Industrial Crops and Products 39 (2012) 139–148

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Industrial Crops and Products

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Aminated cotton fibers loaded with copper(II) ions for enhanced pesticide
removal performance from water in a laboratory scale batch
Amel El Ghali a , Mohamed Hassen V. Baouab b,∗ , Mohamed Sadok Roudesli a
a
Laboratoire des Polymères-Biopolymères, Matériaux Organiques (LPBMO), Faculté des Sciences de Monastir, Bd. de l’environnement, 5019 Monastir, Tunisia
b
Institut Préparatoire aux Etudes d’Ingénieurs de Monastir, 5019 Monastir, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: Diethylenetriamine cotton fibers (DET-cotton) were prepared by amination with diethylenetriamine
Received 15 November 2011 (DET) on chlorodeoxycellulose (CDC-cotton). The evidence of grafting was confirmed by elemental and
Received in revised form 14 February 2012 AFM analysis. Then, the modified fibers were loaded with copper (II) ions and, the abilities of both DET-
Accepted 17 February 2012
cotton and [Cu(II)/DET-cotton] for binding an herbicide, i.e. Linuron (LNR) were investigated. To examine
the underlying mechanism of the adsorption process, pseudo-first, pseudo-second-order, elovich and
Keywords:
intraparticle diffusion models were fitted to experimental kinetic data. Results showed that the pseudo-
Modified cotton
second-order equation was appropriate to describe the pesticide adsorption by [Cu(II)/DET-cotton].
Pesticides removal
Kinetics
However, the adsorption behavior by DET-cotton followed the pseudo-first-order kinetic model. Adsorp-
Adsorption isotherms tion data were further analyzed by the Langmuir, Freundlich and Jossens adsorption approaches. Attempts
have also been made to recover the pesticide from exhausted adsorbent.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction (LNR) is one of the most important phenylurea herbicides that

Water pollution is a major environmental problem faced by
modern society that leads to ecological disequilibrium and health
hazards. Pesticides form a strong class of hazardous compounds
that may pollute water due to their extensive application in
agriculture activities. Therefore, an adequate treatment of the pol-
luted wastewater is required because pesticides are identified as
environmental endocrine disruptors. Several methods have been
extensively used for the removal of these materials from aqueous
solutions including ozonation (Ayala et al., 2010), photo degra-
dation (Derbalah et al., 2004), nanofiltration membranes (Ahmad
et al., 2008), coagulation (El-Dib and Aly, 1977) and adsorption
onto activated carbon (Ioannidou et al., 2010). Nevertheless, the
application of such processes is sometimes restricted because of
technical or economic considerations. In order to overcome these
problems, exploitation of new, cheap and indigenous materials for
the removal of pesticides from wastewater has been the focus of
intense research. Cellulose is regarded as the most abundant and
renewable biopolymer in nature which can be considered as a very
promising raw material for the preparation of various functional
polymers used to purify water contaminated by pesticides and
other hazardous chemicals (Baouab et al., 2000, 2001; Zghida et al.,
2003; El Ghali et al., 2010; Alila and Boufi, 2009; El Ghali et al.,
2011).
inhibit photosynthesis, thus impeding weed growth (Farré et al.,
2006). In fact, it has good contact activity and it may kill emer-
gent weed seedlings (Katsumata et al., 2005). This pesticide has
received particular attention in recent years due to the toxicity,
being frequently detected in the surface and underground waters,
and possible endocrine disrupting properties of (LNR) (Rao and Chu,
2010).
In previous studies (Baouab et al., 2007; Makhlouf et al., 2008),
it has been shown that the adsorption of copper ions onto modified
cellulosic and synthetic materials has greatly enhanced the ability
of the substrate to uptake Acid Blue 25 and calmagite from aqueous
solutions by chelating mechanism process.
Therefore, the purpose of this work was to evaluate, for the
first time, the adsorption potential of modified cotton fibers loaded
with copper ions and unloaded supports for the removal of (LNR)
from aqueous solutions. The effects of the parameters such as ini-
tial concentration, contact time and temperature on the adsorption
properties were reported. The experimental data were correlated
to kinetic and equilibrium sorption models. Desorption study was
also assessed.
2. Materials and methods
2.1. Materials

Cotton fibers used in this study were supplied by SITEX

∗ Corresponding author. Tel.: +216 98 228 210; fax: +216 73 501 787. (Société Internationale de Textile, Sousse, Tunisia). All the reagents
E-mail address: hbaouab@yahoo.fr (M.H.V. Baouab). [Thionyl chloride, Dimethylformamide (DMF), Ammonium

0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2012.02.020
140 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148

2.2. Preparation of modified cellulosic fibers

Nomenclature
The modification of cotton fibers was carried out in two stages
b Langmuir adsorption constant related to the energy using a similar method reported previously (Tashiro and Shimura,
of adsorption (L mmol−1 ) 1982). The first is the preparation of 6-chlorodeoxycellulose (6-
b2 sorption equilibrium constant calculated from Type CDC) and the second is a subsequent amination of 6-CDC with DET
2 Langmuir expression (L mmol−1 ) grafted on the surfaces. In brief, the introduction of nitrogen groups
C constant that gives idea about the thickness of the was done as follows. In a round bottomed flask were placed 1 g of
boundary layer (mmol g−1 ) 6-CDC, 20 mL of distilled water and 5 mL of DET. The mixture was
Ca number of coordinating sites per gram of support stirred for 3 h under reflux. After reaction, the modified cellulose
(mmol/g) was separated by filtration, washed thoroughly with a mixture of
Ce equilibrium solution concentration of the pesticide MeOH/Acetone (1:1, v/v) and rinsed with distilled water up to neu-
(mmol L−1 ) tral pH. The resulting support was then dried at 40 ◦ C under vacuum
Cref highest fluid-phase concentration (mmol L−1 ) for 72 h.
Ct concentration of the pesticide at time t (mmol L−1 )
C0 initial solution concentration of the pesticide
2.3. Characterization of the prepared supports
(mmol L−1 )
i constant in Jossens isotherm (L g−1 )
2.3.1. Elemental analysis
j constant in Jossens isotherm (L mmol−1 )
The amount of DET grafted on cotton fibers was calculated based
Kc equilibrium constant
on the nitrogen content, determined by an elemental analyzer
ki intra-particle diffusion rate constant
(AOAC, 1984).
(mmol g−1 min−1/2 )
k1 equilibrium rate constant of first order kinetics
(min−1 ) 2.3.2. Atomic force microscopy (AFM) analysis
k2 equilibrium rate constant of the pseudo-second- The surface morphology before and after the DET functionaliza-
order kinetics (g mmol−1 min−1 ) tion was evaluated using AFM analyses (Nanoscope III instrument,
LNR Linuron Digital Instruments, Santa Barbara, USA) in tapping mode.
m constant in Jossens isotherm
n adsorption intensity 2.4. Loading of modified cotton fibers with Cu(II) ions
% N nitrogen content of DET-cotton
P measure of adsorption capacity The loading of the DET-cotton with copper ions was carried out
Q theoretical monolayer saturation capacity as follows. An amount of 100 mg of DET-cotton was added to 100 mL
(mmol g−1 ) of the Clark–Lub’s buffer solution of Cu(II) ions (Saliba et al., 2000)
qe quantity of pesticide adsorbed at equilibrium at pH 7. The concentration of Cu2+ used to saturate the adsorbent
(mmol g−1 ) was 240 mg L−1 . The suspension was stirred at room temperature
qt amount of the pesticide adsorbed at time t into a glass bottle. Preliminary runs showed that the time required
(mmol g−1 ) to achieve saturation loading of DET-cotton was about 32 h. The
RL dimensionless constant separation factor resulting adsorbent containing copper ions were then rinsed with
V volume of the solution and (L) an excess of deionised water to remove any unbound metal before
W weight of dry adsorbent (g) filtering and drying at 40 ◦ C under vacuum until further use.
Ye pesticide concentration at equilibrium (mmol g−1 )
Yref maximum solid-phase dye concentration 2.5. Purification of (LNR)
(mmol g−1 )
Yreg adsorption capacity of the regenerated adsorbent Before its application in the adsorption tests, the commercial
(mmol g−1 ) pesticide was purified by precipitation in water. The purity of the
˛ initial sorption rate (mmol g−1 min−1 ) product was confirmed by 1 H- and 13 C-NMR spectral. The spec-
ˇ extent of surface coverage (g mmol−1 ) tral data are detailed as following: 1 H NMR (300 MHz, CDCl3 ): ı
(ppm) 7.53 (HN ), 7.52 (H3), 7.18 (H1), 7.13 (H2), 3.59 (CH3 N ),
3.01 (CH3 O ). 13 C NMR (75 MHz, CDCl3 ): ı (ppm) 157.0 (C O),
137.98–118.95 (aromatic C), 62.10 (CH3 N ), 35.08 (CH3 O ). 1 H
hydroxide, Diethylenetriamine (DET), acetonitrile, ethanol (EtOH), NMR and 13 C NMR were obtained on a Bruker AV 300 spectrometer.
methanol (MeOH), Acetone] and the metal salt [Copper (II) Chloride
(CuCl2 , 2H2 O)] were supplied by Sigma Aldrich company Fallavier, 2.6. Preparation of (LNR) solution
France) and used without further purification. The pesticide (LNR)
was procured from (S.E.P.C Megrine, Tunisia). The physical and The working pesticide solutions were prepared by dissolving
chemical characteristics of (LNR) are given in Table 1. an appropriate mass of the pesticide in a EtOH/ultrapure water

Table 1
Chemical and physical characteristics of the selected pesticide.

Pesticide max (nm) Purity (%) Molecular weight (g mol−1 ) Molecular structure

O
Cl N C
N O CH3
H
Cl
Linuron (LNR) 211 100 249.1
CH3
 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148
Fig. 1. AFM view of (a) untreated cotton fibers and (b) DET-cotton.
mixture (v/v = 10/90) in order to achieve a complete solubilization
of the analyte.
2.7. Adsorption procedures
The sorption of the pesticide on DET-cotton and [Cu(II)/DET-
cotton] were performed using a batch process. Adsorption
experiments were carried out by adding a fixed amount of
adsorbent (0.1 g) to a 100 mL of pesticide solution of initial con-
centrations C0 at pH 7. Then, the suspension was stirred until
reaching equilibrium. Each adsorbent was finally removed by fil-
tration through 0.45 ␮m membrane. The filtrate was analyzed for
residual pesticide concentration by analytical method using an UV
Beckman coulter DU640B instrument at 211 nm. The amount of
equilibrium adsorption, Ye (mmol g−1 ), was calculated according
to equation:
(C0 − Ce ) × V
Ye = (1)
W
where C0 and Ce (mmol L−1 ) are the initial and equilibrium solution
concentration of the pesticide, respectively, V (L) is the volume of
the solution and W (g) is the weight of the used dry adsorbent.
Kinetic experiments were identical to those of equilibrium tests.
The aqueous samples were taken at predetermined time inter-
vals and the concentrations of (LNR) were similarly measured. All
the kinetic experiments were carried out at pH 7 by varying the
initial concentration of (LNR) from 20, 50 and 90 mg L−1 for DET-
cotton and 50, 90 to 140 mg L−1 for [Cu(II)/DET-cotton] complex.
The amount of pesticide sorption at time t, qt (mmol g−1 ), was
calculated as:
(C0 − Ct ) × V
qt = (2)
W
where Ct (mmol L−1 ) is the concentration of pesticide at time t.
2.8. Desorption of pesticide studies
As generally known, the desorption study is a method that helps
us to determine the adsorption mechanism process. In the present
paper, the regeneration treatment could be carried out with an
organic solvent in which, the selected pesticide is highly solu-
ble. For this, different composition of desorption solutions (1:1,
v/v; 1:2, v/v and 2:1, v/v) of a mixture of (acetonitrile/water) and
(ethanol/water) were tested.
Desorption experiments of the support [Cu/DET-cotton] already
saturated with (LNR) were performed as follows: the spent adsor-
bent (0.1 g) was added to 100 mL of the desired eluent and the
mixture was stirred in a closed bottle for 105 min at room tem-
perature. The suspension was then filtered and the liquid phase
141
was analyzed using a UV-spectrophotometer (UV Beckman coulter
DU640B instrument) at the max of 211 nm.
The percentage of desorption was calculated using the following
equation:
Amount of pesticide desorbed
Desorption (%) =
Amount of pesticide adsorbed on the adsorbent
× 100 (3)
The regeneration efficiency (RE) of the adsorbent was also eval-
uated as follows (Kalavathy et al., 2010):
Yreg
Regeneration (%) = × 100 (4)
Yref
where Yreg (mmol g−1 ) is the adsorption capacity of the regenerated
adsorbent and Yref (mmol g−1 ) is the original maximum adsorption
capacity of the adsorbent before the regeneration step.
3. Results and discussion
3.1. Characterization of DET-cotton
3.1.1. Elemental analysis
Elemental analysis results show that DET-cotton is composed
of 2.40% nitrogen. The chemical modification yielded a number of
coordinating sites per gram of support, Ca = 0.571 mmol g−1 . This
was calculated based on the amount of nitrogen atom incorporated
on the pendant chains using the following equation:
(%N) 1
Ca = × 103 mmol g −1 (5)
3.MN 100
where % N is the nitrogen content of DET-cotton and MN is the
molecular weight of nitrogen.
3.1.2. AFM analysis
The morphological characteristics of cotton fibers after the
chemical modification were provided using AFM analyses (Fig. 1).
Topography images show an increment of roughness via the sur-
face modification of the raw material. Indeed, the untreated fibers
display a roughness value of 118.3 nm (Fig. 1a), whereas the DET-
cotton fibers Exhibit 190.37 nm of surface roughness (Fig. 1b),
respectively. This could be attributed to the coverage of the sur-
face fibers with grafting chains highlighting the presence of grafted
amine groups.
142 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148
0,12
0,10
0,08
qt (mmol/g)
0,06
0,04
C0 = 140 mg/L
0,02
C0 = 90 mg/L
C0 = 50 mg/L
0,00
0 20 40 60 80 100 120 140 160
Time (min)
Fig. 2. Effect of contact time on the adsorption of (LNR) onto [Cu(II)/DET-cotton] at
different initial pesticide concentrations.
3.2. Adsorption kinetics
The effect of initial dye concentration on the adsorption kinetics
of (LNR) on [Cu(II)/DET-cotton] was investigated and is shown in
Fig. 2. Similar plots were determined for the adsorption of the same
pesticide on DET-cotton (Figure not shown). The results clearly
indicate that, with the increase of initial pesticide concentrations,
the adsorption uptakes of both DET-cotton and [Cu(II)/DET-cotton]
increased significantly, even though the DET-cotton displayed
lower adsorption capacities. The initial pesticide concentration pro-
vides the necessary driving force to overcome the resistance to the
mass transfer of (LNR) between the aqueous and the solid phase
(Ozer and Akkaya, 2006). Therefore, at higher initial pesticide con-
centration, the number of molecules competing for the available
binding sites on the surface of DET-cotton or [Cu(II)/DET-cotton]
was high, thus, inducing higher (LNR) adsorption capacities. Results
showed also that, the removal of the pesticide by both adsorbents
at the initial stage of adsorption process, increase linearly with the
increment in contact time and gradually slows down until reach-
ing maximum adsorption capacity at about 90 min for DET-cotton
and 105 min for [Cu(II)/DET-cotton]. At higher contact time, the
adsorption uptakes no longer increased indicating that the remain-
ing surface sites of both adsorbents surfaces became difficult to be
occupied by (LNR) molecules.
3.3. Kinetic modeling
In order to investigate the mechanism of adsorption process and
potential rate controlling steps such as mass transfer and chemical
reaction, the experimental kinetic data for the adsorption of (LNR)
on DET-cotton and [Cu(II)/DET-cotton] complex were fitted to
pseudo-first-order, pseudo-second-order, elovich and intraparticle
diffusion models.
The pseudo-first-order equation (Hameed et al., 2009), in its
linear form, could be written as follow:
k1
log(qe − qt ) = log qe − t (6)
2.303
where qe and qt are the quantity of pesticide adsorbed at equilib-
rium and at time t (mmol g−1 ) respectively, t is the time (min) and
k1 is the equilibrium rate constant of the first order kinetic model
(min−1 ). The slope and intercept of plots of log (qe − qt ) versus t
were used to determine the rate constant k1 , and the equilibrium
adsorption capacity, qe .
The pseudo-second-order equation (Hameed et al., 2009) is
written as:
t 1 t
= + (7)
qt k2 qe2 qe
where k2 is the equilibrium rate constant of the pseudo-second-
order kinetic (g mmol−1 min−1 ). If the pseudo-second-order
equation is applicable, the plot of t/qt versus t gives a linear rela-
tionship, and then k2 and qe can be calculated from the slope and
the intercept of the straight line.
The elovich equation (Özacar et al., 2008) is given as:
1 1
qt = Ln(˛ˇ) + Ln t (8)
ˇ ˇ
where ˛ is the initial sorption rate (mmol g−1 min−1 ); ˇ is the
extent of surface coverage (g mmol−1 ). The elovich constants can
be obtained from the slope and the intercept of the plot of qt versus
Ln t.
The intraparticle diffusion model is given by Weber and Morris
using the following equation (Hameed et al., 2009):
qt = ki .t 1/2 + C (9)
where ki is the intraparticle diffusion rate constant
(mmol g−1 min−1/2 ) and C (mmol g−1 ) is a constant that gives
idea about the thickness of the boundary layer. If the plots of
qt against t1/2 pass through the origin, the rate of adsorption is
controlled by intraparticle diffusion for the entire adsorption
period. However, this plot usually shows more than one linear
portion, and if the slope of the first portion is not zero, then the
film (boundary layer) diffusion controls the adsorption rate at the
beginning of adsorption (Hameeda and El-Khaiary, 2008a,b,c).
The values of the adsorption kinetics of pseudo-first-order and
pseudo-second-order models constants as well as the correlation
coefficients are given in Table 2. As can be seen, the pseudo-second-
order model adequately fits the data over the entire course of the
experiment with the high correlation coefficient of above 0.996
for all studied initial pesticide concentrations using [Cu(II)/DET-
cotton] complex as adsorbent. Moreover, the calculated values
of qe,cal estimated from the pseudo-second-order kinetic model
are much closer to the experimental ones (qe,exp ) compared to
those of pseudo-first-order model. This suggested that the adsorp-
tion process was probably dominated by a chemical adsorption
phenomenon which involved valency forces through sharing or
exchange of electrons between the adsorbent and the adsorbate
(Alkan et al., 2008; Ioannou and Simitzis, 2009). From Table 2, it
can be seen that the pseudo-second order kinetic rate constants
decreased with the increase of (LNR) initial concentrations. This
could be attributed to the less competition of sorption surface active
sites at lower concentration. However, at higher concentration, the
competition for the adsorption binding sites will be increased and
therefore, the adsorption rate will become slower.
An opposite trend was observed in the case of DET-cotton sup-
port indicating that the pseudo-first-order kinetic model is more
suitable to describe the adsorption of (LNR) onto this adsorbent.
This suggested that the adsorption mechanism follows in this case a
physisorption process (Simonescu et al., 2011) in which, the adsor-
bate adheres to the surface of the adsorbent through weak binding
interactions.
The elovich equation is used successfully to describe second-
order kinetics, assuming that the actual solid surface is ener-
getically heterogeneous (Razmovski and Šćiban, 2008). Elovich
parameters as well as the correlation coefficients for the adsorp-
tion of (LNR) on DET-cotton and [Cu(II)/DET-cotton] at different
pesticide concentrations are summarized in Table 2. Based on
the correlation coefficient values, it can be concluded that the
elovich model is more suitable to describe the adsorption of (LNR)
 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148 143

0.996
0.998
0.999

0.988
0.984
0.982

0.991
0.991
0.992

0.946
0.955
0.960
C0 = 90 mg/L

R2

R2
0,08
C0 = 50 mg/L
C0 = 20 mg/L

qe,cal (mmol g−1 ) 0,06

C × 102 (mmol g−1 min−1/2 )

qt (mmol/g)
0.1338
0.0438
0.0756

0.0399
0.0791
0.1075
0,04

0,02
Second-order kinetic model

K2 × 102 (g mmol−1 min−1 )

0.36
1.97
4.77

0
0
0
0,00
0 2 4 6 8 10 12
Kiint (mmol g−1 min−1/2 )

1/2 1/2
t (min )
Intraparticle diffusion
73.0162

30.3580
76.269

37.343
33.470
48.002

b 0,12
Pseudo-first, pseudo-second-order, Elovich and Intraparticle diffusion parameters for the adsorption of Linuron on DET-cotton and [Cu(II)/DET-cotton] complex.

C0 = 140 mg/L
0,10 C0 = 90 mg/L
C0 = 50 mg/L
0.0038
0.0042
0.0064

0.0032
0.0063
0.0088
0.913
0.892

0.995
0.993
0.997

0,08
0,898

qt (mmol/g)
0,06
2
R

0.988
0.994
0.965

0.985
0.982
0.978

0,04
R2
−1
)
qe,cal (mmol g

0,02
0.1556
0.0488
0.0961

0.0328
0.0686
0.0919

0,00
␤ (g mmol−1 )
First-order kinetic model

106.382
60.975
16.447

113.636
56.818
41.322

-0,02
0 2 4 6 8 10 12 14
1/2 1/2
t (min )
−1
)
K1 × 10 (min

Fig. 3. Intraparticle diffusion plots for (a) DET-cotton and (b) [Cu(II)/DET-cotton]
adsorption at different initial pesticide concentrations.
2

4.375
5.158
4.974

4.582
5.158
52.047

˛ × 103 (mmol g−1 min−1 )

on [Cu(II)/DET-cotton] by comparison with the pseudo-first-order

kinetic equation, showing the heterogeneous surface active sites of
Elovich model

this adsorbent. It was also observed that the values of ˇ decreased

qe,exp (mmol g−1 )

with initial concentration because of the less surface adsorption

5.2769
6.0332
3.349

12.828

2.638

7.735

sites that were available for (LNR) molecules at higher concentra-

tion. Moreover, values of adsorption rate constants, ˛, increased
0.1128
0.0353
0.0614

0.0289
0.0572
0.0797

with initial concentrations caused by the higher driving force (Chen

et al., 2010).
The kinetic results were further analyzed by the intraparticule
Concentration (mg L−1 )

diffusion model to elucidate the diffusion mechanism. The plots of

Concentration (mg L−1 )

qt against t1/2 for the adsorption of (LNR) on DET-cotton at different

initial concentrations are exhibited in Fig. 3a and the corresponding
parameters are given in Table 2. It may be observed that the straight
lines pass through the origin with correlation coefficient values
slightly lower compared to those obtained from the pseudo-first-
50
90
140

20
50
90

order kinetic model. This implies that the intraparticle diffusion is

50
90
140

20
50
90

the predominating rate step in the adsorption of (LNR) on the DET-

cotton support. Results presented in Table 2 showed also that the
intraparticle diffusion rate increased with the concentration due to
the increase of driving force of diffusion.
Cu(II/)DET-cotton

Cu(II/)DET-cotton

However, in the case of [Cu(II)/DET-cotton] complex, the

straight line at each concentration did not pass through the ori-
DET-cotton

DET-cotton

gin (Fig. 3b) and this indicated that the intraparticle diffusion was
Adsorbent

Adsorbent

not the sole rate determining step (McKay et al., 1980; Popuri
Table 2

et al., 2009). It can be seen from Fig. 3b that the adsorption of

(LNR) onto the studied adsorbent followed three stages. The first
144 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148

0,16
OH6C2N NC2H6O

C C
Cl2H4C6 C6H4Cl2
0,12 HN OH2 OO OH2 NH

Cotton Cu Cu
Ye (mmol/g)

0,08 OH2 OH2

NH NH NH2
CH2 CH2 CH2 CH2

0,04 Fig. 5. Proposal of associative structure between (LNR) and [Cu(II)/DET-cotton]

Cotton fibers complex.
DET-cotton
[Cu(II)/DET-cotton] complex Possible complex structure of [LNR/Cu(II)/DET-cotton] is presented
0,00
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 in Fig. 5.

Ce (mmol/L)
Fig. 4. Adsorption isotherms of cotton fibers, DET-cotton and [Cu(II)/DET-cotton] at
20 ◦ C.
portion could be attributed to the diffusion of pesticide molecules
through the solution to the external surface of the adsorbant (or
the boundary layer diffusion of pesticide molecules) (Hameeda
and El-Khaiary, 2008a,b,c; Gulnaz et al., 2005). The second por-
tion described the gradual adsorption stage, where the intraparticle
diffusion is rate-controlled (Hameeda and El-Khaiary, 2008a,b,c;
Gulnaz et al., 2005). The third portion is the final equilibrium stage
where intraparticule diffusion starts to slow down due probably
to the saturation of the adsorbent (Alila and Boufi, 2009; Hameed
et al., 2008).
The values of kint and C were determined from the slopes of
the second linear portion, and the constants of intraparticle diffu-
3.4.1. Effect of temperature
In order to study the effect of temperature on the adsorption of
(LNR) on DET-cotton and [Cu(II)/DET-cotton] complex, a series of
experiments were performed at 20, 40, 60 and 80 ◦ C and results are
given in Fig. 6a and b, respectively. The decreasing trend of pesticide
removal efficiency with increasing temperature is mainly due to
the low energy attraction indicating the process to be exothermic.
This result can be explained on the basis of solubility. Indeed, when
the temperature increases the pesticide became more soluble in
a
0,08
0,06
Ye( mmol/g)

sion model are given in Table 2. It was observed that the values of
C increasing with the initial concentration of the pesticide, which
0,04
indicated that the thickness (or the resistance to mass transfer) of
the boundary layer increased with the increase of C0 (Hameeda
and El-Khaiary, 2008a,b,c). Table 2 revealed that the intrapartic-
ule diffusion model showed a good fit with experimental data of 0,02 T = 20°C
T = 40°C
second portion at different initial concentrations (R2 > 0.991), jus- T = 60°C
tifying the applicability of this model to describe the uptake of (LNR) T = 80°C
by [Cu(II)/DET-cotton] complex in this step of adsorption process. 0,00
0,00 0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40

3.4. Adsorption isotherms Ce (mmol/L)

Pesticide removal capacity can be evaluated via the adsorp- b 0,16

tion isothermal experiments. In this section, we have investigated

the adsorption equilibrium of (LNR) on cotton fibers, DET-cotton
and [Cu(II)/DET-cotton] complex at 20 ◦ C. Results given in Fig. 4
0,12
revealed that the adsorption efficiency depended on the nature
of the used substrate. Indeed, the virgin fibres displayed a
Ye (mmol/g)

very poor affinity towards (LNR) molecules (Ye = 2.065 mg g−1 or

0.008 mmol g−1 ). However, the adsorption capacity of the selected 0,08
pesticide was improved using DET-cotton (Ye = 20.71 mg g−1 or
0.083 mmol g−1 ). This can be explained by: (1) the presence of NH2
terminal groups in the chemical structure of the modified cotton
0,04
fibers which share hydrogen bonding with the carbonyl function T = 20°C
of the pesticide, (2) the planar structure of (LNR) molecules which T = 40°C
allows further possible diffusion and intercalation of the molecules T = 60°C
T = 80°C
inside the domains formed by the grafted chains (Alila and Boufi, 0,00
2009). The incorporation of Cu(II) ions onto the chemical structure 0,0 0,2 0,4 0,6 0,8
of DET-cotton deals with the enhancement of the uptake capacity Ce (mmol/L)
of the used herbicide (Ye = 36.497 mg g−1 or 0.146 mmol g−1 ). These
results revealed that the pesticide can act as an efficient ligand Fig. 6. Effect of temperature on the adsorption of (LNR) onto (a) DET-cotton and (b)
for coordinating metal already involved in DET-cotton complex. [Cu(II)/DET-cotton].
 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148 145

80

Cu(II)/DET-cotton
60

0.176

0.912

0.962
0.992
0.986

0.196
0.858

0.196
0.858
0.086

0.150

0.014

0.150
0.014
0.009

0.700
1/Ye (g/mmol)

DET-cotton
40

0.997
0.947

0.897

0.999

0.997
0.997
0.994

0.992

0.756

0.992

0.756
0.906

0.870
0.804

0.870
0.804
R1 2

Cu(II)/DET-cotton
20

0.765

1.679

0.253

0.457
0.712

0.266

3.212

1.156
1.797
1.043
1.103

0.906

2.069

0.705
1.064
0

–
0 10 20 30 40

DET-cotton
1/Ce (L/mmol)

0.293
0.468
0.558
0.533

0.299

0.578
0.687
0.723

0.477
0.549
0.514

0.511

0.583
0.301

0.302

0.602
RL a
Fig. 7. Linearzed form of Type 2 Langmuir model for adsorption of (LNR) onto
[Cu(II)/DET-cotton], T = 20 ◦ C.

Cu(II)/DET-cotton
phase solution which lowered its affinity for the adsorbent surface.
Similar trends were also mentioned by Gupta et al. (2006).

0.417

1.848
0.675
0.161

3.774

0.568
4.010
3.4.2. Equilibrium isotherm models

–
–
–

–
–
–

–
–
–
ba (L mmol−1 )
Equilibrium data are usually fitted to isotherm models in order

DET-cotton
to develop an equation which accurately represented the result and

2.136

6.517

1.989
1.225

6.468

2.996
2.213
2.489

6.418

1.782
1.883
6.702
3.103

2.303

2.608
1.010
could be used for design purposes. In this paper, various sorption
models were proposed to test the adsorption experimental data
including Langmuir, Freundlich and Jossens equations.
Cu(II)/DET-cotton

3.4.2.1. Langmuir adsorption isotherms. The Langmuir equation is

given as:
0.652

0.126

0.144
0.224
0.533

0.518
0.150

0.033
QbCe
–
–
–

–
–

–
–
–
Qa (mmol g−1 )

Ye = (10)
1 + bCe
DET-cotton
Langmuir parameters for the adsorption of Linuron onto DET-cotton and [Cu(II)/DET-Cotton] complex.

where Q is the theoretical monolayer saturation capacity

0.1514
0.1731

0.1224

0.2696
0.2773

0.1231

0.1691
0.1358

0.1235

0.1984
0.1659
0.1210

0.1430

0.1703
0.2090

0.155
(mmol g−1 ) and b the Langmuir adsorption constant related to the
energy of adsorption (L mmol−1 ).
Cu(II)/DET-cotton

The Langmuir equation can be linearized at least to four types

as can be seen in Table 3 (Kumar and Sivanesan, 2006). The cal-
culated parameters and the corresponding correlation factors (R12 )
0.1465
0.1196

0.1465

0.1196

0.1465

0.1196

0.1465
0.1196
0.0825
0.0741

0.0825
0.0741

0.0825

0.0825
0.0741
for (LNR) adsorption on DET-cotton and [Cu(II)/DET-cotton] were
0.074

Values Q, b and RL did not computed due to the negative obtained values.
given in Table 3. Results exhibited that the obtained constants is
Yref (mmol g−1 )

a function of each applied linear Langmuir form. The high cor-

DET-cotton

relation coefficients given by type 2 Langmuir equation suggest

0.0831
0.0758
0.0714
0.0626

0.0831

0.0758
0.0714
0.0626

0.0831

0.0758
0.0714
0.0626

0.0831
0.0758
0.0714
0.0626
that this expression could comply with the pesticide adsorption
by both adsorbents. However, Type 1, Type 3 and Type 4 poorly
describe the equilibrium experimental data of (LNR) adsorption on
T (◦ C)

[Cu(II)/DET-cotton] complex with low correlation coefficients.

20
40
60
80

20

40
60
80

20

40
60
80

20
40
60
80

Fig. 7 showed the linearized plot of Type 2 Langmuir equation for

the adsorption of (LNR) onto [Cu(II)/DET-cotton] complex. Results
Ye Ce

vs Ye
1
vsCe

Ce
Ye
vs

Ye vs

revealed that this form of Langmuir model can be represented by

Plot

Ce

Ce
Ye

Ye
1

two lines in a wide range of concentration. This suggested the

presence of two different types of adsorption sites having differ-
1
Q
+

ent binding energies on the surface of the adsorbent (Khraisheh

Ce
Ye
Ce
bQ

1
1

 

et al., 2004). Therefore, two mechanisms may be possible: (i) initial

= bQ − bYe


1
b
= Ce +

adsorption on the external surface of the adsorbent and (ii) migra-

Linear form

bQ
1

Ye = Q −

tion of the selected pesticide inside the functional sites formed by


1
Q

nitrogen grafted chain. This was in agreement with the data found
Ce

Ce
Ye

Ye
Ye
1

in adsorption kinetic study. The obtained results demonstrate that

the Langmuir model cannot be applied for evaluating the adsorp-
Langmuir

tion behavior of (LNR) molecules onto [Cu(II)/DET-cotton] complex.

Type 1

Type 2

Type 3

Type 4
Table 3

The Langmuir model can be also expressed by means of a dimen-

a

sionless constant RL , whose magnitude gives information about the

146 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148

favorability of adsorption process. It was given using the following a 0,10

equation:

1
RL = (11) 0,08
1 + b2 Cref

where Cref is the highest fluid-phase concentration (mmol L−1 ), b2

Ye (mmol/g)
0,06
is the sorption equilibrium constant calculated from the Type 2
Langmuir expression (L mmol−1 ).
The RL values computed for the adsorption systems were in 0,04
range between 0 and 1 (Table 3), indicating thereby the favora-
bility of the ongoing process using the both adsorbents (Gandhia
et al., 2011). The decline in RL values with decreasing temperatures Experimental
0,02 Langmuir
clearly denotes that the present adsorption processes are much
Freundlich
favorable at lower temperatures. In addition to that, a large value of Jossens
b2 at 20 ◦ C also implied a strong bonding of the selected pesticide 0,00
to both substrates. This was also in accord with the results offered 0,0 0,1 0,2 0,3 0,4

by the adsorption equilibrium isotherms. Ce (mmol/L)

3.4.2.2. Freundlich adsorption isotherm. The widely used empirical b 0,16

Freundlich equation based on heterogeneous surface sorption is
presented as:

1 0,12
Ln Ye = Ln P + Ln Ce (12)
n
Ye (mmol/g)
where P and n are the Freundlich constants related to adsorption
capacity and adsorption intensity, respectively. The values of P 0,08
and 1/n were calculated from the intercept and slope of the plot
between Ln Ye versus Ln Ce .
Table 4 summarized the Freundlich constants and the corre-
lation coefficient (R22 ). As can be seen, the highest P value was 0,04
Experimental
observed at 20 ◦ C confirming that the loading capacities of the stud- Langmuir
ied adsorbents decrease with the rise in temperature (Chakraborty Freundlich
et al., 2011). Data given in Table 4 showed also that (LNR) molecules Jossens
0,00
were favorably adsorbed by DET-cotton at all studied temperature 0,0 0,2 0,4 0,6 0,8
since the exponent n was found to be greater than 1 (Ofomaja
Ce (mmol/L)
and Naidoo, 2010). However the adsorption of the selected pes-
ticide on [Cu(II)/DET-cotton] complex was found to be beneficial Fig. 8. Typical plot of comparison between the experimental and modeled isotherm
only at low temperatures. In addition, a high value of n obtained profiles for adsorption of (LNR) onto (a) DET-cotton and (b) [Cu(II)/DET-cotton],
at 20 ◦ C revealed the formation of relatively strong bond between T = 20 ◦ C.
the pesticide and the used supports (Oubagaranadin and Murthy,
2009).

3.4.2.3. Jossens adsorption isotherm. The Jossens model represents

a combination between the two previous models. This isotherm
may be described by the following equation:
iCe
Ye = (13)
1 + j(Ce )m
where i (L g−1 ), j (L mmol−1 ) and m are the Jossens constants which
can be obtained from adsorption data by an iterative procedure.
The theoretical parameters of Jossens equation are given in
Table 4. As can be observed, the m values were not equal to zero
confirming the absence of a linear (Henry’s) relation between Ce
and Ye .
Based on the correlation coefficients of the different tested mod-
els, Jossens seems to be the most suitable model to describe the
adsorption behavior of (LNR) on both the adsorbents. Fig. 8 shows
a comparison between the experimental and theoretical adsorp-
tion isotherms. Results presented in Fig. 8a confirmed that the
Jossens model gives the best fit to the adsorption data of (LNR)
on DET-cotton over the whole concentration range. However, only
the validity of the Freundlich equation was checked at the low-
concentration range in the case of [Cu(II)/DET-cotton] complex as
can be seen in Fig. 8b.
3.4.3. Regeneration of the support
Desorption experiments were performed to investigate the abil-
ity of recuperating the used pesticide. The procedure for conducting
these experiments was described earlier in this paper. Results
revealed that acetonitrile–water mixture with the composition
of 1:1 (v/v) have given the highest desorption efficiency (47%)
compared to the other tested mixture compositions [29% for 1:2
(v/v) and 27% for 2:1(v/v)]. Lesser amount of pesticide was des-
orbed when ethanol–water was employed as eluent: 43% for 1:1
(v/v), 12% for 1:2 (v/v) and 22% for 2:1(v/v). It should be noted
that the amount of the used pesticide was not totally desorbed
from [Cu(II)/DET-cotton] complex. Indeed, only 47% of (LNR) was
released from the adsorbent by using the appropriate eluent. This
finding imply that the mechanism of adsorption of the pesticide
onto [Cu(II)/DET-cotton] complex is characterized by more than
one type of interaction: strong binding bond such as complexation
bonding and weak binding forces such as hydrogen bonding. The
regenerated support was then used in another adsorption cycle by
using the same adsorbent. A decrease in adsorption efficiency was
observed (RE ranged between 9 and 18%). This can be due to the
breakdown of the functional groups of the adsorbent which limit it
reuses in other cycles of adsorption.
 A.E. Ghali et al. / Industrial Crops and Products 39 (2012) 139–148 147

Table 4
Freundlich and Jossens parameters for the adsorption of Linuron onto DET-cotton and [Cu(II)/DET-cotton] complex.

T (◦ C) Freundlich constants

P n R22

DET-cotton Cu(II)/DET-cotton DET-cotton Cu(II)/DET-cotton DET-cotton Cu(II)/DET-cotton

20 0.194 0.190 1.673 1.230 0.9744 0.953

40 0.192 0.172 1.316 1.056 0.9731 0.966
60 0.188 0.132 1.224 0.999 0.9792 0.984
80 0.161 0.108 1.239 0.871 0.9719 0.974

T (◦ C) Jossens constants

i (L g−1 ) ja (L mmol−1 ) m R32

DET-cotton Cu(II)/DET-cotton DET-cotton Cu(II)/DET-cotton DET-cotton Cu(II)/DET-cotton DET-cotton Cu(II)/DET-cotton

20 0.693 0.236 2.249 9.148 1.196 12.460 0.999 0.980

40 0.386 0.054 0.025 – 2.00 0.080 0.999 0.982
60 0.316 0.101 0.002 – 2.390 0.707 0.998 0.984
80 0.286 0.018 0.012 – 2.108 0.119 0.999 0.991
a
Values j did not computed due to the negative obtained values.

4. Conclusion
A specific sorbent namely DET-cotton was prepared by the
reaction of DET with 6-Chlorodeoxycellulose. The prepared sup-
port was then saturated with Cu(II) ions at pH 7 and used for the
removal of pesticides from aqueous solution. Results showed that
when the amino groups of DET-cotton are already implicated in
a Cu(II) ions complex, the improvement of adsorption capacity of
the modified cellulosic fibers was assessed through a metal-ion
coordination process. The adsorption kinetics studies of (LNR) on
DET-cotton and [Cu(II)/DET-cotton] complex were performed using
pseudo-first order, pseudo-second order, elovich and intraparticle
diffusion models. It was found that the pseudo-second order equa-
tion provided the best correlation of the experimental data of the
adsorption of (LNR) on [Cu(II)/DET-cotton] complex. However the
pseudo-first-order kinetic model was more appropriate in the case
of DET-cotton support.
The equilibrium data for the adsorption of (LNR) on both adsor-
bents have been analyzed using Langmuir, Freundlich and Jossens
models. The characteristic parameters for each isotherm and
related correlation coefficients were determined. Jossens model
was found to be the most appropriate to describe the adsorption
of the used pesticide onto DET-cotton. However the theoretical
models were not able to fit experimental data over the whole
concentration range studied for the adsorption of the same pesti-
cide onto [Cu(II)/DET-cotton]. Desorption studies were conducted
to elucidate the mechanism and recovery of the adsorbate from
[Cu(II)/DET-cotton] complex. Results showed that only 47% of
(LNR) was released from the adsorbent by using a mixture of
acetonitrile–water with a composition of 1:1 (v/v).
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