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Contents lists available at SciVerse ScienceDirect

Applied Surface Science


journal homepage: www.elsevier.com/locate/apsusc

Study of malachite green adsorption by organically modied clay


using a batch method
Sofa Arellano-Crdenas , Socorro Lpez-Cortez, Maribel Cornejo-Mazn,
Juan Carlos Mares-Gutirrez
Departamento de Biofsica. Escuela Nacional de Ciencias Biolgicas IPN, Prol. de Carpio y Plan de Ayala, s/n. Col. Santo Toms, Apartado Postal 42-186,
C.P. 11340, D.F., Mexico

a r t i c l e

i n f o

Article history:
Received 13 February 2013
Received in revised form 12 April 2013
Accepted 21 April 2013
Available online xxx
Keywords:
Adsorption
Malachite green
Dye
Organoclay
Modied clay

a b s t r a c t
The adsorption of toxic dye malachite green from aqueous efuents by organically modied clay was
studied in a batch system. The organoclay (OC) used was prepared by the intercalation of cationic surfactant hexadecyltrimethylammonium bromide in a Mexican montmorillonite. The effects of initial dye
concentration, temperature, pH, and contact time were investigated. The OC showed a high dye removal
(99.6%) from an initial dye concentration of 60 mg L1 at pH 6 and 25 C. The adsorption capacity was
independent of pH and increased with the temperature. Equilibrium data were well tted by Langmuir
adsorption model. The rate of sorption was adjusted to a pseudo second-order kinetic model.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Malachite green (MG) is a synthetic dye (Fig. 1) which is widely
used as biocide in the aquaculture as well as a dye in textile industry.
It is also applied as a food coloring agent, food additive, medical disinfectant and anthelminthic [1,2]. However, despite its wide
use, MG represents a risk to the consumers of treated sh because
its adverse effects on the immune and reproductive systems, carcinogenic, genotoxic, mutagenic and teratogenic properties. For
these reasons and because that this colorant is highly accumulative
within edible sh tissues, a zero tolerance has been established. The
United States and the European Council have imposed a strict ban
on the use of malachite green in all categories of food-producing
sh [3]. In addition to this, discharge of MG into the hydrosphere
can cause environmental degradation as it gives undesirable color
to water and reduces sunlight penetration [14]. Therefore, it
is important to remove MG from aqueous efuents before they
are discharged into bodies of water. Many methods have been
developed for color removal such as electrocoagulation, otation,
chemical oxidation, ltration, ion-exchange, ozonation, membrane
separation and microbial degradation [5]. Adsorption processes are

Corresponding author. Tel.: +52 55 57296000x62314.


E-mail addresses: sarellano@ipn.mx, soare@hotmail.com
(S. Arellano-Crdenas).

gaining wider acceptance due to their high efciency and ability to


separate a wide range of compounds from liquids and, although
commercial activated carbon is a preferred adsorbent for dyes
removal its cost and regeneration are elevated [6]. Therefore, much
research concerning adsorbents from natural sources such as clays,
zeolites, and other low-cost and available solid materials to remove
dyes from wastewater has been undertaken [1,5,710]. Clay minerals are suitable for adsorption process due to their large specic
surface area and nanometer-scale size. For example, the expandable montmorillonite clay is composed of two silica tetrahedral
sheets with an octahedral alumina sheet. The montmorillonite surface is negatively charged due to isomorphous substitution of Al3+
for Si4+ in the tetrahedral layer and, Mg2+ for Al3+ in the octahedral
layer. The negative charge is balanced by exchangeable cations such
as Na, K, Ca and Mg in the lattice structure. In the presence of water
these cations are hydrated therefore the clay surface is hydrophilic
[11]. Recent progress in the synthesis of nanostructured materials offers an opportunity to modify surface properties of natural
clays in order to increase their adsorption capacity for organic compounds. The organoclays (OCs) are prepared by introducing cationic
surfactant molecules (e.g. hexadecyltrimethylammonium, HDTMA)
into the interlamellar space of a clay (e.g. montmorillonite) through
ion exchange, changing the surface properties of the natural clay
from hydrophilic to hydrophobic [11]. The OCs are investigated for
removal of a wide variety of organic compounds because of their
unique sorption capacities. For example, phenol and derivatives

0169-4332/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.04.097

Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097

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Fig. 1. Structure of malachite green: 4-[(4-dimethylaminophenyl)-phenyl-methyl]N,N-dimethylaniline [1].

[12,13]; tannins [14], naringin [15], dyes such as Methyl Orange


[16], Reactive Red 141 [17], Reactive Blue 19 [18], Crystal Violet
[19], Congo Red [20] and Direct Red 2 [21], among others.
Given the above, the objective of the present work was to study
the adsorption capacity of a prepared OC to evaluate its applicability
to remove an ionic organic dye from aqueous solutions. The effects
of concentration of solute, temperature, contact time, and pH on
the MG adsorption were also studied.
2. Materials and methods
The host clay utilized was a montmorillonite from northern
Mexico supplied by Arcillas Industriales de Durango, S.A., and
the surfactant HDTMA C19 H42 BrN (99% pure) was purchased from
SigmaAldrich Chemical Co. The MG dye C23 H25 ClN2 (96% pure)
was purchased from SigmaAldrich Chemical. The OC was obtained
by adding amounts of surfactant equivalent to 100% of the value of
the cation exchange capacity of the host clay. The procedure used to
prepare and characterize the OC was described in a previous paper
by Arellano-Crdenas et al. [15]. The characterization of the OC by
X-ray diffraction and nitrogen gas adsorption, showed a basal spacing d(0 0 1) of 2.012 nm, BET specic surface area of 9.3 m2 g1 , and
an average pore diameter of 11.35 nm. The point of zero charge
(pHPZC ) of the OC was of 8.0, as determined by potentiometric
method. The pH was measured by a Hanna HI 2210 pH-meter.
The MG concentration in aqueous solution was determined using
a Thermo Scientic Genesys 10 UV spectrophotometer.
2.1. Batch adsorption experiments
The adsorption of MG on the OC was carried out using a batch
process [22]. A series of asks containing 0.2 g of the OC, 0.025 L of
the solution of MG (concentration ranging from 10 to 500 mg L1 ),
and pH 6 were equilibrated in a temperature-controlled, waterbath shaker at 25 C for 24 h. Preliminary experiments showed that
the sorption was completed within 12 h, but to ensure that the
equilibrium was attained, a 24 h time period was used. After the
equilibrium was reached, the suspensions were ltered through
Whatman No. 42 lter paper. The remaining solutions were analyzed for the concentration of residual MG by spectrophotometry
at 424 nm.
The specic amount of solute adsorbed was calculated using the
following mass balance Eq. (1):
qe = (C0 Ce )

V
W

(1)

where qe is the adsorption capacity of the adsorbent at equilibrium


(mg g1 ); C0 and Ce are the initial and equilibrium concentrations
of solute, respectively (mg L1 ); V is the volume of the aqueous
solution (L) and W is the mass of adsorbent used (g). Adsorption
experiments were also conducted at two additional temperatures,
40 and 60 C, as described above. To determine the inuence of pH,
the adsorption experiments were carried out using 0.2 g of the OC,

Fig. 2. Malachite green adsorption isotherms on the organoclay obtained at different


temperatures (contact time 24 h and pH 6).

0.025 L of MG solution with an initial concentration of 60 mg L1


at 25 C, for 24 h. The pH of the solutions was carefully adjusted
between 2 and 10 with 0.1N HCl or NaOH by using a pH meter. The
MG concentration in aqueous solution was determined at 424 nm
in the pH range of 27, and at 383 nm for pHs values of 810. The
kinetic studies were performed using 0.2 g of the OC, 0.025 L of MG
solution with initial concentration of 60 mg L1 , pH 6, at temperatures of 25, 40 and 60 C, for 24 h. The reported results are the
average of triplicate measurements.
3. Results and discussion
3.1. Adsorption isotherms
The adsorption isotherms were obtained by plotting the amount
of MG adsorbed by the solid phase (OC) qe (mg g1 ), against MG
liquid phase concentration at equilibrium Ce (mg L1 ) (Fig. 2). The
isotherms obtained at different temperatures display an H-type
shape according to the Giles et al. [23] classication, which indicates that the MG has such high afnity for the OC that in solutions
with relative low concentration (<60 mg L1 ) it was completely
adsorbed. Therefore, the initial part of the isotherms was vertical.
The plateau reached after indicating the formation of the monolayer.
The OC had an afnity for MG despite that its surface area
(9.3 m2 g1 ) was smaller than other adsorbents, therefore the distribution and arrangement of the intercalated surfactant in the OC
was responsible for the adsorption efciency rather than the BETN2 surface area.
3.2. Effect of temperature
It is also observed in Fig. 2 that the adsorption capacity increased
from 40.5 to 59 mg g1 for an increase in the temperature from 25 to
60 C, therefore the process was endothermic, indicating that several kinds of interactions could be between the OC and the dye, such
as hydrophobic links between non-polar parts of the MG molecules
and the alkyl chains of the intercalated surfactant, Van der Waals
forces, iondipole interactions, and even chemical bonding. The
endothermic adsorption of dyes has been reported for the cationic
dye Crystal Violet [19], Direct Red 2 [21], and Congo Red [20] by
HDTMA-montmorillonite.

Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097

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Table 1
Freundlich and Langmuir parameters obtained for the adsorption of malachite green
on the organoclay at various temperatures.
Model

Constants

25 C

40 C

60 C

Freundlich

KF
1/n
R2

22.49
0.14
0.913

35.37
0.08
0.923

27.99
0.25
0.995

Langmuir

Q (mg g1 )
b (L mg1 )
R2

40.48
1.36
0.999

51.81
2.09
0.995

56.82
2.75
0.998

3.2.1. Adsorption models


The data obtained from the adsorption of MG were analyzed
according to the traditional models of adsorption. The Freundlich
isotherm is valid for heterogeneous adsorbent surfaces with sites
that have different energies of adsorption and in the linear form is
[24]:
log qe = log KF +

1
log Ce
n

(2)

where KF and 1/n are the Freundlich constants related to adsorption


capacity and intensity of adsorption, respectively.
The Langmuir model assumes that the adsorption takes place at
specic homogeneous sites on the surface of the adsorbent until
monolayer formation, and the well known Langmuir equation is
[24]:
Ce
Ce
1
= +
qe
Q
Q b

(3)

where Q (mg g1 ) and b (L mg1 ) are the Langmuir constants


related to a maximum monolayer capacity and energy of adsorption, respectively.
The values of the constants obtained for the two models are
shown in Table 1. In all cases the Langmuir equation adjusted best
the experimental isotherms with a good correlation coefcients
(R2 = 0.9950.999), which indicate the monolayer coverage onto
the OC particles and the homogeneous distribution of active sites
on the adsorbent. Furthermore, the Langmuir constants Q and b
increased as temperature increased from 25 to 60 C, showing that
the adsorption capacity and intensity were enhanced at higher
temperatures. Langmuir model has been reported to adjust well
the adsorption of aqueous Reactive Red 141 [17], Reactive Blue 19
[18], Congo Red [20], and Amido Naphtol Red G [25] onto HDTMAmontmorillonite.
3.3. Effect of pH
From Fig. 3 it can be seen that the uptake of MG onto the OC
slightly increased from 95% of removal at pH 3 to a maximum of

Fig. 4. Effect of contact time on malachite green adsorption on the organoclay at


different temperatures (malachite green initial concentration = 60 mg L1 , pH 6).

99.6% in the pH interval 410. It is reported that MG color is stable in the pH range 37 and color reduction increases from pH 7
to 11 [26]. Furthermore, the MG molecules (pka = 10.3) get protonated in the acidic medium and deprotonated at higher pHs [5]. Also
surface groups of the OC (pHzpc = 8.0) are protonated below pH 8.
Consequently, there was no electrostatic attraction between MG
molecules and the OC. Therefore, the hydrophobic and chemical
interactions could be the major forces for adsorption. These mechanisms have been reported to explain the adsorption of Reactive
Red 141 [18], Direct Red 2 [21], Reactive Blue 19 [18], and tannins
[14] by OCs.
3.4. Effect of time
Fig. 4 shows the effect of time on the MG adsorption by the OC,
conducted at different temperatures ranging between 25 and 60 C.
All curves show that adsorption capacity increases with time. The
initial rate was rapid and thereafter it was gradual until the equilibrium was reached. The initial stage indicates rapid attachment
of MG molecules to the external surface of the OC. The second stage
is due to diffusion of solute molecules into pores of the adsorbent
or other surface reactions. The third step is the nal equilibrium
stage where MG diffusion is very slow due its low concentration.
The uptake of MG at the equilibrium was of 7.5 mg g1 (99.6% of
removal). As temperature increased, the time to reach equilibrium was lower. Specically, at 25, 40, and 60 C, the equilibrium
was reached in 240, 180 and 30 min, respectively. This implies
an increased surface activity and the kinetic energy of the solute
molecules, resulting in fast interactions between MG and the OC at
high temperatures.
3.4.1. Kinetic model
In order to investigate the sorption processes of MG onto the
OC, pseudo second-order kinetic model of adsorption was used.
This model was developed by Ho and Mckay [27], and is based on
the assumption that the chemical sorption is the rate-limiting step.
Its linear expression is:
t
1
1
=
+
t
qt
qe
k2 q2e

Fig. 3. Effect of pH on malachite green adsorption on the organoclay (malachite


green initial concentration = 60 mg L1 , T = 25 C, contact time 24 h).

(4)

where qt is the amount of solute adsorbed at any time t, qe is


the amount of solute adsorbed at equilibrium (mg g1 ) and k2
(g mg1 min1 ) is the rate constant.
Kinetic data obtained gave very good t with the pseudo-second
order model as shown by the R2 = 0.995 values (Table 2) indicating
a linear variation of t/qt against t. Based on this model a chemisorption reaction could be predominant in the rate-controlling step

Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
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Table 2
Pseudo-second order kinetic parameters obtained for the adsorption of malachite
green on the organoclay at various temperatures.
Model
Pseudo-second order kinetic

Constants
1

k2 (g mg min
qe (mg g1 )
R2

25 C

40 C

60 C

0.006
7.6
0.995

0.027
7.4
0.995

0.597
7.5
0.998

The OC prepared represents a potential adsorbent of malachite


green in aqueous media. Additional research is needed to evaluate
the adsorption efciency of organoclay mixed with other organic
pollutants.
Acknowledgments
Financial support from the Secretara de Estudios de Posgrado
e Investigacin del Instituto Politcnico Nacional de Mxico (SIPIPN) and the Consejo Nacional de Ciencia y Tecnologa (CONACYT)
is appreciated.
References

Fig. 5. Plot of ln b (b is the Langmuir constant) vs. 1/T for malachite green adsorption
on the organoclay.

[27]. The equilibrium adsorption capacity calculated (qe ) was


of 7.5 mg g1 , which is the value found experimentally. Several
authors have been adjusted kinetic data using this model for studies
of sorption of Reactive Red 141 [17], phenol [24], chlorobenzenes
[28], Crystal Violet [19], Amido Naphtol G [25], Direct Red 2 [20],
Congo Red [19], and p-nitrophenol [11] on HDTMA-bentonite.
3.5. Thermodynamic parameters
The thermodynamic parameters such as entropy (S ),
enthalpy (H ), and free energy change (G ) for the adsorption
process were calculating by the following equations [14]:
lnb =

S
H

R
RT

G = RT lnb

(5)
(6)

where b is the Langmuir constant (L mol1 ), R is the ideal gas constant (1.987 cal mol1 K1 ) and T is the absolute temperature (K).
The plot of ln b vs. 1/T was found to be linear (Fig. 5). The positive
H value obtained (3.9 kcal mol1 ) indicates that the adsorption
was endothermic. The S value obtained (26 cal mol1 ) reects
the afnity of the solid for MG [14].
The negative G value decreased with increased temperature.
Specically, at 25, 40 and 60 C the values obtained were 2.9,
4.15, and 4.6, respectively, indicating that the spontaneity of
adsorption is directly proportional to the temperature.
4. Conclusion
The organoclay prepared showed a 99.6% of aqueous malachite
green removal at initial concentrations of 60 mg L1 and a complete
removal at lower concentrations, according to the zero tolerance
imposed by several international legislations.
The Langmuir model predicted well the adsorption in the temperature interval of 2560 C. The adsorption was independent of
pH and increased with the temperature. The adsorption kinetic data
were well described using the pseudo-second order kinetic model,
implying that chemisorption could be the rate-controlling step.

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method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097

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method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097