Chemical Physics Letters 802 (2022) 139758

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Chemical Physics Letters

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

Removal of methylene blue from water by ultrasound-assisted adsorption

using low-cost bentonites
Hakan Çiftçi
Department of Mining Engineering, Afyon Kocatepe University, Afyonkarahisar, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: This study focused on the comparison of ultrasound-assisted (UA) and conventional (shaking or stirring)
Adsorption adsorption techniques, taking into account the time-dependent adsorption capacities. Six different bentonite
Ultrasound samples were used as adsorbents, and methylene blue (MB) was used as adsorbate. Effects of pH, contact time,
Bentonite
MB initial concentration, and temperature on the UA-adsorption were also investigated. XRD analyzes showed
Montmorillonite
Methylene blue
that all the bentonite samples were mostly composed of montmorillonite clay minerals, while XRF analyzes
showed that the samples contained high percentage of silicon and aluminum oxides (≥70 wt%). Maximum zeta
potential values (37.1–42.1 mV) were measured at pH 12 and, to confirm this, maximum adsorption capacities
were also determined at this point. Ultrasound irradiation significantly increased the adsorption capacities of all
bentonite samples in the early stages. For example, the adsorption capacity of the B-1 bentonite sample was
measured as 388 mg/g by UA-adsorption at the first 5th minute, while it was 286 mg/g by conventional (C)
adsorption technique at the same time. All bentonite samples showed increasing adsorption capacity with
increased temperature confirming endothermic reaction. Maximum adsorption capacities of B-1, B-2, B-3, B-4, B-
5, and B-6 bentonite samples with the 96–100 % MB removal percentages at selected conditions (pH: 11–12,
temperature: 25 ◦ C, contact time: 60 min, and MB initial concentrations for B-1: 800, B-2: 700, B-3,4: 650, B-5:
600, and B-6: 500 mg/L) were measured as 398, 342, 320, 296, 288, and 243 mg/g, respectively. Pseudo-second-
order kinetic model and Langmuir isotherm model with higher correlation coefficients were found to be more
suitable to explain the adsorption of MB cations onto bentonites. In addition, maximum adsorption capacities of
B-1, B-2, B-3, B-4, B-5, and B-6 samples at 25 ◦ C calculated from Langmuir isotherm data determined as 500,
454.5, 400, 384.6, 370, and 357.1 mg/g, respectively.

1. Introduction methylene blue (MB) [17], adsorption of MB on acid-activated benton­

Removal of various toxic species from aqueous media by adsorption
method (wastewater purification) is an application that is the most
needed to ensure human and environmental health [1]. For this reason,
various inorganic and organic materials are used as adsorbents such as
activated carbon [2,3], zeolite [4,5], silica gel [6], nanomaterials [7,8],
activated alumina [9,10], polymers [11], and resins [12,13]. However,
many adsorbents’ high cost and regeneration difficulties, especially
activated carbon and nanomaterials, limit their use in adsorption.
Hence, low-cost and readily available adsorbents should be evaluated to
remove various harmful species from aqueous media [14,15]. In this
respect, clay minerals, especially bentonite, are among the most valu­
able adsorbents for removing cationic pollutants [16]. There are many
studies that investigated the adsorption properties of raw and modified
bentonite clays. Preparation of organo-bentonites for adsorption of
ites [18], adsorption of MB on chitosan/bentonite composites [19],
loading of betaxolol hydrochloride on bentonite [20], and adsorption
of chromium ions (III) with the help of bentonite clays [21] can be
shown as examples. In order to explain the adsorption mechanism of
various species on raw or modified clay minerals, the most commonly
used adsorbate type are synthetic dyes, especially MB. Thousands of
synthetic dyes have been discovered and widely used in the chemical,
food, textile, leather, pharmaceutical, and paper industries. These dyes
are highly toxic and difficult to degrade in natural environments due to
their complex structure. The dyed wastewaters resulting from the
various dyeing processes pose a severe problem for the environment and
human health. MB, one of the most used cationic dyes, is also associated
with severe environmental pollutants because of its high toxicity
[14,22,23]. Removal of MB from aqueous media was also investigated
too many times using raw, modified, and synthesis materials by

E-mail address: hciftci@aku.edu.tr.

https://doi.org/10.1016/j.cplett.2022.139758
Received 1 March 2022; Received in revised form 18 May 2022; Accepted 7 June 2022
Available online 9 June 2022
0009-2614/© 2022 Elsevier B.V. All rights reserved.
H. Çiftçi Chemical Physics Letters 802 (2022) 139758

conventional (C) adsorption (stirring or shaking) processes [24,25].
Apart from the C-adsorption, ultrasound-assisted (UA) adsorption of
various species has attracted interest in recent years and investigated by
several studies [26,27]. In general, significant increases in the amount
and efficiency of UA-adsorption were reported compared to C-adsorp­
tion [28–30]. According to the literature, there are few studies on UA-
adsorption, ultrasound irradiation was provided ultrasonic baths, ul­
trasound irradiation was applied continuously throughout the adsorp­
tion, and there is no study to investigate the adsorption of MB onto
bentonites. However, while it was determined that the adsorption ca­
pacity increased, there is no study reporting that the adsorption time
changed except for two studies [26,31]. For example, Zhang et al.
(2019) used a probe for ultrasound irradiation, and investigated the
removal of Congo red from aqueous solution by Mg-Al-CO3 layered
double hydroxide. Dye removal percent was found to be significantly
increased by the UA-adsorption technique compared to shaking and
stirring techniques. Apart from this, the adsorption equilibrium time
decreased to 25 min by UA-adsorption while it was 150 min when
stirring or shaking techniques were used. As important as increasing the
adsorption capacity is, decreasing the adsorption time is also very
important and necessary to increase the efficiency of continuous
adsorption processes. In this context, it is necessary to perform new
studies to decrease the adsorption time by using different ultrasound
irradiation techniques.
UA-adsorption of methylene blue on bentonites was investigated for
the first time in this study using different ultrasound irradiation appli­
cation. Unlike other studies, only 1 min of ultrasound irradiation was
applied at the beginning of the adsorption, using a powerful ultrasound
probe (280 W) instead of an ultrasonic bath to provide a higher amount
of adsorption in a much shorter time. Dispersion of clay samples in
aqueous media before adsorption using a powerful ultrasound probe is
an important application that seriously affects the adsorption time. Low
clay dispersion causes clay minerals to form agglomerates in the
aqueous media and turn into slime. In this case, the adsorption time
increases, and the capacity may decrease. This study compared C- and
UA-adsorption techniques to remove MB by six different bentonite
samples considering the adsorption time and capacities. The effects of
pH, contact time, initial MB concentration, and temperature on the UA-
adsorption technique were also investigated.
2. Experimental
using a laboratory scaled ring mill before all characterization analysis.
The elemental compositions of the samples were determined using a
Rigaku ZSX Primus II XRF (x-ray fluorescence) spectrophotometer. X-ray
diffraction (XRD) patterns were obtained at 40 kV with Cu-Ka radiation
(λ: 1.54184 Å) using a Shimadzu XRD-6000 device to determine
mineralogical components of the bentonite samples. Samples were
scanned at an angular range of 2–40◦ with a scan speed of 0.02◦ /step.
Particle size distributions were determined by the Malvern Master-sizer
2000 instrument using wet analysis apparatus as described in the pre­
vious study [32]. Zeta potential (ζ) is the measurable electric charge on
the surface of a solid particle in an aqueous media. It determines the
electrostatic repulsion forces between particles and, therefore, the sta­
bility of a colloidal system [32]. ζ analysis was performed in 10-2 M NaCl
solution using Malvern Nano-Z model zeta-meter device as described in
the previous study [33]. The pH of the dispersions was adjusted between
2 and 12 using diluted HCl and NaOH solutions when performing ζ
measurements versus pH.
2.2.2. Batch adsorption experiments
Batch adsorption experiments were performed using 100 mL Erlen­
meyer flasks. Firstly, all bentonite samples were dried at 35 ◦ C for 24 h
and then ground for 2 min using a laboratory scaled ring mill. 50 mL of
MB solution was added into a 100 mL beaker containing 0,1 g of
bentonite sample. The prepared mixture was immediately dispersed
using Hielscher UP400S ultrasonic homogenizer for 1 min at 280 Watts,
and then the pH of the mixture was adjusted using diluted HCl and
NaOH solutions. Finally, the mixture was transferred into an Erlenmeyer
flask and shaken using a GFL-1086 shaking water bath at 140 rpm for
180 min. After that, the adsorbent was separated from the solution by
centrifuge for 30 min at 9000 rpm using 25 mL centrifuge tubes. The
remained solution was analyzed for the residual MB determination by
Shimadzu UV-1240 spectrophotometer at 664 nm wavelength. The C-
adsorption process was also carried out in the same way without the
application of ultrasound irradiation. The percentage removal of MB and
the adsorption capacity at equilibrium were calculated using the
following Eqs. (1) and (2).
Ci − Ce
R(%) = *100 (1)
Ci
Ci − Ce
qe = *V (2)
m

2.1. Materials
Six different bentonite samples were obtained from six different
companies operating in various regions of Turkey. Table 1 shows the
regions and companies where bentonite samples were obtained. Meth­
ylene blue (C16H18ClN3S), sodium hydroxide (NaOH, >99%), and hy­
drochloric acid (HCl, 36%) were purchased from Merc Millopore
Cooperation.
where R is the removal percentage of MB adsorbate (%), ci is the initial
concentration of MB (mg/L), ce is the equilibrium concentration of MB
(mg/L), m is the adsorbent (bentonite) amount (g), V is the solution
amount (L), qe is the amount of adsorbed MB per unit adsorbent (mg/g).
3. Results and discussion
3.1. Characterization of bentonites

Elemental compositions provided from XRF analysis (Table 2)

2.2. Methods
Table 2
2.2.1. Characterization studies Elemental compositions of the bentonite samples.
The bentonite samples were dried at 35 ◦ C for 24 h and then ground
Component Content, wt.%

B-1 B-2 B-3 B-4 B-5 B-6

Table 1
Information on bentonite samples used in the study. SiO2 62.23 67.63 60.32 52.59 55.49 71.13
Al2O3 19.06 14.87 17.70 16.75 17.06 13.50
Label Region Company
Fe2O3 3.63 1.53 5.77 6.77 9.94 0.80
B-1 Reşadiye/Tokat/Turkey Karben Bentonite Co. MgO 2.70 3.51 2.89 2.89 1.69 3.12
B-2 Ünye/Ordu/Turkey Bentaş Bentonite Co. Na2O 2.61 0.46 2.46 1.09 1.91 0.24
B-3 Kalecik/Ankara/Turkey Çanbensan Bentonite Co. CaO 2.05 2.07 1.78 5.99 2.78 1.71
B-4 Enez/Edirne/Turkey Amcol Mineral Mining Co. K2O 0.65 0.56 1.30 2.02 0.76 0.91
B-5 Bozüyük/Bilecik/Turkey Esan Eczacıbaşı Industrial Minerals Co. LOI 6.30 8.82 5.87 9.90 7.89 8.12
B-6 Kurşunlu/Çankırı/Turkey Gökmenoğlu Bentonite Co.
LOI: loss of ignition.

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H. Çiftçi Chemical Physics Letters 802 (2022) 139758

showed that the bentonite samples had a high percentage of silicon and
aluminum oxides (≥70 wt%), indicating the possibility of clay minerals.
(Na2O + K2O)/(CaO + MgO) ratios of the samples (B-1,2,3,4,5,6) were
calculated as 0.69, 0.18, 0.8, 0.35, 0.60, and 0.24, respectively. The
values >0.33 can be attributed to Na-bentonites [32]. Therefore, B-1, B-
3, and B-5 samples can be classified as Na+ rich bentonites, while B-2, B-
4, and B-6 samples were Ca2+ rich bentonites.
The XRD patterns of the raw bentonite samples (Fig. 1) revealed that
the samples were mostly composed of montmorillonite and a small
amount of gang minerals such as feldspar, calcite, quartz, opal (C-T),
clinoptilolite (zeolite), kaolinite, and mica. B-1, B-3, and B-5 samples
represented characteristic reflections (2θ: 7.07◦ , 7.01◦ , 7.2◦ ) with the
d001 basal spacings of 12.4–12.6–12.3 Å, respectively. This indicates the
presence of Na+-rich smectites (montmorillonite, saponite, and non­
tronite), which was also confirmed by XRF analysis (Table 2). Basal
reflections of the samples at ~12.5 Å also indicate the dominance of Na+
as exchangeable cations occurred interlayers of smectites. B-2, B-4, and
B-6 samples represented characteristic reflections (2θ: 5.84◦ , 6.09◦ ,
5.88◦ ) with d001 basal spacing of 15.1–14.7–15.0 Å, respectively, con­
firming Ca2+-rich smectites [32,34]. The broader peaks of B-4 and B-5 Fig. 2. Particle size distributions of the bentonite samples.
samples at 2θ: 6–7◦ indicate a low crystallinity degree. Feldspar content
was determined to be higher in B-3 and B-4, while a significant amount
of quartz was seen only in B-3 when considering the reflection in­ Table 3
tensities. B-4 sample showed a significant amount of calcite which is in Particle size distributions of the bentonite samples.
good agreement with XRF analysis (Table 2; CaO: 5.99%). Opal (C-T) B-1 B-2 B-3 B-4 B-5 B-6
minerals were seen in all samples but small amounts in B-4 and B-5.
d10 (µm) 0.89 1.01 1.28 0.68 0.90 1.41
Particle size distributions (Fig. 2) revealed that raw bentonites d50 (µm) 3.08 3.29 3.92 3.56 4.48 3.95
contain large particles >10 µm, attributed to non-clay particles. Some of d90 (µm) 31.11 13.75 11.88 37.60 25.10 14.89
the particles above this size also consist of agglomerated clay particles.
As expected, all raw bentonite samples showed particle size distributions
which changed between 0.3 and 100 µm. d10, d50, and d90 values (Fig. 2 less than 5 µm, which is in good agreement with the definition of clay
and Table 3) indicate the cumulative volumes (10–50–90%) of particles minerals [35]. The minimum particle size for all samples was measured
smaller than certain particle size. For example, d90 of the B-5 sample to be around 300 nm.
means that 90% of the sample consists of particles with a size of less than Zeta potential (ζ) profiles (Fig. 3) revealed that the surface electro­
25.1 µm. The majority of the bentonite samples have a particle size of kinetic of bentonites is highly pH-dependent. It was proved once again
by ζ measurements that the surface of bentonite clay is negatively
charged. The samples showed negative ζ profiles ranging from − 22 mV
to − 42.1 mV as a function of pH. Maximum negative ζ value (− 42.1 mV)
was obtained by B-1 sample at pH 12. The point to note here is that all
samples showed a net negative surface charge even under the lowest pH
values. This can be explained by bentonites’ high cation exchange ca­
pacity and the penetration of hydronium ions into the clay layers [8].

Fig. 1. XRD patterns of the bentonite samples. Fig. 3. Zeta potential profiles of the bentonite samples as a function of pH.

3
H. Çiftçi
3.2. Effect of pH and ultrasound irradiation on the MB concentration
First of all, some tests were performed to determine the correct
definition of MB concentration in adsorption experiments. It was
investigated whether MB molecules undergo any change in concentra­
tion after exposure to acidic and alkaline medias, as well as ultrasound
irradiation. MB solutions of different concentrations were prepared and
the pH of these solutions was adjusted with dilute HCl and NaOH so­
lutions to examine the effect of pH on the MB concentration. Effect of
ultrasound irradiation was also investigated by applying ultrasound to
the solutions using Hielscher UP400S ultrasonic homogenizer for 1 min
at 280 Watts. Concentration measurements were then performed using
UV–vis spectrophotometer at a wavelength of 664 nm.
It was found that pH has no effect on the determination of MB in high
concentration MB solutions such as 500 and 1000 mg/L. In very low
concentration solutions (1–10 mg/L), the result was unchanged in
alkaline medium, and a slight increase in MB concentration was found in
acidic conditions (Table 4). Table 5 also revealed that ultrasound irra­
diation did not affect the MB concentration significantly.
3.3. Batch adsorption experiments
3.3.1. Comparison of ultrasound-assisted and conventional adsorption
Adsorption experiments were performed versus contact time while
pH, adsorbent concentration, and temperature were kept constant as
11–12, 2.0 g/L, and 25 ◦ C, respectively. Initial MB concentrations were
also kept constant as 800, 700, 650, 650, 600, and 500 mg/L for B-1, B-2,
B-3, B-4, B-5, and B-6 samples, respectively. Fig. 4 revealed that strong
ultrasound waves for 1 min at the beginning of the adsorption process
significantly affected the adsorption equilibrium time. In this situation,
observed in all bentonite samples, the adsorption equilibrium time was
determined to be between 30 and 60 min in UA-adsorption. In com­
parison, it was 90 min when the CA method (shaking) was used. Addi­
tionally, the adsorption rate was very fast when the UA-adsorption
technique was used, and 87–97 % MB removal was achieved for all
samples in the first 5 min. The succession of several events can explain
this. First, agglomerated clay particles are well dispersed quickly in the
aqueous media by strong ultrasound waves. Movements of MB mole­
cules and dispersed clay particles reach very high speeds under the effect
of ultrasound waves. As a result, the probability of encountering MB
molecules and clay particles in the media increases, and its duration
decreases. MB removal percentages varied between 60% and 80% in the
first 5 min when considering the C-adsorption technique. Most studies
that used the ultrasound waves provided by the ultrasonic bath during
the adsorption process and compared C- and UA-adsorption reported no
change in the adsorption equilibrium time [28–30]. The absence of any
change in the equilibrium time in these studies can be attributed to the
low-frequency ultrasound waves and the provision of these waves with a
bath instead of the probe. A study investigating MB adsorption onto
activated carbon using an ultrasound bath reported that the adsorption
equilibrium time decreased slightly with ultrasound irradiation [36].
Considering the adsorption capacities (Fig. 4), there was a slight in­
crease in the amount of adsorption in the UA-adsorption for B-2, B-3,
and B-4 samples. At the same time, there was no significant change for B-
1, B-5, and B-6 samples. This can be explained by the fact that these
Table 4
Effect of pH on the MB concentration.
MB concentration, (mg/L)
Conc., (mg/L) pH
2 4 7 10 12
1 1.19 1.10 1.013 0.99 1.05
10 10.24 10.18 9.96 9.87 9.92
500 498.8 500.6 500.2 500.4 501.2
1000 1001.2 1000.8 1000.0 999.6 999.4
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Chemical Physics Letters 802 (2022) 139758
Table 5
Effect of ultrasound irradiation on the MB concentration.
MB concentration, (mg/L)
Before ultrasound 1.1 9.8 103.7 498.2 1023.8
After ultrasound 1.1 9.9 103.6 500.6 1027.0
samples are completely dispersed in the aqueous media without the need
for ultrasound irradiation, and as a result, the active sites are completely
exposed, and therefore MB molecules are easily adsorbed onto and be­
tween the layers. The increase in adsorption amount in the UA-
adsorption technique can be explained by the increase in the surface
area as a result of the disintegration of clay agglomerates at first and
then partial exfoliation of the bentonite into nanosheets under the effect
of ultrasound waves. Furthermore, it can be said that ultrasound waves
acted as a driving force for MB molecules to penetrate towards in­
terlayers of clay particles. The increase in adsorption amount in UA-
adsorption compared to the C-adsorption was also reported by other
researchers [26,31,37,38]. In a study using ultrasound irradiation pro­
vided by a probe, the adsorption of Congo red onto layered double hy­
droxide was investigated. it was reported that the UA-adsorption
performed the best performance with the shortest adsorption equilib­
rium time of 2 h, while it was 5 h for either stirring or shaking [31]. As a
result, it can be said that the change in the adsorption rate and amount
differs according to the ultrasound irradiation technique, irradiation
time, and adsorbent type.
It can be clearly said that the degree of purity, chemical composition,
ζ value, and particle size distributions of bentonites are effective
together on their adsorption capacities when evaluated according to the
characterization test results. For example, the B-1 sample was charac­
terized as Na+ rich bentonite (Table 2), showed average quality purity
(Fig. 1), had average particle size distributions (Fig. 2), and showed
maximum ζ values (Fig. 3) relative to the other samples. As a result, it
showed maximum adsorption capacity (Fig. 4). While the result was
such, the B-6 sample exhibited the lowest adsorption capacity. At the
same time, it was determined as the purest sample according to the XRD
patterns (Fig. 1) compared to the other samples. Na+ rich bentonites are
known to have higher cation exchange capacity (amount of exchange­
able cations in the interlayers of clay particles) than Ca2+ rich benton­
ites. Consequently, the most important properties affecting the
adsorption capacity of bentonites are the ζ value and the cation ex­
change capacity. The higher the cation exchange capacity and ζ value,
the higher the adsorption capacity.
3.3.2. Effect of pH
The effect of pH on MB removal from aqueous media is of great
importance, as the pH value of the media determines the ζ value of the
adsorbent. ζ value, expressing the electrostatic charge on the surface of
particles, determines the electrostatic repulsion or attraction forces and
intensity between the adsorbate and the adsorbent. In MB adsorption
experiments at different pH values, contact time, adsorbent concentra­
tion, and temperature were kept constant as 24 h, 2.0 g/L, and 25 ◦ C,
respectively. Initial MB concentrations were also kept constant as 800,
700, 650, 650, 600, 500 mg/L for B-1, B-2, B-3, B-4, B-5, and B-6 sam­
ples, respectively. Fig. 5 revealed that the pH value of media has a sig­
nificant effect on the adsorption of MB ions onto bentonites which is in
good agreement with other studies [39–41].
The highest adsorption yields (95–100%) for all samples were ob­
tained at pH values between 11 and 12. The main reason for the high
adsorption amounts at high pH values is the strong electrostatic
attraction forces between the negatively charged adsorbent and the
cationic MB adsorbate. Maximum adsorption amounts of B-1,2,3,4,5,6
samples at pH: 11–12 were recorded as 397.7, 341.9, 320.1, 306.9,
288.3, and 243.0 mg/g, respectively. The optimum pH value was
selected to be between 11 and 12 for the ongoing adsorption
experiments.
H. Çiftçi
Fig. 4. Comparison of ultrasound-assisted adsorption (UA) and conventional adsorption (CA) techniques as a function of contact time and adsorption capacity.
3.3.3. Effect of contact time and MB initial concentration
Contact time was the most important investigated UA-adsorption
parameter in this study. Adsorbent concentration, pH, and tempera­
ture were kept constant as 2.0 g/L, 11–12, and 25 ◦ C, respectively, in MB
adsorption experiments at different contact times. Initial MB concen­
trations were also kept constant as 800, 700, 650, 650, 600, and 500 mg/
L for B-1, B-2, B-3, B-4, B-5, and B-6 samples, respectively. Fig. 6(a and
b) revealed that the amount of MB adsorption increased rapidly in the
initial stages and then slowed down until the equilibrium time was
reached. The powerful ultrasound waves at the beginning of the
adsorption process provided a significantly short equilibration time. In
the first 5 min, all samples performed MB adsorption at a very high
speed, and the adsorption percentages changed between 87% and 97%
in the meantime. In this situation, observed in all bentonite samples, the
adsorption equilibrium time was between 30 and 60 min. Apart from
ultrasound irradiation, the fast removal of MB at the beginning of the
5
Chemical Physics Letters 802 (2022) 139758
adsorption process can also be attributed to the higher MB concentra­
tions, which play as driving forces and more active sites on the clay
surface during this period. After a short time, a drastic decrease in the
MB adsorption rate occurred due to decreased MB concentration and
active sites [36]. The curves in Fig. 6(a and b) also showed that the
adsorption had reached an equilibrium, which means that MB adsorp­
tion on the bentonites takes place in a monolayer [7]. The optimum
contact time was selected to be 60 min for the ongoing adsorption ex­
periments for all bentonite samples.
Adsorbent concentration, pH, contact time, and temperature were
kept constant as 2.0 g/L, 11–12, 60 min, and 25 ◦ C, respectively, while
performing MB adsorption experiments at different MB initial concen­
trations. The increase in adsorption capacity with the increase of the
initial MB concentration (Fig. 6(c)) is explained by the increase in the
mass transfer rate (driving force concentration). Fig. 6(d) revealed that
the adsorption efficiencies were higher (92–99%) because of the high
H. Çiftçi
Fig. 5. Effect of the pH on the adsorption of MB onto bentonite samples.
ratio of the effective adsorbent surface to the initial MB concentration at
low MB concentrations. Higher MB initial concentrations resulted in
significant decreases in removal efficiencies (57–73%) for all samples.
Similar results were also reported by other researchers [39,42].
3.3.4. Effect of temperature
Adsorption experiments were performed at three different temper­
atures to investigate the effect of temperature on MB removal. In these
experiments, adsorbent concentration, pH, and contact time were kept
constant at 2 g/L, 11–12, and 60 min, respectively. Initial MB concen­
trations were also kept constant as 1360, 1300, 1240, 1240, 1200, and
1070 mg/L for B-1, B-2, B-3, B-4, B-5, and B-6 samples, respectively.
As can be seen from Fig. 7, the adsorption capacities (mg/g)
increased with the increase in temperature for all bentonite samples.
These results indicate that the adsorption of MB molecules onto ben­
tonites is an endothermic phenomenon that is in good agreement with
previous studies [43]. It was also determined that MB removals
increased from 55–72% to 79–91% with the increase of temperature
from 25 ◦ C to 55 ◦ C for the given MB initial concentrations. Adsorption
amounts for all samples were also increased from 330 to 435 mg/g to
430–610 mg/g values.
4. Adsorption mechanism
Adsorption mechanism of the cationic MB molecules onto negatively
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Chemical Physics Letters 802 (2022) 139758
charged bentonite surface and interface was investigated using kinetic
and isotherm data. Fig. S1 (Supplementary Material) revealed that the
curves reached equilibrium and the initial MB concentration did not
affect the equilibrium time. Accordingly, it can be said that MB
adsorption on the bentonite surface occurs in a monolayer [7,44].
Similar adsorption mechanisms were also reported by other studies
[39,42]. Adsorption kinetics is investigated by fitting the data to pseudo-
first-order and pseudo-second-order models to determine the equilib­
rium time. Linear forms of models were given in Eqs. (3) and (4),
respectively [44].
k1
log(qe − qt ) = log(qe )− t (3)
2.303
t 1 1
= + ( )t(h = k2*qe2) (4)
qt h qe
where qt is the adsorption amount at a certain time (mg/g), qe is the
adsorption amount at equilibrium time (mg/g), k1 is the Lagergren rate
constant (1/mg*min), and k2 is the second-order model rate constant (g/
mg * min).
The k1/2.303 and log(qe) were found from the slope and intercept of
the plot of log(qe-qt) versus t (Fig. S2 (PFO)) (Supplementary Material).
The 1/qe and 1/k2qe2 were found from the slope and intercept of the plot
of t/qt versus t (Fig. S2 (PSO)) (Supplementary Material). Table S1
(Supplementary Material) showed that the calculated adsorption ca­
pacities (qe, cal) from the pseudo-second-order model were very close to
the experimental adsorption capacities (qe, exp) for all bentonite sam­
ples. The pseudo-second-order model also displayed higher correlation
coefficients (R2: 0.9901–1.00) than the pseudo-first-order model (R2:
0.6496–0.9444). It was determined that qe,cal values increased and rate
constants (k2) decreased as the initial concentrations of MB increased
(Table S1) (Supplementary Material). This may be attributed to the
increased competition between MB molecules for active adsorbent sites
with the increase in MB concentration [40].
Adsorption isotherms are one of the best ways to understand the
relationship between an adsorbate and adsorbent. Therefore, adsorption
performances of the samples were investigated as a function of tem­
perature and MB initial concentration (Fig. S3) (Supplementary Mate­
rial). It was concluded that the adsorption capacities increased with
increasing temperature which confirmed the endothermic reaction.
Previous studies which investigated the adsorption of MB onto benton­
ites were also reported the same results [25,43]. Fig. S3 (Supplementary
Material) also showed that the isotherms of all samples were similar to
the “L-2” type in the Giles classification system [45]. The L-type iso­
therms describe high affinity between adsorbate and adsorbent [17]
depending on electrostatic attraction forces.
Langmuir and Freundlich models were used to explain the isotherm
data. The linearized Langmuir isotherm model, dimensionless separa­
tion factor (RL), and Freundlich isotherm model were given by Eqs. (5)–
(7), respectively [40,46,47].
Ce 1 1
= + ce (5)
qe qmax *KL qmax
1
RL = (6)
1 + (KL *Co )
( ) 1
ln(qe ) = ln Kf + ln(ce ) (7)
n
where qmax is the maximum adsorption capacity (constant, mg/g), qe is
the amount of adsorbed per unit adsorbent at equilibrium (mg/g), KL is
the Langmuir constant (L/mg), ce is the adsorbate concentration
remaining in the solution at equilibrium (mg/L), co is the initial con­
centration of the adsorbate, and Kf is the Freundlich constant.
The slope of the line, obtained by transferring the change of ce/qe
values against ce values to the graph, gives the value of 1/qm, and the
H. Çiftçi
Fig. 6. Effect of contact time (a, b) and MB initial concentration (c, d) on the adsorption of MB onto bentonite samples.
cut-off point gives the value of 1/qmKL (Fig. S4) (Supplementary
Material).
The RL value explains the type of adsorption model to be either un­
favorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1), or irreversible
(RL = 0).
The slope of the curve (ln(ce) values versus the ln(qe)) gives the 1/n,
and the cut-off point gives the ln(Kf) (Fig. S4) (Supplementary Material).
1/n is the heterogeneity factor and takes values in the range of 0–1. The
more heterogeneous the surface, the closer to zero the 1/n value. A value
of “n” > 1 indicates that the adsorption process is [48].
Fig. S4 and Table S2 (Supplementary Material) revealed that the
Langmuir isotherm model with higher R2 values is more suitable to
explain the adsorption of MB cations onto bentonites than the Freund­
lich isotherm model, confirming the monolayer adsorption [27,43].
Adsorption of MB cations occurs in specific homogeneous areas on the
bentonite surface, and only one MB cation occupies each of these areas.
The RL values were found to be between 0 and 1, showing that the
adsorption of MB cations onto bentonites is favorable at the desired level
[49]. The maximum MB capacities (qmax) of bentonites calculated from
Langmuir graphs (Table S2) (Supplementary Material) were found to be
very close to the experimental values.
5. Conclusions
Adsorption experiments were successfully performed, and it was
concluded that ultrasound irradiation have a great effect on the
adsorption equilibrium time. Equilibrium times for all bentonites sam­
ples were decreased significantly with the aid of powerful ultrasound
waves provided by a probe for only 1 min at the beginning of the
adsorption process. For example, while the B-1 sample showed an
adsorption amount of 388 mg/g in 5 min with the UA-adsorption
technique, this value was determined as 286 mg/g with the C-
7
Chemical Physics Letters 802 (2022) 139758
adsorption technique for the same sample. In some bentonite samples
(B-2, B-3, B-4), a slight increase in the amount of adsorption was
observed at the adsorption equilibrium time (60 min for UA-adsorption).
This can be attributed to the formation of new active surfaces by over­
coming the physical forces holding the non-dispersible clay aggregates
by ultrasound waves. As proved in this study and other studies, changes
in adsorption equilibrium time and adsorption capacity are determined
according to the UA-adsorption technique used and the type of adsor­
bent. Cation exchange capacity and zeta potential value were also found
to be the most effective characteristics on adsorption capacities.
Maximum adsorption capacities of B-1, B-2, B-3, B-4, B-5, and B-6
samples with the 96–100 % MB removal percentages at optimum con­
ditions (pH: 11–12, temperature: 25 ◦ C, contact time: 60 min, and MB
initial concentrations for B-1: 800, B-2: 700, B-3,4: 650, B-5: 600, and B-
6: 500 mg/L) were determined to be as 398, 342, 320, 296, 288, and
243 mg/g, respectively. Pseudo-second-order kinetic model and Lang­
muir isotherm model with higher correlation coefficients were found to
be more suitable to explain the adsorption of MB cations onto benton­
ites. In addition, maximum adsorption capacities of B-1, B-2, B-3, B-4, B-
5, and B-6 samples at 25 ◦ C calculated from Langmuir isotherm data
determined as 500, 454.5, 400, 384.6, 370, and 357.1 mg/g, respec­
tively. In conclusion, the UA-adsorption technique described in this
study can be used effectively in continuous adsorption processes using
fixed bed columns to provide higher adsorption amounts in a shorter
time. Furthermore, the method can be used for other porous and nano
adsorbents such as activated carbon to see adsorption performance as a
function of time.
CRediT authorship contribution statement
Hakan Çiftçi: Conceptualization, Methodology, Data curation,
Writing – original draft, Visualization, Investigation, Supervision,
H. Çiftçi Chemical Physics Letters 802 (2022) 139758

residue, Powder Technol. 366 (2020) 239–248, https://doi.org/10.1016/j.

powtec.2020.02.013.
[3] Q.X. Liu, Y.R. Zhou, M. Wang, Q. Zhang, T. Ji, T.Y. Chen, D.C. Yu, Adsorption of
methylene blue from aqueous solution onto viscose-based activated carbon fiber
felts: kinetics and equilibrium studies, Adsorp. Sci. Technol. 37 (3–4) (2019)
312–332, https://doi.org/10.1177/0263617419827437.
[4] L.D. Lin, Y. Lin, C.J. Li, D.Y. Wu, H.N. Kong, Synthesis of zeolite/hydrous metal
oxide composites from coal fly ash as efficient adsorbents for removal of methylene
blue from water, Int. J. Miner. Process 148 (2016) 32–40, https://doi.org/
10.1016/j.minpro.2016.01.010.
[5] M. Canli, Y. Abali, S.U. Bayca, Removal of methylene blue by natural and Ca and K-
exchanged zeolite treated with hydrogen peroxide, Physicochem. Probl. Miner.
Process 49 (2) (2013) 481–496, https://doi.org/10.5277/ppmp130210.
[6] A.K. Kushwaha, N. Gupta, M.C. Chattopadhyaya, Enhanced adsorption of
methylene blue on modified silica gel: equilibrium, kinetic, and thermodynamic
studies, Desalin. Water Treat. 52 (22–24) (2014) 4527–4537, https://doi.org/
10.1080/19443994.2013.803319.
[7] H. Çiftçi, B. Ersoy, A. Evcin, Synthesis, characterization and Cr(VI) adsorption
properties of modified magnetite nanoparticles, Acta Phys. Pol. A 132 (3) (2017)
564-569. doi:10.12693/APhysPolA.132.564.
[8] H. Çiftçi, B. Ersoy, A. Evcin, Pillared magnetite/clay structures as a function of Ctab
and Teos concentrations, Emerg. Mater. Res. 9 (1) (2020) 24–30, https://doi.org/
10.1680/jemmr.18.00148.
[9] W.J. Zou, L. Gong, M.F. Pan, Z.J. Zhang, C.B. Sun, H.B. Zeng, Effect of salinity on
adsorption and interaction forces of hydrophobically modified polyacrylamide on
silica and alumina surfaces, Miner. Eng. 150 (2020) 106280, https://doi.org/
10.1016/j.mineng.2020.106280.
[10] K.W. Corum, A.A. Tamijani, S.E. Mason, Density functional theory study of
arsenate adsorption onto alumina surfaces, Minerals 8 (3) (2018) 91, https://doi.
org/10.3390/min8030091.
[11] C.L. Yu, F. Bian, S.F. Zhang, X. Xu, P. Ren, F.C. Wang, F.A. Zhang, Preparation of
the monodispersed carboxyl-functionalized polymer microspheres with
disproportionated rosin moiety and adsorption of methylene blue, Adsorp. Sci.
Technol. 36 (5–6) (2018) 1260–1273, https://doi.org/10.1177/
0263617418766774.
[12] O. Kerkez, S.S. Bayazit, H.A. Uslu, Comparative study for adsorption of methylene
blue from aqueous solutions by two kinds of amberlite resin materials, Desalin.
Water Treat. 45 (1–3) (2012) 206–214, https://doi.org/10.1080/
19443994.2012.692057.
[13] M.A. Khan, Z.A.A.L. Othman, M. Naushad, M.R. Khan, M. Luqman, Adsorption of
methylene blue on strongly basic anion exchange resin (Zerolit DMF): kinetic,
isotherm, and thermodynamic studies, Desalin. Water Treat. 53 (2) (2015)
515–523, https://doi.org/10.1080/19443994.2013.838527.
[14] L. Pardo, J.A. Cecilia, C. Lopez-Moreno, V. Hernandez, M. Pozo, M.J. Bentabol,
F. Franco, Influence of the structure and experimental surfaces modifications of 2:1
clay minerals on the adsorption properties of methylene blue, Minerals 8 (8)
(2018) 359, https://doi.org/10.3390/min8080359.
[15] M.T. Amin, A.A. Alazba, M. Shafiq, Adsorptive removal of reactive black 5 from
wastewater using bentonite clay: isotherms, kinetics and thermodynamics,
Sustainability 7 (2015) 15302–15318, https://doi.org/10.3390/su71115302.
[16] A. Ramesh, H. Hasegawa, T. Maki, K. Ueda, Adsorption of inorganic and organic
Fig. 7. Effect of the temperature on the adsorption of MB onto arsenic from aqueous solutions by polymeric Al/Fe modified montmorillonite, Sep.
bentonite samples. Purif. Technol. 56 (2007) 90–100, https://doi.org/10.1016/j.seppur.2007.01.025.
[17] M. Bergaoui, A. Nakhli, Y. Benguerba, M. Khalfaoui, A. Erto, F.E. Soetaredjo,
S. Ismadji, B. Ernst, Novel insights into the adsorption mechanism of methylene
Validation, Writing – review & editing. blue onto organo-bentonite: adsorption isotherms modeling and molecular
simulation, J. Mol. Liq. 272 (2018) 697–707, https://doi.org/10.1016/j.
molliq.2018.10.001.
Declaration of Competing Interest [18] M. Hajjaji, H. El Arfaoui, Adsorption of methylene blue and zinc ions on raw and
acid-activated bentonite from Morocco, Appl. Clay Sci. 46 (2009) 418–421,
https://doi.org/10.1016/j.clay.2009.09.010.
The authors declare that they have no known competing financial [19] Y. Bulut, H. Karaer, Adsorption of methylene blue from aqueous solution by
interests or personal relationships that could have appeared to influence crosslinked chitosan/bentonite composite, J. Dispers. Sci. Technol. 36 (1) (2015)
the work reported in this paper. 61–67, https://doi.org/10.1080/01932691.2014.888004.
[20] D. Hou, S. Hu, Y. Huang, R. Gui, L. Zhang, Q. Tao, C. Zhanga, S. Tian,
S. Komarneni, Q. Ping, Preparation and in vitro study of lipid nanoparticles
Acknowledgments encapsulating drug loaded montmorillonite for ocular delivery, Appl. Clay Sci. 119
(2016) 277–283, https://doi.org/10.1016/j.clay.2015.10.028.
[21] M. Malovanyy, O. Palamarchuk, I. Trach, H. Petruk, H. Sakalova, K. Soloviy, T.
This work was supported by the Afyon Kocatepe University Mining Vasylinych, I. Tymchuk, N. Vronska, Adsorption extraction of chromium ions (III)
Engineering Department, Afyonkarahisar, Turkey. with the help of bentonite clays, J. Ecol. Eng. 21 (7) (2020) 178–185. doi:
10.12911/22998993/125545.
[22] X. Pan, M. Zhang, H. Liu, S. Ouyang, N. Ding, P. Zhang, Adsorption behavior and
Appendix A. Supplementary material mechanism of acid orange 7 and methylene blue on self-assembled three-
dimensional Mg-Al layered double hydroxide: experimental and DFT investigation,
Supplementary data to this article can be found online at https://doi. Appl. Surf. Sci. 522 (2020) 146370, https://doi.org/10.1016/j.
apsusc.2020.146370.
org/10.1016/j.cplett.2022.139758. [23] C. Sarici-Ozdemir, Adsorption and desorption kinetics behavior of methylene blue
onto activated carbon, Physicochem. Probl. Miner. Process 48 (2) (2012) 441–454,
References https://doi.org/10.5277/ppmp120210.
[24] Q.Z. Zhai, Y. Dong, H. Liu, Q.S. Wang, Adsorption of methylene blue onto nano
SBA-15 mesoporous material from aqueous media: kinetics, isotherms and
[1] A. Mlayah, S. Jellali, Study of continuous lead removal from aqueous solutions by
thermodynamic studies, Desalin. Water Treat. 158 (2019) 330–342, https://doi.
marble wastes: efficiencies and mechanisms, Int. J. Env. Sci. Technol. 12 (2015)
org/10.5004/dwt.2019.24229.
2965–2978, https://doi.org/10.1007/s13762-014-0715-8.
[2] Q.N. Han, J. Wang, B.A. Goodman, J.K. Xie, Z.G. Liu, High adsorption of methylene
blue by activated carbon prepared from phosphoric acid treated eucalyptus

8
H. Çiftçi
[25] S. Hong, C. Wen, J. He, F. Gan, Y.S. Ho, Adsorption thermodynamics of methylene
blue onto bentonite, J Hazard Mater. 16 (2009) 630–633, https://doi.org/
10.1016/j.jhazmat.2009.01.014.
[26] G. Jing, Z. Zhou, L. Song, M. Dong, Ultrasound enhanced adsorption and
desorption of chromium (VI) on activated carbon and polymeric resin, Desalination
279 (2011) 423–427, https://doi.org/10.1016/j.desal.2011.06.001.
[27] S. Sonawane, P. Chaudhari, S. Ghodke, S. Ambade, S. Gulig, A. Mirikar, A. Bane,
Combined effect of ultrasound and nanoclay on adsorption of phenol, Ultrason.
Sonochem. 15 (2008) 1033–1037, https://doi.org/10.1016/j.
ultsonch.2008.03.006.
[28] O. Acisli, A. Khataee, S. Karaca, M. Sheydaei, Modification of nanosized natural
montmorillonite for ultrasound enhanced adsorption of Acid Red 17, Ultrason.
Sonochem. 31 (2016) 116–121, https://doi.org/10.1016/j.ultsonch.2015.12.012.
[29] A. Hassani, R.D.C. Soltani, M. Kıranşan, S. Karaca, C. Karaca, A. Khataee,
Ultrasound-assisted adsorption of textile dyes using modified nano-clay: central
composite design optimization, Korean J. Chem. Eng. 33 (1) (2016) 178–188,
https://doi.org/10.1007/s11814-015-0106-y.
[30] Z. Dankova, A. Mockovčiaková, S. Dolinská, Influence of ultrasound irradiation on
cadmium cations adsorption by montmorillonite, Desalin. Water Treat. 52 (2014)
5462–5469, https://doi.org/10.1080/19443994.2013.814006.
[31] W. Zhang, Y. Liang, J. Wang, Y. Zhang, Z. Gao, Y. Yang, K. Yang, Ultrasound-
assisted adsorption of Congo red from aqueous solution using Mg-Al-CO3 layered
double hydroxide, Apl. Clay Sci. 174 (2019) 100–109, https://doi.org/10.1016/j.
clay.2019.03.025.
[32] H. Çiftçi, B. Ersoy, A. Evcin, Purification of Turkish bentonites and investigation of
the contact angle, surface free energy and zeta potential profiles of organo-
bentonites as a function of ctab concentration, Clays Clay Miner. 68 (3) (2020)
250–261, https://doi.org/10.1007/s42860-020-00070-0.
[33] H. Çiftçi, M.D. Arpa, I.M. Gülaçar, L. Ozcan, B. Ersoy, Development and evaluation
of mesoporous montmorillonite/magnetite nanocomposites loaded with 5-
Fluorouracil, Micropor. Mesopor. Mater. 303 (2020) 110253, https://doi.org/
10.1016/j.micromeso.2020.110253.
[34] G. Brown, G.W. Brindley, X-ray diffraction procedures for clay mineral
identification, in: G.W. Brindley, G. Brown (Eds.), Crystal Structures of Clay
Minerals and Their X-ray Identification, Mineralogical Society of Great Britain and
Ireland Monograph 5, London, 1980, pp. 305–360. doi:10.1180/mono-5.5.
[35] G. Lagaly, I. Dekany, Colloid clay science, in: G. Lagaly, F. Bergaya (Eds.),
Developments in Clay Science, Elsevier, Netherlands, 2013, pp. 243–345, https://
doi.org/10.1016/B978-0-08-098258-8.00010-9.
[36] Z. Heidarinejad, O. Rahmanian, M. Fazlzadeh, M. Heidari, Enhancement of
methylene blue adsorption onto activated carbon prepared from date press cake by
low frequency ultrasound, J. Mol. Liq. 264 (2018) 591–599, https://doi.org/
10.1016/j.molliq.2018.05.100.
Chemical Physics Letters 802 (2022) 139758
[37] S.K. Low, M.C. Tan, N.L. Chin, Effect of ultrasound pre-treatment on adsorbent in
dye adsorption compared with ultrasound simultaneous adsorption, Ultrason.
Sonochem. 48 (2018) 64–70, https://doi.org/10.1016/j.ultsonch.2018.05.024.
[38] L. Iglesias, M.G. Álvarez, R.J. Chimentão, J.L. Leganés, F. Medina, On the role of
ultrasound and mechanical stirring for iodide adsorption by calcined layered
double hydroxides, Appl. Clay Sci. 91 (2014) 70–78, https://doi.org/10.1016/j.
clay.2014.02.012.
[39] R.L.M. Pandey, Enhanced adsorption capacity of designed bentonite and alginate
beads for the effective removal of methylene blue, Appl. Clay Sci. 169 (2019)
102–111, https://doi.org/10.1016/j.clay.2018.12.019.
[40] J. Chang, J. Ma, Q. Ma, D. Zhang, N. Qiao, M. Hu, H. Ma, Adsorption of methylene
blue onto Fe3O4/activated montmorillonite nanocomposite, Appl. Clay Sci. 119
(2016) 132–140, https://doi.org/10.1016/j.clay.2015.06.038.
[41] C.A.P. Almeida, N.A. Debacher, A.J. Downs, C.L. Cotteta, A.D. Mello, Removal of
methylene blue from colored effluents by adsorption on montmorillonite clay,
J. Colloid Interface Sci. 332 (2009) 46–53, https://doi.org/10.1016/j.
jcis.2008.12.012.
[42] M.L.F.A. De Castro, M.L.B. Abad, D.A.G. Sumalinog, R.R.M. Abarca, P. Paoprasert,
M.D.G. de Luna, Adsorption of Methylene Blue dye and Cu(II) ions on EDTA
modified bentonite: isotherm, kinetic and thermodynamic studies, Sustain.
Environ. Res. 28 (5) (2018) 197–205, https://doi.org/10.1016/j.serj.2018.04.001.
[43] I. Feddal, A. Ramdani, S. Taleb, E.M. Gaigneaux, N. Batis, N. Ghaffour, Adsorption
capacity of methylene blue, an organic pollutant, by montmorillonite clay, Desalin.
Water Treat. 52 (2014) 2654–2661, https://doi.org/10.1080/
19443994.2013.865566.
[44] H. Çiftçi, B. Ersoy, Adsorption of Cr(VI) ions on magnetite nano-particles (Fe3O4):
kinetic and thermodynamic studies, El-Cezeri J. Sci. Engin. 3(3) (2016) 417–427.
doi:10.31202/ecjse.258568.
[45] C.H. Giles, D. Smith, A. Huitson, A general treatment and classification of the
solute adsorption isotherm, I. Theoretical, J. Colloid Interf. Sci. 47 (1973)
755–765, https://doi.org/10.1016/0021-9797(74)90252-5.
[46] İ. Langmuir, The adsorption of gases on plane surfaces of glass, mica and platinum,
J. Am. Chem. Soc. 40 (9) (1918) 1361–1403, https://doi.org/10.1021/
ja02242a004.
[47] H.M.F. Freundlich, Over the adsorption in solution, Am. J. Phys. Chem. 57 (385)
(1906) 292, https://doi.org/10.4236/ss.2011.24042.
[48] S. Kang, Y. Zhao, W. Wang, T. Zhang, T. Chen, H. Yi, F. Rao, S. Song, Removal of
methylene blue from water with montmorillonite nanosheets/chitosan hydrogels
as adsorbent, Appl. Surf. Sci. 448 (2018) 203–211, https://doi.org/10.1016/j.
apsusc.2018.04.037.
[49] M.S. Chiou, Equilibrium and kinetic modeling of adsorption of reactive dye on
cross linked chitosan beds, Chemosphere 50 (2002) 1095–1105.