.
FIG. 4.
capacity (minimizing diffusional limitation in CA mesopores), with valuable benets in an industrial scale process.
Effect of Alpha-Cypermethrin Concentration
When initial alpha-cypermethrin concentration was
considered as a parameter in the adsorption process, the
following conclusions can be depicted:
a. concentration has an abrupt decrease in the rst 10 minutes from the beginning of the experiment;
FIG. 3. SEM (a), TEM (b) and AFM (c) images of CA; magnication
(a) 120000, (b) 600000 and (c) 400000. (Color gure available online)
FIG. 6. The effect of adsorbent grain size (CA and CX) over the alphacypermethrin adsorption capacity; Ci 40 mg=L, 0.01 g, 25 C, 5.88 pH,
500 rpm. (Color gure available online)
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TABLE 2
Langmuir and Freundlich coefcients for alpha-cypermethrin adsorption on CA and
CX; Ci 1070 mg=L, 0.01 g, d < 0.25 mm, 25 C, 5.88 pH, 500 rpm
Langmuir coefcients
CA
CX
Freundlich coefcients
KL (L=mg)
Qmax (mg=g)
R2
Kf (mg(11=n) L1=n=g)
R2
0.0603
0.0583
66.22
61.73
0.9806
0.9740
1.13
1.14
3.54
3.21
0.9580
0.9632
Table 2. According to the Langmuir isotherm, the monolayer adsorption capacity was calculated to be 66.22 and
61.73 mg=g for CA and CX, respectively, suggesting that
the considered adsorbents have high ability to retain
alpha-cypermethrin from aqueous solutions. The high
values of Kf and n Freundlich constants conrms the fact
that both adsorbents have high adsorption capacity and
increased adsorption intensity towards the considered pesticide molecule. From the linearity of the two plots,
expressed by R2, Table 2, it can be concluded that as the
Langmuir plot is closer to the linearity (higher R2 values),
alpha-cypermethrin adsorption onto CA and CX is described better by the Langmuir model.
Adsorption Kinetics
Several adsorption kinetic models, such as pseudo-rst(Lagergren) (32) and pseudo-second-order (Ho) (33,34),
intra-particle diffusion (35), and liquid lm diffusion (36),
were used to test experimental data in order to investigate
the adsorption mechanism and potential rate determining
steps (11,37).
The pore diffusion coefcient, D (cm2=s) for the removal
of alpha-cypermethrin by CA and CX was also calculated
Time evolution of alpha-cypermethrin, on both considered adsorbents is similar: high adsorption rate in the
rst 10 minutes, while subsequently the adsorption rate
decreases slowly until equilibrium is reached.
Regression coefcients obtained when the pseudo-rstorder kinetic model was applied to alpha-cypermethrin
adsorption, Table 3, have very low values. Also, calculated
adsorption capacities values show great differences by
comparison to experimental values. Based on this remark
D 0:003
r20
t1=2
1
k2 Qe
TABLE 3
Pseudo-rst-order and pseudo-second-order rate constants, calculated and experimental Qe values for
alpha-cypermethrin adsorption on CA and CX using different initial concentrations; Ci 1070 mg=L,
0.01 g, d < 0.25 mm, 25 C, 5.88 pH, 500 rpm
Pseudo-rst-order
C (mg=L)
CA
10
20
40
70
CX
10
20
40
70
Pseudo-second-order
2
Qe (exp) (mg=g)
k1 (1=min)
Qe (calc) (mg=g)
k2 (g=mg min)
Qe (calc) (mg=g)
R2
6.24
14.28
28.44
50.47
1.18 102
2.79 102
1.66 102
3.45 102
2.32
3.40
6.45
11.99
0.6725
0.8516
0.6604
0.8105
1.94 102
2.66 102
0.97 102
1.05 102
6.20
14.43
28.57
50.76
0.9928
0.9999
0.9991
0.9999
5.18
13.44
27.20
47.35
0.55 102
3.38 102
3.86 102
3.94 102
1.35
6.93
12.03
21.31
0.2750
0.6796
0.8353
0.8677
3.13 102
1.75 102
1.07 102
0.59 102
5.05
13.51
27.62
48.31
0.9924
0.9991
0.9998
0.9999
FIG. 9. Alpha-cypermethrin concentration evolution in time for adsorption on CA, after 1st and 2nd regeneration; Ci 55 mg=L, 0.01 g,
d < 0.25 mm, 25 C, 5.88 pH, 500 rpm. (Color gure available online)
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FIG. 11. Plots of the intra-particle diffusion model for alphacypermethrin adsorption on CA and CX; Ci 70 mg=L, 0.01 g,
d < 0.25 mm, 25 C, 5.88 pH, 500 rpm. (Color gure available online)
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TABLE 4
Intra-particle diffusion rate coefcients for alpha-cypermethrin adsorption on CA and CX;
Ci 1070 mg=L, 0.01 g, d < 0.25 mm, 25 C, 5.88 pH, 500 rpm
Region 1, 1030 minutes
C (mg=L)
CA
10
20
40
70
CX
10
20
40
70
D (cm2=s)
R2
R2
R2
3.76 109
1.20 108
8.72 109
1.67 108
0.25
0.28
0.57
1.57
0.9963
0.9309
0.8818
0.9287
0.07
0.16
0.12
0.35
0.5787
0.9823
0.7876
0.8626
0.32
0.06
0.36
0.30
0.9951
0.9926
0.8858
0.8026
4.94 109
7.39 109
9.26 109
8.86 109
0.19
0.96
2.08
4.26
0.9941
0.8126
0.8713
0.9084
0.03
0.08
0.11
0.30
0.9969
0.9873
0.7092
0.9707
0.25
0.28
0.31
0.16
0.8620
0.9972
0.8528
0.9631
TABLE 5
Liquid lm diffusion rate coefcients for
alpha-cypermethrin adsorption on CA and CX; Ci 10
and 70 mg=L, 0.01 g, d < 0.25 mm, 25 C, 5.88 pH, 500 rpm
C (mg=L)
CA
10
70
CX
10
70
kfd (1=min)
Intercept
R2
0.83 102
2.95 102
1.32
1.92
0.8839
0.8271
0.52 102
2.52 102
1.58
1.59
0.8372
0.9356
TABLE 6
Thermodynamic parameters for alpha-cypermethrin
adsorption on CA and CX at various temperatures
CA
CX
DG , (kJ=mol)
DS
(kJ=K mol)
DH
(kJ=mol)
298 K
308 K
318 K
13.55 102
3.53 102
37.42
7.69
2.97
2.82
4.32
3.18
5.68
3.53
CONCLUSIONS
In this work, prepared carbon aerogel (CA) and carbon
xerogel (CX) materials with interesting morpho-structural
characteristics as high surface area, controllable nanoporosity, and good mechanical properties were proposed as
adsorbents for alpha-cypermethrin pesticide removal from
aqueous solutions.
These materials were prepared by polycondensation of
resorcinol and formaldehyde in Na2CO3 catalysis, followed
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