Environmental Science and Pollution Research (2019) 26:28622–28632

https://doi.org/10.1007/s11356-019-04641-0

ALTERNATIVE ADSORBENT MATERIALS FOR APPLICATION IN INDUSTRIAL PROCESSES

Use of bentonite calcined clay as an adsorbent: equilibrium

and thermodynamic study of Rhodamine B adsorption
in aqueous solution
Fernanda Ribeiro dos Santos 1 & Heloísa Carolina de Oliveira Bruno 1 & Lisbeth Zelayaran Melgar 1

Received: 1 September 2018 / Accepted: 19 February 2019 / Published online: 6 March 2018
# Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
The Rhodamine B adsorption was realized in batch using calcined bentonite clay. The effects of Rhodamine B initial concen-
tration, pH, and temperature were evaluated and the conditions where the adsorption was favored were in 500 mg L−1, pH 3, and
35 °C. The equilibrium isotherms studied were from Langmuir and Freundlich. The coefficients of determination (R2 > 0.99)
were found to confirm the best fitted to Langmuir isotherm, with a monolayer adsorption capacity (qmax) of 552.49 mg g−1. The
kinetic data agreed well with the pseudo-second order model (R2 > 0.99). The in natura and calcined clay were characterized by
the techniques of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 physisorption (BET), and
scanning electron microscopy (SEM). Thermodynamic parameters including Gibbs free energy (ΔG°), enthalpy change
(ΔH°), and entropy change (ΔS°) were calculated to estimate the nature of Rhodamine B adsorption in clay. The results
suggested that the adsorption was endothermic and spontaneous, with the enthalpy adsorption increasing with the increase of
temperature. Therefore, calcined bentonite can be used as an efficient adsorbent for discoloration of large volume of residual
water, presenting low-cost and high adsorptive capacity.

Keywords Rhodamine B . Adsorption . Isotherms . Kinetic and thermodynamic study . Bentonite clay . Characterization

Introduction et al. 2009); in addition, some may be bioaccumulative

In the course of the years, water quality is suffering losses. The
main causes of hydric deterioration resources are associated
with anthropogenic activities, disordered population growth,
unplanned urbanization, fast industrialization, and unspecial-
ized water use (De Gisi et al. 2016). The effluents that come
from textile, leather, paper, and printing industries contain
toxic dyes that are stable to the processes of photo-degrada-
tion, biodegradation, and oxidation (Khan et al. 2012). Dyes
present a high-colored charge and when discharged into the
receptor bodies, they prevent light penetration, reduce the
photosynthetic activity, and inhibit the biota growth (Han
Responsible editor: Tito Roberto Cadaval Jr
* Fernanda Ribeiro dos Santos
fernandaribeirods@hotmail.com
1
Department of Chemical Engineering, Federal University of São
João del-Rei, MG 443 (Kilometer 7), Ouro Branco, Minas
Gerais 36420-000, Brazil
(Robinson et al. 2001), carcinogenic (Banat et al. 1996;
Clarke and Anliker 1980; Gupta et al. 1990; Mishra and
Tripathy 1993; Rammel et al. 2001), and mutagenics
(Yagub et al. 2014) and can cause kidney, reproductive
system, liver, brain, central nervous system (Kadirvelu
et al. 2003), gastrointestinal tract, skin, and lung dysfunc-
tion (Karthikeyan and Jothi Venkatachalam 2014). That is
the reason why it is essential to treat dye effluents before
pouring them the recipient bodies.
The methods used for dye removal were precipitation, floc-
culation, incineration, ion exchange, coagulation, reverse os-
mosis, electrochemistry, membrane filtration (Zheng et al.
2013), advanced oxidation processes, and biological methods
(Hayat et al. 2015; Punzi et al. 2015) which have many de-
grees of efficiency (Zhu et al. 2016) depending on the selected
compound (Salleh et al. 2011). Following this perspective,
these processes can have disadvantages such as high costs,
high energy demand and sludge production (Chuah et al.
2005), and by-products formation that can be toxic or difficult
to recover and discard (Singh et al. 2018), besides being used
for a restricted group of compounds.
28623 Environ Sci Pollut Res (2019) 26:28622–28632

The adsorption is an efficient physicochemical separation bentonite, it was possible to study the adsorption mechanism,
method of mixtures for the residual water decontamination, to obtain parameters and characteristics of the adsorbent, and
non-destructive, simple, without interaction with toxic sub- to evaluate the efficiency of the use of this system in the
stances and low-cost operation (Bentahar et al. 2018). The treatment of water effluents.
adsorption process depends on the nature and adsorbent type,
with the possible use of organic and inorganic materials
(Vakili et al. 2014). The most widely used adsorbents are as Methods and materials
follows: activated carbon (Guibal et al. 2003), alumina (Iida
et al. 2004), zeolites (Alver and Metin 2012; Han et al. 2007), Materials
silica gel (Gaikwad and Misal 2010), industrial by-products
(Bhatnagar and Jain 2005), agricultural solid waste (Wang The adsorbate studied was the Rhodamine B (RB) cationic
et al. 2008b), clays (Lian et al. 2009; Öztürk and Malkoc dye with 90% purity grade (m/m), provided by the company
2014), turf (Fernandes et al. 2007), bacterial biomass Contemporary Chemical Dynamics LTDA. Table 1 shows us
(Ratnamala and Brajesh 2013), and polysaccharides (Saha the RB physicochemical properties. The clay used was the
et al. 2011). However, many of these adsorbents present slow Brazilian natural sodium bentonite, provided by the indus-
adsorption or inconvenient separation and regeneration rates, try Latin Alliance Commerce LTDA from the city of
which prevent them from being applied in large scale in the Uruguaiana/RS.
water treatment. Moreover, the adsorbent with characteristics
such as fast rate adsorption and easy separation is extremely
desirable (Zeng et al. 2014). Experimental procedures
The bentonite clay is an abundant and low-cost natural
material; it has high cation exchange capacity, large specific Calcined clay preparation The in natura clay granulometric
area, possible interlamellar expansion, and a large volume of analysis was realized by sieving in a Bertel sieve shaker, with
intercalation molecules (Pereira et al. 2017). Bentonites ad- a set of ABNT (Brazilian Association of Technical Standards)
sorptive property is attributed to the lamellar structure formed sieves with opening dimensions of 32, 48, 60, 100, and 200
by octahedron aluminum layers between two others of silicon mesh, for 30 min and 8 rpm. The in natura clay, classified and
tetrahedron. The substitution of Al3+ by Mg2+ or Fe2+ in the selected in a 200 mesh sieve, was subjected to the calcination
octahedral leaves results in negative charges that are process in the Mufla SP Labor furnace, SP-1200 model, at
counterbalanced by exchangeable cations, such as Na+, 500 °C for a period of 24 h.
Ca2+, K+, and Mg2+, located in the interlamellar space
(Kausar et al. 2018). In the adsorption process, these cations Adsorbent characterization The in natura and calcined clay
can be replaced by other molecules or neutralize the active were classified and selected with a particle size of 0.074 mm
hydroxyl groups. Looking at this perspective, the cationic (200 mesh). The X-ray diffraction patterns were obtained
molecules have good interaction with clays (Kittinaovarat using a diffractometer (Rigaku Rotaflex, model RU200B),
et al. 2010; Wang et al. 2008a) and Rhodamine B adsorption equipped with Cu anode, operating at 60 mA and 40 kV.
may be viable. The standards were recorded from 5° to 40° (2θ), range where
This mineral capacity to absorb water and expand prevents the peaks are observed concerning Montmorillonite interest
it from being applied in fixed beds for dye removal on an (Bertagnolli et al. 2011; Nones et al. 2015; Vieira et al.
industrial scale (Bertagnolli et al. 2011). In order to modify 2010) and speed of 2° min−1. The specific surface area and
the bentonites physicochemical properties, they can be sub-
jected to treatments with temperature, acids, functionalization, Table 1 Physicochemical Rhodamine B dye properties
pillarization, and composition with other materials (Huang
Parameter Character/value
et al. 2016); the method choice depends on the final purpose.
In the thermal treatment, non-crystalline phase transforma- Class Triphenylmethanea
tions occur that aim to increase the adsorption and improve CAS number 81-88-9
the mechanical properties in the material, increasing its usabil- Molecular formula C28H31CIN2O3b
ity beyond the natural form (Auta and Hameed 2014). Molecular weight 479.02 g mol−1b
In this paper, the bentonite clay calcination and character- Maximum wavelength (λmax) 554 nma
ization were performed with the main objective of obtaining a pKa 3.7c
material with a high capacity and a simple removal rate, prac-
a
tical, and low-cost. The pH effects, temperature, and dye ini- Baddouh et al. (2018)
b
tial concentration were investigated. Based on the kinetic and Khamparia and Jaspal (2017)
c
thermodynamic study of Rhodamine B adsorption in Wang et al. (2014)
Environ Sci Pollut Res (2019) 26:28622–28632
pore distribution were determined by BET, N2 quantification
technique to form a monolayer adsorbed on a solid surface of
an adsorbent. We used the model 2020 ASAP, Micromeritics
equipment temperature of − 196.5 °C. The morphology of the
surface of bentonite was investigated in a scanning electron
microscope (SEM), JEOL JSM-6360LV with secondary elec-
tron detector for high vacuum, electron backscattered detector
for high and low vacuum, EDS detector (energy dispersive X-
ray spectrometer), and EBSD detector (electron backscatter
diffraction), running the tests with 15 and 30 kV. For this,
samples of in natura and calcined bentonite clay were previ-
ously atomized with gold, making the electron conductive
surface. The structural bentonite composition was analyzed
by infrared absorption test (FTIR). Initially, we measured the
cesium iodide (CsI) spectra, which showed a low water quan-
tity, remembering that this control is important, since CsI is
very hygroscopic. Thus, the existing water is a component of
the sample. The spectra were measured using Nicolet 6700
model equipment. The test conditions were 64 SCANS,
4 cm−1 resolution and spectral range 400 to 4000 cm−1. This
analysis was performed with a single particle size fraction
(0.074 mm), by evaluating the chemical bonds of the groups
present in the clay, which are not altered by changes in the size
of the particles (Bertagnolli et al. 2011).
Adsorption experiments The studies here performed to eval-
uate adsorption were by adding (1 g L−1) thermally modified
clay in 50 mL of RB dye solution, both maintained at constant
stirring and temperature of 200 rpm and 25 °C, respectively.
The system was monitored using the Lucadema Shaker incu-
bator, Luca-223 model, controlling time contact of 120 min
that was settled. The pH (3–10) was controlled using solutions
of HCl (1.0 and 0.1 mol L−1) and NaOH (1.0 and 0.1 mol L−1)
with the aid of a benchtop pH meter (Hanna PH21 model),
keeping the RB initial concentration constant, 400 mg L−1.
Then varied the dye initial concentration (300–500 mg L−1)
and remained fixed in pH 3. In order to analyze equilibrium
concentrations, absorbances were measured using the
Micronal UV-VIS spectrophotometer, AJX-1600 model spec-
trophotometer, 554 nm wavelength, using a 1 cm optical path
quartz cuvette. The assays to obtain the isotherms adsorption
equilibrium were performed at pH 3; it was kept doing the
necessary solution applications HCl (1.0 and 0.1 mol L−1)
and NaOH (1.0 and 0.1 mol L−1) with the aid of a benchtop
pH meter for the its control. This way, RB initial concentration
varied (350–600 mg L−1) and temperature (15–35 °C).
Calcined clay (50 mg) was added to 50 mL RB solution and
the system was kept under stirring (200 rpm) for 60 min.
Kinetic adsorption models
The kinetic study is performed in order to know the rate law,
mechanisms that govern the adsorption and limiting step
28624
determination. The limiting or slower step is the one which
is responsible to control the process, and may be the mass
adsorbate transfer from the fluid phase to the adsorbent outer
surface, adsorbate diffusion into the material pores, and the
physical interaction or chemical reaction between adsorbent/
adsorbate (Fogler 2009). The kinetic parameters were cal-
culated from the adsorbed quantity qe (mg g−1) data, dye
initial concentration Co (mg L−1), equilibrium concentra-
tion in solution Ce (mg L−1), solution volume V (L), and
adsorbent mass m (g) that can be related by Eq. 1 (Auta
and Hameed 2014).
ðC 0 −C e ÞV
qe ¼ ð1Þ
m
The kinetic adsorption behavior was obtained by experi-
mental data fit to the linearized pseudo-first order (Eq. 2) and
pseudo-second order (Eq. 3) models (Nascimento et al. 2014).
lnðqe −qt Þ ¼ lnðqe Þ−k 1 t ð2Þ
t 1 t
¼ þ ð3Þ
qt k 2 q2e qe
where k1 is adsorption constant rate of pseudo-first order
(min−1); qe and qt are amounts adsorbed per gram of ad-
sorbent at equilibrium and at time t (min) in mg g−1; k2 is the
pseudo-second order adsorption rate constant (g mg−1 min−1).
The values of k1 and k2 were found from linear regression of
ln(qe − qt) against t and t qt−1 against t, respectively.
Isotherm models and thermodynamic study
Starting from the isotherms, it is possible to obtain the maxi-
mum amount adsorbed by the adsorbent mass and to calculate
the parameters related to the thermodynamic adsorption prop-
erties. The isothermal models studied were Langmuir (Eq. 4)
and Freundlich (Eq. 5) (Konggidinata et al. 2017) that allowed
inferring in the adsorption mechanism and in the adsorbent
characteristics.
C eq 1 C eq
¼ þ ð4Þ
qe qmax K L qmax
1
lnqe ¼ lnK F þ lnC eq ð5Þ
n
where Ceq (mg L−1) is the equilibrium concentration, qe
(mg g−1) is the amount adsorbed by adsorbent mass, qmax
(mg g−1) is the maximum adsorbed per adsorbent mass, and
K L (L mg −1 ) is the Langmuir adsorption constant; K F
(mg−(1/n) g−1L(1/n)) and n are Freundlich isotherm constants
for a given system at a specific temperature. qmax and KL were
calculated from the slope and intercept of plot of Ceq qe−1
against Ceq, while n and KF were calculated from the slope
and intercept of plot of ln qe against ln Ceq, respectively.
28625 Environ Sci Pollut Res (2019) 26:28622–28632

Table 2 Granulometric analysis

of in natura clay Mesh Upper diameter (mm) Bottom diameter (mm) Mass retained (g) Fraction retained (x%)

− 32 + 48 0.500 0.295 0.040 0.040

− 48 + 60 0.295 0.250 0.060 0.060
− 60 + 100 0.250 0.149 0.220 0.220
− 100 + 200 0.149 0.074 18.520 18.520
− 200 0.074 0.000 81.160 81.160

Three thermodynamic parameters were studied: Gibbs free
energy (ΔG°), enthalpy change (ΔH°), and entropy change
(ΔS°). The values of ΔH° and ΔS° were calculated from the
Eq. 7 (Ratnamala and Brajesh 2013), whereas Gibbs free en-
ergy was obtained by Eq. 8 (Konggidinata et al. 2017).
K ads ¼ ρw K L
ΔS ° ΔH °
lnK ads ¼ − ð7Þ
R RT
ΔG° ¼ ΔH ° −TΔS °
1 nm in width, and is considered a nanoparticulate material.
Clay classification on sieves with smaller openings guarantees
the attainment of free clay impurities, such as quartz and ka-
olinite, which are naturally found on this type. Besides that, a
granulometry with great fines presence provides the capacity
for cation exchange and a specific area increasing (Ferreira
ð6Þ 2009). Therefore, the sieve fraction 0.074 mm (200 mesh),
corresponding to 81% of the sample, it was selected for the
kinetic and thermodynamic tests in order to standardize the
adsorbent granulometry effect in the adsorption process.
ð8Þ

where Kads is the equilibrium constant, ρw is the water density Characterizations

(mg L−1), R the ideal gas constant (8.314 J/mol K), T the
absolute temperature (K), ΔS° (KJ mol−1 K−1), ΔG°, and
ΔH° (KJ mol−1) (Frantz et al. 2017). The ΔH° and ΔS°
values were calculated from the slope and intercept, respec-
tively of plot of ln Kads against T−1, by the Van’t Hoff’s
method.
Results and discussion
Granulometric classification
The data of granulometric analysis are shown in Table 2.
The bentonite is composed of submicrometric lamellar par-
ticles with sizes in the order of 100 to 200 nm in length and
Figure 1 shows the X-ray in natura and calcined clay
diffractogram. It can be observed that the in natura clay peak
2θ = 6.52° is observed in 2θ = 8.24° in the calcined clay.
These peaks represent the basal interplanar distance of the
montmorillonite which could be calculated by Bragg’s Law.
Following this perspective, it was found that the interplanar
distance was 13.53 Å for the in natura clay and reduced to
10.72 Å after the thermal clay treatment. This result was
shown to be consistent since it indicates plane interlayer dis-
tances (d001) reductions due to the hydration water elimination
from interlamellar cations (Rossetto et al. 2009). It happens
because at 500 °C, the mineral clay dehydration and dehy-
droxylation causes structural alteration and mass loss

Fig. 1 X-ray in natura and calcined clay diffractogram Fig. 2 Nitrogen adsorption and desorption isotherms at − 196.5 °C
Environ Sci Pollut Res (2019) 26:28622–28632
Fig. 3 Increase in intrusion (cm3 g−1) versus pore diameter (nm) on
bentonite clay
(Bojemueller et al. 2001). In addition, the system can be ap-
plied in fixed bed, as the basal spacing reduction minimizes
the clay expansion in water, preventing the column filling and
effluent flow passage.
Through this work, by BET analysis, it can be inferred that
the N2 adsorption isotherms in natura and calcined bentonite
clay would from type II, as shown in Fig. 2, according the
updated classification of isotherms of physisorption was pre-
sented by Thommes et al. (2015) on his IUPAC (International
Union of Pure and Applied Chemistry) technical report. The
type II isotherm presents itself in the form of S or sigmoidal,
being found in non-porous solids or with larger pores than
micropores (Vieira et al. 2010). Another characteristic of this
model is in unrestricted monolayer adsorption to high values
of p p0−1 and the thickness of multilayered sound increases
without limits when p p0−1 = 1. The point B, which marks the
beginning of the section approximately linear, represents the
end of monolayer coverage. A more curvature, at point B,
means that there is a large overlap monolayer coverage and
the beginning of multilayer adsorption. The hysteresis loop
shape that was found is very similar to H4 type, suggest-
ing that the adsorption is more pronounced at low values
of p p0−1, being associated with the micropore completion.
In addition, the H4 type is found in crystals of some zeolites,
some mesoporosos, and micro-mesoporosos (Thommes et al.
2015).
The IUPAC (1985) classifies in your reporting the
pore diameter as those smaller than 2 nm micropores,
Table 3 Structural parameters of
natural bentonite and calcined Clay Surface area
−1
2
(m g )
Natural 46.177
Calcined 30.299
28626
mesoporous those comprising between 2 and 50 nm di-
ameter and finally macropores, those greater than 50 nm.
As shown in Fig. 3, it can be noticed the predominance
of mesoporous in natura and calcined clays. The
mesopority bentonite clay result was also found by
Bertagnolli et al. (2011).
The values obtained for the surface area by the BET meth-
od and pore volume for samples of in natura and calcined clay
are shown in Table 3. From the N2 adsorption isotherms, the
micropore volume was obtained by reading the volume
adsorbed at p p0−1 = 0.10 and the mesopore volume given by
the value found in p p0−1 = 0.95 subtracted the value in
p p0−1 = 0.10 (Gañán-Gómez et al. 2006). The calcination
contributed to the surface area reduction and volume of mi-
cropore and mesopore, which also occurs at the pore collapse
structure (Anadão et al. 2014; Auta and Hameed 2012).
The electronic microscopes have the function of observing
the morphological aspects of the materials surface, with a
large increase (in the order of 2 to 5 nm) and good spatial
resolution. In this way, they provide pictures with very easy
interpretation. Thus, analyzing the micrographs, Fig. 4, it was
possible to note a typical lamellar morphology of the benton-
ite, both in natura and calcined clay. Structural collapse after
calcination was visible, as it can be viewed in Fig. 4a and b, in
which the clay presented an Bexpanded^ appearance when
compared to Fig. 4d and e, which showed to be more
compacted. This aspect prove the interllamelar spacing reduc-
tion presented in the analysis of the XRD and it is in line with
the BET result, since the structure collapse favors the material
surface area reduction. It was also possible to notice a slight
increase in surface roughness after thermal treatment, when
observing Fig. 4c and f (Anadão et al. 2014; Nones et al. 2015;
Rossetto et al. 2009).
The FTIR spectra were used to evaluate the group chemical
bonds in bentonite samples, before and after calcination, as
illustrated in Fig. 5. Tracks from bands between 470 and
1120 cm−1 correspond to the filosilicate structure, which is
associated with the elongation and angular deformation of
Si–O–Si and Si–O–Al. Such vibrations occur within the crys-
talline structures and are not affected by other cations present
in all cuts (Li et al. 2008). In this track, we observed three
relevant spectra: stretching of the Si–O bond in the 1120 and
1040 cm−1, circular deformation of Si–O around 470 cm−1,
octahedral layers represent in the range between 790 and
800 cm−1 (Bertagnolli et al. 2011). The range of 1625–
R2 Volume of micropore Volume of mesopore
(cm3 g−1) (cm3 g−1)
0.999 11.837 16.224
0.999 7.684 14.943
28627
Fig. 4 Micrographs clay samples: in natura with the resolution 2 μm (a), 1 μm (b), and 500 nm (c); calcined with resolution 2 μm (d), 1 μm (e), and
500 nm (f)
1635 cm−1 corresponds to the H–O–H angular deformation,
while the 3500 to 3645 cm−1 corresponds to O–H stretching
(Xu et al. 2000). The range intensity has been reduced by
calcination. This suggests the water and silicon displacement
caused by thermal treatment.
Fig. 5 FTIR spectrum in natura and calcined bentonite clay
Environ Sci Pollut Res (2019) 26:28622–28632
pH effect
For pH (3 to 10) effect analysis, the experiment was per-
formed in acid and alkaline medium, maintaining the initial
concentration of RB of 400 mg L−1. It can be seen in Fig. 6
that the pH reduction slightly favored the RB dye increased
removal. Below pH 3.5, Rhodamine B molecules are in the
Fig. 6 Kinetic study to evaluate the pH variation effect (3, 6, and 10) on
the RB adsorption (400 mg L−1) in calcined bentonite (1 g L−1) at 25 °C
Environ Sci Pollut Res (2019) 26:28622–28632 28628

Fig. 8 Adsorption isotherms of RB in calcined clay (1 g L−1), for a range

Fig. 7 Kinetic study to evaluate the initial concentration variation effect
(300, 400, and 500 mg L−1) on the RB adsorption in calcined bentonite
(1 g L−1), pH 3 at 25 °C
monomeric form, so that the molecule can easily go into ad-
sorbent pores. Above pH 3, Rhodamine B in water takes the
zwitterionic form, in which there is an aggregation of
Rhodamine B molecules, resulting in larger molecules.
In this way, the input of this molecule inside the pores
is hampered, reducing the adsorption (Anandkumar and
Mandal 2011; Ma et al. 2016).
Initial concentration effect
The initial concentration effect study was performed by vary-
ing the RB concentration of 300 to 500 mg L−1, maintaining
pH 3 and 25 °C. Through Fig. 7 analysis, it is observed that the
initial concentration increasing favors a better dye adsorption.
It can be explained by the fact that the initial concentration
enlargement, a driving force for the occurrence of adsorption
increases (Goel et al. 2005), furthering the mass transfer of
dye from the solution to the surface of the adsorbent.
of dye concentration 350 to 600 mg L−1, at temperatures of 15, 25, and
35 °C, at pH 3
The experimental data were fitted to the pseudo-first order
and pseudo-second order. The best-correlated model was the
pseudo-second order, as can be seen in Table 4. This model is
based on the adsorption capacity of the solid phase and con-
siders that the driving force of the adsorption is the difference
between the solid phase concentration at any time and at equi-
librium (Mesquita et al. 2017).
Adsorption isotherms
The adsorption isotherms were performed at the initial con-
centration range of 350–600 mg L−1 at pH 3, at 15, 25, and
35 °C temperatures. The isotherms are shown in Fig. 8 and
from these data, it was possible to determine the thermody-
namic properties and the best correlated isotherm model.
It can be seen in Table 5 the Langmuir and Freundlich
correlations and the respective values of the calculated param-
eters of each model. Thus, it can be observed that the exper-
imental data were better fitted by the Langmuir model,

Table 4 Parameters and fit values of pseudo-first and pseudo-second order to the experimental data obtained by the kinetic adsorption assays of RB in
calcined clay

Parameters Pseudo-first order Pseudo-second order

qe (mg g−1) k1 (min−1) R2 qe (mg g−1) k2 (g mg−1 min−1) R2

pH
3 65.171 0.028 0.568 400.000 0.002 0.999
6 128.161 0.016 0.732 377.358 0.001 0.998
10 112.739 0.023 0.830 381.679 0.002 0.999
Initial concentration
(mg L−1)
300 113.309 0.322 0.838 319.488 0.001 0.999
400 65.171 0.028 0.568 400.000 0.002 0.997
500 75.776 0.025 0.852 500.000 0.002 0.999
28629 Environ Sci Pollut Res (2019) 26:28622–28632

Table 5 Adsorption parameters for Langmuir and Freundlich models Table 7 Thermodynamic Rhodamine B adsorption in calcined
RB clay in batch fit bentonite parameters

Isotherms Parameter 15 °C 25 °C 35 °C Parameter 15 °C 25 °C 35 °C

Langmuir Kads × 10 6.30 9.60
(L g−1)
qmax 467.29 483.09
(mg g−1)
R2 0.99 0.99
Freundlich KF 329.60 378.50
(mg−(1/n) g−1 L(1/n))
n 13.62 20.17
R2 0.93 0.85
according to the coefficient of determination found (R2). The
Langmuir model admits that adsorption is homogeneous and
monolayer, occurring only in finite numbers of identical and
equivalent sites without interaction between adsorbed mole-
cules (Patil et al. 2016). In addition, it was observed that the
maximum amount adsorbed and the Langmuir adsorption
constant were favored with increasing temperature. This can
be explained by the fact that the increase in temperature can
lead to the increase of the kinetic energy and the mobility of
the adsorbate species, increasing the rate of intraparticle dif-
fusion of adsorbate (Jimenez et al. 2004), thus furthering the
adsorption. This can also be observed in Fig. 8.
Table 6 shows the adsorption capacity of other adsorbents
widely used in RB retention. Making a comparison of the
maximum adsorbed amount per gram of adsorbent found by
the Langmuir isotherm (552.49 mg g−1), it can be seen that the
calcined bentonite is an efficient adsorbent in dye removal,
besides having low-cost, it also has desirable characteristics
for treatment of large effluent volume.
The thermodynamic parameters, enthalpy, entropy, and
Gibbs energy were studied to understand the effect of temper-
ature on adsorption. The data obtained are shown in Table 7.
As it can be observed, positive values of ΔH° were found for
different RB concentrations indicating the endothermic nature
of the interactions between adsorbent and adsorbate. This
trend is confirmed by examining Fig. 8 and Table 5 which
show that with increasing temperature, there was an adsorp-
tive increasing capacity. Medium positive values of ΔS°
18.30 ΔH° (KJ mol−1) 19.33 39.82 58.97
ΔS° (KJ mol−1 K−1) 0.17 0.24 0.31
552.49
ΔG° (KJ mol−1) − 31.98 − 34.12 − 36.92
0.99
403.90
favored the disorder increase and randomness at the solid so-
11.26 lution interface. The ΔG° was negative and increased in mod-
0.88 ulus with increasing temperature, indicating that the adsorp-
tion process is spontaneous and more favorable at higher tem-
peratures (Nascimento et al. 2014).
Conclusion
The study showed that the clay can be used as Rhodamine B
adsorbent in aqueous solutions, being efficient in dye removal
and low-cost compared to other adsorbents and retention
methods. The bentonite clay was submitted to calcination
which is a simple treatment for modifying the structure of
the material and which results in the improvement of mechan-
ical properties, minimization of expansion in water, allowing
it to be used in fixed bed columns. Besides loss of hydration
water, which caused the collapse of the structure and, conse-
quently, reducing the surface area and pore volume, but without
changing the morphology and chemical composition of the
clay in a significant way. At this paper, it was possible to con-
clude that the Rhodamine B adsorption was favored at acid pH
and the increase of the initial dye concentration, increasing the
adsorption rate. The analysis made of kinetics adsorption re-
vealed that the data were better correlated to the pseudo-second
order model (R2 > 0.99). The Langmuir isotherm obtained a
better fitted (R2 > 0.99), showing that the adsorption occurs in
monolayer and homogeneously, in addition to obtaining a max-
imum adsorption capacity of 552.49 mg g−1. Going through
thermodynamic parameters, it can be inferred that the adsorp-
tion was endothermic (ΔH° from 19.33 to 58.97 KJ mol−1) and
spontaneous (ΔG° from − 31.98 to − 36.92 KJ mol−1).

Table 6 Langmuir adsorptive

comparison capacities of isotherm Adsorbent pH qmax (mg g−1) References
for RB in other adsorbents
Activated carbon – 478.5 Ding et al. (2014)
Fe-montmorillonite 4 258.76 Ma et al. (2016)
Fe-bentonite 5 98.62 Hou et al. (2011)
Sodium montmorillonite 7 42.19 Selvam et al. (2008)
Acid-treated montmorillonite 6.9 188.67 Bhattacharyya et al. (2014)
Acid-treated kaolinite 6.9 23.70 Bhattacharyya et al. (2014)
Environ Sci Pollut Res (2019) 26:28622–28632
Publisher’s note Springer Nature remains neutral with regard to jurisdic-
tional claims in published maps and institutional affiliations.
References
Alver E, Metin AÜ (2012) Anionic dye removal from aqueous solutions
using modified zeolite: adsorption kinetics and isotherm studies.
Chem Eng J 200-202:59–67. https://doi.org/10.1016/j.cej.2012.06.
038
Anadão P, Pajolli ILR, Hildebrando EA, Wiebeck H (2014) Preparation
and characterization of carbon/montmorillonite composites and
nanocomposites from waste bleaching sodium montmorillonite clay.
Adv Powder Technol 25:926–932. https://doi.org/10.1016/j.apt.
2014.01.010
Anandkumar J, Mandal B (2011) Adsorption of chromium (VI) and
Rhodamine B by surface modified tannery waste: kinetic mechanis-
tic and thermodynamic studies. J Hazard Mater 186:1088–1096.
https://doi.org/10.1016/j.jhazmat.2010.11.104
Auta M, Hameed BH (2012) Modified mesoporous clay adsorbent for
adsorption isotherm and kinetics of methylene blue. Chem Eng J
198-199:219–227. https://doi.org/10.1016/j.cej.2012.05.075
Auta M, Hameed BH (2014) Chitosan-clay composite as highly effective
and low-cost adsorbent for batch and fixed-bed adsorption of meth-
ylene blue. Chem Eng J 237:352–361. https://doi.org/10.1016/j.cej.
2013.09.066
Baddouh A, Bessegato GC, Rguiti MM, El Ibrahimi B, Bazzi L, Hilali M,
Zanoni MVB (2018) Electrochemical decolorization of Rhodamine
B dye: influence of anode material, chloride concentration and cur-
rent density. J Environ Chem Eng 6:2041–2047. https://doi.org/10.
1016/j.jece.2018.03.007
Banat IM, Nigam P, Singh D, Marchant R (1996) Microbial decoloriza-
tion of textile-dye containing effluents: a review. Bioresour Technol
58:217–227. https://doi.org/10.1016/S0960-8524(96)00113-7
Bentahar S, Dbik A, El Khomri M, El Messaoudi N, Lacherai A (2018)
Removal of a cationic dye from aqueous solution by natural clay.
Groundw Sustain Dev 6:255–262. https://doi.org/10.1016/j.gsd.
2018.02.002
Bertagnolli C, Kleinübing SJ, da Silva MGC (2011) Preparation and
characterization of a Brazilian bentonite clay for removal of copper
in porous bed. Appl Clay Sci 53:73–79. https://doi.org/10.1016/j.
clay.2011.05.002
Bhatnagar A, Jain AK (2005) A comparative adsorption study with dif-
ferent industrial wastes as adsorbents for the removal of cationic
dyes from water. J Colloid Interface Sci 281:49–55. https://doi.org/
10.1016/j.jcis.2004.08.076
Bhattacharyya KG, SenGupta S, Sarma GK (2014) Interactions of the
dye, Rhodamine B with kaolinite and montmorillonite in water.
Appl Clay Sci 99:7–17. https://doi.org/10.1016/j.clay.2014.07.012
Bojemueller E, Nennemann A, Lagaly G (2001) Enhanced pesticide ad-
sorption by thermally modified bentonites. Appl Clay Sci 18:277–
284. https://doi.org/10.1016/S0169-1317(01)00027-8
Chuah TG, Jumasiah A, Azni I, Katayon S, Choong SYT (2005) Rice
husk as a potentially low-cost biosorbent for heavy metal and dye
removal: an overview. Desalination 175:305–316. https://doi.org/
10.1016/j.desal.2004.10.014
Clarke EA, Anliker R (1980) Organic dyes and pigments. Anthropogenic
Compounds 3:181–215. https://doi.org/10.1007/978-3-540-38,522-
6_7
De Gisi S, Lofrano G, Grassi M, Notarnicola M (2016) Characteristics
and adsorption capacities of low-cost sorbents for wastewater treat-
ment: a review. Sustain Mater Technol 9:10–40. https://doi.org/10.
1016/j.susmat.2016.06.002
Ding L, Zou B, Gao W, Liu Q, Wang Z, Guo Y, Wang X, Liu Y (2014)
Adsorption of Rhodamine-B from aqueous solution using treated
28630
rice husk-based activated carbon. Colloids Surf A Physicochem
Eng Asp 446:1–7. https://doi.org/10.1016/j.colsurfa.2014.01.030
Fernandes AN, Almeida CAP, Menezes CTB, Debacher NA, Sierra
MMD (2007) Removal of methylene blue from aqueous solution
by peat. J Hazard Mater 144:412–419. https://doi.org/10.1016/j.
jhazmat.2006.10.053
Ferreira HS (2009) Optimization of the organophilization process of ben-
tonites for their use in non-aqueous drilling fluids. Dissertation,
Federal University of Campina Grande (in Portuguese)
Fogler HS (2009) Elements of chemical reaction engineering. Pearson
Education, USA (in Portuguese)
Frantz TS, Júnior NS, Quadro MS, Andreazza R, Barcelos AA, Júnior
TRSC, Pinto LAA (2017) Cu(II) adsorption from copper mine water
by chitosan films and the matrix effects. Environ Sci Pollut Res 24:
5908–5917. https://doi.org/10.1007/s11356-016-8344-z
Gaikwad RW, Misal AS (2010) Sorption studies of methylene blue on
silica gel. Int J Chem Eng Appl 1:342–345
Gañán-Gómez J, Macías-García A, Díaz-Díez MA, González-García C,
Sabio-Rey E (2006) Preparation and characterization of activated
carbons from impregnation pitch by ZnCl2. Appl Surf Sci 252:
5976–5979. https://doi.org/10.1016/j.apsusc.2005.11.011
Goel J, Kadirvelu K, Rajagopal C, Garg VK (2005) Removal of lead(II)
by adsorption using treated granular activated carbon: batch and
column studies. J Hazard Mater 125:211–220. https://doi.org/10.
1016/j.jhazmat.2005.05.032
Guibal E, McCarrick P, Tobin JM (2003) Comparison of the sorption of
anionic dyes on activated carbon and chitosan derivatives from di-
lute solutions. Sep Sci Technol 38:3049–3073. https://doi.org/10.
1081/SS-120022586
Gupta GS, Prasad G, Singh VN (1990) Removal of chrome dye from
aqueous solutions by mixed adsorbents: fly ash and coal. Water Res
24:45–50. https://doi.org/10.1016/0043-1354(90)90063-C
Han R, Wang Y, Zou W, Wang Y, Shi J (2007) Comparison of linear and
nonlinear analysis in estimating the Thomas model parameters for
methylene blue adsorption onto natural zeolite in fixed-bed column.
J Hazard Mater 145:331–335. https://doi.org/10.1016/j.jhazmat.
2006.12.027
Han R, Wang Y, Zhao X, Wang Y, Xie F, Cheng J, Tang M (2009)
Adsorption of methylene blue by phoenix tree leaf powder in a
fixed-bed column: experiments and prediction of breakthrough
curves. Desalination 245:284:297–284:297. https://doi.org/10.
1016/j.desal.2008.07.013
Hayat H, Mahmood Q, Pervez A, Bhatti ZA, Baig AS (2015)
Comparative decolorization of dyes in textile wastewater using bio-
logical and chemical treatment. Sep Purif Technol 154:149–153
Hou MF, Ma CX, Zhang WD, Tang XY, Fan YN, Wan HF (2011)
Removal of rhodamine B using iron-pillared bentonite. J Hazard
Mater 186:1118–1123. https://doi.org/10.1016/j.jhazmat.2010.11.
110
Huang R, Zhang L, Hu P, Wang J (2016) Adsorptive removal of Congo
red from aqueous solutions using crosslinked chitosan and
crosslinked chitosan immobilized bentonite. Int J Biol Macromol
86:496–504. https://doi.org/10.1016/j.ijbiomac.2016.01.083
Iida Y, Kozuka T, Tuziuti T, Yasui K (2004) Sonochemically enhanced
adsorption and degradation of methyl orange with activated alu-
minas. Ultrason 42:635–639. https://doi.org/10.1016/j.ultras.2004.
01.092
International Union of Pure and Applied Chemistry – IUPAC (1985)
Physical chemistry division commission on colloid and surface
chemistry including catalysis. Reporting physisorption data for
gas/solid systems with special reference to the determination of sur-
face area and porosity. Pure Appl Chem 57:603–619. https://doi.org/
10.1351/pac198557040603
Jimenez RS, Bosco SMD, Carvalho WA (2004) Removal of heavy metals
from aqueous effluents by natural zeolite – influence of temperature
and pH on adsorption in monoelement systems (in portuguese).
28631
New Chemistry 27:734–738. https://doi.org/10.1590/S0100-
40422004000500011
Kadirvelu K, Kavipriya M, Karthika C, Radhika M, Vennilamani N,
Pattabhi S (2003) Utilization of various agricultural wastes for acti-
vated carbon preparation and application for the removal of dyes and
metal ions from aqueous solutions. Bioresour Technol 87:129–132
Karthikeyan KT, Jothi Venkatachalam K (2014) Removal of acid yellow
17 dye from aqueous solution using turmeric industrial waste acti-
vated carbon. J Environ Nanotechnol 3:69–80. https://doi.org/10.
13074/jent.2014.03.142070
Kausar A, Igbal M, Javed A, Aftab K, Nazli Z, Bhatti HN, Nouren S
(2018) Dyes adsorption using clay and modified clay: a review. J
Mol Liq 256:395–407. https://doi.org/10.1016/j.molliq.2018.02.
034
Khamparia S, Jaspal DK (2017) Xanthium strumarium L. seed hull as a
zero cost alternative for Rhodamine B dye removal. J Environ
Manag 197:498–506. https://doi.org/10.1016/j.jenvman.2017.03.
099
Khan TA, Dahiya S, Ali I (2012) Use of kaolinite as adsorbent: equilib-
rium, dynamics and thermodynamic studies on the adsorption of
Rhodamine B from aqueous solution. Appl Clay Sci 69:58–66.
https://doi.org/10.1016/j.clay.2012.09.001
Kittinaovarat S, Kansomwan P, Jiratumnukul N (2010) Chitosan/
modified montmorillonite beads and adsorption Reactive Red 120.
Appl Clay Sci 48:87–91. https://doi.org/10.1016/j.clay.2009.12.017
Konggidinata MI, Chao B, Lian Q, Subramaniam R, Zappi M, Gang DD
(2017) Equilibrium, kinetic and thermodynamic studies for adsorp-
tion of BTEX onto ordered mesoporous carbon (OMC). J Hazard
Mater 336:249–259. https://doi.org/10.1016/j.jhazmat.2017.04.073
Li Z, Jiang WT, Hong H (2008) An FTIR investigation of
hexadecyltrimethylammonium intercalation into rectorite.
Spectrochim Acta Part A 71:1525–1534. https://doi.org/10.1016/j.
saa.2008.05.015
Lian L, Guo L, Guo C (2009) Adsorption of Congo red from aqueous
solutions onto Ca-bentonite. J Hazard Mater 161:126–131. https://
doi.org/10.1016/j.jhazmat.2008.03.063
Ma L, Xi Y, He H, Ayoko GA, Zhu R, Zhu J (2016) Efficiency of Fe-
montmorillonite on the removal of Rhodamine B and hexavalent
chromium from aqueous solution. Appl Clay Sci 120:9–15. https://
doi.org/10.1016/j.clay.2015.11.010
Mesquita PL, Cruz MAP, Souza CR, Santos NTG, Nucci ER, Rocha SDF
(2017) Removal of refractory organics from saline concentrate pro-
duced by electrodialysis in petroleum industry using bone char.
Adsorption 23:983–997. https://doi.org/10.1007/s10450-017-9917-
y Removal of nickel on Bofe bentonite calcined clay in porous bed.
Mishra G, Tripathy M (1993) A critical review of the treatments for
decolourization of textile effluent. Colourage 40:35–45
Nascimento RF, Lima ACA, Vidal CB, Melo DQ, Raulino GSC (2014)
Adsorption: theoretical aspects and environmental applications.
University Press, Brazil (in portuguese)
Nones J, Nones J, Riella HG, Poli A, Trentin AG, Kuhnen NC (2015)
Thermal treatment of bentonite reduces aflatoxin b1 adsorption and
affects stem cell death. Mater Sci Eng C 55:530–537. https://doi.org/
10.1016/j.msec.2015.05.069
Öztürk A, Malkoc E (2014) Adsorptive potential of cationic Basic Yellow
2 (BY2) dye onto natural untreated clay (NUC) from aqueous phase:
mass transfer analysis, kinetic and equilibrium profile. Appl Surf Sci
299:105–115. https://doi.org/10.1016/j.apsusc.2014.01.193
Patil SP, Bethi B, Sonawane GH, Shrivastava VS, Sonawane S (2016)
Efficient adsorption and photocatalytic degradation of Rhodamine B
dye over Bi2O3-bentonite nanocomposites: a kinetic study. J Ind Eng
Chem 34:356–363. https://doi.org/10.1016/j.jiec.2015.12.002
Pereira FAR, Sousa KS, Cavalcanti GRS, França DB, Queiroga LNF,
Santos IMG, Fonseca MG, Jaber M (2017) Green biosorbents based
on chitosan-montmorillonite beads for anionic dye removal. J
Environ Sci Pollut Res (2019) 26:28622–28632
Environ Chem Eng 5:3309–3318. https://doi.org/10.1016/j.jece.
2017.06.032
Punzi M, Anbalagan A, Börner RA, Svensson B, Jonstrup M, Mattiasson
B (2015) Degradation of a textile azo dye using biological treatment
followed by photo-Fenton oxidation: evaluation of toxicity and mi-
crobial community structure. Chem Eng J 270:290–299. https://doi.
org/10.1016/j.cej.2015.02.042
Rammel RS, Zatiti AS, Jamal MMEL (2001) Biosorption of crystal violet
by chaetophora elegans alga. J Chem Technol Metall 46:283–292
Ratnamala GM, Brajesh K (2013) Biosorption of remazol navy blue dye
from as aqueous solution using Pseudomonas Putida. International
Journal of Science, Environment and Technology 2:80–89
Robinson T, McMullan G, Marchant R, Nigam P (2001) Remediation of
dyes in textile effluent: a critical review on current treatment tech-
nologies with a proposed alternative. Bioresour Technol 77:247–
255
Rossetto E, Beraldin R, Penha FG, Pergher SBC (2009) Characterization
of bentonites and diatomite clays and their application as adsorbents.
New Chemistry 32:2064–2067 (in portuguese)
Saha TK, Bhoumik NC, Karmaker S, Ahmed MG, Ichikawa H,
Fukumori Y (2011) Adsorption characteristics of reactive black 5
from aqueous solution onto chitosan. Clean Soil Air Water 39:984–
993. https://doi.org/10.1002/clen.201000315
Salleh MAM, Mahmoud DK, Karim WAWA, Idris A (2011) Cationic and
anionic dye adsorption by agricultural solid wastes: a comprehen-
sive review. Desalination 280:1–13. https://doi.org/10.1016/j.desal.
2011.07.019
Selvam PP, Preethi S, Basakaralingam P, Thinakaran N, Sivasamy A,
Sivanesan S (2008) Removal of Rhodamine B from aqueous solu-
tion by adsorption onto sodium montmorillonite. J Hazard Mater
155:39–44. https://doi.org/10.1016/j.jhazmat.2007.11.025
Singh NB, Nagpal G, Agrawal S, Rachna (2018) Water purification by
using adsorbents: a review. Environ Technol Innov 11:187–240.
https://doi.org/10.1016/j.eti.2018.05.006
Thommes M, Kaneko K, Neimark A, Olivier JP, Reinoso FR, Rouquerol
J, Sing KSW (2015) Physisorption of gases, with special reference
to the evaluation of surface area and pore size distribution (IUPAC
technical report). Pure Appl Chem 87:1051–1069. https://doi.org/
10.1515/pac-2014-1117
Vakili M, Rafatullah M, Salamatinia B, Abdullah AZ, Ibrahim MH, Tan
KB, Gholami Z, Amouzgar P (2014) Application of chitosan and its
derivatives as adsorbents for dye removal from water and wastewa-
ter: a review. Carbohydr Polym 113:115–130. https://doi.org/10.
1016/j.carbpol.2014.07.007
Vieira MGA, Almeida Neto AF, Gimenes ML, da Silva MGC (2010)
J Hazard Mater 176:109–118. https://doi.org/10.1016/j.jhazmat.
2009.10.128
Wang L, Zhang J, Wang A (2008a) Removal of methylene blue from
aqueous solution using chitosan-g-poly (acrylic acid)/montmorillon-
ite superadsorbent nanocomposite. Colloids Surf A Physicochem
Eng Asp 322:47–53. https://doi.org/10.1016/j.colsurfa.2008.02.019
Wang XS, Zhou Y, Jiang Y, Sun C (2008b) The removal of basic dyes
from aqueous solutions using agricultural by-products. J Hazard
Mater 157:374–385. https://doi.org/10.1016/j.jhazmat.2008.01.004
Wang P, Cheng M, Zhang Z (2014) On different photodecomposition
behaviors of Rhodamine B on laponite and montmorillonite clay
under visible light irradiation. Journal of Saudi Chemical Society
18:308–316. https://doi.org/10.1016/j.jscs.2013.11.006
Xu W, Johnston CT, Parker P, Agnew SF (2000) Infrared study of water
sorption on Na-, Li-, Ca-, and Mg-exchanged (SWy-1 and SAz-1)
montmorillonite. Clay Clay Miner 48:120–131. https://doi.org/10.
1346/CCMN.2000.0480115
Yagub MT, Sen TK, Afroze S, Ang HM (2014) Dye and its removal from
aqueous solution by adsorption: a review. Adv Colloid Interf Sci
209:172–184. https://doi.org/10.1016/j.cis.2014.04.002
Environ Sci Pollut Res (2019) 26:28622–28632
Zeng S, Duan S, Tang R, Li L, Liu C, Sun D (2014) Magnetically sepa-
rable Ni0.6Fe2.4O4 nanoparticles as an effective adsorbent for dye
removal: synthesis and study on the kinetic and the thermodynamic
behaviors for dye adsorption. Chem Eng J 258:218–228. https://doi.
org/10.1016/j.cej.2014.07.093
Zheng Y, Yao G, Cheng Q, Yu S, Liu M, Gao C (2013) Positively
charged thin-film composite hollow fiber nanofiltration mem-
brane for the removal of cationic dyes through submerged fil-
28632
tration. Desalination 328:42–50. https://doi.org/10.1016/j.desal.
2013.08.009
Zhu R, Chen Q, Zhou Q, Xi Y, Zhu J, He H (2016) Adsorbents based on
montmorillonite for contaminant removal from water: a review.
Appl Clay Sci 123:239–258. https://doi.org/10.1016/j.clay.2015.
12.024