Applied Clay Science 179 (2019) 105145

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Applied Clay Science

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Research Paper

Adsorption of a cationic methylene blue dye on an Algerian palygorskite T

a a,b,⁎ c
Lamia Dali Youcef , Lala Setti Belaroui , Alberto López-Galindo
a
Laboratoire de Chimie des Matériaux (LCM), Faculté des Sciences Exactes et Appliquées, Université Oran1, BP 1524 Oran El M'Naouer, Oran, Algeria
b
Département de Pharmacie, Faculté de Médecine, Université Oran1, BP 1510 Oran El M'Naouer, Oran, Algeria
c
Instituto Andaluz de Ciencias de la Tierra, CSIC-University of Granada, Avda. de las Palmeras, 4, 18100 Armilla, Granada, Spain

ARTICLE INFO ABSTRACT

Keywords: The capacity of an Algerian Tertiary sedimentary palygorskite to remove methylene blue was studied. The raw
Algerian palygorskite material was characterized using X-ray diffraction, infrared spectroscopy, and chemical, granulometric and
Fibrous clay micotextural analyses. Kinetic experiments were carried out to study the effect of contact time, stirring speed,
Methylene blue initial dye concentration and adsorbent mass on the adsorption processes. The palygorskite-rich material mainly
Cationic dye
consists of this fibrous clay (72%) and calcite (19%) with minor amounts of dolomite (5%), illite (2%) and quartz
Adsorption
(2%). After 5 min contact time at room temperature, the adsorption reaction of a 50 mL solution containing
10 ppm of methylene blue on 50 mg of Cal-Pal as adsorbent reached equilibrium, and 97% of cationic dye was
fixed. Temperature did not have a significant influence on methylene blue adsorption. The obtained adsorption
isotherm indicates high affinity between the adsorbent and the adsorbate. The use of the studied Algerian pa-
lygorskite-rich sediment may have great potential for the elimination of textile dyes.

1. Introduction Bhattacharyya, 2002), montmorillonite (Ma et al., 2004), sepiolite and

Dyes are used extensively throughout the world in a wide range of
products. Until the 19th century, natural products were used to paint
the skin and to give color to fabrics (Tabak et al., 2009). At present,
approximately 700.000 t world of industrial dyes are produced an-
nually (Ollggaard et al., 1998), and the waste generated from industrial,
agricultural and domestic activities are dealt with at specialized treat-
ment centres or directly discharged into the environment, usually into
nearby water sources such as rivers, lakes and seas, causing a harmful
effect on their living organisms. Wastewater treatment may be simple
or complex, including a combination of physical, chemical, and biolo-
gical purification methods (Jank et al., 1998; Deng et al., 1998; Knapp
and Newby, 1999) in an attempt to recover water quality and, conse-
quently, the physical and ecological properties of the environment.
Among the several common removal technologies, the use of clays
as natural filters for the adsorption and fixation of contaminants is of
particular interest, due to the ease of treatment and relatively low cost
involved. Activated carbon is a commonly used absorbent for this
purpose (Yu-Li Yeh and Thomas, 1995; Yang and Al-Duri, 2001), but it
is an expensive material for wastewater treatment, particularly in de-
veloping countries. Several studies have examined the adsorption be-
havior of basic dyes in clay minerals such as kaolinite (Ghosh and
palygorskite (Shariatmadari et al., 1999). Smectites and fibrous clays
have a high specific surface structure and, therefore, high adsorption
capacities, making them very useful (McKay et al., 1985; Al-Futaisi
et al., 2007; Huang et al., 2007; Guo et al., 2008; Chen and Zhao, 2009;
Xue et al., 2010; Ouali et al., 2015; Belaroui et al., 2018; Habibi et al.,
2018). Palygorskite (also known as attapulgite in trade circles) is a 2:1
clay mineral, with a fibrous morphology resulting from the 180° in-
version occurring in every 4 silicon tetrahedra, creating a structure of
chains aligned parallel to the a axis, with open channels, 3.7 × 6.4 Å in
cross section, containing both “zeolitic” and crystallization water. Its
ideal formula is (Mg, Al, Fe)5VI (Si, Al)8IV O20 (OH)2 (OH2)4 R2+,4H2O
(Bradley, 1940) with R2+as divalent cation, H2O represent zeolitic
water in the channels, (OH2) is the coordinated water linked to octa-
hedral cations and (OH) is the structural water located in the center of
the octahedral sheet (Brindley and Brown, 1980); the fibrous crystalline
habit and the presence of zeolitic channels are the main reasons why
palygorskite has notable adsorbent properties. In addition, some iso-
morphic substitutions in the tetrahedral sheet (such as Al3+ for Si4+)
result in negative charges, thus enhancing adsorption of cationic dyes
on the surface or in the channels.
In recent years, some Algerian sedimentary Tertiary outcrops have
been described close to the cities of El Ghoufi and Sidi Khaled and
containing a relatively important quantity of palygorskite (Lamouri,

⁎
Corresponding author at: Laboratoire de Chimie des Matériaux (LCM), Faculté des Sciences Exactes et Appliquées, Université Oran1, BP 1524 Oran El M'Naouer,
Oran, Algeria.
E-mail address: belaroui.lalasetti@univ-oran1.dz (L.S. Belaroui).

https://doi.org/10.1016/j.clay.2019.105145
Received 21 December 2018; Received in revised form 19 May 2019; Accepted 22 May 2019
0169-1317/ © 2019 Published by Elsevier B.V.
L. Dali Youcef, et al. Applied Clay Science 179 (2019) 105145

Fig. 1. XRD of Cal-Pal sample obtained from the bulk sample (Raw Cal-Pal), oriented aggregate (Cal-Pal OA) and oriented aggregate solvated with ethylene-glycol
(Cal-Pal OA + EG).

Fig. 2. FTIR spectra of Cal-Pal sample.

2008). A description of the mineralogy, chemistry and micro-
morphology of this mineral was done by Belaroui et al. (2014).
The main aim of this study is to investigate the capacity of this
Algerian palygorskite to remove a typical cationic dye, methylene blue,
from aqueous solutions by changing initial palygorskite mass, contact
time, stirring rate, temperature, and dye concentration. The nature of
the adsorption reaction between the dye molecules and the clay was
also studied.
2. Materials and methods
The studied palygorskite was sampled in a Lutetian (Eocene), sub-
horizontal lenticular sedimentary layer, which is part of the formations
constituting the heart of the Ghassira syncline (Laffitte, 1939; Guiraud,
1973), close to the balconies of El Ghoufi (35°03′29″ N, 6°10′07″ E),
varying in thickness from 1 to 5 m and several hundred meters in
length.
The original material was crushed and sieved to obtain a < 90 μm
powder, called “Cal-Pal”.
The dye used is methylene blue (MB) or chlorhydratete-
tramethylonium. It is a synthetic cationic thiazine dye with molecular
formula C16H18C1N3S (molecular weight 319.87 g.mol−1). In aqueous
solution it dissociates into a cation and chloride anion. Its molecular
dimensions are 14.3 Å wide, 6.1 Å deep, 4 Å thick, with a molecular
diameter of 8Å and molecular volume of 241.9 cm3.mol−1 (Pelekani
and Snoeyink, 2000). A stock solution of MB (100 ppm) was prepared
by dissolving this dye in distilled water.
The mineralogical composition was determined by X-ray diffraction
(XRD) using a Panalytical X-Pert Pro diffractometer with Cu Kα ra-
diation (45 kV, 40 mA), Ni filter, RTMS X'Celerator detector, 4°-
69.9928° scan range, 0.0084° step size, 10.150 s counting time, for a
total of 7898 points and 11 min/sample. Semi-quantitative analyses
were performed following Moore and Reynolds (1989), and the final
contents of the different mineral phases were calculated by combining
XRD and chemical analytical data, following Torres-Ruiz et al. (1994)
and López-Galindo et al. (1996).
The granulometry of the material was analyzed using a Malvern®
Mastersizer 2000 LF granulometer, which allows measurements in the
0.020–2000 μm range. Samples were dispersed in water and treated
with ultrasound for 10 s. Data were collected online and statistical
particle diameters (d10, d50, d90) were calculated.
The texture of the samples was studied using a Zeiss DSM 950
scanning electron microscope (SEM) equipped with an EDX Link
Analytical Pentafet detector, Si (Li) and a Link Isis microanalysis system

2
L. Dali Youcef, et al.
Fig. 3. Microtextures, as observed by SEM, found in Cal-Pal (a, b, c, d), and loose palygorskite fibers (e, f) observed by TEM.
by Oxford. Transmission electron microscopy (TEM) observations were
performed in a Philips® CM20 STEM equipment by depositing a drop of
diluted dispersion onto a microscope grid. Quantitative microanalyses
were carried out in STEM mode using a EDAX-Genesis system equipped
with a Si(Li) detector, using a 7-nm beam diameter and a 20 × 100 nm
scanning area. The average crystal-chemical formula of palygorskite
was obtained from 10 TEM microanalyses of individual fibers. The two
electron microscopes belong to the Scientific Instrument Centre of the
University of Granada.
The Fourier transform infrared (FTIR) spectrum of the Cal-Pal
sample was recorded using KBr pellets on a Bruker (Model Alpha)
spectrometer at room temperature scanning over a 400–4000 cm−1
range.
Chemical analyses were carried out using a commercial wavelength
dispersive X-ray fluorescence instrument (BRUKER S4 Pioneer)
equipped with an Rh anode X-ray tube (60 kV, 150 mA); three analyzer
crystals (OVO-55, LiF 200 and PET) and a flow proportional counter for
light element detection and a scintillation counter for heavy elements.
Quantification was made by the fundamental parameters method using
the software linked to the equipment (SpectraPlus). To determine loss
on ignition (LOI), the sample was heated to 900 °C for 1 h.
Kinetic experiments were performed to study the effect of contact
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Applied Clay Science 179 (2019) 105145
time, stirring speed, initial dye concentration and adsorbent mass on
the adsorption processes, using 50 mg of Cal-Pal as adsorbent and
50 mL of solution with a variable concentration of MB as adsorbate.
Batch experiments were carried out using the rapid increase uptake of
dye with the increased clay amount from 5 to 100 mg MB remaining in
the supernatant before and after adsorption was determined with a
1.0 cm light path quartz cell using a Schimadzu 12,040 spectro-
photometer at λmax of 665 cm−1. Furthermore, the dye concentration
was calculated from a calibration curve of absorbance versus dye con-
centration. The amount of adsorbed MB at equilibrium, qe (mg.g−1)
was calculated by the following expression:
Co Ce
qe = V
W
where Co and Ce (mg.L−1) are the initial and equilibrium concentra-
tions of MB solution, V (L) is the volume of dye solution, and W (g) is
the weight of Cal-Pal.
For comparative purposes, essays were performed on a new
Algerian bentonite-like clay called lalithe (Belaroui et al., 2004;
Belaroui, 2008), a Spanish palygorskite supplied by the TOLSA com-
pany, and Cal-Pal treated with HCl 4 N acid at room temperature, using
50 mg of solid, 10 ppm of MB solution and 5 min contact time.
L. Dali Youcef, et al. Applied Clay Science 179 (2019) 105145

Fig. 4. Granulometry of Cal-Pal before (A) and after (B) sieving.

hydroxyl groups (3608.77 cm−1). In the SiO stretching region the ab-
Table 1 sorptions were detected at 976.67 and 1191.47 cm−1. Other weak ab-
Chemical composition of Cal-Pal. sorption was found at 649.55 cm−1, which could be attributed to
quartz. The characteristic band of calcite at 1431.20 cm−1 was also
Major elements (%) Trace elements (ppm)
identified.
SiO2 39.319 S 1387
Al2O3 8.770 Cl 559
Fe2O3 2.789 Cr 94 3.3. Micromorphology
MgO 7.930 Ni 24
CaO 12.383 Cu 35
Na2O 0.170 Zn 37 The morphological study of the Cal-Pal sample found that well de-
K2O 0.854 Rb 32 fined palygorskite fibers (1 to 10 μm in length, but normally < 5 μm,
TiO2 0.426 Sr 226 Fig. 3a) formed groups in roughly globular aggregates with a nested
MnO 0.035 Ba 21
array (Fig. 3b and c). Idiomorphic rhombohedral calcite crystals, cov-
P2O5 0.085
LOI 26.800
ered by palygorskite fibers (Fig. 3a), were frequent, sometimes over-
Total 99.561 lying sets of palygorskite fibers without any preferential orientation
(Fig. 3d). The TEM study detected palygorskite needles 2000–5000 nm
in length, and 10–50 nm in diameter (Fig. 3e and f).
3. Results

3.1. Mineralogy 3.4. Granulometry

Cal-Pal is mainly made up of palygorskite (72%) and calcite (19%).
Minor amounts of dolomite (5%), illite (2%) and quartz (2%) are also
present (Fig. 1).
3.2. FTIR spectroscopy
The FTIR spectrum of Cal-Pal (Fig. 2) presents the characteristic
bands of the three types of water molecules existing in palygorskite:
zeolitic water (1655.22 cm−1), coordinated water (3539.15 cm−1), and
As observed in SEM, the raw material mainly consists of paly-
gorskite aggregates cemented by calcite. Although individual paly-
gorskite fibers are normally < 5 μm in size, after light hand-crushing of
the raw material, the aggregates present a bimodal granulometric dis-
tribution (Fig. 4A), with peaks around 30 μm and 170 μm, and almost
50% of the material is over 100 μm in diameter (d10: 7.8 μm; d50:
102.8 μm; d90: 277.8 μm). Once the material was passed through a
90 μm sieve, the average size of aggregates fell to around 30–40 μm
(d10: 3.8 μm; d50: 19.2 μm; d90: 57.4 μm; Fig. 4B).

4
L. Dali Youcef, et al.
Fig. 5. Effect of contact time on the fixation percentage of MB on Cal-Pal.
Fig. 6. Effect of adsorbent quantity on MB adsorption on Cal-Pal (Contact time:
5 min).
3.5. Chemistry
Table 1 summarizes the chemical composition of the Cal-Pal sample,
including major oxides and trace elements. The mineralogical formula
of the palygorskite, obtained from TEM microanalysis, is as follows:
(Si7.88Al 0.12) O20 (Mg1.69 Al1.71 Fe 0.43) (OH)2 (K 0.06 Ca 0.05 Na 0.15) (OH2 )4 .
4H2 O
3.6. Study of the adsorption parameters
3.6.1. Effect of contact time
The experiments were performed for different contact times (1, 3, 5,
10, 15, 30 and 60 min) for a constant 50 mg clay mass and a MB con-
centration of 10 ppm. The uptake of dye from solution reached a
maximum value (97%) after a contact time of 5 min, so adsorption of
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Applied Clay Science 179 (2019) 105145
MB from solution by the studied fibrous clay is very fast (Fig. 5).
3.6.2. Effect of adsorbent mass
Different quantities (5 to 80 mg) of the fibrous clay material were
used for the adsorption of 10 ppm of MB over a contact time of 5 min.
Equilibrium was reached with a palygorskite mass of 50 mg (Fig. 6),
and this was later taken as the optimal mass of adsorbent for this ad-
sorption reaction.
3.6.3. Effect of dye concentration
Different MB concentrations (3 to 30 ppm) were tested (Fig. 7) for a
contact time of 5 min and a Cal-Pal mass of 50 mg. The curve obtained
rises as the dye solution concentrations increase, reaching a maximum
at 10 ppm dye concentration, however, it becomes almost stable
thereafter at higher concentrations. Therefore, maximum capacity of
dye uptake from the aqueous solution was reached at a lower initial dye
concentration with the availability of adsorption sites in Cal-Pal,
whereas, the studied adsorbent reached its quasi-saturation at high dye
concentration (Khattri and Singh, 2009; Zeroual et al., 2006).
3.6.4. Effect of temperature
Different temperatures were also considered (25 °C–70 °C) to con-
sider their impact on the palygorskite's capacity for adsorption of dye
molecules. For this purpose, previous optimum results (50 mg ad-
sorbent, 10 ppm dye solution concentration and 5 min contact time)
were chosen. As there is only a slight increase in BM adsorption with
temperature (from 97% at 25 °C to 99.3 at 70 °C, Fig. 8), isotherm
modelling was made at room temperature.
4. Discussion
4.1. Adsorption isotherms
The amounts of adsorbed dye at equilibrium (qe) versus equilibrium
dye concentration are plotted in Fig. 9. The isotherm of MB adsorption
on palygorskite is an H type isotherm (Giles et al., 1974), meaning high
affinity between the adsorbent and the adsorbate. This type of isotherm
is a particular case of the L isotherm, where the initial slope is confused
with infinity, and thus, isotherm representation could allow modelling
of the maximum adsorption capacity following Langmuir (1918) and
L. Dali Youcef, et al.
Fig. 7. Effect of the initial dye concentration on equilibrium adsorbed quantity of MB (Contact time: 5 min; Cal-Pal mass: 50 mg).
Fig. 8. Effect of temperature on the percentage adsorption of cationic dye on
the Algerian fibrous clay.
Freundlich (1906). The intermediate flat region in the isotherm corre-
sponds to the saturation of the surface of the solid by the formation of a
monolayer.
The data obtained from MB adsorption were fitted to the Langmuir
1 1 1
model (1918), following the linear equation: q = q + (q × K × C )
L e
e m m
where qe is the amount of the dye adsorbed (mg) per gram of ad-
sorbent, Ce is the equilibrium concentration of the cationic dye
(mg.L−1) per unit of Cal-Pal (g), qm is the Langmuir monolayer ad-
sorption capacity (mg.g−1) and gives the amount of dye required to
occupy all the available sites per unit mass of the sample, and finally KL
is the equilibrium constant (L.g−1).
The qm of MB obtained in Fig. 10 is estimated to be 57.47 mg.g−1.
The Freundlich isotherm model (1906) is expressed by the formula:
Ln (q e) = Ln Kf + 1/n. Ln Ce
where Kf and n are related to adsorption capacity and adsorption
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Applied Clay Science 179 (2019) 105145
intensity, respectively, and indicate if adsorption is favored or not.
These two parameters are obtained from the correlation shown in
Fig. 11.
It is generally stated that if the value of 1/n is included in the 0.1–1
range, it represents good adsorption.
The essential characteristics of a Langmuir isotherm can be ex-
pressed by a dimensionless constant called the equilibrium parameter,
RL, which is calculated by the following equation (Hall et al., 1966).
RL = 1/(1 + KL Ce)
The value of RL indicates the type of isotherm to be either un-
favorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irre-
versible (RL = 0). The RL values reported suggest that the adsorption
behavior of MB dye was favorable (0 < RL < 1) (Table 2).
If the correlation coefficient found in the monolayer adsorption
model (0.972) is compared with that of the Freundlich model (0.884), it
can be inferred that the adsorption of MB dye on the studied sample
follows the Langmuir model (Table 2). The explanation for this is
clearly related to the increase in the dimensions of the MB molecules
due to hydration (16.32 Å × 5.64 Å × 5.41 Å), thus preventing them
from entering the zeolitic palygorskite channels, so that they were ad-
sorbed onto the external surface of the palygorskite fibers (Homem-de-
Mello et al., 2005; Basu et al., 2007).
The acid activation of Cal-Pal promotes an increase in qm from
57.47 mg.g−1 to 96.15 mg.g−1, almost the same value obtained for the
studied Spanish palgorskite (102.04 mg.g−1). The highest value was
found in lalithe (181.81 mg.g−1), due to the structure of the smectite,
which favors an oxidation reaction between the cationic dye and the
exchangeable cations contained in the interlayer space of this clay
mineral, meaning that the process is not a simple adsorption reaction,
but rather an intercalation reaction.
Table 3 summarizes some published data of qm obtained for paly-
gorskites from China and Oman. It should be pointed out that in com-
parison Cal-Pal has slightly higher values of this parameter, and dif-
ferences may be due to small variations in palygorskite richness and/or
in fiber dimensions.
L. Dali Youcef, et al. Applied Clay Science 179 (2019) 105145

Fig. 9. Adsorption isotherm of MB on Cal-Pal (Contact time: 5 min).

Fig. 10. Langmuir adsorption isotherm of MB dye on Cal-Pal (Contact time: 5 min).

4.2. Thermodynamic adsorption parameters The values of ΔH and ΔS (Table 4) were determined from the slopes
and intercepts of the plots of lnKd vs 1/T (Fig. 12). The calculated Gibbs
The thermodynamic parameters of the adsorption process were energy values (ΔG) are very low and negative, and they decrease with
determined from the experimental data using the Van't Hoff equations: increase in temperature. It can therefore be inferred that the reaction is
fast. In addition, the positive enthalpy value (ΔH) confirms that this
Ln K d = ( S/R) ( Hs /RT) (1)
adsorption reaction is endothermic.
G= RT Ln K d (2)
4.3. Adsorption kinetics
K d = q e/Ce (3)
In order to study the specific rate constant of MB/Cal-Pal system,
where Kd is the distribution coefficient for adsorption; ΔH, ΔS and ΔG the well-known pseudo-first order rate equation was used (Ln
are the variations of enthalpy, entropy and Gibbs energy, respectively; (qe − qt) = Ln qe − (k/2.303)t) (Ho and Mckay, 1998) where qe is the
T is the studied temperature (K) of this adsorption reaction and R (Kj/ amount of adsorbate at equilibrium, qt is the amount of adsorbate at
mol K) is the gas constant. any time, k is the kinetic constant, and t is the time (Fig. 13).

7
L. Dali Youcef, et al. Applied Clay Science 179 (2019) 105145

Fig. 11. Freundlich adsorption isotherm of MB dye on Cal-Pal (Contact time: 5 min).

Table 2
Constants for both models of adsorption, Langmuir and Freundlich, for Cal-Pal.
Langmuir Freundlich

Constants 1/qm 1/qm*KL qm (mg.g−1) KL RL 1/n LnKf n Kf

0.0174 0.373 57.47 0.0466 0.682 0.5338 1.287 1.87 3.62

Table 3
The maximum adsorption capacity, qm (mg.g−1), for different adsorbents from
literature.
Adsorbents qm (mg.g−1) References

Chinese palygorskite 48.39 (Chen et al., 2011)

Palygorskite of Oman 50.76 (Al-Futaisi et al., 2007)
Cal-Pal 57.47 This work

The rate constants of MB adsorption on Cal-Pal can be calculated by

using the equation t/q(t) = 1/(k2*qe2) + (1/qe)t (Lagergren, 1898).
The straight line (R2 = 0.999) obtained (Fig. 14) indicates that the MB
adsorption on the Cal-Pal sample follows pseudo-second order kinetics,
with k = 0.203. Therefore, adsorption is an irreversible reaction, and
implies both the rapid fixation of the dye molecules and long fixation on
the weak energy sites (Calvet, 2003).
Fig. 12. Van't Hoff plot for the cationic dye adsorption on Cal-Pal.
5. Conclusion
of temperature on the MB adsorption was not significant. The de-
At room temperature, after 5 min contact time, the adsorption re- termination of the thermodynamic parameters confirms that the reac-
action of a 10 ppm solution of MB and 50 mg of Cal-Pal in 50 mL tion was endothermic, with positive enthalpy. The negative value of
reached equilibrium, and 97% of cationic dye was fixed. The influence Gibbs energy for all the studied temperatures (25 to 70 °C) indicates

Table 4
Thermodynamic parameters for the adsorption of MB dye onto Cal-Pal.
∆G (kJ mol−1) ∆H (kJ mol−1) ∆S (J mol−1 K−1) R2

298 K 313 K 333 K 343 K

Cal-Pal −2.86 −5.29 −8.53 −10.15 45.38 0.16 0.999

8
L. Dali Youcef, et al.
Fig. 13. Pseudo-first order kinetic for MB dye adsorption on Cal-Pal.
Fig. 14. Pseudo-second order kinetic for MB dye adsorption on Cal-Pal.
that adsorption was a pseudo-second order reaction.
The adsorption isotherm obtained indicates strong affinity between
the adsorbent and the adsorbate. This result was confirmed by the
Langmuir model, which showed perfect linearity of the experimental
points. The Cal-Pal sample presented a capacity for adsorption of MB of
57.47 mg.g−1.
The use of the studied Algerian palygorskite clay may have great
potential for the elimination of textile dyes, because it is a low cost
product, and there is no need for expensive equipment.
Acknowledgments
The authors acknowledge funding from the FP7 Marie-Curie Action
IRSES-MEDYNA, action under grant number PIRSES-GA-2013-612572.
The revisions made by Dr. Massimo Setti (Univ. Pavia, Italy) and one
anonymous referee have greatly improved the manuscript.
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Applied Clay Science 179 (2019) 105145
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