Applied Clay Science 90 (2014) 159–164

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Applied Clay Science

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

Research paper

High removal capacity of silver ions from aqueous solution onto

Halloysite nanotubes
Gholamreza Kiani ⁎
School of Engineering-Emerging Technologies, University of Tabriz, Tabriz, Iran

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

Article history: The adsorption of silver ions onto Halloysite nanotubes (HNTs) was investigated in aqueous solution in a batch
Received 30 December 2012 system. The natural HNTs used as adsorbent in this work were initially characterized by TEM. The amounts of
Received in revised form 16 January 2014 the silver ions adsorbed onto HNTs were influenced by initial silver ion concentration, temperature, pH, contact
Accepted 24 January 2014
time and adsorbent dose.
Available online 14 February 2014
Adsorption increased with increasing initial silver ion concentration, initial pH, and temperature. Pseudo-first-
Keywords:
order, pseudo-second-order and intraparticle diffusion models were considered to evaluate the rate parameters.
Halloysite nanotubes The adsorption followed pseudo-second-order kinetic model with correlation coefficients greater than 0.999. The
Silver ion experimental isotherm data were analyzed using the Langmuir, Freundlich and Temkin equations. The Langmuir
Adsorption isotherm model showed significant fit to the equilibrium adsorption data and the maximum adsorption capacity
Nanoadsorbent of 109.79 mg g−1 (99.8% removal) of silver ions was achieved. The thermodynamic parameters of activation such
Thermodynamic parameter as Gibbs free energy, enthalpy and entropy were also evaluated. The results indicate that HNTs could be
employed as effective nanoadsorbent for the removal of heavy metal ions.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction nanomaterials, Halloysite nanotubes (HNTs) are cheap, abundantly

Silver is a very useful raw material in various industries due to its
excellent malleability, ductility, electrical and thermal conductivity,
photosensitivity and antimicrobial properties. Significant amounts of
silver are lost in the effluents discharged from such industries and due
to the toxicity of silver to living organisms; the removal of this metal
from wastewaters is an important concern (Mahmoud et al., 2010).
Although some conventional methods for instance chemical precipita-
tion (Kim et al., 2002), ion exchange resin (Hubicki et al., 2008), oxida-
tion (Chen et al., 2013) and separation membrane (Chamoulaud and
Bélanger, 2005) can remove silver ions from their effluents, they are
partially not economical and are not efficient for low concentrations.
Therefore, new techniques such as adsorption should be sought.
Adsorption phenomenon in solution systems plays a vital role in many
areas of practical environmental technology, which are mainly in
water and wastewater treatment due to several advantages such as
high efficiency, simple operation and easy recovery/reuse of adsorbent
(Liu et al., 2009).
In recent years, natural mineral materials, due to their large surface
area, high cation exchange capacity and low costs, have been studied
for potential applications as environmental remediation agents to re-
move heavy metals from wastewater. Also nanoscopic materials are of
great interests to be developed as efficient adsorbents for metal ions, be-
cause of their high surface area to unit mass ratios. Among these
⁎ Tel.: +98 4 113393853; fax: +98 4 113294626.
E-mail address: g.kiani@tabrizu.ac.ir.
available, and durable, with high mechanical strength and biocompati-
ble (Yuri et al., 2008). Also various sorbents have been used in studies
to remove Ag ions and the heavy metals from water and wastewater
by sorption. Several studies have been proposed in the literature
about the use of new sorbents, in relation with silver ion sorption
from water solutions. These materials have some comparative advan-
tages in contrast to common sorbent materials. Literature data are sum-
marized in Table 1.
As seen in Table 1, there are researches all over the world, on the
understanding of the mechanisms of removing Ag ions through new
sorbents. HNT sorbents have been employed in literature. However,
no studies on Ag+ removal with the HNT nanoabsorbent were found.
So in this study, we have considered it of great interest to assess the abil-
ity of commercially available Halloysite nanotubes for the removal of
silver ions from aqueous solution and optimization of conditions for
its maximum adsorption. To increase the efficiency of metal removal,
various parameters have been studied. Also, the thermodynamic and
kinetic parameters of the Ag+ adsorption have been investigated.
2. Experimental details
2.1. Materials
Halloysite (premium grade) was obtained from New Zealand China
Clays Ltd (New Zealand). Halloysite was first sieved (125 μm mesh) to
remove granules to obtain 42% fine powder (HNT). A TEM image was
obtained with a JEOL JEM-2100 (Japan). The metal adsorption capacities

0169-1317/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2014.01.010
160 G. Kiani / Applied Clay Science 90 (2014) 159–164

Table 1
Comparison of maximum adsorption of Ag+ ions onto various adsorbents.

Absorbents qt (mg/g) Reference

Polyacrylonitrile nanofiber mats 105.7 Pimolpun and Pitt (2010)

Valonia tannin resin 97.08 Yurtseveri and Şengil (2012)
Natural bentonite 80 Hefne et al. (2010)
Alfalfa biomass 27.37 Herrera et al. (2003)
Conducting electroactive polymers 35 Ansari and Fallah Delavar (2008)
Calcium alginate beads 52 Torres et al. (2005)
Functionalized polyacrylonitrile 85.99 Kiani et al. (2011a,b)
Halloysite nanotubes 109.79 This study

of HNTs were measured by atomic adsorption spectrophotometer

(AA 55B, Varian SLM) at room temperature.

2.2. Adsorption experiments

The 100-mL samples containing known concentration of silver ions
and HNTs were added to Erlenmeyer flasks. The flasks were stirred
with a rate of 300 rpm in a water bath (Pars Azma, Iran). The pH of
the silver ion solutions was adjusted in the range of 4–6 with 0.1 N
HCl by using a WTW (pH720, Germany) pH-meter with a combined
pH electrode. The pH-meter was standardized with buffers before mea-
surement. At the end of the adsorption period, the solution was centri-
fuged (Hettich, EBA20, Germany) for 10 min at 4000 rpm.
The amounts of silver ion adsorbed on HNTs at any time, t, were cal-
culated from the concentrations in solutions before and after adsorp-
tion. At any time, the amount of silver ion adsorbed (mg g−1) (qt) by
HNTs was calculated from the mass balance equation as follows:
qt ¼ VðC 0 −C t Þ=W
where qt is the amount of silver ions adsorbed into HNTs at any time
(mg g−1), C0 and Ct are the concentration of silver ion before adsorption
and after contact time (mg L−1), respectively; V is the volume of silver ion
solution (L), and W is the mass of HNT sample used (g) (Kiani et al.,
2011a,b). In order to determine the best kinetic model which fits the ad-
sorption experimental data, the pseudo-first-order, pseudo-second-order
and intraparticle diffusion models were examined. The linear forms of
these models can be described by Eqs. (2)–(4):
ln ðqe −qt Þ ¼ ln qe −k1 t
t 1 1 adsorption increases with increasing initial silver ion concentration. The
¼ þ t
qt k2 qe 2 qe
Fig. 1. TEM image of HNTs.
3.1. Adsorption
3.1.1. Effect of pH
pH of the solution plays an important role in the adsorption of metal
ions from solution (Saha et al., 2010). As shown in Fig. 2, a consistent in-
crease in adsorption capacity of the HNTs was noticed as the pH in-
creased from 4 to 6. As shown in Fig. 2 the amount adsorbed does not
change with an increase of the pH from 4 to 5, but increases at pH =
6. This is attributed to the electrostatic attraction of the positively
charged silver ions with the negatively charged surface of HNTs. The
surface of HNTs bears abundant Si–OH and Al–OH groups, which can
ionize by Eq. (5):
ð1Þ
þ –
Si=Al−OH2 ←Si=Al−OH→Si=Al−O : ð5Þ
With the decreasing pH, the negatively charged HNT sites tend to be
saturated by protons, thereby the adsorption capacity decreases. In ad-
dition, the observed lower uptake in an acidic medium may be attribut-
ed to the partial protonation of the active groups and the competition of
H+ with silver ions for adsorption sites on HNTs (Luo et al., 2010).
3.1.2. Effect of contact time and initial silver ion concentration
The effect of initial silver ion concentration and contact time on the ad-
sorption rate of silver ions onto HNTs is shown in Fig. 3. The amount of sil-
ð2Þ ver ions adsorbed at any time increases from 0.449 to 1.01 m mol g−1
(48.11 (96.22 removal %) to 109.79 (99.8 removal %) mg g−1) by increas-
ing the initial silver ion concentration from 50 to 110 mg L−1. Therefore,
ð3Þ

1=2
qt ¼ ki t þC ð4Þ

where qe is the amount of the adsorbed silver ion at equilibrium per unit
mass of the adsorbent (mg g−1), k1 (min−1), k2 (g mg−1 min−1) and ki
(mg g−1 min−1/2) are the rate constants of the adsorption in pseudo-
first-order (Eq. (2)), pseudo-second-order (Eq. (3)) and intraparticle dif-
fusion models (Eq. (4)), respectively (Doğan et al., 2004; Taty-Costodes
et al., 2003; Vadivelan and Kumar, 2005).

3. Results and discussion

In Fig. 1 TEM image of the Halloysite nanotubes is shown. A mainly

hollow tubular structure is clearly visible from TEM images. The
Halloysite is predominately tubular with a length of 0.5–1 μm and an Fig. 2. Effect of contact time and initial pH on adsorption of silver ions onto HNTs from
inner diameter of 10–20 nm. aqueous solutions.
 G. Kiani / Applied Clay Science 90 (2014) 159–164 161

Fig. 3. Effect of contact time and initial silver ion concentration on adsorption from
aqueous solutions.

results show that uptake of silver ion is rapid for the first 20 min reaching
equilibrium within about 30 min. Fig. 5. Effect of contact time and temperature on the removal rate of silver ions onto HNTs
from aqueous solutions.

3.1.3. Effect of adsorbent concentration
Adsorbent dose is a significant parameter in the determination of ad-
sorption capacity. In order to study the effect of adsorbent mass on the
adsorption of silver ions, a series of adsorption experiments was carried
out with different adsorbent dosages at initial silver ion concentration of
50 mg L−1. Fig. 4 shows the effect of adsorbent dose on the removal of
silver ions. This may be attributed to the aggregation of adsorbent
particles at high dosage, which reduces the total surface area of the ad-
sorbent and results in an increase in the diffusion path length. Also in-
creasing the dosage of HNTs and keeping the silver ion concentration
constant make a large number of sites available for a fixed concentration
of sorbate, hence the reduction in the value of qt. Consequently, the ad-
sorbent dose was maintained at 0.1 g in all the subsequent experiments,
which was considered to be sufficient for the removal of metal ions
(Kiani and Soltanzadeh, 2013).
3.1.4. Effect of temperature
To study the effect of temperature on the adsorption of silver
ions by HNTs, the experiments were performed at temperatures of
293, 308, and 323 K. Fig. 5 shows the influence of temperature on
the adsorption of Ag(I) onto HNTs. The adsorption of silver ions in-
creases with temperature. This is indicative of an endothermic ad-
sorption process. The activation energy and adsorption enthalpy
are calculated to be 7.28 kJ mol − 1 (Section 3.3) and 11 kJ mol− 1
(Section 3.5), respectively. So small values of activation energy
and adsorption enthalpy changes indicate that the adsorption is
consistent with the description of the process as physisorption.
This result also supports the suggestion that the adsorption capacity
of HNTs for silver ions increases with increasing temperature.
3.2. Kinetics of adsorption
Several steps can be used to examine the controlling mechanism
of adsorption processes such as chemical reaction, diffusion control,
and mass transfer. Here, kinetic models are used to test experimen-
tal data from the adsorption of silver ion onto HNTs. the kinetics of
silver ion adsorption onto HNTs were analyzed using pseudo-first-
order (Doğan et al., 2004), pseudo-second-order (Taty-Costodes
et al., 2003) and intraparticle diffusion kinetic models (Vadivelan
and Kumar, 2005). The conformity between experimental data and
the model-predicted values was expressed by the correlation coefficients
(R2, values ≈ 1). The relatively higher value is the more applicable model
to the kinetics of silver ion adsorption onto HNTs. The corresponding re-
sults are shown in Table 2. It is seen that the pseudo-second order
model well represented the experimental data (R2 N 0.99). For instance,
Fig. 6 showed the pseudo-second order curves of HNTs with silver ion
at various temperatures.
3.3. Activation parameters
From three of the pseudo-second-order rate constants, k2 (here Ksm),
each at a different temperature, and using the Arrhenius equation
(Eq. (6)), it is possible to gain some insight into the type of adsorption.
ln ksm ¼ ln A–Ea =RT ð6Þ

Table 2
.Adsorption kinetic parameters of silver ions onto HNTs.

Temperature (°C) 20 35 50

Pseudo-first-order
K1, min−1 0.0004 0.0004 0.0004
R2 0.826 0.782 0.817

Pseudo-second-order
K2, g/mg min 0.0042 0.0035 0.0037
qe, cal (mg/g) 50 49.75 50
R2 1 1 1

Intraparticle diffusion
ki, mg g−1 min1/2 0.187 0.196 0.194
C 47.772 47.742 47.787
R2 0.915 0.878 0.906
Fig. 4. Effect of adsorbent dose on adsorption of silver ions onto HNTs.
162 G. Kiani / Applied Clay Science 90 (2014) 159–164

The amount of silver ion adsorbed is determined as a function of the

concentration at a constant temperature, which could be explained by
adsorption isotherms. In this study, three isotherms Langmuir (Eq. (7))
(Huang and Chen, 2009), Freundlich (Eq. (8)) (Dinu and Dragan, 2008)
and Temkin (Eq. (9)) (Hameed, 2009) were tested.

Ce 1 a
¼ þ LC ð7Þ
qe K L K L e

1
log qe ¼ log K F þ log C e ð8Þ
n

qe ¼ B1 ln K T þ B1 ln C e ð9Þ

Here qe is the solid phase equilibrium concentration, i.e., the amount

Fig. 6. Pseudo-second-order plots for the adsorption of silver ions onto HNTs at various
temperatures.
Here Ea is the activation energy (J mol−1), ksm is the pseudo-second-
order rate constant for adsorption (g mol−1 s−1), A is the temperature-
independent Arrhenius factor (g mol− 1 s− 1), R is the gas constant
(8.314 J K−1 mol−1), and T is the solution temperature (K). The slope
of the plot of lnksm vs. T−1 can then be used to evaluate Ea. Low activa-
tion energies (5–40 kJ mol−1) are characteristic of physical adsorption,
while higher ones (40–800 kJ mol−1) suggest chemisorption (Doğan
et al., 2006). The present results give Ea = ~ + 7.28 kJ mol− 1 for the
adsorption of silver ions onto HNTs, indicating that the adsorption has
a low potential barrier and corresponds therefore to physisorption.
The value is consistent with those found in the literature for the adsorp-
tion of these silver ions onto many adsorbents, e.g., Ag (I) onto valonia
tannin resin (Yurtseveri and Şengil, 2012) and Ag (I) onto natural ben-
tonite (Hefne et al., 2010), and silver ion into calcium alginate beads
(Torres et al., 2005).
3.4. Adsorption isotherms
of silver ions adsorbed per unit weight of the HNTs (mg g−1); Ce is the
liquid phase equilibrium concentration (mg L− 1), KL and aL are the
Langmuir constants found from the intercept and slope of the straight
line of the plot Ce/qe versus Ce. The aL constant is related to the free en-
ergy or net enthalpy of adsorption (L mg−1) (aL α e−ΔH/RT) (Rytwo et al.,
2006), and KL is the equilibrium constant of Langmuir (L g−1).
Freundlich constant indicative of the relative adsorption capacity of
the adsorbent (mg g−1) and 1/n is the adsorption intensity. B1 = RT / b,
KT is the equilibrium binding constant (L mg−1) and B1 is the heat of ad-
sorption (Eq. (9)).
The results obtained from the Langmuir model for the removal of
silver ion onto HNTs are shown in Table 3. The correlation coefficients
reported in Table 3 showed strong positive evidence that the adsorption
of silver ion onto HNTs follows the Langmuir isotherm. The applicability
of the linear form of the Langmuir model to HNTs was proved by the
high correlation coefficients R2 N 0.999. This suggests that the Langmuir
isotherm provides a good model for the sorption system (Fig. 7). Also
the essential characteristic of a Langmuir isotherm, related to the iso-
therm shape, can be expressed in terms of a dimensionless constant
separation factor, also called the equilibrium parameter (Shawabkeh
and Tutunji, 2003), RL, which is defined in relation to aL and C0 by
Eq. (10):

The relationship between the amount of a substance adsorbed at 1

constant temperature and its concentration in the equilibrium solution
is called the adsorption isotherm. The adsorption isotherm is important
from both a theoretical and a practical point of view. In order to opti-
mize the design of an adsorption system to remove the metal ions, it
is important to establish the most appropriate correlations of the equi-
librium data of each system. Equilibrium isotherm equations are used
to describe the experimental adsorption data. The parameters obtained
from the different models provide important information on the ad-
sorption mechanisms and the surface properties and affinities of the ad-
sorbent. Three famous isotherm equations, the Langmuir, Freundlich
and Temkin, were employed for further interpretation of the obtained
adsorption data. The analysis of the isotherm data by seeing how well
they can be accommodated by different models is an important step in
establishing a model that can be successfully used for design purposes.
Linear regression is frequently used to determine the best-fitting iso-
therm, and the applicability of isotherm equations is compared by judging
the correlation coefficients.
RL ¼ : ð10Þ
1 þ aL C 0
The value of RL indicates the type of the isotherm to be (i) unfavor-
able (RL N 1), (ii) linear (RL = 1), (iii) favorable (0 b RL b 1), or (iv) irre-
versible (RL = 0) (Rytwo et al., 2006). The degree of favorability is
generally related to the irreversibility of the system, giving a qualitative
assessment of silver ion and HNT interactions.
Due to pH-dependent adsorption of silver ion onto HNTs, modified
Langmuir–Freundlich (MLF) isotherm was employed which can used
to simulate pH-dependent adsorption (Jeppu and Clement, 2012). The
solid-phase equilibrium concentration can be expressed in-terms of
pH and Ceq using the MLF isotherm by Eqs. (11) and (12):

n
qm C eq K L ðpH Þ
qe ¼ h in ð11Þ
C eq K L ðpHÞ þ 1

Table 3
Parameters of Langmuir, Freundlich and Temkin adsorption isotherm models for Ag+ onto HNTs at different temperatures.

Temperature (°C) Langmuir Freundlich Temkin

2 2
KL aL RL R 1/n KF R B1 KT R2

20 341 7.31 0.021 0.998 0.045 2.011 0.994 17.4 8.7 0.965
35 260 5,82 0.027 0.997 0.043 2.089 0.991 – – –
50 187 4.31 0.034 0.999 0.042 2.108 0.992 – – –
 G. Kiani / Applied Clay Science 90 (2014) 159–164
Fig. 7. Langmuir plot of adsorption of silver ions onto HNTs at various temperatures.
h in
  C eq K L
f C eq ¼ C eq −C init þ Sqm þ h in ¼ 0:
1 þ C eq K L
The Eq. (12) can be solved using a non-linear equation solver to
compute the value Ceq. We used the Newton–Raphson (NR) method
(Stoer and Bulirsch, 2002). Using the NR method, the value of Ceq at
the (K + 1)th iteration can be found. Fig. 8a shows the comparison of
MLF and Longmuir adsorption models of silver ions onto HNTs at
20 °C. This result indicates that the MLF model was able to closely
match Longmuir experimental data. So the best-fit adsorption isotherm
was achieved with the Langmuir model.
Also in order to understand the relationship between KL and pH, we
plotted the fitted value of KL against pH, as shown in Fig. 8b. The figure
shows that the value of KL increases linearly with increase in pH values.
Fundamentally, one should expect the affinity for surface sites (indicat-
ed by KL) to increase with increase in pH due to increase in negatively
charged surface species (Si/Al–O−). As the pH increases, the number
of negative sites increases thus the affinity of HNTs for adsorbing the
positively charged silver ion is increased (Abdullayev et al., 2011;
Jeppu and Clement, 2012).
3.5. Adsorption thermodynamics
The thermodynamic parameters of the adsorption, i.e. the standard
enthalpy ΔH°, Gibbs free energy ΔG° and entropy ΔS° were calculated
using Eqs. (13) and (14)

ΔG ¼ −RT ln K L
Fig. 8. a) Langmuir and MLF plots of adsorption of silver ions onto HNTs at 20 °C and b) plot of pH vs. affinity constant KL for the adsorption of silver ions onto HNTs.
163
  
ΔG ¼ ΔH −TΔS ð14Þ
where KL is the Langmuir constant when concentration terms are
expressed in L mol−1, R (8.314 J mol−1 K−1) is the universal gas con-
stant and T (K) is the temperature. The ΔH° and ΔS° values can be calcu-
lated from the slope and intercept of the plot of ΔG° versus T (Li et al.,
2004).
The negative value for the Gibbs free energy (ΔG° = −6.63 KJ mol−1)
for silver adsorption shows that the adsorption process is spontaneous
and that the degree of spontaneity of the reaction increases with increas-
ing temperature. The overall adsorption process seems to be endothermic
(ΔH° = 11 kJ mol−1). This result also supports the suggestion that the ad-
sorption capacity of HNTs for silver ions increases with increasing tem-
perature. Also results show that the ΔS° (60.2 KJ mol−1 K−1) value was
positive. The positive value of ΔS° infers increase of randomness at
solid–solution interface during the adsorption of metal ions on the active
sites of HNTs. Moreover, positive value of ΔS° reflects the affinity of the
adsorbent for silver ions (Ho, 2006; Xiong, and Yao, 2010).
ð12Þ 3.6. Desorption studies
In metal ion removal process, it is important to study desorption of
the adsorbed metal ions under suitable conditions. Desorption experi-
ment was conducted at low pH values and the solution of HCl was
used for desorption. Desorption process was done in the three pH
(4, 2 and 1) and results demonstrate that desorption yield % were
found 95.16, 96.26 and 98.04 respectively. Results show that experi-
ment in pH = 1 was very efficient. Studies reveal that HNTs are great
potential to be used as relative low-cost and reusable adsorbent for
the removal of silver ions from wastewater.
4. Conclusions
The results of this investigation show that Halloysite nanotubes have
a suitable adsorption capacity for the removal of silver ions from aque-
ous solutions. The equilibrium adsorption practically is achieved in
30 min. A maximum efficiency of 99.8% has been obtained for the initial
Ag (I) concentration of 110 mg/L. The experimental results were ana-
lyzed by using the Langmuir, Freundlich and Temkin isotherm models
and the correlation coefficients for Langmuir well fitted. The adsorption
behavior is described by a monolayer Langmuir-type isotherm. The ad-
sorption kinetics followed pseudo-second-order kinetic equation. The
rate constant decreased with an increase in temperature indicating en-
dothermic nature of adsorption. The dimensionless separation factors
(RL) showed that HNTs could be used to remove silver ion from an aque-
ous solution. Comparison of MLF and Longmuir adsorption models of
silver ions onto HNTs at 20 °C indicates that the MLF model was able
ð13Þ to closely match Longmuir experimental data. The activation energy Ea
164 G. Kiani / Applied Clay Science 90 (2014) 159–164
was estimated using the Arrhenius equation. Gibbs free energy
(ΔG°) was spontaneous for all interactions showing the feasibility
of the adsorption process. The adsorption process was exothermic
accompanied by positive entropy. The results suggest that due to
the relative low cost and easy availability of Halloysite nanotubes,
it may be an effective nanosorbent for the removal of metal ions
from aqueous solution.
Acknowledgment
The author would like to acknowledge University of Tabriz, Iran.
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