Separation Science and Technology

ISSN: 0149-6395 (Print) 1520-5754 (Online) Journal homepage: http://www.tandfonline.com/loi/lsst20

Alpha-Cypermethrin Pesticide Adsorption on

Carbon Aerogel and Xerogel
L. Cosmin Cote , Andrada Micneanu , C. Ioana For & Virginia Danciu
To cite this article: L. Cosmin Cote , Andrada Micneanu , C. Ioana For & Virginia Danciu
(2013) Alpha-Cypermethrin Pesticide Adsorption on Carbon Aerogel and Xerogel, Separation
Science and Technology, 48:17, 2649-2658, DOI: 10.1080/01496395.2013.805782
To link to this article: http://dx.doi.org/10.1080/01496395.2013.805782

Accepted author version posted online: 02

Aug 2013.
Published online: 02 Aug 2013.
Submit your article to this journal

Article views: 84

View related articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=lsst20
Download by: [188.24.10.154]

Date: 13 September 2016, At: 01:40

Separation Science and Technology, 48: 26492658, 2013

Copyright # Taylor & Francis Group, LLC
ISSN: 0149-6395 print=1520-5754 online
DOI: 10.1080/01496395.2013.805782

Alpha-Cypermethrin Pesticide Adsorption on Carbon

Aerogel and Xerogel
L. Cosmin Cotet, Andrada Maicaneanu, C. Ioana Fort, and Virginia Danciu
Faculty of Chemistry and Chemical Engineering, Babes -Bolyai University, Cluj-Napoca, Romania

Carbon aerogel (CA) and xerogel (CX) are proposed for

pesticide adsorption as new carbon adsorbent materials. These
materials are prepared by polycondensation of resorcinol and formaldehyde in Na2CO3 catalysis, followed by a drying step, in
CO2 supercritical or normal conditions to obtain organic aerogel
or xerogel, and a pyrolytic step to obtain CA or CX. Adsorption
experiments were carried out in batch conditions under magnetic
stirring. Adsorbent quantity and grain size, pH, and temperature,
and alpha-cypermethrin concentration inuence on the adsorption
efciency were considered. The optimum parameters were established to be as follows: 0.01 g adsorbent, d < 0.025 mm, and 318 K.
In all cases, CA proved to be more efcient than CX for
alpha-cypermethrin removal from water samples. Equilibrium
(Langmuir and Freundlich isotherms), kinetics (pseudo-rst- and
pseudo-second-order, intra-particle diffusion, and liquid lm diffusion models) and thermodynamics of the considered adsorption
process were discussed in detail. Equilibrium was best described
by the Langmuir isotherm, while the kinetic of the process was best
described by the pseudo-second-order model. Thermodynamic
parameters showed that alpha-cypermethrin adsorption is an endothermic process.
Keywords adsorption equilibrium; alpha-cypermethrin; carbon
aerogel and xerogel; kinetics; thermodynamics

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

JMPR Joint FAO=WHO Meeting on Pesticide Residues

held in 1980 and 1982, the highest mean concentrations of
alpha-cypermethrin is found in body fat, liver, kidney,
muscle, skin, and milk of the animals, which were fed with
contaminated food and waters. Also, carcinogenicity, neurotoxicity, and acute toxicity risks for human beings are
reported. For these reasons, it becomes essential to study
and improve different methods to remove these pesticides,
especially from waters.
There are a wide variety of treatment technologies such
as precipitation, coagulationocculation, sedimentation,
otation, ltration, membrane processes, electrochemical
techniques, biological process, chemical reactions, adsorption, and ion exchange that were involved in the wastewater treatment processes (1). From these, the adsorption
process is recognized as the most efcient and promising
approach in pesticide removing. As adsorbents, most carbon materials such as activated carbon (711), multi-walled
carbon nanotubes (7,8), C18 cartrid-ges (7), shale ash (12),
and carbon bers (13) were tested for the removal of pesticides from water samples.
In the last decades, new forms of carbon materialcarbon aerogel (CA) and carbon xerogel (CX) have been
promoted as adsorbents. Because of their unique properties, such as controllable porosity, thermal stability, large
pore volume, and high surface area (14), CA and CX were
successfully applied in adsorption of both organic compounds, for example, dye (1517), toluene (18), phenol
(19), or methane (20), and inorganic metallic ions (21,22).
The aim of this paper was to investigate the feasibility of
using CA and CX for alpha-cypermethrin pesticide
removal from aqueous solution by adsorption. Therefore,
CA and CX were prepared using a sol-gel method based
on polycondensation reaction between resorcinol and formaldehyde in Na2CO3 catalysis followed by a supercritical
drying (for CA) and evaporation (for CX) of the resulted
wet gels. The nal structure of CA and CX adsorbents were
obtained after pyrolysis. Taking into consideration that
until now, CA and CX have not been tested for pesticide
adsorption, different parameters (adsorbent quantity and
grain size, pH and temperature, alpha-cypermethrin

2649

2650

L. C. COTET
ET AL.

by Brunauer-Emmett-Teller (BET), Horvath-Kawazoe

(HK) and Barrett-Johner-Halendar (BJH) theories.

FIG. 1. Alpha-cypermethrin structure.

concentration) were considered in order to establish the

optimum conditions for the adsorption process. Equilibrium (Langmuir and Freundlich isotherm), kinetics
(pseudo-rst- and pseudo-second-order, intra-particle diffusion, and liquid lm diffusion models), and thermodynamics of the considered adsorption process were
discussed in detail.
MATERIALS AND METHODS
Adsorbent Preparation (CA and CX)
For carbon aerogel and xerogel preparation, resorcinol
(R, 98% purity, Aldrich), formaldehyde (F, 37% solution,
Aldrich), Na2CO3 (C, 99.9% purity, Merck), and bidistillated water (W) were used. Resorcinol (0.29 moles) was
dissolved in bidistillated water (R=W 0.2 g=mL). Formaldehyde solution was added to resorcinol solution (R=F
0.5 molar ratio) under vigorous stirring. Catalytic solution
0.1 M of Na2CO3 was added drop by drop to the previous
mixture (R=C 50 molar ratio). The resulted solution was
placed into tightly closed glass moulds and cured 1 day at
room temperature and 4 days at 70
C. After 15 days of
aging at room temperature, in a closed glass mould the
obtained resorcinol-formaldehyde wet gel was washed with
acetone (at least 3 days and 3 times with fresh solvent). Part
of this wet gel was dried with CO2 in supercritical condition
(more than 74 atm and 32
C) when the aerogel was
obtained, while the other part was dried under normal condition (1 atm and 23
C) when the xerogel was obtained.
Then, the organic samples were pyrolyzed in Ar atmosphere for 2 h at 750
C when carbon aerogel and xerogel,
respectively, were obtained.
Characterization of Adsorbent Materials
Measurement of the Pore Parameters and Pore Size
Distribution
Approximately 0.1 g sample was heated to 120
C for 10 h
to remove all the adsorbed species. Nitrogen adsorption
and desorption isotherms were then recorded using a
Sorptomatic 1990 (Thermo Electron Corporation). According to the resulting isotherms, BET surface area (SBET),
micropore volume (VHK), micro-pore surface area (SHK),
mesopore volume (VBJH), mesopore surface area (SBJH),
and pore size distribution of the samples were analyzed

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

2651

CA AND CX FOR PESTICIDE ADSORPTION

efciency, E (%), values, calculated according to Eqs. (1)

and (2).

Qe

Ci  Ce V

1000
m

Ci  Ce
 100
Ci

where Ci, initial alpha-cypermethrin concentration in

solution, in mg=L; Ce, alpha-cypermethrin concentration
in solution at equilibrium, in mg=L; V, sample volume,
10 mL and m, adsorbent quantity, in g.
Experimental data were used to determine the equilibrium time and the optimum working parameter values:
adsorbent quantity, grain size, pH, for maximum efciency, and to establish isotherm and kinetics models and
to calculate thermodynamic parameters. All the experiments were repeated three times, and the values presented
were calculated using averaged concentration values.
RESULTS AND DISCUSSION
Adsorbents Characterization
According to N2 adsorption and desorption isotherm
investigations (Table 1, Fig. 2) CA is a micro-mesoporous
material and CX is a microporous one. The difference of
the BET surface area between CA and CX is given by drying conditions of precursor wet gels. Supercritical liquid
CO2 drying conditions provide high BET surface area of
the obtained material because of a less mesopore collapse
than by drying in normal conditions (Table 1). Only CA
presents a IV type N2 adsorption-desorption isotherm
specic for mesopore materials with diverse shape (23),
mono-modal mesopore size distribution (Fig. 2a) and multimodal micropore size distribution (Fig. 2b).
The SEM, TEM, and AFM images of CA used as
pesticide adsorbent material are shown in Fig. 3. A
nanoporous structure formed by interconnected carbon
nanoparticles was visualized.
The X-ray diffraction analysis shows an amorphous
structure both for CA and CX. Due to the fact that the
shape of the X-ray spectra is similar for both samples in
Fig. 4 only CA spectra is presented (14). XRD patterns

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.

2652

L. C. COTET
ET AL.

FIG. 4.

XRD pattern of CA sample.

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. 2. BJH pore size distribution, N2 adsorption-desorption isotherm

(a) and HK pore size distribution (b) for CA.

be further used to determine the thermodynamic

parameters of adsorption. Temperature inuence on the
pesticide removal is presented in Fig. 7. Evolution of the
adsorption capacity with temperature suggests that we are
dealing with an endothermic process (Qe, mg=g, increases
with increase of temperature). Comparing CA and CX
adsorbents, the same trend between the two can be observed, which is in favor of CA. As temperature increases,
adsorption capacity will increase much more for CA
(14.28%) than CX (4.41%), suggesting that a small increase
in temperature can lead to a great increase in adsorption

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. 5. The effect of CA and CX quantity on the alpha-cypermethrin

adsorption over the (a) adsorption capacity and (b) removal efciency; Ci
40 mg=L, d < 0.25 mm, 25
C, 5.88 pH, 500 rpm. (Color gure available online)

CA AND CX FOR PESTICIDE ADSORPTION

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)

b. next, concentration decreases slowly until equilibrium;

c. equilibrium was reached in about 60 minutes for 10 and
20 mg=L solutions, and in about 90 minutes for 40 and
70 mg=L solutions, Fig. 8;
d. adsorption capacity increases with the increase in
concentration, Table 3.
Higher adsorption capacities at higher concentrations
indicate that if alpha-cypermethrin concentration in solution increases, the difference in concentration between
bulk solution and the adsorbent surface also increase, intensifying the mass transfer processes. Accordingly, a higher
quantity will be adsorbed, proving that CA and CX have
high adsorption capacities towards alpha-cypermethrin.
CA adsorbent proved to be more efcient that CX in all
cases, Table 3.
Concentration evolution in time obtained after 1st and
2nd regenerations of CA (550
C for 2 h) are presented in
Fig. 9 (in order to maintain image clarity, due to the fact

FIG. 7. Temperature inuence over the alpha-cypermethrin adsorption

capacity for CA and CX; Ci 55 mg=L, 0.01 g, d < 0.25 mm, 5.88 pH,
500 rpm. (Color gure available online)

2653

FIG. 8. Inuence of the initial alpha-cypermethrin concentration over

the time evolution in case of CA; 0.01 g, d < 0.25 mm, 25
C, 5.88 pH,
500 rpm. (Color gure available online)

that the evolutions for the fresh and 1st regenerated

adsorbent are very close, fresh-CA evolution was removed). It can be clearly observed that after the 2nd regeneration the drop in the pesticide concentration in time is
smaller. An average decrease of 10.30% and 9.94% in
adsorption capacity, in comparison with the fresh sample
and 1st regenerated sample, respectively, was observed.
Up to this moment there are just a few studies regarding
alpha-cypermethrin adsorption that realized using cork,
activated carbon (25), or rice bran (26). On cork and activated carbon, maximum amount of adsorbed alphacypermethrin was 303 mg=g, while on rice bran an efciency
value of 95.6% was reported for concentrations smaller
than 1 lg=L. For deltamethrin, which has a similar chemical structure, adsorption from aqueous solution on oil
shale ash was studied (12,27), and the maximum amount
adsorbed was 11.4 mg=g. Taking into consideration that
for alpha-cypermethrin adsorption on CA and CX studied
samples, the amount adsorbed reaches values up to 50.47
and 47.35 mg=g, respectively, (experimental values) we concluded that the results are promising for an applicative
development of the pesticide removal process from
wastewaters.
Adsorption Isotherms
The equilibrium adsorption study in aqueous phase is an
important step in the design of adsorption systems. In the
present study two equilibrium models were considered,
Langmuir (28) and Freundlich (29) isotherm models, which
are the most used models to describe adsorption equilibrium and were applied successfully in many adsorption
processes studies realized on carbonaceous materials
(9,11,15,30,31). The linear plot of the Langmuir isotherm
for CA adsorbent is presented in Fig. 10. The Langmuir
and Freundlich calculated coefcients for alphacypermethrin adsorption on CA and CX are presented in

2654

L. C. COTET
ET AL.

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.

(assuming a spherical geometry of the adsorbentsaverage

size 0.25 mm) using the following equation (37,38):

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

where, r0 is the particle diameter (cm), and t1=2 is the time

for half adsorption (s).
Based on the pseudo-second-order model, t1=2 was
estimated using equation (37,38):
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

CA AND CX FOR PESTICIDE ADSORPTION

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)

it can be concluded that the adsorption process cannot be

classied as rst-order. When the pseudo-second-order
kinetic model was applied for the considered adsorption
process regression coefcients higher than 0.99 were
obtained. A comparison between calculated and experimental adsorption capacities, Table 3, showed a good
agreement. It was concluded that alpha-cypermethrin
adsorption on CA and CX obeyed the pseudo-secondorder kinetic model.
Intra-particle plots for CA and CX adsorbents are presented in Fig. 11. It was observed that data present
multi-linear plots. Beside the initial region, from 0 to 10
minutes, which is usually attributed to bulk diffusion, three
regions were identied (Fig. 11). These regions (three linear
plots) are ascribed to boundary layer diffusion (liquid lm
diffusion), intra-particle diffusion, and to the nal equilibrium stage (11,30,37). Plots of Qt against t1=2 are linear, (R2
values, Table 4), but with intercepts ranging between 1.98

FIG. 10. Langmuir plot for alpha-cypermethrin adsorption on CA;

Ci 1070 mg=L, 0.01 g, d < 0.25 mm, 25
C, 5.88 pH, 500 rpm. (Color
gure available online)

2655

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)

and 46.57 (plots do not pass through origin). Calculated

intra-particle diffusion rate constants and pore diffusion
coefcients (assuming a spherical geometry for the adsorbents) are presented in Table 4. The pore diffusion coefcients have values in 108 109 cm2=s range, higher
values than rate determining range (1011 1013 cm2=s)
(30,37). Therefore, it can be concluded that intra-particle
diffusion is not the rate determining step. Comparing CA
and CX adsorbents, we observed that the pore diffusion
coefcients are all smaller in case of CX, all in 109 range,
in concordance with the porous structure (mesopores for
CA, easier to access, and micropores for CX, more difcult
to access), suggesting that intra-particle diffusion it is likely
to have a higher inuence over the overall adsorption rate
in case of CX adsorbent. Liquid lm model was also
applied to alpha-cypermethrin adsorption, and exemplied
in Fig. 12 for two concentrations (10 and 70 mg=L) in case
of CA. Linear plots of -ln(1-F) against t were obtained, and
rate constants and intercepts calculated (Table 5). As the
concentration decreased, rate constant decreased, suggesting that liquid lm diffusion (external mass transfer) could
control the adsorption process at small concentrations.
Taking into consideration all the results obtained by applying kinetic models on alpha-cypermethrin adsorption on
CA and CX experimental data it can be concluded that
the rate determining step is the adsorption process, but
intra-particle diffusion and liquid lm diffusion can have
an important inuence when porous structure is formed
mainly from micropores (CX) and, respectively, at small
adsorbate concentration.
Thermodynamic Parameters
In order to describe the thermodynamic behavior of pesticide adsorption, thermodynamic parameters: enthalpy

2656

L. C. COTET
ET AL.

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

Region 2, 3090 minutes

Region 3, 90180 minutes

D (cm2=s)

kip (mg=g  min1=2)

R2

kip (mg=g  min1=2)

R2

kip (mg=g  min1=2)

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

(DH
, kJ=mol), entropy (DS
, kJ=K  mol), and Gibbs free

energy (DG
, kJ=mol), were calculated using well-known
equations (37).
Results obtained on alpha-cypermethrin adsorption on
CA and CX are presented in Table 6. As discussed before
(section titled Effect of Temperature, Fig. 7) adsorption
capacity values as a function of temperature suggested
an endothermic interaction. Calculated enthalpy values
conrmed this assumption. Also, smaller DG
values, and
higher DS
value, in case of CA indicate a favorable
adsorption and a higher afnity of alpha-cypermethrin
towards carbon aerogel by comparison to carbon xerogel.

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

FIG. 12. Plots of the liquid lm diffusion model for alpha-cypermethrin

adsorption on CA; Ci 10 and 70 mg=L, 0.01 g, d < 0.25 mm, 25
C,
5.88 pH, 500 rpm. (Color gure available online)

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

CA AND CX FOR PESTICIDE ADSORPTION

by a drying step in supercritical conditions of liquid CO2 to

aerogel obtaining and normal conditions to xerogel obtaining, and a pyrolytic step. CA and CX were characterized
using BET analysis, scanning electron microscopy (SEM),
transmission electron microscopy (TEM), and X-ray diffraction (XRD). According to N2 adsorption and desorption isotherm investigations CA is a micro-mesoporous
material and CX is a microporous one. SEM, TEM, and
AFM images showed a nanoporous structure formed by
interconnected carbon nanoparticles, while XRD spectra
showed an amorphous structure both for CA and CX.
Adsorption experiments were carried out in batch conditions under magnetic stirring. The adsorption capacity
value varied as follows when the following parameters were
changed: decreased with an increase of the adsorbent
quantity and grain size, and increased with and increase of
temperature and pesticide concentration in solution. CA
proved to be more efcient than CX for alpha-cypermethrin
removal from water samples, in all cases. CA reusability was
also studied and was realized by pyrolysis. A decrease in
adsorption capacity, in comparison with the fresh sample
was observed. Taking into consideration the high values
obtained for the amount of alpha-cypermethrin adsorbed
on CA and CX (up to around 50 mg=g) we concluded that
results are promising for an applicative development of the
pesticide removal process from wastewaters.
Adsorption equilibrium was studied using the Langmuir
and Freundlich isotherms, the results showed that the
considered adsorbents have high ability to retain alphacypermethrin from aqueous solutions and increased
adsorption intensity towards the considered pesticide molecule, and the equilibrium was best described by the Langmuir isotherm.
Four kinetic models (pseudo-rst- and pseudo-secondorder, intra-particle diffusion, and liquid lm diffusion
models) were taken into consideration to describe the
adsorption process, a comparison between all the models
lead to the conclusion that the process was best described
by the pseudo-second-order model, but intra-particle diffusion and liquid lm diffusion can have an important
inuence when the porous structure is formed mainly from
micropores and, respectively at small adsorbate concentration. Thermodynamic parameters calculated for the
considered adsorption process showed that alphacypermethrin adsorption is an endothermic process.
ACKNOWLEDGEMENTS
This work was possible with the nancial support of the
Sectoral Operational Program for Human Resources
Development 2007-2013, co-nanced by the European
Social Fund, under the project number POSDRU
89=1.5=S=60189 with the title Postdoctoral Programs for
Sustainable Development in a Knowledge Based Society.

2657

REFERENCES
1. Foo, K.Y.; Hameed, B.H. (2010) Detoxication of pesticide waste via
activated carbon adsorption process. J. Hazard. Mater., 175: 111.
2. Cheng, X.; Zhang, Z.; Tian, S. (2007) A novel long path length
absorbance spectroscopy for the determination of ultra trace organophosphorus pesticides in vegetables and fruits. Spectrochim. Acta,
Part A, 67: 12701275.
3. Ojha, A.; Yaduvanshi, S.K.; Srivastava, N. (2011) Effect of combined
exposure of commonly used organophosphate pesticides on lipid peroxidation and antioxidant enzymes in rat tissues. Pestic. Biochem.
Physiol., 99: 148156.
4. Cioroiu, M.; Tarcau, D.; Mocanu, R.; Cucu-Man, S.; Nechita, B.;
Luca, M. (2010) Organochlorine pesticides in colostrums in case of
normal and preterm labor (Iasi, Romania). Sci. Total Environ., 408:
26392645.
5. Clementia, M.; Tibonib, G.M.; Causinc, R.; La Roccad, C.;
Maranghid, F.; Raffagnatoa, F.; Tenconia, R. (2008) Pesticides and
fertility: An epidemiological study in Northeast Italy and review of
the literature. Reprod. Toxicol., 26: 1318.
6. Zhou, P.; Wu, Y.; Yin, S.; Li, J.; Zhao, Y.; Zhang, L.; Chen, H.; Liu,
Y.; Yang, X.; Li, X. (2011) National survey of the levels of persistent
organochlorine pesticides in the breast milk of mothers in China.
Environ. Pollut., 159: 524531.
7. El-Sheikh, A.H.; Sweileh, J.A.; Al-Degs, Y.S.; Insisi, A.A.;
Al-Rabady, N. (2008) Critical evaluation and comparison of
enrichment efciency of multi-walled carbon nanotubes, C18 silica
and activated carbon towards some pesticides from environmental
waters. Talanta, 74: 16751680.
8. Al-Degs, Y.S.; Al-Ghouti, M.A.; El-Sheikha, A.H. (2009)
Simultaneous determination of pesticides at trace levels in water using
multiwalled carbon nanotubes as solid-phase extractant and multivariate calibration. J. Hazard. Mater., 169: 128135.
9. Ignatowicz, K. (2011) A mass transfer model for the adsorption of
pesticide on coconut shell based activated carbon. Int. J. Heat Mass
Transfer, 54: 49314938.
10. Ioannidou, O.A.; Zabaniotou, A.A.; Stavropoulos, G.G.; Islamb,
M.A.; Albanis, T.A. (2010) Preparation of activated carbons from
agricultural residues for pesticide adsorption. Chemosphere, 80:
13281336.
11. Dhaouadi, A.; Monser, L.; Adhoum, N. (2010) Removal of rotenone
insecticide by adsorption onto chemically modied activated carbons.
J. Hazard. Mater., 181: 692699.
12. Al-Qodah, Z.; Shawaqfeh, A.T.; La, W.K. (2007) Two-resistance
mass transfer model for the adsorption of the pesticide deltamethrin
using acid treated oil shale ash. Adsorption, 131: 7382.
13. Faur, C.; Metivier-Pignon, H.; Le Cloirec, P. (2005) Multicomponent
adsorption of pesticides onto activated carbon bers. Adsorption, 11:
479490.
14. Cotet, L.C.; Roig, A.; Popescu, I.C.; Cosoveanu, V.; Molins, E.;
Danciu, V. (2007) Synthesis of the Meso and Macro Carbon Aerogels.
Rev. Roum. Chim., 52: 10771081.
15. Wu, X.; Wu, D.; Fu, R. (2007) Studies on the adsorption of reactive
brilliant red X-3B dye on organic and carbon aerogels. J. Hazard.
Mater., 147: 10281036.
16. Chang, X.; Chen, D.; Jiao, X. (2010) Starch-derived carbon aerogels
with high-performance for sorption of cationic dyes. Polymer, 51:
38013807.
17. Paez, C.A.; Contreras, M.S.; Leonard, A.; Blacher, S.; OliveraFuentes, C.G.; Pirard, J.-P.; Job, N. (2012) Effect of CO2 activation
of carbon xerogels on the adsorption of methylene blue. Adsorption
DOI: 10.1007=s10450-012-9394-2.
18. Maldonado-Hodar, F.J.; Moreno-Castilla, C.; Carrasco-Marn, F.;
Perez-Cadena, A.F. (2007) Reversible toluene adsorption on monolithic carbon aerogels. J. Hazard. Mater., 148: 548552.

2658

L. C. COTET
ET AL.

19. Maicaneanu, A.; Cotet, L.C.; Danciu, V.; Stanca, M. (2009) Phenol
removal from water using carbon aerogel as adsorbant. Studia UBB
Chemia, 41: 3342.
20. Chathoth, S.M.; Mamontov, E.; Melnichenko, Y.B.; Zamponi, M.
(2010) Diffusion and adsorption of methane conned in nanoporous carbon aerogel: A combined quasi-elastic and small-angle
neutron scattering study. Microporous Mesoporous Mater., 132:
148153.
21. Kadirvelu, K.; Goel, J.; Rajagopal, C. (2008) Sorption of lead,
mercury and cadmium ions in multi-component system using carbon
aerogel as adsorbent. J. Hazard. Mater., 153: 502507.
22. Meena, A.K.; Mishra, G.K.; Rai, P.K.; Rajagopal, C.; Nagar, P.N.
(2005) Removal of heavy metal ions from aqueous solutions using
carbon aerogel as an adsorbent. J. Hazard. Mater., 122: 161170.
23. Rouquerol, E.; Rouquerol, J.; Sing, K. (1999) Adsorption by Powders
and Porous Solids: Principles, Methodology and Applications; Academic
Press: San Diego.
24. Bhattacharyya, K.G.; Gupta, S.S. (2008) Adsorption of Fe(III),
Co(II) and Ni(II) on ZrO-kaolinite and ZrO-montmorillonite surfaces
in aqueous medium. Colloids Surf. A, 317: 7179.
25. Dominguez, V.F.; Priolo, G.; Alves, A.C.; Cabral, M.F.; DelerueMato, C. (2007) Adsorption behavior of a-cypermethrin on cork
and activated carbon. J. Env. Sci. Health B, 42: 649654.
26. Bhattacharjee, S.; Fakhruddin, A.N.M.; Chowdhury, M.A.Z.;
Rahman, M.A.; Alam, M.K. (2012) Monitoring of selected pesticides
residue levels in water samples of paddy elds and removal of cypermetrin and chlorpyrifos residues from water using rice bran. Bull.
Environ. Contam. Toxicol., 89: 348353.

27. Al-Qodah, Z.; Shawaqfeh, A.T.; La, W.K. (2007) Adsorption of

pesticide from aqueous solutions using oil shale ash. Adsorption,
208: 294305.
28. Langmuir, I. (1918) The adsorption of gases on plane surfaces of
glass, mica and platinum. J. Am. Chem. Soc., 40: 13611403.
29. Freundlich, H.M.F. (1906) Uber die adsorption in losungen.
Zeitschrift fur Physikalische Chemie (Leipzig), 57A: 385470.
30. Ioannou, Z.; Simitzis, J. (2009) Adsorption kinetics of phenol and
3-nitrophenol from aqueous solutions on conventional and novel
carbons. J. Hazard. Mater., 171: 954964.
31. Haghbeen, K.; Legge, R.L. (2009) Adsorption of phenolic compounds
on some hybrid xerogels. Chem. Eng. J., 150: 17.
32. Lagergren, S. (1898) Zur theorie der sogenannten adsorption geloster
stoffe. Kungliga Svenska Vetenskapsakademiens, 24: 139.
33. Ho, Y.S.; McKay, G. (1999) Pseudo-second order model for sorption
processes. Process Biochem., 34: 451465.
34. Ho, Y.S. (2006) Review of second-order models for adsorption
systems. J. Hazard. Mater., 136: 681689.
35. Weber, W.J.; Morris, J.C. (1963) Kinetics of adsorption of carbon
from solutions. J. Sanit. Eng. Div. Am. Soc. Civ. Eng., 89: 3163.
36. Boyd, G.E.; Adamson, A.W.; Myers Jr., L.S. (1947) The exchange
adsorption of ions from aqueous solutions on organic zeolites,
Kinetics II. J. Am. Chem. Soc., 69: 28362842.
37. Srihari, V.; Das, A.; (2008) The kinetic and thermodynamic studies of
phenol-sorption onto three agro-based carbons. Desalination, 225:
220234.
38. Pang, X.-Y.; Gong, F. (2008) Study on the Adsorption kinetics of
Acid Red 3B on expanded graphite. E-J. Chem., 5: 802809.