Journal of Cleaner Production xxx (2016) 1e13

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Journal of Cleaner Production

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Evaluation of physicochemical methods in enhancing the adsorption

performance of natural zeolite as low-cost adsorbent of methylene
blue dye from wastewater
Kar Yan Hor a, 1, Jasmine Mun Cheng Chee a, 1, Meng Nan Chong a, b, *, Bo Jin c,
Christopher Saint d, Phaik Eong Poh a, b, Rupak Aryal d
a
School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500, Malaysia
b
Sustainable Water Alliance, Advanced Engineering Platform, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway,
Selangor DE 47500, Malaysia
c
School of Chemical Engineering, The University of Adelaide, North Terrace Campus, Adelaide, 5005 South Australia, Australia
d
Centre for Water Management and Reuse, University of South Australia, Mawson Lakes Campus, Mawson Lakes, 5095 South Australia, Australia

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

Article history: The main aim of this study was to evaluate different facile and cost-effective physicochemical methods in
Received 10 September 2015 enhancing the adsorption capacity of natural zeolite and subsequently demonstrate the removal of
Received in revised form methylene blue (MB). Four different physicochemical methods, namely: acid treatment (AT), base
14 January 2016
treatment (BT), combined acid-thermal (ATT) and base-thermal treatments (BTT) were investigated. This
Accepted 24 January 2016
was followed by understanding the impact of the physicochemical methods on the surface characteristics
Available online xxx
and properties of modified zeolite through advanced characterisations using field emission-scanning
electron microscopy, Fourier-transformed infrared spectroscopy and BrunauereEmmetteTeller specific
Keywords:
Adsorption
surface area and porosity measurements. Batch adsorption studies were carried out using the modified
Modified zeolite zeolite adsorbents, in order to evaluate the highest removal efficiency of MB under varying adsorption
Acidebase treatment conditions of: pH, initial MB concentration and modified zeolite loading. Results showed that both the
Thermal treatment physicochemical methods of AT (using 0.4 M HCl) and BT (using 4.0 M NaOH) are able to enhance the
Adsorption isotherm adsorption capacity of natural zeolite from 41% to 98.8% and 52.2%, respectively. Surprisingly, the
Kinetic model combined physicochemical methods of ATT and BTT showed a reduction in adsorption performance
when benchmarked to AT and BT alone. The adsorption data were analysed and modelled using Lang-
muir, Freundlich, Redlich-Peterson and Koble-Corrigan isotherm models, also the adsorption kinetics
were evaluated using pseudo-first and pseudo-second order models. It was found that the adsorption
data and kinetics were best represented using the Koble-Corrigan and pseudo-second order models. The
improvements yielded through both the AT and BT modified zeolites were found to be promising and
have the potential to be used as low-cost adsorbents for wastewater treatment.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction microbes (Chong et al., 2010, 2011a) unless it is properly treated

Wastewater is a by-product that consists of a mixture of solid
and liquid after the usage of water from households, industries and
commercial establishments. Typically wastewater is no longer
serving a useful purpose compared to high-quality mains water
usage, and may contain significant amount of pollutants and
* Corresponding author. School of Engineering, Chemical Engineering Discipline,
Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE
47500, Malaysia. Tel.: þ60 3 5514 5680; fax: þ60 3 5514 6207.
E-mail address: Chong.Meng.Nan@monash.edu (M.N. Chong).
1
Joint first author.
(Malik et al., 2015). If wastewater remains untreated and is
discharged directly into the environment, water pollutants can
enter the natural water systems and cause negative impacts
towards the environment and public health (Chong et al., 2011b).
Various industries such as textiles, cosmetics, plastics and paper
industries are known to heavily use synthetic dyes in their
production to impart colour to their finished products. A significant
amount of dyes are commonly present in the effluents of these
industries and need to be treated before being discharged into the
environment (Reddy et al., 2012). In the absence of proper treat-
ment methods, synthetic dyes which have aromatic structures may
pose a threat to aquatic life due to their non-biodegradable nature,

http://dx.doi.org/10.1016/j.jclepro.2016.01.056
0959-6526/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
2 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13
and some are even carcinogenic (Gupta and Suha, 2009). There can
also be significant secondary effects of dyes, such as hindering
sunlight from penetrating into the water bodies and thus, depriving
aquatic life of vital light-sensitive chemical reactions (Robinson
et al., 2001; Zhou et al., 2014). Thus, the proper treatment and
removal of synthetic dyes from wastewater is essential before the
remaining effluent is discharged into the environmental water
streams.
At present, there are various wastewater treatment methods
available for the proper treatment and removal of synthetic dyes
from wastewater sources, such as anaerobic digestion, membrane
separation, adsorption (Vimonses et al., 2010; Toor et al., 2015),
sedimentation, filtration and photocatalysis (Hameed et al., 2007;
Chong et al., 2015). Anaerobic digestion (AD) occurs in the
absence of oxygen, whereby large amounts of organic matter are
broken down into fundamentally carbon dioxide. AD demands low
energy input while having a minimal sludge formation and nutri-
ents demand for its microbial processes. Although AD is an
attractive method due to the low energy requirement, the presence
of inhibitory substances (i.e., phenolic compounds) are toxic and
hinder the activities of vital constituents of the AD process, such as
methanogenic bacteria (Jime
nez et al., 2003). On the other hand,
the membrane bioreactor (MBR) is another widely used waste-
water treatment method for the removal of synthetic dyes from
wastewater sources. This is due to the high reliability of MBR
operation, which is independent of solid and hydraulic loads, low
space requirements, as well as producing high-quality treated ef-
fluents (Laera et al., 2011). However, it is known that MBR is subject
to high operational cost due to the cross-flow along the membrane
and required pressure gradient for optimum removal efficiency
(Busch et al., 2007). Thus far, adsorption using activated carbon (AC)
is the most common and effective wastewater treatment method
(Akgül and Karabakan, 2011). This is due to the large specific sur-
face area to volume ratio of AC. However, the effective adsorption
using AC comes at the expense of material, treatment and regen-
eration costs (Gupta and Suha, 2009).
Previously, various alternative adsorbents such as rice husk ash
(Liu et al., 2012), sawdust (Shukla et al., 2002), industrial waste (Ali
et al., 2012; Crini, 2006), and natural clays (Yan et al., 2009;
Cantuaria et al., 2016) have been investigated for their potential
applications in the removal of synthetic dyes from wastewater
sources. Among all, natural clays have proven to have a high
potential to be used as adsorbents in wastewater treatment due to
the fact that they are naturally abundant and environmental
friendly. Zeolite is a type of naturally abundant clay adsorbent that
has a high potential to be used as a low-cost and alternative to AC
adsorbent in wastewater treatment. Typically, zeolite has a rela-
tively lower specific surface area (SSA) but pore structure of mo-
lecular dimensions, high thermal stability that permits
regenerative uses and the ability to host strong Bronsted and Lewis
acid sites compared to AC adsorbent (Tarach et al., 2014). However,
the adsorption performance of natural zeolite in the removal of
synthetic dyes from wastewater sources is limited by its micropore
structure as the dye molecules are usually bulky and measure over
1 nm in size (Yan et al., 2009). Previously, Christensen et al. (2007)
reported that the adsorption of dyes on natural zeolite is highly
restricted by its diffusional limitations. In order to enhance the
adsorption performance of natural zeolite, previous studies have
attempted various modification approaches such as using acid
pre-treatment, surfactant modification and thermal activation on
natural zeolite (Li et al., 2011; Le Van Mao et al., 1997). All these
studies have shown considerably positive results in terms of
enhancing the adsorption performance of natural zeolite.
The main aim of this study was to evaluate different facile and
cost-effective physicochemical methods in enhancing the
Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
adsorption capacity of natural zeolite and subsequently demon-
strating these utilising removals of methylene blue (MB). Four
different physicochemical methods, namely: acid treatment (AT),
base treatment (BT), combined acid-thermal (ATT) and base-
thermal treatments (BTT) were investigated. This was followed by
investigating the impact of the physicochemical methods on the
surface characteristics and properties of modified zeolite through
advanced characterisations using field emission-scanning electron
microscopy (FE-SEM), Fourier-transformed infrared spectroscopy
(FTIR) and BrunauereEmmetteTeller (BET) specific surface area
and porosity measurements. A batch adsorption study was carried
out using the modified zeolite adsorbents, in order to evaluate for
the highest removal efficiency of MB under varying adsorption
conditions of: pH, initial MB concentration and modified zeolite
loading. The adsorption data were analysed and modelled using
Langmuir, Freundlich, Redlich-Peterson and Koble-Corrigan
isotherm models, in addition adsorption kinetics were evaluated
using pseudo-first and pseudo-second order models. Through this
study, it is anticipated that a facile and cost-effective physico-
chemical method can be determined to enhance the adsorption
performance of natural zeolite in promoting it as a low-cost and
alternative adsorbent for wastewater treatment.
2. Materials and methods
2.1. Materials
Natural zeolite (particle size < 45 mm, catalogue no.: 1318-02-1,
SigmaeAldrich) was subjected to four different physicochemical
modification methods, as proposed in this study. MB (catalogue no.:
440167-09087, HmbG Chemicals) was prepared to the experi-
mental concentrations by dissolving the solid dye powder in
aliquot volume of deionised water. Hydrochloric acid (HCl) 37%
(catalogue no.: H8040-1-2500, Friendemann Schmidt) and sodium
hydroxide (NaOH) pellets (catalogue no: S5158-1-1000, Friend-
emann Schmidt) were prepared accordingly in deionised water, as
the pH corrective chemicals.
MB is a cationic dye and is also classified as a heterocyclic aro-
matic chemical compound (Jamil et al., 2011). Supplementary Fig. 1
shows the molecular structure of MB, with the molecular formula
of C16H18N3SCl. Despite the variety of applications of MB in the
biology and chemistry fields, it has been reported that the presence
of MB could cause harm to human health and the environment
(Valde
s et al., 2012; Wang et al., 2005). Thus, the removal of MB
from wastewater sources before environmental discharge is of
paramount importance to ensure a healthy ecosystem. In this study,
MB was chosen as the surrogate indicator for treatment efficiency
due to its positively charged surface, which could readily be drawn
towards the anionic layers of zeolite. This made MB suitable for the
evaluation of adsorption performance in modified zeolites (Gürses
et al., 2006).
2.2. Physicochemical methods for modification of natural zeolite
Different aqueous HCl solutions with concentrations of 0.05 M,
0.1 M, 0.3 M, 0.4 M and 0.5 M were prepared. In order to carry out
the AT method, natural zeolite was mixed with the acid solution in
the ratio of 1:10 (g zeolite:mL acid). A magnetic stirrer was used to
mix the sample mixture solution for 20 min at 300 rpm. The AT was
terminated by adding a large amount of deionised water. The
sample mixture solution was then filtered using a vacuum filtration
pump set. The filtrate samples were washed repeatedly with
deionised water until neutral pH was obtained. Finally, the filter
cake was left to dry at 60  C for 12 h before being stored in a
desiccator.
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13
Different aqueous NaOH solutions with concentrations of 0.1 M,
2 M, 3 M, 4 M and 5 M were prepared. In order to perform the BT
method, natural zeolite was mixed with the base solution in the
ratio of 1:10 (g zeolite:mL base). A magnetic stirrer was used to mix
the sample mixture solution for 20 min at 300 rpm. The BT was
terminated by adding a large amount of deionised water. The
sample mixture solution was then filtered using a vacuum filtration
pump set. The filtrate samples were washed repeatedly using
deionised water until neutral pH was obtained. Finally, the filter
cake was left to dry at 60  C for 12 h before being stored in a
desiccator.
The combined treatment was performed by heating 2 g each of
AT and BT modified zeolites to the desired thermal treatment
temperature of 200  C and 400  C, respectively. The temperature
rate during the thermal treatment was set at 10  C/min and
maintained at the desired temperature for 10 min. The thermally
treated samples were left to cool and stored in a desiccator.
2.3. Characterisation of modified zeolites
FE-SEM images were obtained using the Hitachi SU8010 elec-
tron microscope at an accelerating voltage of 5 kV, in order to
measure and observe the particle size and morphology of the
modified zeolites. BET specific surface area and porosity measure-
ments of modified zeolites were carried out using adsorption iso-
therms obtained from the Micromeritics BET ASAP 2020 surface
area and porosity analyser at 77 ± 0.5 K in liquid nitrogen and by
using the BET equation. The sample vessels containing modified
zeolites were degassed at high temperatures overnight before
being analysed for SSA, pore size and volume. FTIR spectroscopy
was used to understand the impact of physicochemical methods on
the surface chemistry of modified zeolites. The FTIR spectra were
collected and recorded in the region of 500e4000 cm1. Prior to the
analysis, the modified zeolite samples were placed in an oven for
2 h at 60  C and kept in a desiccator while cooling down in order to
prevent contact with humidity in the surrounding air.
2.4. Batch adsorption experiments
100 ppm stock solution of MB was prepared by dissolving 0.1 g
of MB powder in 1 L of deionised water. The stock solution was
diluted subsequently to obtain the desired concentrations of MB
solution for batch adsorption experiments. Unless specified other-
wise, the batch adsorption experiment was generally carried out at
modified zeolite loading of 0.6 g, neutral pH, room temperature of
25  C and 18 ppm MB solution. During the batch adsorption
experiments, the MB solution was added and agitated with modi-
fied zeolite adsorbent at a constant speed of 200 rpm. Each set of
data was collected over a period of 120 min, whereby aliquots of
samples were taken at 1, 5, 9, 13, 17, 21, 40, 60, 80, 100 and 120 min.
At each sampling interval, the extracted samples were centrifuged
using a micro centrifuge at 13,500 rpm for 4 min. The supernatant
was then extracted using a micropipette to be tested for its absor-
bance using the UVeVis spectrophotometer at the MB character-
istic monochromatic wavelength (lmax) of 668 nm. For the studies
on the effects of pH, initial MB concentration and modified zeolite
loading, one adsorption parameter was varied while the remaining
parameters remain unchanged. All the batch adsorption experi-
ments were carried out in triplicate and the average values were
reported in order to minimise the random experimental and
systematic errors.
Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
3
2.5. Analytical method and error analysis
Since the MB concentration was determined colorimetrically, a
calibration curve between the measured absorbance values at
lmax ¼ 668 nm and concentrations of stock MB solution was
established. This was to enable a quick estimation of the attenuated
MB concentrations over time. The percentage (%) removal of MB
and the amount of MB uptake per unit of modified zeolite adsor-
bent (q) were estimated using the Eqs. (1) and (2):
%MB removal ¼ ðCi  Ce Þ  100=Ci (1)
q ¼ ðCi  Ce Þ  V=m (2)
where Ci is the initial MB concentration (mg/L), Ce is the MB
concentration at adsorption equilibrium (mg/L), V is the volume of
MB solution (mL) and m is the mass of modified zeolite adsorbent
used (g).
Furthermore, the Chi-squared (c2) test was used to analyse the
errors in experimental data. Typically, the Chi-squared test was
conducted to identify the inherent bias due to the linearisation of
the isotherm model. Chi-squared is calculated according to Eq. (3):
X .
c2 ¼ ðqee  qec Þ2 qec (3)
where qee is the equilibrium capacity of modified zeolite adsorbent
obtained from experiments (mg/g) and qec is the calculated equi-
librium capacity according to the dynamic model (mg/g). A low
value of Chi-squared indicates the experimental data fitted better
to the isotherm model. In order to confirm and validate the best-fit
isotherm and kinetic model for modified zeolite adsorption, it is
necessary to analyse the experimental data set using the combined
Chi-squared test with the correlation coefficient (R2).
2.6. Adsorption isotherms
Adsorption isotherm represents the equilibrium relationship
between the amount of adsorbate in adsorbed and solution phases,
respectively. In addition, it is also useful in determining the affinity
of an adsorbate for a particular adsorbent as well as estimating its
adsorption capacity. In this study, four different isotherm models
were investigated for representing the adsorption data including
Langmuir, Freundlich, Redlich-Peterson and Koble-Corrigan models
(Han et al., 2009).
Langmuir isotherm is the most straightforward and useful
isotherm for physical and chemical adsorption types. This isotherm
model assumes a homogeneous surface with no interaction
between adsorbate molecules, presence of dynamic equilibrium
between adsorption and desorption, and the maximum adsorption
analogous to a complete monolayer (Vafajoo et al., 2014). The
saturated monolayer isotherm model can be expressed in Eq. (4):
qm KL Ce
qe ¼ (4)
1 þ KL Ce
where qe is the amount of MB adsorbed onto per unit mass of
modified zeolite (mg/g), qm is maximum adsorption capacity at
monolayer (mg/g), KL is the Langmuir adsorption constant (L/mg)
related to the binding sites affinity and energy of adsorption and Ce
is the equilibrium concentration (mg/L).
From previous studies, it was known that the separation factor
(RL) is crucial in determining the suitability of Langmuir isotherm
model to model the adsorption process (Yan et al., 2009; Fil et al.,
2012). A value of 0 <RL < 1 indicates that it is a favourable
adsorption process, while RL > 1 shows that it is an unfavourable
4 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13
adsorption, RL ¼ 1 means linear adsorption, and RL ¼ 0 signifies
irreversible adsorption. Mathematically, RL can be estimated by
using Eq. (5):
1
RL ¼
1 þ KL Ci
where RL is the separation factor (dimensionless), KL is the Lang-
muir adsorption constant (L/mg) and Ci is the initial concentration
of MB (mg/L).
Meanwhile, Freundlich isotherm is an empirical equation that is
derived by assuming a heterogeneous surface with a non-uniform
distribution of the heat of adsorption over the surface of adsor-
bent. It is commonly expressed as per Eq. (6):
qe ¼ KF Ce
1=n
where both KF (mg/g) (L/mg) (1/n) and n are the Freundlich con-
stants related to the adsorption capacity and intensity of the
modified zeolite adsorbent used, respectively.
The Redlich-Peterson isotherm model is a three-parameter
empirical model, which consists of both Langmuir and Freundlich
isotherm models. Due to the versatility of this isotherm model, it
can be used for either homogeneous or heterogeneous systems. It
can be represented by Eq. (7):
AR Ce
qe ¼
1 þ BR Ceg
where AR, BR and g are the Redlich-Peterson isotherm parameters
and g has a value of 0 < g < 1.
Another three-parameter isotherm model, the Koble-Corrigan
isotherm model is also used to represent the equilibrium adsorp-
tion data in this study. This isotherm model is given in Eq. (8):
AK Ccn
qe ¼
1 þ BK Cen
where AK, BK and n are the Koble-Corrigan isotherm parameters.
This adsorption isotherm model is only valid when the value of n is
greater than 1.
2.7. Kinetic models
Generally adsorption kinetics is the base in determining the
performance of a fixed-bed or a flow-through adsorption system. In
order to determine the rate of MB adsorption on modified zeolites,
adsorption kinetic models such as pseudo-first-order and pseudo-
second-order models can be used (Qiu et al., 2009). The pseudo-
first order kinetic model is given in Eq. (9):
dq=dt ¼ k1 ðqe  qt Þ2
An integrated form of Eq. (9), after applying boundary condi-
tions t ¼ 0 to t ¼ t and qt ¼ 0 to qt ¼ qt is as follows:
log ðqe  qt Þ ¼ log qe  k1 t=2:303
where qt is the amount of adsorbate adsorbed at time t (mg/g), qe is
the adsorption capacity at equilibrium (mg/g), k1 is the
pseudo-first-order adsorption rate constant (min1), and t is the
adsorption contact time (min). In this instance, the values of the
pseudo-first order adsorption rate constants, k1, were determined
from the plot of log (qe e qt) against t. Meanwhile, the pseudo-
second order kinetic model is given in Eq. (11) as below:
Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
t 1 t
¼ þ (11)
qt k2 q2e qe
where k2 is the pseudo-second order rate constant (g mg1 min1).
(5)
3. Results and discussion
3.1. Optimisation of physicochemical methods
3.1.1. Acid and base treatment
In this study, natural zeolite was treated with HCl and NaOH to
produce AT and BT modified zeolites and subsequently used for
batch adsorption studies on the removal of MB dye. The rationale of
acid and base treatment was to enhance the dealumination and
(6) desilication processes whereby; Al3þ and Si4þ ions were removed
respectively from zeolite leaving behind a structure of high SSA and
porosity. In order to determine the optimum concentration of HCl
and NaOH required, the adsorption removal efficiency of MB was
measured. This is to ensure the cost-effectiveness of the treatment
(i.e. minimal amount of HCl and NaOH required in the aqueous
solution). Fig. 1 shows the adsorption removal efficiency of modi-
fied zeolites that are treated with different HCl and NaOH
concentrations. It was found that the general trend of acid and base
treatment enhanced the adsorption removal efficiency with
increasing concentration until it reached a plateau. From Fig. 1, it
can be observed that the maximum adsorption removal efficiencies
(7)
were achieved when 0.4 M HCl and 4 M NaOH were used during the
acid and base treatment, respectively. The higher adsorption
removal efficiency is due to the physical enhancement in specific
surface area as characterised in Section 3.2.2 (Toor et al., 2015).
Whilst the decrease in adsorption removal efficiency after the
plateau is likely attributed to the decrease in specific surface area
due to diffusion of HCl and NaOH into the voids, causing extreme
leaching of Al3þ and Si4þ ions respectively. This eventually leads to
the collapse of the layered structure in zeolite and hence results in
(8)
close packing of the particles and a significant reduction of surface
area and adsorption sites (Korichi et al., 2012). Subsequently, the
maximum adsorption removal efficiencies of both AT and BT
modified zeolites were compared against the natural zeolite that
was used as a control sample. From Fig. 2, it can be observed that
adsorption removal efficiencies of AT and BT modified zeolites were
significantly enhanced as compared to the natural zeolite sample.
In this instance, the AT modified zeolite showed a better adsorption
performance than the BT modified zeolite. This could be due to the
duration of acid and base treatment used, whereby the BT modified
zeolite might require a longer duration in order for NaOH to
effectively and adequately leach the Si4þ ions from the zeolite
structure. Owing to the better adsorption performance and signif-
icantly reduced requirements in terms of acid concentration and
treatment duration, the AT modified zeolite is preferred and proven
to be a cost-effective solution.
(9)
3.1.2. Combined acid/base-thermal treatment
Previously, it was discovered that thermal pre-treatment only
would contribute to a higher adsorption removal efficiency of
(10) organic compounds owing to the removal of physisorbed and
chemisorbed water molecules and other bound volatile compounds
(Vimonses et al., 2009a, 2009b). This will contribute directly to a
zeolite structure with higher SSA and porosity. However, there have
been limited studies that investigated this combined treatment. In
this study, the combined treatment involving sequential acid and
base treatment followed by thermal treatment was performed to
modify the physicochemical properties of natural zeolite. The
resultant ATT and BTT modified zeolites were evaluated for their
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 5

Fig. 1. Removal efficiency of zeolites treated by (a) HCl and (b) NaOH. Conditions: zeolite loading 0.6 g; MB concentration 18 ppm; operating temperature 25  C; neutral pH; average
relative error ±5%.

adsorption removal efficiency of MB in the batch adsorption study
and the results are shown in Fig. 3. From Fig. 3, it can be observed that
the adsorption removal efficiency of AT modified zeolite was higher
at 200  C while the highest was observed at 400  C for BT modified
zeolite. However, it was found that the adsorption performance
obtained after thermal treatment yielded lower removal efficiency
as compared to the zeolite samples without thermal treatment.
Thus, it can be concluded that the combined treatment within the
range of 200e400  C was unable to enhance the adsorption
performance of ATT and BTT modified zeolite adsorbents. This might
be due to the insufficient duration and temperature used during
thermal treatment to alter the zeolite structure.
3.2. Characterisation of modified zeolites
3.2.1. Field Emission-Scanning Electron Microscopy (FE-SEM)
Fig. 4 shows the FE-SEM images of the AT, BTT and combined
ATT and BTT modified zeolite adsorbents investigated in this study.
From Fig. 4, it can be observed that the surface morphology of
natural untreated zeolite is different when compared to the
modified zeolites. The surface morphology of the natural untreated
zeolite (Fig. 4(a)) appeared to be smooth with regular edges. In
contrast, the surface morphologies of the AT modified zeolites with
different HCl concentrations (Fig. 4(bed)) show a rougher appear-
ance with worn-out edges. Such an edge modification will poten-
tially increase the overall specific surface area as well as the pore
size and volume of the natural zeolite adsorbent. The impact of acid
treatment on the BET specific surface area, pore size and volume
was verified in Section 3.2.2. Generally, it was found that the
surface roughness increases with HCl concentration whereby this
was also linearly correlated to the increasing removal efficiencies of
MB during the batch adsorption experiments. On the other hand,
the BT modified zeolites with different NaOH concentrations
(Fig. 4(eeg)) were observed to have intermediate surface rough-
ness between that of natural untreated zeolite and AT modified
zeolites. In this instance, the surface morphologies of the BT

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
6 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

Fig. 2. Comparison of the adsorption performance of natural, AT and BT zeolites based on their MB removal efficiency. Average relative error ±5%.

Fig. 3. Effect of thermal treatment on the MB removal efficiency by modified zeolites. Conditions: zeolite loading 0.6 g; MB concentration 18 ppm; operating temperature 25  C;
neutral pH; average relative error ±5%.

zeolites showed relatively smooth surfaces with a non-distinctive
change when observed on the FE-SEM images. However, the
impact of base treatment on the BET specific surface area, pore size
and volume was subsequently quantified in Section 3.2.2 while the
adsorption removal efficiency of MB is detailed in Section 3.3.
Surprisingly, the surface morphologies of combined ATT and BTT
modified zeolites (Fig. 4(hei)) did not show obvious change when
compared to the FE-SEM images obtained prior to heat treatment.
This was well reflected in the adsorption removal efficiencies of MB
in Section 3.3.
3.2.2. BrunauereEmmetteTeller (BET)
Table 1 presents BET analysis of the four physicochemical
modified types of zeolites, namely AT, BT, ATT and BTT as well as the
natural zeolite as sample control. From the results presented in
Table 1, it can be observed that the specific surface areas of both AT
(21.40 m2/g) and BT (6.50 m2/g) modified zeolites are higher than
that of natural zeolite (2.90 m2/g). Generally, the increase in specific
surface area leads to a better adsorption performance for the
modified zeolites adsorbents. The impact of higher specific surface
area on the adsorption removal efficiency of MB was subsequently
investigated and validated in Section 3.3. On the other hand, it was
observed that the acid treatment actually induced the formation of
mesopores within the natural zeolite. This was evident from the
shift in pore size from 1.81 nm (natural zeolite) to 3.09 (AT modified
zeolite). Typically, the threshold value for micropores is a diameter
below 2 nm while the mesopore has a diameter between the range
of 2 nm and 50 nm. Similarly, the base treatment also induced the
formation of mesopores in natural zeolite but to a less profound
effect, where the pore size was only shifted from 1.81 nm to
2.06 nm. The formation of mesopores within natural zeolite upon
acid and base treatment are linked to the dealumination and
desilication processes, respectively (Akgül and Karabakan, 2011).
The increase in pore size also facilitates the adsorption process, as
the large MB molecules are able to bind onto the adsorption sites
more easily, and thus improves the adsorption capacity and overall
adsorption removal efficiency.

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zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 7

Fig. 4. FE-SEM images of natural and modified zeolites: (a) natural zeolite; (b) AT modified zeolite (0.05 M HCl); (c) AT modified zeolite (0.1 M HCl); (d) AT (0.4 M HCl); (e) BT
modified zeolite (0.1 M NaOH); (f) BT modified zeolite (2 M NaOH); (g) BT modified zeolite (4 M NaOH); (h) ATT modified zeolite (0.4 M HCl at 200  C); (i) BTT modified zeolite (4 M
NaOH at 400  C).

Table 1 stretching. It was also observed that there was a strong peak around
BET analysis data for natural and modified zeolites. the wavenumber of 1000 cm1for the natural, acid-treated and
Sample SBET (m2/g)a Vtotal (cm3/g)b DBET (nm)c base-treated zeolites samples. Previously, Korichi et al. (2012) dis-
Natural zeolite 2.90 0.00131 1.81
cussed that this peak is due to the SieO stretch. From Fig. 5, it can be
0.4 M HCl zeolite 21.40 0.00949 3.09 observed that the intensity of SieO stretching was the weakest for
4 M NaOH zeolite 6.50 0.00291 2.06 base-treated zeolite and this indicates that the amount of Si in the
200  C HCl zeolite 22.40 0.01747 3.12 zeolite structure has been reduced due to the desilication process.
400  C NaOH zeolite 7.60 0.00446 2.06
The small peaks around wavenumber 1650 cm1 are linked to the
a
BET surface area. adsorbed water in the zeolite samples. Meanwhile, the impact of
b
Total pore volume. the dealumination process as induced by the acid treatment was
c
Pore size.
evident between wavenumbers of 3000 and 3700 cm1. This is an
OeH stretch with hydrogen-bonded molecules. The broad stretch
in this wavenumber range is attributed to the loosely-bound water
3.2.3. Fourier-Transformed Infrared (FTIR) spectroscopy molecules hydrogen bonded SieOH groups in nest defects due to
FTIR analysis was used to determine the minerals and functional vacancies of Al in the zeolite structure (Garcia-Basabe et al., 2010).
groups that present in the natural and modified zeolite adsorbents.
Fig. 5 shows the FTIR spectra of the natural and modified zeolites in
the range of 500e4000 cm1. The characteristic of zeolite, which 3.3. Adsorption studies
consists of a tetrahedral ring, was reflected by the peaks at the
wavenumber of 550e580 cm1 (Deepesh et al., 2013). A weak peak The adsorption studies were carried out only based on both the
was observed at the wavenumber 670 cm1, indicating AleOeSi AT (0.4 M HCl) and BT (4 M NaOH) modified zeolites adsorbents,

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
8 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13
Fig. 5. FTIR spectra of natural, AT and BT modified zeolites.
since they possess higher adsorption capacity and removal effi-
ciency than the ATT and BTT modified zeolites as per Section 3.1.
3.3.1. Effect of pH
Generally, pH is an important parameter in the batch adsorption
study as it is capable of influencing the adsorption process through
changes in the surface charge distribution of adsorbents used
(Li et al., 2013). In this study, the effect of pH on the adsorption of
MB using both AT and BT modified zeolites was investigated in the
range of pH 3 to pH 11. Fig. 6 shows the effect of pH on the
adsorption removal efficiency of MB using both AT and BT modified
zeolite adsorbents. From Fig. 6(a), it can be seen that there is an
increasing trend in the adsorption removal efficiency of MB when
pH increases from pH 3 to pH 11. Initially, there was a distinct
increase in the adsorption removal efficiency of MB from 82.5% (at
pH 3) to 97.4% (at pH 5). Thereafter, there was only a small increase
in the adsorption removal efficiency of MB from pH 5 up to the
maximum of 99.6% (at pH 11). Similarly, the BT modified zeolites
also exhibit an increasing trend in the adsorption removal
efficiency of MB when the pH increases from pH 3 to pH 11
(Fig. 6(b)). In this instance, the adsorption removal efficiency of MB
was seen to increase from 47.4% (at pH 3) to the maximum of 54.3%
(at pH 11).
Previously, Sohrabnezhad and Pourahmad (2010) also reported
such an increasing trend in the adsorption removal efficiency of MB
whereby both the AT and BT modified zeolite adsorbents have
shown better adsorption performance at higher pH conditions. This
is mainly attributed to the cationic nature of the MB dye. In acidic
medium (pH < 7), there will be excess Hþ ions present in the
solution to compete for the available adsorption sites with the
cationic MB dye molecules and thus, decreasing the dye uptake on
the modified zeolite adsorbents (Sohrabnezhad and Pourahmad,
2010). In addition, the presence of Hþ ions will also protonate the
surface of modified zeolites and this would lead to electrostatic
repulsion between the positively-charged surface of modified
zeolites and the cationic MB dye molecules (Fil et al., 2012). On the
contrary, the surface of modified zeolites will be deprotonated in an
alkaline medium (pH > 7). This is due to the decrease in positive
charge density on the adsorption edges caused by the increase in
the number of hydroxyl groups (Fil et al., 2012). This results in a
strong electrostatic attraction between the negatively charged
modified zeolites with positively charged MB molecules, which
Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
eventually leads to an overall enhancement in adsorption
performance.
3.3.2. Effect of zeolite loading
In this study, the effect of zeolite loading on the adsorption
capacity was evaluated by varying the dosages of both AT and BT
modified zeolites used between 0.2 g and 1.5 g. From Fig. 7(a), it can
be observed that the adsorption removal efficiency increased from
95.3% to 99.25% when the AT modified zeolite dosage was increased
from 0.2 g to 1.5 g. In this instance, the increase in adsorption
removal efficiency is likely attributed to the presence of more
adsorption sites (Alver and Metin, 2012; Liu et al., 2014). Whilst
Fig. 7(a) also shows that the adsorption capacity of AT modified
zeolite adsorbent decreased with increasing zeolite loading. This is
possibly the consequence of agglomeration of AT modified zeolite
particles when high dosage was utilised (Li et al., 2011).
Similarly, the BT modified zeolite adsorbent also experienced an
increase in the adsorption removal efficiency when the dosage was
increased from 0.2 g to 1.5 g. In this instance, however, the increase
in the adsorption removal efficiency by BT modified zeolite adsor-
bent was more significant from 16.9% to 85.5%. This indicated that
the BT modified zeolite adsorbent is more dependent on the zeolite
loading as compared to the AT modified zeolite adsorbent. As
shown in Fig. 7(b), the adsorption capacity of BT modified zeolite
adsorbent increased from 0.720 mg/g to 0.788 mg/g when the
zeolite loading was increased from 0.2 g to 0.4 g, before dropping
abruptly to 0.487 mg/g when 1.5 g of zeolite was used. The initial
increase in adsorption capacity is likely due to the considerable
differences in the amount of dye removed when the zeolite loading
was increased from 0.2 g to 0.4 g. Thus, the optimum loading for BT
modified zeolite adsorbent was found at 0.4 g loading as it led to
more than the doubling of adsorption removal efficiency without
compromising the adsorption capacity.
3.3.3. Effect of initial MB concentration
In this study, the effect of initial MB concentration on the
adsorption capacity of AT and BT modified zeolites was examined
by varying the initial MB concentration between 5 ppm and
20 ppm. Fig. 8(a) and (b) show the general trend is such that the
adsorption capacity increases with the increase in the initial MB
concentration. Such an observation is likely attributed to the
accelerated diffusion of MB molecules onto the modified zeolites
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 9

Fig. 6. Effect of pH on adsorption removal efficiency of MB using: (a) AT modified zeolite and (b) BT modified zeolite. Conditions: zeolite loading 0.6 g; MB concentration 18 ppm;
operating temperature 25  C; average relative error ±5%.

due to the increase in concentration gradient between MB mole-
cules and zeolite adsorbents (Vimonses et al., 2009b; Liu et al.,
2010). It can be proposed that an increase in the initial MB
concentration would lead to an eventual increase in adsorption
capacity due to the driving force of increasing concentration
gradient, causing an increase in mass transfer of MB molecules onto
the surface of both AT and BT modified zeolite adsorbents (Han
et al., 2009).
3.4. Adsorption isotherms and kinetic modelling
3.4.1. Adsorption isotherms
In order to evaluate the different physicochemical methods in
enhancing the adsorption performance of natural zeolite, it
necessitates a similar equilibrium condition to provide a better
comparison and understanding of the adsorption process. For this
study, four different adsorption isotherm models of Langmuir,
Freundlich, Redlich-Peterson and Koble-Corrigan models were
used to evaluate the adsorption systems utilising various
physicochemical-modified zeolite adsorbents.
Generally, an adsorption isotherm model is distinguished by the
respective parameters in the model that indicate the affinity and
surface properties of a particular adsorbent used (Han et al., 2009).
Table 2 shows the parameters for each adsorption isotherm model
evaluated, together with the computed c2 values. The Langmuir
isotherm model is based on the assumption that all adsorption sites
are alike and equally energetic, making the surface homogeneous
(Vimonses et al., 2009b). Whilst the Langmuir constant (qm)
represents monolayer saturation at equilibrium when the adsor-
bent surface is covered by dye molecules and helps to explain the
adsorption performance. From the fitting of experimental data
using the Langmuir isotherm, it was found that there were differ-
ences between the model-fitted and experimentally measured
adsorption capacities. These differences could be due to the steric
hindrance originating from the bulky size of MB molecules (Alver
and Metin, 2012). The other Langmuir constant (KL) is used to

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
10 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

Fig. 7. Effect of zeolite loading on the removal efficiency and the adsorption capacity (mg/g) of: (a) AT modified zeolite and (b) BT modified zeolite. Conditions: initial MB con-
centration 18 ppm; neutral pH; operating temperature 25  C; average relative error ±10%.

indicate the affinity of dye molecules for the adsorbents used,
whereby a lower KL value dictates lower affinity and vice versa. It
was found that the affinity of MB molecules for AT modified zeolite
was significantly higher than that of BT modified zeolite. The sep-
aration factor (RL) for both AT and BT modified zeolites were
computed to be within the favourable range of 0 < RL < 1. This
validated a favourable adsorption process of MB removal using
physicochemical-modified zeolite adsorbents.
On the other hand, the Freundlich isotherm model is usually
used to describe a heterogeneous adsorption system. From this
study, it was found that the Freundlich constant (KF) for both AT and
BT modified zeolites was in the range of 0.3e1.6. In addition, it was
also found that one of the Freundlich parameters (1/n) had values
within the range of 0.39e0.45 that the isotherm deemed favourable
for the experimental data. As for the Redlich-Peterson isotherm
model, it can be seen that the g-values for both AT and BT modified
zeolites were close to unity, indicating that the isotherm was
approaching that of the Langmuir isotherm model. Meanwhile, the
Koble-Corrigan isotherm model is exponentially dependent to the
equilibrium concentration. According to the c2 values in Table 2, it
was shown that the Koble-Corrigan isotherm model was best
correlated to the experimental data. In this instance, the c2 value
obtained for this model was the lowest among the evaluated
adsorption isotherm models, indicating the least deviation
between the model-fitted and experimental-measured adsorption
capacities. Thus, this confirmed that the Koble-Corrigan isotherm
model provided the best fit for MB adsorption on AT and BT
modified zeolite adsorbents.
3.4.2. Adsorption kinetics
According to Vimonses et al. (2009b), the Lagergren's kinetics
equation (i.e., more commonly known as pseudo-first order equa-
tion) is used for the adsorption process in an aqueous solution. It
assumes that the solute uptake rate is directly proportional to the

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zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 11

Fig. 8. Effect of initial MB concentration on the adsorption capacity (mg/g) of: (a) AT modified zeolite and (b) BT modified zeolite. Conditions: zeolite loading 0.6 g; neutral pH;
operating temperature 25  C; average relative error ±5%.

Table 2
Adsorption isotherm model parameters and error analysis for the adsorption of MB molecules onto modified zeolites.

Isotherm model Parameters AT modified zeolite BT modified zeolite

Langmuir qm (mg/g) 2.113 1.089

KL (L/mg) 3.032 0.3575
RL 0.0171 0.1275
c2 0.1338 0.07535
(1/n)
Freundlich KF (mg/g)$(L/mg) 1.624 0.3524
1/n 0.449 0.3928
c2 0.1917 0.09589
Redlich-Peterson AR 6.413 0.3898
BR 3.036 0.3589
g 0.999 0.999
c2 0.1339 0.07539
Koble-Corrigan AK 357.51 0.01506
BK 235.8 0.01915
n 3.345 5.968
c2 0.00098 0.00171

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12 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

Table 3
(a) Pseudo-first order analysis for AT modified zeolite and BT modified zeolite in the adsorption of MB dye. (b) Pseudo-second order analysis for AT modified zeolite and (b) BT
modified zeolite in the adsorption of MB dye. Conditions: zeolite loading 0.6 g; neutral pH; operating temperature 25  C.

MB concentration (ppm) AT modified zeolite BT modified zeolite Experimental data

AT modified zeolite BT modified zeolite

1 1
qec (mg/g) k1 (min ) c2
qec (mg/g) k1 (min ) c2
qex (mg/g) qex (mg/g)

(a) Pseudo-first order kinetic Parameters (R2 ¼ 0.0652e0.12147)

5 0.0783 0.0053 6.0338 0.2121 0.0023 4.8689 0.4127 0.2890
10 0.1768 0.0032 0.1066 0.0053 0.8450 0.6362
15 0.3567 0.0018 0.1952 0.0044 1.2021 0.7592
20 1.2034 0.0018 1.8493 0.0009 1.5033 0.8122
(b) Pseudo-second Order Kinetic Parameters (R2 ¼ 0.99994e1)
5 0.4106 116.5356 0.00012 0.2845 322.6825 0.00048 0.4127 0.2890
10 0.8382 21.9299 0.6316 41.2936 0.8450 0.6362
15 1.1962 110.9359 0.7555 48.0050 1.2021 0.7592
20 1.4972 446.0904 0.7953 21.9591 1.5033 0.8122

difference between saturation concentration and the amount of
solid uptake with time. Table 3(a) shows the pseudo-first order
analysis for AT and BT modified zeolites in the adsorption of MB
dye. From the table, it is apparent that the pseudo-first order model
provides a poor fitting for the experimental data obtained by
varying the initial MB concentration between 5 ppm and 20 ppm. It
can also be observed that the computed equilibrium adsorption
capacities based on the kinetic model were not acceptable, as they
were essentially lower than that of the experimental data. These
disparities are further substantiated by lower R2 values of
0.06e0.12, and higher c2 values ranging from 4 to 6 for both AT and
BT modified zeolites. Therefore, it is validated that the adsorption of
MB on both AT and BT modified zeolites does not follow the
pseudo-first-order model in all the studied cases.
This kinetic model is applicable through the assumption that the
overall adsorption rate is limited by the rate of adsorbate diffusion
in the adsorbent pores (Plazinski et al., 2013). Table 3(b) shows the
pseudo-second order analysis for AT and MT modified zeolites.
From the table, it can be observed that the experimental data fit to
the pseudo-second order kinetic model for both AT and BT modified
zeolites. It was found that the experimental data were perfectly
fitted to this model, as supported by exceptionally high R2-values of
greater than 0.9999, as well as insignificant c2 values that are lower
than 0.0005. The fitting of experimental data to the pseudo-second
order kinetics model implies that the adsorption mechanism re-
volves around the adsorbate and adsorbent (Vimonses et al.,
2009a).
performance. Following the physicochemical methods, batch
adsorption studies were carried out to evaluate the highest removal
efficiency of MB under varying adsorption conditions of: pH, initial
MB concentration and modified zeolite loading. Results showed
that the AT modified zeolite (using 0.4 M HCl) and BT modified
zeolite (using 4 M NaOH) are capable of enhancing the adsorption
capacity of natural zeolite from 41% to 98.8% and 52.2%, respec-
tively. The fitting of adsorption data to isotherm and kinetic models
showed that the data were best represented using the Koble-
Corrigan and pseudo-second order models. Owing to the better
adsorption performance and significantly lesser requirements in
terms of acid concentration and treatment duration, the AT modi-
fied zeolite is preferred and proven to be a cost-effective solution to
be used as low-cost adsorbent for wastewater treatment.
Acknowledgement
The authors are grateful to the financial support from the
Chemical Engineering Discipline, School of Engineering, Monash
University Malaysia. Similar gratitude also goes to the Advanced
Engineering Platform (AEP), Monash University Malaysia. In addi-
tion, the authors are also highly indebted to the endless assistance
given by the Subject Editor, Dr. Krzysztof Urbaniec, on improving
the quality of the manuscript.
Appendix A. Supplementary data

Supplementary data related to this article can be found at http://

4. Conclusion
Through this study, it was found that simple physicochemical
methods of treating natural zeolite with acid, base and combined
thermal treatment are capable of enhancing its adsorption capacity
and therefore its removal efficiency. From the optimisation studies
involving different physicochemically modified zeolite adsorbents
of AT, BT, ATT and BTT types, it was found that both the AT and BT
modified zeolites are far superior to those involving combined
acid/base and thermal treatment (i.e. ATT and BTT modified zeo-
lites). Further understanding on the impact of acid and base
treatments on the surface characteristics and properties of AT and
BT modified zeolites were achieved through advanced characteri-
sation using FE-SEM, FTIR and BET measurements. It was found that
acid treatment was more effective than base treatment in
increasing the overall BET specific surface area of up to 21.40 m2/g,
as well as the formation of mesopores with diameter range of
2 nme50 nm for AT modified zeolite. These physical changes are
found to be strongly correlated to the enhancement in adsorption
dx.doi.org/10.1016/j.jclepro.2016.01.056.
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zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
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