Indones. J. Chem.

, 2018, 18 (4), 733 - 741 733

1
Adsorption of Methylene Blue on the Composite Sorbent
Based on Bentonite-Like Clay and Hydroxyapatite

Alexandr Ivanovich Vezentsev1, Dang Minh Thuy1,2,*,

Lidia Fedotovna Goldovskaya-Peristaya1, and Nadezhda Alexandrovna Glukhareva1
1Belgorod State National Research University, 85 Pobedy St., Belgorod 308015, Russia
2Russian-Vietnamese Tropical Center, 44 Nguyen Van Huyen St., Cau Giay, Hanoi, Vietnam

Received July 16, 2018; Accepted September 25, 2018

ABSTRACT

The adsorption of methylene blue from model aqueous solutions on bentonite-like clay, hydroxyapatite, and a
composite sorbent has been investigated. The kinetic and thermodynamic parameters of adsorption in the temperature
range 298–333 К have been calculated. The process is found to obey Langmuir isotherm equation. It is spontaneous
but slightly endothermic. The maximal sorption capacity of the composite sorbent toward methylene blue is 175.4 mg/g
at 25 °С that is 1.3 times higher than that for bentonite-like clay and 17.8 times hgiher than that for hydroxyapatite.
Kinetics of the process is due to the combination of external and internal diffusion and can be described better by the
model of pseudo-second order reaction.

Keywords: adsorption; thermodynamics; methylene blue; composite sorbent

ABSTRAK

Telah dilakukan penelitian mengenai adsorpsi metilen biru dari model larutan berair pada lempung bentonit,
hidroksiapatit, dan komposit sorben. Parameter kinetik dan termodinamik dari adsorpsi pada rentang suhu 298-333 К
telah dihitung. Dari perhitungan didapatkan bahwa proses adsorpsi mengikuti persamaan isoterm Langmuir yang
bersifat spontan tetapi sedikit endotermik. Kapasitas penyerapan maksimum metilen biru menggunakan komposit
sorben adalah 175,4 mg/g pada 25 °C. Kapasitas penyerapan maksimum ini 1,3 kali lebih tinggi dibanding adsorpsi
dengan lempung bentonit dan 17,8 kali lebih tinggi dibanding menggunakan hidroksiapatit. Kinetika proses ini
disebabkan oleh kombinasi difusi eksternal dan internal dan dapat digambarkan dengan lebih baik menggunakan
model kinetika reaksi pseudo orde dua.

Kata Kunci: adsorpsi, termodinamik; metilen biru; sorben komposit

INTRODUCTION There are some ways to remove organic dyes,

namely biodegradation [5], coagulation [6], oxidative
Dyes have been known to be important raw catalytic degradation [7], membrane technologies [8],
materials in textile, polygraphic industry, and other related electrochemical degradation [9], adsorption [10].
branches. The discharge of wastes containing organic However many organic dyes are resistant to sunlight,
dyes into natural water sources results in the decrease in temperature effect, and many chemical reagents
dissolved oxygen concentration. It prevents light because of their complicated aromatic molecular
penetration and inhibits photosynthesis in plants. Many structures, so they are difficult to remove from water by
organic dyes are harmful to human beings and toxic to usual chemical methods [11-12]. On the contrary, the
microorganisms. Besides, they can form coordination adsorption technique is one of the most popular
compounds with some poisonous metal ions. methods of organic dyes removal because it is easy and
Methylene blue (MB) is used as a disinfectant in highly efficient.
medicine, in pharmaceutical formulations, in pesticides Nowadays search of inexpensive and readily
production, varnish and lacquer manufacturing, among available adsorbents brings scientists to find the more
others [1]. Cationic dyes such as MB are reported to be efficient use of natural, artificial, and synthetic materials
more toxic than anionic ones [2]. MB irritates human skin, as sorbents [13-14]. Clay minerals are the most
eyes, and can even have a carcinogenic effect [3-4]. That widespread among natural minerals applied as
is why the removal of MB and other dyes from wastewater adsorbents. Clay minerals of structural type 2:1 with
is a serious ecological problem all over the world. changing basal spacing (montmorillonites) are known to
* Corresponding author. Tel : +7-952-438-86-25 DOI: 10.22146/ijc.37050
Email address : [email protected]

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734 Indones. J. Chem., 2018, 18 (4), 733 - 741

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Table 1. Some colloidal properties of the adsorbents
Adsorbents
Parameters
ВТ6 HA C-HA
Zeta-potential of particles in water at рН = 7, mV – 25 +2 – 22
Specific surface area, m2/g 52.11 85.78 96.81
рНpzc. (zero point of charge) 5.7 6.9 6.8

be effective. Molecules of water and organic substances The preparation of the composite sorbent (C-HA):
as well as positively or negatively charged ions can be A 5 g sample of bentonite-like clay was added to a 5 L
included in the inter-package cavities of the minerals. Ion vessel containing 1880 mL of the saturated solution of
exchange with the ions from the surroundings can take Ca(OH)2. The suspension was stirred with the stirring
place in them. The clay minerals concerned can swell shaft mentioned above for 2 h. The required volume of a
because of increase of space between basal layers where 10% solution of orthophosphoric acid was added with
absorbed ions or molecules are located [15]. the rate of 1 mL/min at intensive stirring (1000 rpm) to
The application of apatite materials for adsorption provide the mole relation Са:Р equal to 1.67. Then the
and immobilization of various pollutants is a promising solution was stirred for 2 h. The precipitate formed was
technique because of their high absorptivity, ease of use allowed to settle for 24 h at room temperature and then
and environmental friendliness [16]. Hydroxyapatite (HA) separated, filtered, dried and powdered as described
Ca10(PO4)6(OH)2 has been known as the main inorganic above.
constituent of bones and teeth of mammals and the Some characteristics of the adsorbents are given
component of phosphate mineral rocks [17]. HA has been in Table 1. Methylene blue, C16H18ClN3S·3H2O supplied
used for the removal of toxic heavy metal ions, dyes, by Sigma-Aldrich was used as the adsorbate.
fluoride ions from aqueous solutions [18-22]. However, to
separate suspended highly dispersed solid particles of HA Instrumentation
from the aqueous solutions after adsorption is quite
difficult [19-23]. Positive results of the application of To estimate if a surface is positively or negatively
composite materials based on HA for water purification charged, zeta-potential of particles of the sorbents
are known. dispersed in distilled water was measured by
The aim of the work is the investigation of methylene electrophoresis method on Zetasizer Nano ZS (Malvern
blue sorption on bentonite-like clay, hydroxyapatite, and Instruments).
the composite sorbent based on bentonite-like clay and The ability of the investigated materials to adsorb
hydroxyapatite (C-HA) prepared by the chemical methylene blue was studied at static conditions at 25 ±
precipitation. 2 °С using model aqueous solutions of the dye with initial
concentrations from 5 to 350 mg/L. 50 mL of the model
EXPERIMENTAL SECTION solutions were added to 100 mL cone flasks containing
the samples of the sorbents 0.1 ± 0.001 g, the mixtures
Materials were shaken thoroughly. After the process had been
completed the suspensions were centrifuged with the
Three materials were used as sorbents, namely rate 6000 rpm for 10 min. The residual concentration of
bentonite-like clay (ВТ6) from Tam Bo deposited (Lam MB in the solutions was measured by
Dong Province, Vietnam), hydroxyapatite (HA), and the spectrophotometry on SPECORD 120 PLUS (Germany)
composite sorbent (C-HA) prepared by the method at λ = 663 nm in a 10 mm cuvette.
described earlier [24]. Adsorption was calculated according to the
Hydroxyapatite synthesis: HA was synthesized by following eq. (1):
adding a 10% (mass) solution of orthophosphoric acid to
qe 
Ci  Ce  V
(1)
Ca(OH)2 solution with the rate 1.5–2.2 mL/min per liter of m
the saturated solution of calcium hydroxide. The reaction where qe is mass of MB adsorbed on adsorbents, mg/g;
mixture was stirred for 20–30 minutes with the stirring Ci, Ce are the initial and equilibrium concentrations of MB
(1000 rpm) till the pH of the mixture achieved 10.5 ± 0.5, solutions respectively, mg/L; V is the volume of the
then the mixture was allowed to settle for 24 h. The solution, L; m is mass of absorbent, g.
product obtained was separated from the mother liquor by рН of solutions varied from 4 to 12 by adding 0.1
filtration, rinsed with distilled water and then dried in a М HCl and 0.1 М NaOH solutions. pH was measured
baker at 105 ± 5 °С for 5 h. The samples were powdered with the pH meter Multitest IPL-101 (Russian
in a porcelain mortar. Federation).

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The effectiveness of adsorption of MB from model
aqueous solutions was calculated as:
Ci  Ce
H 100 % (2)
Ci

RESULT AND DISCUSSION

pH Effect on the Effectiveness of Adsorption of MB

from Model Aqueous Solutions

рН value of dye solutions is essential to adsorption

and influences substantially on its effectiveness because
properties of the adsorbent surface depend on it. The Fig 1. The dependence of the effectiveness of
dependence of the effectiveness of adsorption of MB from adsorption of MB from model aqueous solutions on pH
model aqueous solutions on pH is shown in Fig. 1. for the adsorbents
The results demonstrate that the effectiveness of
MB adsorption increases more significantly as pH raises
from 8 to 12. It increases from 92 to 100% for ВТ6, from
7 to 38% for HA, and from 96 to 100% for C-HA in the pH
range mentioned above. At lower pH, the effectiveness of
MB adsorption decreases. This behavior can be
explained by the reactions on the hydroxyapatite surface
in aqueous media [25]. The scheme of the elementary Fig 2. The scheme of the elementary fragment of HA
fragment of HA surface is shown in Fig. 2. The surface
dissociation of main groups on the surface according to
the schemes Ca – OH+  Ca2+ + OH– and H2PO4– 
HPO42– + H+ is accompanied by the release of OH– or H+
ions to the outer side of the double-electric layer, which
provides a positive or negative charge of HA particles.
pH values of zero point of charge (рНpzc.) for HA and
C-HA are 6.9 and 6.8 respectively. In basic media (pH >
рНpzc) protons split out and the surface of HA and C-HA
gets a negative charge that promotes adsorption of MB
cations. The surface of both of HA and C-HA is negatively
charged at acidic pH (pH < рНpzc) mainly due to the
dissociation like as Ca – OH+  Ca2+ + OH–. As a result,
the positively charged surface cannot absorb MB cations
effectively because of electrostatic repulsion [14]. Fig 3. The mechanism of MB sorption on HA surface:
However, despite low pH, electrostatic repulsion, and (a) – Electrostatic attraction; (b) – Lewis acid-base
competitive adsorption of Н+ ions, a substantial amount of interaction; (c) – Hydrogen bonding
amount of MB is absorbed.
The effectiveness of MB adsorption in pH range 4– The analysis of these results showed that the
8 is 80–92% for BT6, 6–7% for HA and 91–96% for C-HA. removal efficiency MB on the BT6 sorbent increased
This result can be explained by other mechanisms of MB with increasing pH values and reached than 92%. The
adsorption on both of HA and C-HA. As it is reported in removal efficiency for pH < 4 is lower due to the
Ref. [14], the group ≡P-OH can bind with the group С=N competition between the cations MB and protons H +
of MB molecule by hydrogen bond. Besides, the nitrogen from the acidic medium. These can be explained: For
atom of MB can interact with Ca2+ in HA through Lewis bentonite-like clay have finely divided layered silicate
acid-base interaction. The scheme of possible processes can be a source of both a constant (not dependent on
in MB adsorption on HA surface is shown in Fig. 3. pH) and variable surface charge (dependent on pH). The
At рН < рНpzc the adsorption is mainly due to the constant charge is characterized mainly by three-
mechanisms (b) and (c), whereas at рН > рНpzc it goes by layered and four-layered clay silicate and is associated
(a) and (b). with the manifestation of heterovalent isomorphism in

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1
the crystal lattice-isomorphous substitution of Si4+ toAl3+ ln(qe  qt )  lnqe  k1.t (3)
in a tetrahedral grid and/or isomorphic substitution of Al3+ t 1 1
to Mg2+ in octahedral. The source of the variable charge,   .t (4)
qt k2.qe2 qe
which is localized on the lateral cleavages of clay
crystallites. Hydroxyl groups located on the lateral where k1 is the rate constant in the pseudo-first-order
cleavages of clay crystallites are capable of protonation- model, min–1; k2 is the rate constant in the pseudo-
deprotonation reactions depending on the pH of the second-order model, g∙mg–1∙min–1; qt is mass of
surrounding solution [26]. adsorbed MB on unit mass of an adsorbent at time
The broken bonds and M–OH bonds along the moment t, mg∙g–1.
surfaces of the clay crystals result in hydrolysis [27]. The dependences ln(qe-qt) = f(t) and t/qt= f(t) for
At low pH (pH < рНpzc), electrostatic repulsion MB adsorption process on the sorbents are shown in
occurred between the MB cations and the edge groups Fig. 5.
with a positive charge (M-OH2+) on the surface as follows: The pseudo-first order kinetic equations are found
to describe satisfactorily the experimental data just for
MOH  H  MOH2
initial stages of the process, whereas the pseudo-
At high pH (pH > рНpzc), the surface of clay becomes second-order model is acceptable in all time interval
negatively charged and electrostatic repulsion decreases, investigated. Values of k 1, k2, and qe calculated
the MB cations in solution will be attracted to the surface according to the eq. (3) and (4) are given in Table 2.
according to the following reactions: Correlation coefficients (R2) are better when the
MOH  OH  MO  H2O pseudo-second-order model is applied. Values of
where M is the cation of Si2+, Al3+ or Fe2+ equilibrium concentrations qe calculated from the
There might be another mode of adsorption (ion dependencies are in close agreement with experimental
exchange) and the results are in harmony with the
literature reports [27-28].

Kinetics of MB Adsorption on the Experimental

Sorbents

Adsorption kinetics is one of the most important

issues that are used to estimate the effectiveness of
adsorbents. The obtained kinetic curves for MB
adsorption on the sorbents involved are given in Fig. 4.
As it can be seen the adsorption equilibrium is achieved
in 20–40 min.
The pseudo-first and pseudo-second-order models
are widely used to describe the kinetics of adsorption on
a solution–solid boundary [11,29]. The corresponding
Fig 4. The kinetic curves for MB adsorption on the
linearized kinetic equations are as follows:
experimental sorbents

Fig 5. The kinetic dependences for MB adsorption on the experimental sorbents as a pseudo-first (a) and pseudo-
second (b) order process

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Table 2. Kinetic parameters of MB adsorption on the experimental sorbents
pseudo-first model pseudo-second order model
qe experimental,
Adsorbent k1 qe k2 qe
mg∙g–1 R2 R2
min–1 mg∙g–1 g∙mg–1∙min–1 mg∙g–1
ВТ6 65.85 0.0955 14.73 0.885 0.0176 66.67 0.999
HA 8.57 0.0678 2.07 0.812 0.0583 8.81 0.999
C-HA 72.08 0.0726 8.16 0.886 0.0251 72.46 0.999

data in this case. On the contrary, calculated and

experimental values qe are quite different if the pseudo-
first-order equation is used.
The most part of sorption processes occurs by a
series of steps. These multi-step mechanisms include (i)
diffusion of a sorptive through a liquid film surrounding
solid particles (the process of external mass transport), (ii)
diffusion inside the particles (intraparticle diffusion), and
(iii) a physical or chemical adsorption [30].
First, to describe the mechanism of MB adsorption
on the investigated sorbents and to determine its limiting
stage we used Weber and Morris model [31], which is
applicable to intraparticle diffusion. According to the
Fig 6. The experimental dependences of qt on t1/2 for the
model, qt depends on time as
experimental sorbents
qt  k i ( t1/2 ) (5)
where ki – the rate constant for intraparticle diffusion,
(mg/g min1/2).
The dependences of adsorption qt on t1/2 calculated
from experimental data are given in Fig. 6. A linear
approximation of the experimental data for all three
sorbents gives two straight-lined segments which point to
two stages of MB diffusion to the sorbents. Here the
kinetic parameters corresponding to intraparticle diffusion
are characterized by the slope of the second segment.
The Y-intercept is proportional to the thickness of the film
surrounding the particles of the sorbents [30-31].
To determine the limiting stage of the sorption Fig 7. The dependence of Bt on t
process the equation given by Boyd [29,31] was used
F  1  (6 / π 2 ) exp  Bt    (6) Adsorption Isotherms
where F is the fraction of solute adsorbed at different
times t, and Bt is a mathematical function of F , which are To interpret experimental data the linearized
given by the following relationships Langmuir and Freundlich equations were used
Сe C 1
F  qt / qe (7)  e (9)
qe qm qm. KL
Bt   0.4977  ln(1 qt / qe ) (8)
1
Using experimental data for qt and qe we calculated ln qe  lnKF  ln Ce (10)
n
Bt. The linear dependence of Bt on t (Fig. 7) is considered
where qm is the maximal adsorption (adsorption
to argue for interdiffusion limiting [31].
capacity) mg/g; KL Langmuir constant, L/mg; KF, n are
Our dependences are linear for all investigated
constants in Freundlich sorption isotherm.
sorbents but they do not pass through the origin. This
The experimental adsorption isotherms at 298 К,
means that the external mass transfer seems to control
рН = 8–9, and the dependences linearized according to
the process of sorption [29,31].
both of Langmuir and Freundlich equations are shown in
Fig. 8.

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738 Indones. J. Chem., 2018, 18 (4), 733 - 741

Fig 8. The isotherms of MB adsorption on the experimental sorbents (a). The linearized isotherms according to
Langmuir (b) and Freundlich (c) equations

Table 3. Parameters of Langmuir and Freundlich equations for MB adsorption isotherms on the investigated sorbents
Parameters
Sorbent T, (K) Langmuir Freundlich
qm, mg/g KL, L/mg R2 KF n R2
ВТ6 298 136.98 0.323 0.996 31.928 2.255 0.955
313 138.89 0.391 0.994 35.769 2.377 0.961
333 140.85 0.483 0.992 39.721 2.395 0.956
HA 298 9.88 0.216 0.996 2.380 2.433 0.970
313 10.67 0.213 0.992 2.559 2.427 0.979
333 11.21 0.229 0.989 2.808 2.480 0.985
C-HA 298 175.44 0.252 0.995 36.98 2.322 0.946
313 181.82 0.314 0.992 41.89 2.321 0.950
333 185.19 0.422 0.991 49.01 2.392 0.954

Adsorption ability of the sorbents can be seen to 52.11; HA = 85.78; C-HA = 96.81 m 2/g). Parameters of
increase in the same consequence like as the rate of MB both Langmuir and Freundlich equations calculated from
adsorption HA < BT6 < C-HA. The maximal adsorption the linearized isotherms are given in Table 3.
(adsorption capacity) for the composite sorbent C-HA is Data from Table 3 and Fig. 8 (b, c) demonstrate
175.4 mg/g at 298 К which is 1.28 times more than that that Langmuir equation seems to be a bit more
for bentonite-like clay, and 17.8 times more than that for preferable to describe adsorption of MB on bentonite-
HA. This behavior can be explained: The adsorption of like clay BT6, hydroxyapatite HA, and composite sorbent
MB is primarily influenced by the surface charge on the C-HA (R2 > 0.99).
adsorbent [32] (Zeta-potential of BT6 = – 25 mV; HA = +
2 mV; C-HA = – 22 mV). In addition, methylene blue can Thermodynamics of MB Adsorption on the Sorbents
be adsorbed both on the surface of montmorillonite and in
the interlayer space (ion exchange). The large specific To describe thermodynamics of MB adsorption the
surface area of C-HA promotes an increase in the isotherms at three values of temperature, namely 298,
adsorption of the dye (Specific surface area of BT6 = 313, and 333 К, were obtained (рН = 10.0). The constant

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 Indones. J. Chem., 2018, 18 (4), 733 - 741 739

Fig 9. MB adsorption isotherms at three temperatures on the experimental sorbents: (a) BT6, (b) HA, (c) C-HA

Table 4. Thermodynamic functions for MB adsorption on the investigated sorbents

Т G0 Н0 S0
Sorbent
(К) kJ/mol kJ/mol J/mol∙K
298 – 38.56
ВТ6 313 – 40.98 9.47 161.2
333 – 44.21
298 – 37.52
HA 313 – 39.48 1.43 130.7
333 – 42.09
298 – 37.93
C-HA 313 – 40.45 12.17 168.1
333 – 43.81

of adsorption equilibrium and its dependence on H0 S0

temperature make it possible to estimate Gibbs free lnK0    (13)
RT R
energy change, enthalpy, and entropy for the process.
The experimental isotherms of MB adsorption at
The standard Gibbs free energy change was
different temperatures are shown in Fig. 9. Values of
calculated as follows:
enthalpy Н0 and entropy S0 were found from the slope
G0  RT lnK0 (11) and intercept of linear dependence of lnK0 on reciprocal
where R is gas constant, T is absolute temperature, K0 is temperature (Fig. 10). The results are given in Table 4.
the constant of adsorption equilibrium (dimensionless). As it can be seen the enthalpy changes Н0 are slightly
Values K0 can be found using Langmuir constants KL positive in the temperature range investigated that
according to the relationship [33]: argues for the endothermic character of the process.
K 0  KL L / mg  1000  MMB (g / mol)  55.5 (12) Values of standard Gibbs free energy change G0 are
MMB = 319.85 (g/mol) is the molar mass of MB. negative and they decrease in the range of temperature
Temperature dependence of the equilibrium 298–333 К. They point out the spontaneity of MB
constant can be written as adsorption on the adsorbent involved and the values are

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1
M.C., 2012, Adsorption studies of cationic dyes
onto Ashoka (Saraca asoca) leaf powder, J. Taiwan
Inst. Chem. Eng., 43 (4), 604–613.
[4] Brown, M.A., and DeVito, S.C., 1993, Predicting
azo dye toxicity, Crit. Rev. Environ. Sci. Technol.,
23 (3), 249–324.
[5] Kapdan, I.K., and Kargi, F., 2002, Simultaneous
biodegradation and adsorption of textile dyestuff in
an activated sludge unit, Process Biochem., 37 (9),
973–981.
[6] Prasad, R.K., 2009, Color removal from distillery
spent wash through coagulation using Moringa
oleifera seeds: Use of optimum response surface
Fig 10. The dependences of ln K0 on reciprocal methodology, J. Hazard. Mater., 165 (1-3), 804–
temperature for MB adsorption on the experimental 811.
sorbents [7] Solozhenko, E.G., Soboleva, N.M., and Goncharuk,
V. V., 1995, Decolourization of azodye solutions by
consistent with other results [34]. The process becomes a Fenton’s oxidation, Water Res., 29 (9), 2206–2210.
bit more preferable as the temperature rises. Positive [8] Buckley, C.A., 1992, Membrane technology for the
entropy changes S0 correspond to the increase of treatment of dyehouse effluents, Water Sci.
freedom in the system because of MB adsorption. Entropy Technol., 25 (10), 203–209.
increase can be explained by the release of hydrated [9] Panizza, M., Barbucci, A., Ricotti, R., and Cerisola,
inorganic cations from adsorbents and structural changes G., 2007, Electrochemical degradation of
as a result of MB molecules interaction with an active methylene blue, Sep. Purif. Technol., 54 (3), 382–
group on the surfaces of adsorbents [35]. 387.
[10] Ngapa, Y.D., Sugiarti, S., and Abidin, Z., 2016,
CONCLUSION Hydrothermal transformation of natural zeolite from
Ende-NTT and its application as adsorbent of
The results of the investigation have shown that cationic dye, Indones. J. Chem., 16 (2), 138–143.
adsorption of methylene blue on the adsorbents involved [11] Zhang, J., Ping, Q., Niu, M., Shi, H., and Li, N.,
obeys Langmuir isotherm equation. It is spontaneous but 2013, Kinetics and equilibrium studies from the
slightly endothermic. The maximal sorption capacity of the methylene blue adsorption on diatomite treated with
composite sorbent is found to be equal 175.4 mg/g at sodium hydroxide, Appl. Clay Sci., 83-84, 12–16.
25 °С that is 1.3 times higher than that for bentonite-like [12] Akar, T., Anilan, B., Gorgulu, A., and Akar, S.T.,
clay and 17.8 times higher than that for hydroxyapatite. 2009, Assessment of cationic dye biosorption
Kinetics of the process is due to the combination of characteristics of untreated and non-conventional
external and internal diffusion and can be described better biomass: Pyracantha coccinea berries, J. Hazard.
by the model of pseudo-second order reaction. The Mater., 168 (2-3), 1302–1309.
results can be useful in the development of adsorption [13] Ciobanu, G., Ilisei, S., Harja, M., and Luca, C.,
technology of natural and wastewater purification from 2013, Removal of Reactive Blue 204 dye from
methylene blue and other organic cationic dyes using the aqueous solutions by adsorption onto
composite sorbent based on bentonite-like clay and nanohydroxyapatite, Sci. Adv. Mater., 5 (8), 1090–
hydroxyapatite. 1096.
[14] Wei, W., Yang, L., Zhong, W.H., Li, S.Y., Cui, J.,
REFERENCES and Wei, Z.G., 2015, Fast removal of methylene
blue from aqueous solution by adsorption onto
[1] Zhang, F., Zhao, Z., Tan, R., Guo, Y., Cao, L., Chen, poorly crystalline hydroxyapatite nanoparticles, Dig.
L., Li, J., Xu, W., Yang, Y., and Song, W., 2012, J. Nanomater. Biostruct., 10 (4), 1343–1363.
Selective and effective adsorption of methyl blue by [15] Muzakky, and Supriyanto, C., 2016, Modification of
barium phosphate nano-flake, J. Colloid Interface three types of bentonite with zirconium oxide
Sci., 386 (1), 277–284. chloride (ZOC) of local products using intercalation
[2] Hao, O.J., Kim, H., and Chiang, P.C., 2000, process, Indones. J. Chem., 16 (1), 14–19.
Decolorization of wastewater, Crit. Rev. Environ. Sci. [16] Scheckel, K.G., Diamond, G.L., Burgess, M.F.,
Technol., 30 (4), 449–505. Klotzbach, J.M., Maddaloni, M., Miller, B.W.,
[3] Gupta, N., Kushwaha, A.K., and Chattopadhyaya, Partridge, C.R., and Serda, S.M., 2013, Amending

Alexandr Ivanovich Vezentsev et al.

 Indones. J. Chem., 2018, 18 (4), 733 - 741 741

1
soils with phosphate as means to mitigate soil lead Properties of Soils. Adsorption. Cation Exchange,
hazard: A critical review of the state of the science, eds., Chukov, S.N., and Pinski, D.L., Tula, Moskva,
J. Toxicol. Environ. Health Part B, 16 (6), 337–380. 172.
[17] Sunarso, Sutarno, Tsuru, K., Ana, I.D., and Ishikawa, [27] Tahir, S.S., and Rauf, N., 2006, Removal of a
K., 2011, Effect of crosslinking to the mechanical cationic dye from aqueous solutions by adsorption
property of apatite gelatin hybrid for bone substitution onto bentonite clay, Chemosphere, 63 (11), 1842–
purposes, Indones. J. Chem., 11 (3), 267–272. 1848.
[18] Wang, Y., Chen, N., Wei, W., Cui, J., and Wei, Z., [28] Weng, C.H., and Pan, Y.F., 2007, Adsorption of a
2011, Enhanced adsorption of fluoride from aqueous cationic dye (methylene blue) onto spent activated
solution onto nanosized hydroxyapatite by low- clay, J. Hazard. Mater., 144 (1-2), 355–362.
molecular-weight organic acids, Desalination., 276 [29] Kumar, K.V., Ramamurthi, V., and Sivanesan, S.,
(1-3), 161–168. 2005, Modeling the mechanism involved during the
[19] Dong, L., Zhu, Z., Qiu, Y., and Zhao, J., 2010, sorption of methylene blue onto fly ash, J. Colloid
Removal of lead from aqueous solution by Interface Sci., 284 (1), 14–21.
hydroxyapatite/magnetite composite adsorbent, [30] Porkodi, K., and Kumar, V., 2007, Equilibrium,
Chem. Eng. J., 165 (3), 827–834. kinetics and mechanism modeling and simulation of
[20] Jang, S.H., Jeong, Y.G., Min, B.G., Lyoo, W.S., and basic and acid dyes sorption onto jute fiber carbon:
Lee, S.C., 2008, Preparation and lead ion removal Eosin yellow, malachite green and crystal violet
property of hydroxyapatite/polyacrylamide composite single component systems, J. Hazard. Mater., 143
hydrogels, J. Hazard. Mater., 159 (2-3), 294–299. (1-2), 311–327.
[21] Jang, S.H., Min, B.G., Jeong, Y.G., Lyoo, W.S., and [31] Wang, S., and Li, H., 2007, Kinetic modelling and
Lee, S.C., 2008, Removal of lead ions in aqueous mechanism of dye adsorption on unburned carbon,
solution by hydroxyapatite/polyurethane composite Dyes Pigm., 72, 308–314.
foams, J. Hazard. Mater., 152 (3), 1285–1292. [32] Chandrasekhar, S., and Pramada, P.N., 2006, Rice
[22] Hou, H., Zhou, R., Wu, P., and Wu, L., 2012, husk ash as an adsorbent for methylene blue-effect
Removal of Congo red dye from aqueous solution of ashing temperature, Adsorption, 12, 27–43.
with hydroxyapatite/chitosan composite, Chem. Eng. [33] Zhou, X., and Zhou, X., 2014, The unit problem in
J., 212-213, 336–342. the thermodynamic calculation of adsorption using
[23] Choi, S., and Jeong, Y., 2008, The removal of heavy the Langmuir equation, Chem. Eng. Commun., 201
metals in aqueous solution by hydroxyapatite/ (11), 1459–1467.
cellulose composite, Fibers Polym., 9 (3), 267–270. [34] Hong, S., Wen, C., He, J., Gan, F., and Ho, Y.S.,
[24] Vezentsev, A.I., Peristaya, F.L., Glukhareva, N.A., 2009, Adsorption thermodynamics of Methylene
and Thuy, D.M., 2018, A composite sorbent based Blue onto bentonite, J. Hazard. Mater., 167 (1-3),
on bentonite-like clay and hydroxyapatite, J. 630–633.
Fundam. Appl. Sci., 10 (4S), 1099–1111. [35] Almeida, C.A.P., Debacher, N.A., Downs, A.J.,
[25] Tarasevich, Y.I., Shkutkova, E.V., and Janusz, W., Cottet, L., and Mello, C.A.D., 2009, Removal of
2012, Sorption of ions of heavy metals from aqueous methylene blue from colored effluents by adsorption
solutions on hydroxylapatite, J. Water Chem. on montmorillonite clay, J. Colloid Interface Sci.,
Technol., 34 (3), 125–132. 332 (1), 46–53.
[26] Sokolova, T.A., and Trofimov, S.Ya., 2009, Sorption

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