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Author’s Accepted Manuscript

Removal of a cationic dye from aqueous solution

by natural clay

Safae Bentahar, Abdellah Dbik, Mohammed El

Khomri, Noureddine El Messaoudi, Abdellah

PII: S2352-801X(17)30062-0
Reference: GSD107
To appear in: Groundwater for Sustainable Development
Received date: 9 June 2017
Revised date: 5 February 2018
Accepted date: 9 February 2018
Cite this article as: Safae Bentahar, Abdellah Dbik, Mohammed El Khomri,
Noureddine El Messaoudi and Abdellah Lacherai, Removal of a cationic dye
from aqueous solution by natural clay, Groundwater for Sustainable
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Removal of a cationic dye from aqueous solution by natural clay

Safae Bentahar*, Abdellah Dbik, Mohammed El Khomri, Noureddine El Messaoudi,

Abdellah Lacherai*,
Ibn Zohr University, Faculty of Science, Department of Chemistry, Laboratory of Applied
Chemistry and Environment, BP 8106, 80000,Agadir, Morocco


S. Bentahar, Tel: +212673740331;

A. Lacherai, Tel: +212661858956;


In this work, removal of methylene blue (MB) dye from aqueous solution by natural clay of
Agadir region was carried. The parameters influencing the adsorption of MB such as contact
time (20 - 120 min), adsorbent dose (0.4 - 4 g.L-1), initial dye concentration (100 - 900
mg.L-1), temperature (22 - 60 °C) and pH of the solution (3 - 10) were studied. The obtained
results showed that the adsorption of MB onto clay is strongly dependent on the temperature,
the initial dye concentration and the pH of the solution. The Kinetic study indicated that the
adsorption of MB on the clay was well adapted to the pseudo-second-order kinetic with a
correlation coefficient R2 = 1. Langmuir model described better the adsorption of MB with a
maximum adsorption capacity of 322.58 mg.g-1. The Thermodynamic study suggested that the
adsorption of cationic dye is physisorption, spontaneous and endothermic. Desorption and
regeneration studies showed that the studied support can be considered as an effective,
regenerable and reuse adsorption material.
Graphical abstract

Removal of a cationic dye from aqueous solution by Leave this area blank for abstract info.
natural clay

Safae Bentahar, Abdellah Dbik, Mohammed El Khomri, Noureddine El Messaoudi, Abdellah Lacherai,

Keywords: methylene blue, clay, cationic dye, kinetic study, adsorption, isotherms

1. Introduction

Synthetic dyes are used extensively in many industrial sectors, such as food, textile, paper,
rubber, plastics, cosmetics and pharmaceutical [1,2]. These industries discharged large
quantities of wastewater into waterways no previous treatment. These discharges constitute a
very important source of pollution and lead to the deterioration human and environmental
health [3]. The protection of environments and the improvement of water quality by the
removal of colorants from industrial effluents have become more and more severe in recent
years. In this context, several processes have been used for the purpose of water
decontamination including adsorption, coagulation/ flocculation, advanced oxidation
processes, ozonation, membrane filtration and biological treatment [4-6]. These methods are
effective, but in most cases, they are very onerous. Among them, adsorption remains the most
efficient methods used for water decontamination; due to it is low cost, not destructive,
flexibility, simplicity, ease of operation, insensitivity to toxic substances, lack of interaction
with toxic substances and readily available [3,7-12]. The use of activated carbon in the
adsorption process is highly demanded. Because the activated carbon has a high adsorption
capacity, essentially due to a large specific surface, but this process remains very expensive,
due to its high cost of manufacturing and regeneration which limits his use in many
developing countries and onerous [13,14]. It has also become necessary to have cheap and
efficient alternative materials which are capable of simultaneously removing organic and
inorganic pollutants. Clays could be interesting adsorbent materials for the adsorption of
various pollutants for reason of their high surface area, porosity, thermal stability, specific
active sites, high cation exchange capacity, easy availability and attractive adsorptive
properties [15-17]. In this work, we chose methylene blue as a cationic dye model to test the
adsorbent power of our natural clay (Fig. 1). Methylene blue also is known as
methylthioninium chloride is very used in medicine, pharmaceutics, dye industry, and
analytical chemistry, the molecular formula C16H18ClN3S.3H2O, a molar mass of 373.90
g.mol−1 and a maximum absorbance is equal 661 nm (Scheme 1). This dye is toxic and causes
shock, cyanosis, jaundice, and tissue necrosis [18,19]. The objective of this work is to study
all the parameters influencing in the removal of the methylene blue onto natural clay of the
Agadir region in the south of Morocco also to valorize the studied material for use in
wastewater treatment as an alternative, low-cost, eco-friendly adsorbent and re-usable several

2. Material and methods

2.1. Materials

The natural clay was collected from Agadir region (south Morocco) and was crushed in two
-The jaw crusher which permits to obtain the fragments with a diameter < 1cm.
-The tungsten mill which makes the fragments previously crushed by the jaw crusher in
powder. This powder was sieved to obtain fragments with a diameter < 50 µm [20].

2.2. Characterization
Our support has been characterized by XRD, FTIR, BET, SEM, and EDXS. The results
obtained have been published in our previous works [20,21]. The analysis of XRD shows the
existence of two phases, the dolomite (majority phase) and silica (the minority phase
compared with the dolomite), the FTIR spectrum indicates the presence of the characteristics
bands of the silica, the hydroxyl group OH and the deformation of H2O molecules adsorbed
between the layers. The SEM images indicate that the morphology is uniform and consists of
grains which are characterized by the presence of cavities and pores at the surface. The local
analysis by EDXS is relatively in good agreement with the nominal composition of the clay
phase obtained by X-ray diffraction. The specific surface area was determined by
the Brunauer–Emmet–Teller (BET), it is equal to 76.971 m2.g-1.

2.3. Batch studies

The adsorption of methylene blue onto the natural clay was carried out in a batch system. All
the parameters influencing the removal of MB on the clay were studied, such as adsorbent
dose, contact time, initial dye concentration, temperature, and pH of the solution. The
adsorption was carried out in a thermostatic bath by adding 0.05 g of our support to 50 mL of
a MB solution at different initial concentrations. The mixture is stirred at a desired
temperature and pH for varying periods. pH is adjusted by adding a few drops of HCl (0.1 M)
and NaOH (0.1 M). After, each experiment, the solution is centrifuged at 4000 rpm for 10
min. The MB concentration is determined by measuring the absorbance of the supernatant at
661 nm (λ max for MB) by UV-Vis spectrophotometer (Techcomp UV2300).The adsorbed
amount at equilibrium was calculated by the following equation (1):
(𝐶0 −𝐶𝑒𝑞 )
qe = *V (1)
Where qe (mg.g-1) is the amount of the MB adsorbed on the absorbent; C0 (mg.L-1) is the
initial concentration of MB; Ce (mg.L-1) is the equilibrium concentration of MB; V (L) is the
volume of the solution used and m (g) is the mass of absorbent used.

2.4. Data evaluation

2.4.1. Adsorption kinetics

In this study, we focused on two kinetic models commonly used namely pseudo-first order
and pseudo-second order. These models are particularly easy and have good ability to
describe the adsorption.

The pseudo-first-order model [22-24] is based on a linear relationship between the amounts of
solute attached to the material surface over time. Several authors have used this irreversible
kinetic model to describe the adsorption of organic and inorganic solutes on heterogeneous
surfaces. It is represented by equation (2) [25]:
log (qe - qt) = log qe - t (2)

The pseudo-second-order kinetics models [23, 26-29] have been developed to approximate as
much as possible the real reaction mechanism. It is expressed by equation (3):
𝑑𝑞 𝑡
= k2 (qe– qt)2 (3)
Where qe and qt are the amounts of MB molecules adsorbed (mg.g-1) on the natural clay at
equilibrium and at time t, respectively and k1 (min-1) and k2 ( are the pseudo-first
and pseudo-second-order rate constants, respectively.

2.4.2. Adsorption isotherms

Several Adsorption isotherm models have been developed by different researchers to predict
validity of the experimental data. The most commonly used are Langmuir [30], Freundlich
[31] and Timken [32].
Langmuir model assumes that the maximum adsorption corresponds to monolayer coverage
of the adsorbent surface, that the adsorption sites are homogeneous and also the adsorbed
molecules do not exhibit interactions between them [25,33].
The linear form of the Langmuir equation is given by the following equation (4):
𝐶𝑒 𝐶𝑒 1
= + (4)
𝑞𝑒 𝑞𝑚 𝐾𝐿 𝑞 𝑚

Where Ce (mg.L-1), qe(mg.g-1), qm (mg.g-1) et KL ( are the equilibrium concentration of

the dye, the amount of dye adsorbed at equilibrium, the maximum adsorption capacity, and
the Langmuir constant.
The essential characteristics of the Langmuir isotherm can be expressed in terms of a
dimensionless separation factor (RL) [34,35], which is defined by equation (5):
RL = (5)
1+𝐾𝐿 𝐶0

Freundlich isotherm admits the existence of an interaction between adsorbed molecules and
that the adsorption of adsorbate has taken place on a heterogeneous surface with a non-
uniform distribution of the heat of adsorption [25]. It is represented by the following equation
lnqe = ln KF + ln 𝑛𝑒 (6)

Where Ce (mg.L-1), qe (mg.g-1), KF ((mg.g-1) ( and n represent the equilibrium

concentration, the amount adsorbed, the Freundlich isotherm constant related to adsorption
intensity, respectively [36]. The n value indicated the favorability of adsorption process, the
adsorption is favorable if the values of n > 1 and it is unfavorable if n < 1 [37-40].
Temkin isotherm assumes that the heat of adsorption of all molecules decreases linearly with
coverage due to adsorbate-adsorbent interactions [32].The Temkin isotherm is represented by
the following equation (7):
qe = B ln KT+ B ln Ce (7)
Where B is a constant related to the heat of adsorption (J.mol ) and KT is the Temkin
isotherm constant (

2.4.3. Thermodynamic study

Thermodynamic parameters such as change in free energy (ΔG°) (J.mole-1), enthalpy (ΔH°)
(J.mole-1) and entropy (ΔS°) (J.K-1.mole-1) were calculated to determine the nature of the
adsorption of MB onto natural clay using the following equations (8), (9) and (10) [41-44]:
Kd= (8)

ΔG0 =- RT ln Kd (9)
ΔG0 =ΔH° - TΔS° (10)

Where Ce (mg.g-1), Cads (mg.L-1), Kd, R, and T are the liquid phase concentration at
equilibrium, the solid phase concentration at equilibrium, the distribution coefficient, the gas
constant and absolute temperature, respectively. The values of ΔH° and ΔS° were calculated
from the slopes and intercepts of the plots of ln Kd vs. 1/T (Figure not shown).

3. Results and discussion

3.1. Contact time effect

The contact time required to reach the methylene blue adsorption equilibrium on the natural
clay is determined by varying the contact time between 20 and 120 minutes with an adsorbent
dose of 1 g.L-1, an initial dye concentration of 100 mg.L-1 at room temperature and initial pH
of the dye solution, the obtained results are illustrated in Fig. 2. The adsorbed amount of
methylene blue increases rapidly in the first twenty minutes of contact to reach 96.38 mg.g-1
(fast step). After it slowed until reaching equilibrium with a quantity of the order of 98.12
mg.g-1 (slow step). This behavior can be explained by the presence, at the beginning, of a
large number of vacant surface sites that are available for the adsorption of the dye molecules
(first step). Over time, these sites become saturated, which causes forces between the solute
molecules on the surface of the solid. [45,46].

3.2. Adsorbent dose effect

Effect of the adsorbent dose on MB adsorption on clay is investigated by varying the dose
from 0.4 to 4 g.L-1 at room temperature with an initial dye concentration of 100 mg.L-1 and for
60 minutes of stirring. The pH is that of the initial solution. Fig. 3 shows that the efficiency of
adsorption increases from 89.05 to 98.17 % with an increase in the adsorbent dose from 0.4 to
4 g.L-1 and the optimal dose to achieve equilibrium is 1 g.L-1. Thus, the increase of the
adsorbent dose leads to an increase in the number of available adsorption sites which favors
the increase of the adsorption capacity [47].

3.3. Effect of initial dye concentration and temperature

The effect of initial MB concentration on the adsorbed amount at different temperatures was
performed in the concentration range (100 - 900 mg.L-1), and at 22, 30, 40, 50 and 60 °C, with
the initial dye solution pH, the adsorbent dose and the contact time were fixed at 1 g.L-1 and
60 minutes respectively (Fig. 4). According to the Fig. 4, it is found that the initial dye
concentration positively affects the adsorption of MB onto the natural clay. As the initial dye
concentration increased from 100 to 900 mg.g-1, the adsorbed amount increased from 97.60 to
256.85 mg.g-1. This is due to the fact that increase in concentration causes increases the
interaction between the dye and adsorbent surface and providing a necessary driving force to
overcome the resistance to mass transfer of dye [48,49]. In regards to the effect of
temperature, the adsorption capacity increases with the increasing temperature from 22 to
60 °C, this increase can be explained by the fact that the temperature has an effect on the
solubility and mobility of the dyes molecules [50-54], with a rise in temperature, the dye
becomes more soluble and the intensity of the interaction forces between the adsorbate and
surface of adsorbent become important [55], thereby promoting adsorption of the adsorbate
molecules. The temperature may also influence the kinetics and the adsorption capacity.

3.4. pH effect

The pH of the solution is a very important parameter to be taken into account in adsorption
studies of methylene blue onto natural clay. It affects the surface charge of the adsorbents as
well as the degree of ionization of dye molecules [56]. The pH effect was studied in the pH
range of 3 - 10 (by adjusting the pH with HCl (0.1N) and NaOH (0.1N) solutions), the initial
dye concentration and the adsorbent dose were maintained at 100 mg.L-1 and 1g.L-1
respectively, at room temperature for 60 minutes (Fig. 5). Fig. 5 shows that the maximum
adsorption capacity was observed at higher pH of the solution which can explain by the effect
of the electrostatic attraction between the sites on the surface which are negatively charged
and the positively charged MB at high pH [57]. Whereas in the case of the acidic pH, the
concentration of H+ ions is very high and consequently the adsorption capacity is decreased
because there is competition between the cationic dye molecules and the H+ protons to occupy
the adsorption sites [58,59], thus, in acidic pH, the clay is positively charged which leads to
an electrostatic repulsion between the MB cations and the adsorbent surface [60].

3.5. Adsorption kinetics

The kinetics of adsorption of cationic dye on the natural clay was carried out in the contact
time range 20 - 120 minutes; the results obtained are illustrated in Fig.6 and 7.
The kinetic parameters of both models are summarized in Table 1. As can be seen in Table 1,
the R2 values obtained for second-order kinetics (R2=1) is higher than that of pseudo-first-
order (R2= 0.885).This suggests that the adsorption of MB on natural clay well fitted to the
pseudo-second-order kinetic [6,57,60]. In addition, the calculated value of qe (qe= 98.039
mg.g-1) from the pseudo-second-order kinetic model matched well with the experimental data
which indicates that the adsorption process could be best described by the pseudo-second-

3.6. Adsorption isotherms

Adsorption isotherms were realized in the concentration range (100 - 900 mg.L-1), and at 22,
30, 40, 50 and 60 °C, the results obtained are shown in Fig. 8, 9 and 10, the isotherm
parameters are summarized in Table 2.
The calculated values of the constants and the correlation coefficients (R2) of the three
isotherms were shown in Table 2. According to the results obtained, it is found that the
correlation coefficient of the Langmuir (R2=0.99) is much higher than for other two models
Freundlich (R2 = 0.97) and Timken (R2 = 0.92), indicating that the Langmuir model exhibited
the best fit to the experimental data and a monolayer adsorption taking place on the adsorbent
surface [6,45,60,61]. Moreover, the theoretical maximum adsorption capacity (qthe= 322.58
mg.g-1) is closer to the experimental data (qexp). Furthermore the value (0< RL <1) proved that
the adsorption of MB on natural clay is favorable.
Maximum adsorption of methylene blue onto various clay-based adsorbents was illustrated in
Table 3. It is easy to note the high performance of our support to adsorb the dye studied.

3.7. Thermodynamic study

The thermodynamic values obtained are summarized in Table 4. As can be seen in Table 4,
The values of ΔG° at the temperatures of 22 °C, 30 °C, 40 °C, 50 °C and 60 °C are found to
be negative, which indicated that the adsorption of methylene blue onto the natural clay is
feasible and spontaneous [62,63]. Thereby the values of change in Gibb’s free energy (is
between -0.950010048 and -2.665494208) is in the range of -20 to 0 kJ.mol-1, which implies
that the physical adsorption [63,64]. The positive value of ΔH° confirms the endothermic
nature of adsorption process [6,65,66]. The positive values of ΔS° suggest the increased
randomness at the solid-solution interface with the increasing of temperature [67,68].

3.8. The probable adsorption mechanisms of MB onto natural clay

Adsorption tests carried out on the clay treated with HCl (5M) showed that MB is not
adsorbed on the latter.
According to the X-ray diffraction analysis of clay before [20] and after treatment with
hydrochloric acid (5 M) (Fig. 11), the absence of the dolomite phase after treatment is noted.
It is concluded that dolomite is responsible for MB adsorption.
On the other hand, the value of the zero charge point for the studied material is 8.49 [20],
which means that the clay surface is positively charged below 8.6 and negatively above this
Thus, based on these results, we proposed the MB adsorption mechanism on the surface of
clay illustrated by the scheme shown in Fig. 12. For the two pH ranges, we introduced both
types of active sites on the surface of the clay (-COOH and -COO-).
In acidic medium, the COO- sites of the support are protonated, and hence methylene blue is
adsorbed on the surface clay through hydrogen bonds involving sulfur and or nitrogen atoms
of MB not positively charged.
On the other hand, in the basic medium, Methylene Blue is fixed on the surface of the clay by
the electrostatic interactions between the oxygen of the carboxylate group of the surface of the
clay with the positively charged atoms of sulfur and or nitrogen dye.

3.9.Desorption and regeneration of natural clay

After the adsorption of MB using 0.05 g of the natural clay, initial MB concentration of 100
mg.L-1 at room temperature and the initial dye solution pH, the desorption was carried out by
eluting the MB dye-adsorbed natural clay with a HNO3 solution (0.3 M). The adsorption /
desorption process was repeated five times in order to examine the efficiency of re-use of the
adsorbent and to keep the process-cost low. The results obtained are illustrated in Fig.13 and
14. Fig. 13 shows that desorption of MB is rapid for the first 40 min (88.68%) and then
increases slightly to reach saturation at 60 min (96.67%). Concerning to reuse of support (Fig.
14), we found that the reduction of the percentage adsorption of methylene blue was only
7.6 % after the fifth cycle. This implies that our support can be considered as an effective and
regenerable material for adsorption of methylene blue.

4. Conclusion

The main objective of this study was the application of a clay from the Agadir region, for the
elimination of methylene blue. The parameters affecting the adsorption of MB are studied.
The results obtained show that the optimal adsorbent dose and the contact time to reach
equilibrium are 1 g.L-1 and 60 min. Also, the adsorption is strongly influenced by the
temperature and the initial concentration which have a positive effect on the MB elimination
by the natural clay. In addition, the adsorption of MB is better at basic pH. The kinetic study
shows that the adsorption of MB is described by a pseudo-second-order equation with a
correlation coefficient equal 1. Langmuir model perfectly describes MB adsorption with a
maximum adsorption capacity of 322.58 mg.g-1. The thermodynamic study indicates that the
adsorption is physisorption, spontaneous and endothermic in nature.
Thus, this work confirms the possibility of using this natural clay as an effective, economical,
ecological and regenerable adsorbent for the removal of cationic dyes from wastewater.


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Fig.1 Molecular structure of Methylene blue
Fig.2 The effect of contact time on MB removal, in conditions: adsorbent dose = 1 g.L-1;
C0=100 mg.L-1; T=22 °C; initial pH
Fig.3 The effect of adsorbent dosage on MB removal, in conditions: C0=100 mg.L-1;
T=22 °C; initial pH; equilibrium time = 60 min
Fig.4 The effect of initial dye concentration and temperature on MB removal, in conditions:
adsorbent dose = 1 g.L-1; initial pH; equilibrium time = 60 min
Fig.5 The effect of pH values on MB removal in conditions: adsorbent dose = 1g.L-1; C0 =
100 mg.L-1; T = 22°C; equilibrium time =60 min
Fig.6 Pseudo- first-order model for removal of MB by natural clay, in conditions: adsorbent
dose = 1 g.L-1; C0=100 mg.L-1; T=22 °C; initial pH
Fig.7 Pseudo-second-order model for removal of MB by natural clay, in conditions: adsorbent
dose = 1 g.L-1; C0=100 mg.L-1; T=22 °C; initial pH
Fig.8 Langmuir isotherm for adsorption of MB onto natural clay, in conditions: adsorbent
dose = 1 g.L-1; contact time= 60 min; C0=100 - 900 mg.L-1; T=22 - 60 °C; initial pH
Fig.9 Freundlich isotherm for adsorption of MB onto natural clay, in conditions: adsorbent
dose = 1 g.L-1; contact time= 60 min; C0=100 - 900 mg.L-1; T=22 - 60 °C; initial pH
Fig.10 Timken isotherm for adsorption of MB onto natural clay, in conditions: adsorbent
dose = 1 g.L-1; contact time= 60 min; C0=100 - 900 mg.L-1; T=22 - 60 °C; initial pH
Fig.11 XRD patterns of the acid treated clay
Fig.12 Schema illustrating the probable adsorption mechanism of MB onto natural clay
Fig.13 Desorption kinetic of methylene blue from natural clay
Fig. 14 Regeneration of natural clay using HNO3 (0.3 M)

Figure 1

Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12
Figure 13
Figure 14
Kinetic model parameters for MB adsorption on natural clay

Pseudo first-order kinetic model Pseudo second-order kinetic model

qe (mg.g-1) K1 R2 qe (mg.g-1) K2 R2
353671.447 1.263 0.885 98.039 0.026 1

Table 2
Parameters characteristics of adsorption isotherms

T (K) Langmuir

KL (L .mg-1) Qm(mg.g-1) RL R2
295.15 0.023 263.157 0.302 – 0.045 0.99
303.15 0.025 277.777 0.285 – 0.042 0.992
313.15 0.028 322.58 0.262 – 0.037 0.993
323.15 0.015 400 0.39 – 0.066 0.97
333.15 0.014 400 0.403 – 0.069 0.95
T (K) Freundlish
KF ((mg.g-1) ( 1/n) nF (L.g-1) R2
295.15 80.182 5.672 0.98
303.15 79.439 5.382 0.977
313.15 78.296 4.535 0.971
323.15 73.552 4 0.955
333.15 73.921 4.014 0.94
T (K) Timken
KT ( B (J.mol-1) R2
295.15 7.166 24.079 0.929
303.15 5.6 26.01 0.927
313.15 2.788 34.306 0.924
323.15 1.5 42.147 0.86
333.15 1.5 42.269 0.822
Table 3

Comparison of maximum adsorption of methylene blue onto various clay based adsorbents

Adsorbent Maximum adsorption Reference

capacities (mg.g-1)
Montmorillonite 289.1 [52]
Montmorillonite clay modified with iron oxide 71.12 [6]
montmorillonite 150.2 [62]
Dodecylsulfobetaine surfactant-modified 254.0 [62]
Acid activation of kaolinite / γ-Fe2O3 50.2 [60]
Plasma treated bentonite 303 [59]
raw kaolinite 78.1 [57]
Acid activation of kaolinite 101.5 [57]
montmorillonite 64.43 [61]
Fe3O4/activated 106.38 [61]
montmorillonite nanocomposite
Natural clay 322.58 This study

Table 4

Thermodynamic parameters of adsorption of methylene blue onto clay

ΔH° ΔS° ΔG° (kJ.mol-1)

(kJ.mol-1) (J.mol-1.K-1) 295.15K 303.15K 313.15K 323.15K 333.15 K

4.435 45.711 -9.056 -9.422 -9.879 -10.336 -10. 793


The natural clay was used as an adsorbent to remove cationic dyes.

The parameters influencing the adsorption of MB were realized.
Adsorption kinetics, isotherm, and thermodynamics were systematically investigated.
The natural clay can be used as cost-effective adsorbent in wastewater treatment.