Sustainable Environment Research 28 (2018) 197e205

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Original Research Article

Adsorption of Methylene Blue dye and Cu(II) ions on EDTA-modified

bentonite: Isotherm, kinetic and thermodynamic studies
Maria Leah Flor A. De Castro a, b, Melody Love B. Abad a, Divine Angela G. Sumalinog a,
Ralf Ruffel M. Abarca a, c, Peerasak Paoprasert d, Mark Daniel G. de Luna a, e, *
a
Environmental Engineering Program, National Graduate School of Engineering, University of the Philippines Diliman, Quezon City 1101, Philippines
b
Department of Chemical Engineering, Ateneo de Davao University, Davao City 8000, Philippines
c
Department of Chemical Engineering and Technology, Mindanao State University e Iligan Institute of Technology, Iligan City 9200, Philippines
d
Department of Chemistry, Thammasat University, Pathumthani 12121, Thailand
e
Department of Chemical Engineering, University of the Philippines Diliman, Quezon City 1101, Philippines

a r t i c l e i n f o a b s t r a c t

Article history: Dyes and metals are hazardous pollutants commonly found in industrial wastewaters requiring complex
Received 24 July 2017 and expensive removal technologies. This study investigated the potential of ethylenediaminetetraacetic
Received in revised form acid-modified Philippine bentonite (EMB) as a low-cost adsorbent material for the removal of Methylene
6 March 2018
Blue dye (MB) and copper ions (Cu(II)) from aqueous solutions. Batch adsorption experiments showed
Accepted 12 April 2018
Available online 18 April 2018
that EMB has superior adsorption capacity compared to the unmodified bentonite, with an enhancement
of up to 40% for MB and more than 100% for Cu(II). The adsorption capacity of EMB improved with
increasing solution pH and contact time and decreased with higher solution temperature and higher salt
Keywords:
Adsorption
concentration in solution. The Langmuir isotherm model was found to best describe MB and Cu(II)
Bentonite adsorption on EMB with maximum capacity of 160 and 27 mg g
1, respectively. The pseudo-second order
Copper kinetic model best fit the experimental data with R2 > 0.99. Lastly, the thermodynamic study confirmed
Dye that the adsorption process was spontaneous, exothermic and reversible.
EDTA © 2018 Chinese Institute of Environmental Engineering, Taiwan. Production and hosting by Elsevier B.V.
Wastewater treatment This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).

1. Introduction Various wastewater treatment technologies such as ion-

The textile industry is one of the most water-consuming in-
dustries in the world and an average-sized textile mill uses about
1.6 million liters of water for a daily output of around 8000 kg of
fabric [1]. As a result, the industry produces large volumes of
wastewaters which contain hazardous compounds such as dyes,
heavy metals like Cu(II), and surfactants. These chemical species
can have an important ecological impact on ecosystems due to their
strong toxicity, environmental persistence, and tendency to bio-
accumulate and thus have to be removed from industrial effluents
prior to discharge to recipient waters [2].
* Corresponding author. Department of Chemical Engineering, University of the
Philippines Diliman, Quezon City 1101, Philippines.
E-mail address: mgdeluna@up.edu.ph (M.D.G. de Luna).
Peer review under responsibility of Chinese Institute of Environmental
Engineering.
exchange, adsorption, chemical precipitation, membrane filtra-
tion, flocculation, coagulation, flotation and electrochemical
methods have been employed to treat dye and heavy metal
contaminated effluents. Of these, adsorption has been widely used
with bentonite as one of the most extensively studied adsorbent
material because it is naturally available, inexpensive and has good
adsorption capacity mainly due to its physical and chemical sta-
bility, high superficial area and good cation exchange capacity [2,3].
The surface characteristics of bentonite are critical to its ability to
attract various chemical species. However, bentonite from different
parts of the world varies in mineralogy as this is affected by the
geochemical conditions during its formation. Bentonite also has a
swelling capacity potential that allows modifying agents to enter its
interlayer regions thereby improving the adsorption performance
of the material [4].
Ethylenediaminetetraacetic acid or EDTA is a synthetic chelating
agent that has been used to improve the surface properties of
conventional adsorbent materials such as bagasse fly ash [5], maize

https://doi.org/10.1016/j.serj.2018.04.001
2468-2039/© 2018 Chinese Institute of Environmental Engineering, Taiwan. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
198 M.L.F.A. De Castro et al. / Sustainable Environment Research 28 (2018) 197e205
cobs [6], chitosan [7], mesoporous silica [8], chitosanesilica hybrid
materials [9], and zinc oxide nanoparticles [10]. Recently, EDTA was
used to modify the surface of chitosan/SiO2/Fe3O4 adsorbent with
water-soluble carbodiimide as cross-linker for the adsorption of
heavy metals [11].
In this study, EDTA-modified bentonite was synthesized and
used as an adsorbent material for the removal of Methylene Blue
(MB) dye and copper ions from aqueous solutions. The effects of
initial concentration, adsorbent dosage, salt concentration and
solution pH on the adsorption process were investigated. The raw
and modified bentonite were characterized through particle size
distribution, scanning electron microscopy, X-ray diffraction (XRD)
spectroscopy, energy dispersive X-ray fluorescence and Fourier
transform infrared analyses. Isotherm, kinetics and thermody-
namic studies were conducted to evaluate the controlling mech-
anisms of MB and copper adsorption onto EDTA-modified
bentonite.
2. Experimental
2.1. Materials
Bentonite was collected from a processing company in Northern
Luzon, Philippines. All reagents used were analytical grade and
were not subjected to additional purification. MB dye
(C16H18ClN3S), copper sulfate (CuSO4) and EDTA disodium salt
(C10H14N2Na2O8) were all purchased from Ajax Finechem Pty. Salts,
namely sodium chloride (NaCl), potassium chloride (KCl) and so-
dium nitrate (NaNO3) were all obtained from J.T. Baker. Distilled
water was used to prepare all aqueous solutions in the study.
2.2. Synthesis of EDTA-modified bentonite
The EDTA-modified bentonite (EMB) was prepared similar to the
methods described in previous studies [5,12]. A mixture of 20 g
bentonite and 2 g EDTA were added to 1.0 M NaOH and stirred in a
water bath shaker (LSB-030S, Daihan LabTech) for 1 h at 30  C. It
was then kept soaked in the solution for 24 h. The EMB was then
filtered from the mixture, washed with distilled water and, dried at
55  C for 24 h.
2.3. Batch Cu(II) and MB adsorption
Batch adsorption experiments were done by adding known
amounts of EMB to 50-mL solutions of MB dye (10e100 mg L
1) and
Cu(II) (1e12 mg L
1). The solution pH was adjusted accordingly
using NaOH and HNO3 solutions. Different salts (NaCl, KCl and
NaNO3) were also added at varying concentrations (0.1e0.4 M) to
study the effect of ionic strength. Then, the mixture was placed in a
water bath shaker set at 120 rpm at the desired temperature
(30e50  C) and duration (1e120 min). After the reaction, the spent
EMB was filtered and dried at 55  C for 4 h, while the filtrate was
collected for residual MB or Cu(II) concentration analysis.
The concentration of MB was measured at a maximum wave-
length of 665 nm using a UVeVis spectrophotometer (UVmini-
1240, Shimadzu), while Cu(II) concentration was determined with
copper Vacu-vials® instrumental kit and a multi-analyte photom-
eter (V-2000, CHEMetrics). Respective calibration curves were
established to calculate the concentration of each compound. The
adsorption capacity (q), or the amount adsorbed per gram of EMB
(mg g
1), was obtained using Eq. (1), where Ci and Cf (mg L
1) are
the initial and final concentrations, respectively, V (L) is the solution
volume, and M (g) is the amount of EMB used.


V Ci
Cf
q¼ (1)
M
2.4. Adsorbent characterization
The adsorbent particle size was analyzed through dynamic light
scattering (Quadix Scatterscope I) by preparing a 1% bentonite so-
lution in water. The elemental composition of the samples was
determined through energy dispersive X-ray fluorescence (EDXRF-
720, Shimadzu). Information on the crystalline structures was ob-
tained through XRD analysis (XRD-600, Shimadzu). The surface
morphology of the adsorbents was examined using a scanning
electron microscope (S-3400N, Hitachi), set at an accelerating
voltage of 5.0 kV and 1000 magnification. The surface functional
groups were investigated using Fourier transform infrared spec-
troscopy (FTIR) analysis (Nicolet 6700).
The point of zero charge (PZC), or the pH at which the adsorbent
material has a net zero surface charge, was obtained using pH drift
method [13]. Solutions of 0.01 N NaCl were prepared with pH levels
varying from 2 to 8. The adsorbent, weighing 0.15 g, was added to
the NaCl solutions, and the mixtures were placed in a water bath
shaker for 48 h. The initial pH of the NaCl solutions was plotted
against the final pH to determine the pHPZC (pHinitial ¼ pHfinal).
3. Results and discussion
3.1. Characterization of unmodified and EDTA-modified Philippine
bentonite
The scanning electron micrographs in Fig. 1a and b show raw
bentonite as aggregated crystal-like flakes and EMB as larger ag-
gregates compared to raw bentonite. This is supported by the re-
sults from the particle size distribution analysis (Fig. 1c) where the
average particle size for raw bentonite and EMB were found to be
201 and 256 nm, respectively. During EDTA modification of
bentonite, the swelling of bentonite d mainly separation of clay
particles sometimes coupled with intra-aggregate and inter-
aggregate adsorption, and diffuse double layer formation [14] d
exposed the positively-charged metal ions in its interlayer region
and at the same time, allowed the entry of EDTA molecules in its
layers. This facilitated the attraction between the interlayer cations
and the negatively-charged carboxyl groups of EDTA. The swelling
also allowed the exposure of sites with a negative charge, which is
favorable to the adsorption of cationic MB and Cu(II).
The XRD patterns of the raw bentonite and EMB samples are
shown in Fig. 1d. The diffraction peaks at around 6.5 and 20
confirmed the presence of montmorillonite [(Na,Ca)0.33(Al,Mg)2(-
Si4O10)(OH)2$nH2O] which is the usual main component of
bentonite that gives it its swelling properties. Other minerals, such
as quartz (SiO2), anorthite (CaAl2Si2O8) and calcite (CaCO3), were
also detected. The characteristic diffraction peaks were found to be
the same for both raw bentonite and EMB although the spectra for
EMB had sharper and more intense peaks.
The FTIR spectra of raw bentonite and EMB are shown in Fig. 1e
and f. Characteristic peaks of raw bentonite were found at
3000e3750, 1635, 900e1200, and 517 cm
1. The broad absorption
bands observed at 3000e3750 cm
1 correspond to OeH stretching
and HeOeH bending. Bending vibrations of HeOeH is signified by
the peak found at 1635 cm
1. The strong band between 900 and
1200 cm
1, centered at 995 cm
1, represents the stretching vibra-
tions of the SieO groups, while the small peaks at around 517 cm
1
are due to the AleOeSi and SieOeSi bending vibrations [15,16].
Similar characteristic peaks were found for EMB with new peaks at
 M.L.F.A. De Castro et al. / Sustainable Environment Research 28 (2018) 197e205 199

Fig. 1. Characterization results of unmodified and EDTA-modified bentonite by (a, b) SEM; (c) particle size distribution; (d) XRD; and (e, f) FTIR analyses.

around 1500e1300 and 1440e1425 cm
1, which pertain to
carboxylate groups and C]C aromatic stretching, respectively
[17,18].
3.2. Effects of solution pH, adsorbent dosage and ionic strength on
MB and Cu(II) adsorption
Solution pH is an essential parameter in adsorption studies as it
affects the surface charge of the adsorbent, and the degree of
ionization and speciation of adsorbate [15]. Fig. 2 shows the
changes in adsorption capacity of the EMB for MB and Cu(II) at
varying solution pH. In Fig. 2a, the adsorption capacity for MB
significantly increased when the solution pH was adjusted from 2
to 6 and remained generally unchanged with less than 2% differ-
ence at pH levels higher than its natural pH (5.4e5.6). The favorable
adsorption at higher pH values is attributed to the nature of MB as a
cationic dye and the surface chemistry of EMB. The pHPZC of EMB
was found at 2.3, which is similar to other materials, such as EDTA-
cross-linked b-cyclodextrin (pHPZC ¼ 2.23) [12] and natural
bentonite (pHPZC ¼ 2.6) [19]. The net surface charge of EMB be-
comes positive at pH lower than its pHPZC and negative at higher pH
levels. At high solution pH, the electrostatic attraction of MB cation
(pKa ¼ 3.8) onto the negatively-charged surface of EMB is
enhanced. At acidic pH > 3.8, on the other hand, the presence of
excess Hþ ions may compete with the cations in solution for the
available adsorption sites. Similarly, the adsorption capacity for
200 M.L.F.A. De Castro et al. / Sustainable Environment Research 28 (2018) 197e205

Fig. 2. Effects of solution pH (aeb), adsorbent dose (ced) and ionic strength (eef) on MB and Cu(II) adsorption [contact time ¼ 120 min].

Cu(II) ions (Fig. 2b) was low at around pH 2 and improved when the
pH was increased to 4 to 6 due to the attraction of Cu(II) ions to the
negative sites of EMB. However, beyond pH 6, the adsorption ca-
pacity for Cu(II) ions had a notable decline due to the formation of
insoluble Cu(OH)2 precipitates [20].
Adsorbent dosage is another critical parameter in the study of
adsorption in order to determine the most economical amount of
adsorbent that can effectively remove the target chemical species
from the wastewater. The adsorption capacity of EMB for both MB
and Cu(II) adsorbates had an initial increase when the adsorbent
dosage was raised from 10 to 20 mg as shown in Fig. 2c and d due to
the increase in available active sites. However, further increase in
adsorbent dosage caused a decline in the adsorption capacity for
each of the adsorbates. The overlapping of adsorption sites lowered
the number of effective active sites for adsorption. There is also a
significant difference in adsorption capacities between raw
bentonite and EMB at low adsorbent dosage (10e40 mg) with a
maximum at 20 mg which clearly confirms the enhancement in
bentonite adsorptive performance with EDTA modification. At
dosages of 50 mg and above, the difference in adsorption capacities
was negligible.
Since wastewaters commonly contain high salt concentrations,
it is vital to investigate the effect of ionic strength on the adsorption
process. Fig. 2e and f shows the influence of salt concentration on
MB and Cu(II) adsorption by EMB. As shown, the adsorption ca-
pacities for the two adsorbates were generally lower when higher
concentrations of salts were added. This could be partly due to the
competition between Naþ and Kþ ions with MB and Cu(II) for
available EMB active sites. As shown in Fig. 2e, Kþ exhibited a
stronger negative effect on MB adsorption compared to Naþ. Since
Kþ has a smaller hydrated radius (2.32 Å) than Naþ (2.76 Å), it could
easily occupy more adsorption sites on the adsorbent surface and
could not as easily escape [21]. As mentioned, Cu(II) adsorption
onto EMB is governed solely by electrostatic interaction while MB
 M.L.F.A. De Castro et al. / Sustainable Environment Research 28 (2018) 197e205 201

adsorption is by electrostatic interaction and H-bonding. In addi-

tion, Cu(II) ions are considerably smaller than the MB molecules.
Thus, during coordinate bonding with Cu(II) ions, the exposed li-
gands of EMB will fold and completely envelope the smaller Cu(II)
ions but not MB molecules. Hence, more ligand sites will be avail-
able to MB molecules compared to Cu(II) ions resulting in greater
MB uptake by EMB. The presence of anions surrounding the
adsorption sites and adsorbates also hinders MB and Cu(II)
adsorption as these anion species compete in the electrostatic
attraction. For MB, the inhibiting effect of chloride and nitrate ions
are comparable because these negatively charged anions can
disrupt adsorption almost equally as sites for electrostatic attrac-
tion are numerous and well-distributed. Anion effect, however, is
different for Cu(II) adsorption. The inhibiting effect of nitrate ions
on Cu(II) adsorption is more notable compared to chloride ions
because the hydrated radii of nitrate (1.77 Å) is smaller compared to
chloride (1.80 Å) making it easier for nitrate ions to be more
attracted to the electron-deficient sites of the adsorbent.
3.3. Adsorption isotherms
Adsorption isotherms provide a better understanding of the
mechanism of adsorption and give an indication of the surface
properties, affinity and adsorption capacity of the adsorbent. The
Langmuir isotherm assumes monolayer adsorption at its binding
sites, homogeneous distribution of active sites on the adsorbent
surface, and no interaction between adsorbate molecules [22]. It is
given in Eq. (2) where qe is the adsorption capacity at equilibrium
(mg g
1), qm is the maximum adsorption capacity at monolayer
coverage (mg g
1), Ce is the equilibrium concentration of the
adsorbate solution (mg L
1), and KL is a constant related to free
energy of adsorption (L mg
1). On the other hand, the Freundlich
isotherm assumes heterogeneous multilayer adsorption and is
described by Eq. (3), where KF is the Freundlich constant associated
to the relative adsorption capacity (mg g
1 mg
1/n), and n is the
affinity of the adsorbate to the adsorbent. The Temkin isotherm
accounts for the heterogeneous surface of the adsorbents and that
the fall in the heat of adsorption is linear rather than logarithmic
[23]. The model is described by Eq. (4), where R is the universal gas
constant (8.31 J mol
1 K
1), T is the absolute temperature (K), A is the
Temkin isotherm constant (L g
1), and b is the constant Temkin
parameter related to the heat of adsorption (J mol
1). Finally, the
DubinineRadushkevich (DeR) isotherm is used to determine if the
adsorption process is chemical or physical in nature [24,25], and it is
given in Eq. (5), where qs is the theoretical saturation capacity
(mg g
1), KD is the activity coefficient related to mean sorption en-
ergy (mol2 kJ
2), and ε is the Polanyi potential (kJ mol
1) calculated
based on Eq. (6). The adsorption mean free energy, E (kJ mol
1), can
also be obtained from the DeR isotherm using Eq. (7).
1
E ¼ pffiffiffiffiffiffiffiffiffi (7)
2KD
Table 1 summarizes the calculated coefficients of determination
(R2) and model parameters of the Langmuir, Freundlich, Temkin
and DeR isotherms. As shown, the Langmuir isotherm (R2 > 0.98)
best fits the equilibrium data for both MB and Cu(II) adsorption by
EMB. This indicates that both systems follow homogeneous
adsorption, where an adsorption site becomes unavailable to other
molecules once a molecule is adsorbed on it. The maximum
adsorption capacities for MB and Cu(II) were 160 and 27 mg g
1,
respectively. In addition, the adsorption process is considered
favorable when the separation factor (RL), as expressed in Eq. (8),
has values between 0 and 1; irreversible for RL ¼ 0; linear for RL ¼ 1;
and unfavorable for RL > 1 [26]. As shown in Fig. 3, the RL values
calculated for both MB and Cu(II) adsorption were all in the range of
0e1. The RL values were also observed to decrease with increasing
initial concentration which implies that the adsorption becomes
more favorable. This could be due to the increase in driving force
when more MB and Cu(II) solute was present.
1
RL ¼ (8)
1 þ KL Ci
3.4. Kinetics study
Kinetics study is essential in understanding the adsorption
process as it provides information on the rate of adsorption and the
mechanism that controls it. In this study, the kinetic data was
analyzed using the pseudo-first order (PFO) [27], the pseudo-
second order (PSO) [28], and the intraparticle diffusion (ID) [29]
kinetic models, given in Eqs. (9)e(11), respectively, where k1
(min
1), k2 (g mg
1 min
1), and kid (mg g
1 min
1/2) are the PFO,
PSO and ID rate constants, respectively; qt (mg g
1) is adsorption
capacity at time t (min); and di is thickness of the boundary layer.
k1
logðqe
qt Þ ¼ qe
t (9)
2:303
t 1 1
¼ þ t (10)
qt k2 q2e qe
qt ¼ kid t 0:5 þ di (11)
From the experimental data, adsorption occurred in three
stages: (1) fast stage, (2) slow stage and (3) equilibrium. The fast

qm KL Ce
qe ¼ (2) Table 1
1 þ KL Ce Adsorption isotherm parameters for MB and Cu(II) adsorption.

Isotherm Parameter MB adsorption Cu(II) adsorption

1=n
qe ¼ KF Ce (3)
Langmuir qm 160 27
KL 3.45 8.56
RT R2 0.998 0.984
qe ¼ lnðACe Þ (4) Freundlich n 3.61 2.10
b
KF 84.8 30.8

 R2 0.774 0.684
qe ¼ qs exp
KD ε2 (5) Temkin A 336 100
b 137 446
R2 0.929 0.870
  DeR qs 145 310
1
ε ¼ RTln 1 þ (6) KD 0.018 2.62  10
8
Ce E 5.24 4082
R2 0.988 0.895
202 M.L.F.A. De Castro et al. / Sustainable Environment Research 28 (2018) 197e205

Fig. 3. Separation factor values (RL) at varying initial (a) MB and (b) Cu(II) concentrations.

stage is seen in the first 15 min of adsorption. At this phase, the energy change (DG ), change in enthalpy (DH ) and change in en-
solutes freely attach onto the available EMB active sites. The slow tropy (DS ), were determined using Eqs. (12)e(15), where Ke is
phase follows until around t ¼ 45 min for MB and t ¼ 60 min for thermodynamic equilibrium constant. The activation energy, Ea
Cu(II), whereby the active sites are being gradually filled up as (kJ mol
1), which determines the temperature dependence of the
adsorption progressed. Afterwards, a steady capacity is reached reaction rate, was computed from the Arrhenius equation in Eq.
denoting the saturation of the effective EMB adsorption sites. (16), where k2 is the PSO rate constant (g mg
1 min
1), and ko is a
Further increase in the adsorption duration will no longer cause any temperature-independent parameter (g mg
1 min
1).
improvement on the adsorption capacity. The experimental equi-
librium adsorption capacity, qe, was computed at 161 and 25 mg g
1 qe
Ke ¼ (12)
for MB and Cu(II), respectively. Ce
Listed in Table 2 are the calculated R2 values and model pa-

rameters of the PFO, PSO and ID kinetic models. PSO best fit equi- DG ¼
RT ln Ke (13)
librium data (R2 > 0.99) and this suggests that the main mechanism
that controls MB and Cu(II) adsorption onto EMB is chemisorption. 
DG ¼ DH
T DS
 
(14)
The ID model for the MB adsorption also exhibits high R2 values
(> 0.97) at temperatures 30 and 50  C. The ID model plots shown in  

Fig. 4 show the two stages in the adsorption process for MB mol- qe DS DH
ln ¼
(15)
ecules and Cu(II) ions. The first one is the rapid adsorption caused Ce R RT
by strong electrostatic attractions between the adsorbate mole-
cules and adsorbent surface, while the second stage is a noticeably Ea
ln k2 ¼
þ ln ko (16)
more gradual adsorption caused by the diffusion of solute particles RT
into the pores of the adsorbent until most or all of the active sites As in Table 3, the negative DG values indicate the spontaneity of
are occupied. Also, as these plots do not pass through the origin, ID adsorption for both solutes. In addition, the DG values became less
cannot be taken as the sole rate-limiting step [30]. negative at higher temperatures making the adsorption less
favorable due of the weakening of the adsorbenteadsorbate bonds.
3.5. Thermodynamics study and comparison of EMB performance The DH values of
7.6 and
43 kJ mol
1 confirm the exothermic
with related studies nature of adsorption for MB and Cu(II) adsorption, respectively,
and this explains the decline in adsorptive performance at
The calculated thermodynamic parameters for MB and Cu(II) elevated temperatures [13,15,16]. The DS values of MB
adsorption are summarized in Table 3. The standard Gibb's free (
0.012 kJ mol
1 K
1) and Cu(II) (
0.10 kJ mol
1 K
1) suggest a
decrease in randomness in the adsorption process and imply that
the process may be reversible. A more positive entropy is indicative
Table 2 of stronger affinity between adsorbate and adsorbent. Thus, MB is
Kinetic model parameters for MB and Cu(II) adsorption.
more attracted to the adsorbent. The difference in entropy values
Kinetic model Parameter MB adsorption Cu(II) adsorption between the two systems is highly dependent on the mode of
30  C 40  C 50  C 30  C 40  C 50  C adsorption, Cu(II) being limited to electrostatic force while MB can
attach via electrostatic force and H-bonding.
PFO qe 137 127 119 1.26 1.20 1.15
k1 0.071 0.057 0.047 0.056 0.060 0.086
The negative Ea values of MB and Cu(II) at
10 and
41 kJ mol
1,
R2 0.966 0.967 0.953 0.923 0.903 0.860 respectively go with the exothermic nature of adsorption and
PSO qe 173 169 171 26 17 9 denote that the process is more effective at lower temperatures.
k2 0.0011 0.0010 0.0008 1.006 1.547 2.754 Similar study on adsorption of dyes using the green alga Chlorella
R2 0.997 0.999 0.999 0.997 0.999 0.999
vulgaris resulted in activation energies of
10.6 kJ mol
1 for
ID Kid,1 22.4 21.7 22.6 3.86 3.80 4.63
d1 21.2 18.5 13.4 3.5 6.2 5.9 Remazol Red RR and
23.15 kJ mol
1 for Remazol Golden Yellow
R2 0.941 0.915 0.904 0.927 0.959 0.967 RNL, where the authors reported that since the negative Ea values
Kid,2 0.78 2.66 2.89 0.72 0.49 0.22 hold no obvious physical significance, the adsorption studies
d2 156.0 133.3 130.1 17.61 20.20 22.65 should be conducted at much lower temperatures to obtain Ea [31].
R2 0.988 0.432 0.9771 0.473 0.657 0.508
In Table 4, the adsorption capacity of EMB for MB or Cu(II) species
 M.L.F.A. De Castro et al. / Sustainable Environment Research 28 (2018) 197e205 203

Fig. 4. Intraparticle diffusion model for (a, c, e) MB and (b, d, f) Cu(II) adsorption at different solution temperatures.

Table 3
Thermodynamic parameters of MB and Cu(II) adsorption.

Adsorbate Temperature ( C) DG (kJ mol
1) DH (kJ mol
1) DS (kJ mol
1 K
1) Ea (kJ mol
1)

MB 30
4.0
7.6
0.012
10.0

40
3.8
50
3.7
Cu(II) 30
10.8
43
0.10
41.4
40
13.2
50
8.5
204 M.L.F.A. De Castro et al. / Sustainable Environment Research 28 (2018) 197e205

Table 4
Maximum adsorption capacities of various adsorbents for MB and Cu(II) adsorption.

Base adsorbent Modification/Enhancer Adsorbate Co (mg L
1) Temperature ( C) qm (mg g
1) Reference

Bentonite
Philippines EDTA MB 5e100 30 160 This work
Egypt Fe3O4 nanoparticles MB 2000 25 1600 [19]
Eskisehir Cold plasma treatment MB 100e250 30 303 [16]
Montmorillonite H2SO4 activation MB 80e400 60 192.3 [32]
Kaolinite H2SO4 activation MB 50e350 60 58.8 [32]
Pyrophyllite Picklingegrinding MB 10 20 4.2 [33]
Zeolite e MB 16e230 60 29.2 [34]
Palygorskite Ion beam bombardment MB 20e100 20 135 [21]
Activated biochar
MSW KOH-thermal activation MB 10e250 40 40.3 [35]
Tea Hydrothermal-NaOH activation MB 25e500 30 487 [36]

Bentonite
Philippines EDTA Cu(II) 1e12 30 27 This work
Commercial Chitosan Cu(II) 50e200 25 12.1 [37]
Commercial E. japonica seed mixing Cu(II) 75 45 46.9 [38]
Çankırı e Cu(II) 20e160 23 44.8 [39]
Montmorillonite ZnO nanocomposite Cu(II) 50e150 e 54.1 [40]
Kaolinite H2SO4 activation Cu(II) 1e100 25 29.4 [41]
Activated biochar
C. lacryma-jobi L. Thermal-HNO3 activation Cu(II) 50e100 25 17.2 [42]
Brewers draff KOH-thermal activation Cu(II) 1.3e127 e 10.3 [43]
Farmyard manure Thermal activation Cu(II) 2e50 25 45.5 [44]

are compared with other adsorbent materials. As shown, EMB is k2 Pseudo-second order rate constant (g mg
1 min
1)
superior to most materials for MB adsorption. For Cu(II) adsorption, KD DubinineRaduskevich isotherm constant (mol2 kJ
2)
however, EMB is generally inferior compared to most clay adsor- Ke Thermodynamic equilibrium constant
bents but comparable to biomass-derived adsorbents. KF Freundlich isotherm constant (mg g
1 mg
1/n)
kID Interparticle diffusion rate constant (mg g
1 min
1/2)
4. Conclusions KL Langmuir isotherm constant (L mg
1)
M Amount of EMB (g)
This study demonstrated that EDTA modification enhanced the MB Methylene Blue dye
effectiveness of Philippine bentonite as adsorbent material for the n Freundlich model parameter
removal of MB dye and copper ions from aqueous solutions. PZC Point of zero charge
Overall, the adsorption process was found to be spontaneous, q Adsorption capacity (mg g
1)
reversible, exothermic, controlled by chemical interactions and qe Adsorption capacity at equilibrium (mg g
1)
inhibited by the presence of salt species in solution. qm Maximum adsorption capacity at monolayer coverage
(mg g
1)
Acknowledgement qt Adsorption capacity at time t (mg g
1)
R Universal gas constant (8.31 J mol
1 K
1)
The authors are grateful to the Department of Science and R2 Coefficient of determination
Technology, Philippines for providing financial support for this RL Separation factor
research undertaking. SEM Scanning electron microscopy
T Temperature (K)
Nomenclature t Time (min)
V Solution volume (L)
DG Gibbs free energy (kJ mol
1) XRD X-ray diffraction
DH Change in enthalpy (kJ mol
1)
DS Change in entropy (kJ mol
1 K
1)
ε Polanyi potential (kJ mol
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