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Preparation and evaluation of magnetic nanoparticles impregnated

chitosan beads for arsenic removal from water


Jing Wang, Weihong Xu

, Liang Chen, Xingjiu Huang, Jinhuai Liu

Nano-Materials and Environmental Detection Laboratory, Hefei Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, Anhui 230031, PR China
h i g h l i g h t s
Fe
3
O
4
@Zr(OH)
4
-impregnated chitosan beads for arsenic removal were prepared.
The adsorbent kept good adsorption performance for arsenic after 5 cycles of reuse.
The adsorbent exhibited good arsenic removal performance in real underground water.
a r t i c l e i n f o
Article history:
Received 29 January 2014
Received in revised form 14 April 2014
Accepted 16 April 2014
Available online 24 April 2014
Keywords:
Arsenic
Magnetic nanoparticles impregnated
chitosan beads
Adsorption
a b s t r a c t
Magnetic nanoparticles impregnated chitosan beads (MICB) synthesized by using chitosan template was
investigated for uptake capacity of arsenic in batch studies. The adsorption isotherm could be better
described by the Langmuir model than the Freundlich model. The Langmuir maximum capacity of the
MICB was calculated to be 35.7 mg/g for As(V), and 35.3 mg/g for As(III) at pH 6.8, respectively, which
was reasonably good compared with that of other granular adsorbents reported previously. The effects
of various factors such as adsorbent dose, pH, contact time, arsenic concentration and co-existing anions
on arsenic removal were systematically studied. Furthermore, the as-prepared adsorbent showed an
excellent arsenic removal performance in real underground water. A distinct advantage of this adsorbent
was that the adsorbent could readily be isolated from solutions by application of an external magnetic
eld. The study of adsorption mechanism indicated that the hydroxyl groups on the adsorbent surface
were involved in arsenic adsorption.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Arsenic is a kind of toxic pollutant found in groundwater with
serious health effects upon long-term intake of even low concen-
trations through drinking water consumption [1]. Human activities
(e.g., use of arsenical pesticides) and natural processes (e.g., disso-
lution of arsenic-containing minerals) have caused the release of
arsenic into groundwater. Due to the negative impacts of arsenic
on human health, most countries are implementing the maximum
permissible limit of arsenic in drinking water of 10 lg/L recom-
mended by the World Health Organization. Thus, the elimination
and reduction of arsenic in the aquatic systems is imperative.
Several methods have been applied to remove excessive arsenic
from water, such as precipitation [2], membrane separation, ion
exchange, and adsorption [36]. The method of precipitation can
produce large amounts of toxic sludge, which poses serious
environmental problems [7,8]. Membrane separation is known to
be more effective for removing As(V) than As(III). Thus, the
addition of an extra oxidizing agent is necessary to convert As(III)
to As(V). Unfortunately, these agents often ruin the membranes,
consequently shortening their life time [9]. Ion exchange is identi-
ed an available technology for As(V) removal. However, strong
competition from some co-existing anions affected the poor
selectivity for As(V) and prohibitively retarded [10]. Compared
with these methods, adsorption seems to be a more attractive
method for the removal of arsenic in terms of cost, simplicity of
design and operation, especially for individual homes and small
community systems.
Since solid adsorbents are easy to handle and appropriate for
use in country side where high arsenic concentration in groundwa-
ter mostly occurs, adsorption has received much attention on
arsenic removal. Many adsorbents such as activated alumina, iron
oxide, mixed metal oxides, resin, and modied bers were
reported to be effective for arsenic removal [1117]. Among these
adsorbents, zirconium-based materials have been paid more
http://dx.doi.org/10.1016/j.cej.2014.04.061
1385-8947/ 2014 Elsevier B.V. All rights reserved.

Corresponding authors. Tel.: +86 551 65595607; fax: +86 551 65592420.
E-mail addresses: whxu@iim.ac.cn (W. Xu), jhliu@iim.ac.cn (J. Liu).
Chemical Engineering Journal 251 (2014) 2534
Contents lists available at ScienceDirect
Chemical Engineering Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ cej
attention in recent investigations due to their high binding afnity
with arsenic and acceptable cost [18]. In addition, it was reported
that Fe
3
O
4
-based materials were very effective in the removal of
arsenic because of their strong adsorption activities and the
properties of being easily separated by an external magnetic eld
[19,20]. Thus, composites combined iron and zirconium oxide/
hydroxides nanomaterials would be expected to benet from the
advantages of these two kinds of adsorbents for the enhanced
adsorptive removal of arsenic.
The nanopowder form of metal oxides/hydroxides provides a
high surface area for increased adsorption capacity, but this small
particle size also drives the need for energy-intensive post-treat-
ment ltration to recover the nanoparticles for regeneration and
reuse [21]. To address this limitation, it is necessary to embed
nanocomposites in a porous matrix [8,9]. Use of biopolymers has
been gaining wide attention due to their low cost, high contents
of amino and hydroxyl functional groups, which show signicant
adsorption potential for the removal of various heavy metal ions
[22,23]. Among the biopolymers, chitosan was regarded as the base
material for immobilization because of its biodegradability,
biocompatibility, nontoxicity in nature and easy availability [7,24].
Herein, magnetic nanoparticles Fe
3
O
4
@Zr(OH)
4
-impregnated
chitosan beads (MICB) were successfully synthesized as a novel
arsenic adsorbent. The uptake capacity and adsorption kinetics
for both As(V) and As(III) were investigated. The effects of adsor-
bent dose, pH, contact time, arsenic concentration and co-existing
anions were systematically examined. And the reusability and
adsorption mechanism of the adsorbent for arsenic was explored.
Furthermore, removal of arsenic from real underground water by
the adsorbent was also evaluated.
2. Material and methods
2.1. Chemicals
All chemicals are of analytical grade, which are commercially
available from Shanghai Chemical Reagent Co., China and used in
this study without further purication. As(III) standard reference
sodium arsenite (1000 mg/L) was purchased from Shanghai
Canspec Scientic Instruments Co., China. Different solutions of
As(III) and As(V) were prepared by diluting As(III) standard solu-
tion and Na
3
AsO
4
12H
2
O solution with deionized water according
to experiment requirements and pH was adjusted using 0.1 mol/L
HCl and 0.1 mol/L NaOH, respectively. Underground water sample
was taken from Tuoketuo County in Inner Mongolia of China.
2.2. Preparation of magnetic nanoparticles Fe
3
O
4
@Zr(OH)
4
The synthesis of Fe
3
O
4
nanoparticles was based on a facile
modied solvothermal method [25]. FeCl
3
6H
2
O (2.43 g, 9 mmol)
was dissolved in ethylene glycol (72 mL) to form a clear solution,
followed by the addition of NaAc (6.48 g) and polyethylene glycol
(1.8 g). The mixture was stirred vigorously for 30 min and then
sealed in a Teon lined stainless-steel autoclave (100 mL capacity).
The autoclave was heated to and maintained at 200 C for 10 h. The
obtained Fe
3
O
4
nanoparticles were separated from the reaction
medium by magnetic eld, and washed with deionized water
several times, then resuspended in 100 mL deionized water.
15 mL 0.5 mol/L ZrOCl
2
solution was added dropwise into the
Fe
3
O
4
NPs suspension and the pH value of the mixture was
adjusted to 8.0 by addition of 2 mol/L NaOH within 1 h. The
mixture was stirred for 2 h after the addition. During the whole
process, temperature was maintained at 80 C and nitrogen gas
was used to prevent the intrusion of oxygen. Finally, the formed
NPs were then thoroughly washed with deionized water till
neutral pH was obtained. The solid residue was dried at 60 C in
an air oven.
2.3. Preparation of magnetic particles Fe
3
O
4
@Zr(OH)
4
-impregnated
chitosan beads
The magnetic particles Fe
3
O
4
@Zr(OH)
4
-impregnated chitosan
beads (MICB) were synthesized by a template method. 4 g chitosan
were dissolved in 400 ml of 4% acetic acid with constant stirring on
mechanical stirrer for 1 h. 8 g magnetic nanoparticles Fe
3
O
4
@-
Zr(OH)
4
were added to the chitosan gel with stirring for 3 h. The
resulting FeZr-chitosan slurry was added drop wise into 2 mol/L
NaOH solution under vigorous stirring, using a glass syringe. The
gel macro spheres formed were allowed to stabilize in NaOH
solution for 60 min. The beads were separated from the NaOH
solution and rinsed with deionized water until the pH of ltrate
was neutral and dried by freeze-drying for one day.
2.4. Characterization
MICB was characterized on an X-ray powder diffractometer
(XRD) (XPert Pro Super, Philips Co., the Netherlands) with Cu Ka
radiation (k = 1.541874 ). The scanning electron microscopy
(SEM) images were taken by using a eld-emission scanning
electron microscopy (SEM, FEI Sirion 200 FEG, operated at 10 kV).
The BrunauerEmmettTeller (BET) surface area and pore struc-
ture were measured by N
2
adsorption/desorption using an Ommi-
shop 100CX surface area analyzer (Coulter Inc., USA). The Fourier
transform infrared (FT-IR) spectra of the obtained samples were
recorded with a NEXUS-870 FT-IR spectrometer in the range of
4000400 cm
1
. A thermo-VG Scientic ESCALAB 250 instrument
was used for X-ray photoelectron spectroscopy (XPS)
measurement.
2.5. Arsenic adsorption experiments
Batch equilibrium adsorption isotherm studies were conducted
with As(III) and As(V) solutions of variable initial concentrations
from 0.2 to 50 mg/L in 125 mL erlenmeyer asks, followed by
shaking at 140 rpm to achieve equilibrium. Amount of adsorbent
used was 0.05 g (FA1004 analytical balance, the accuracy limit of
0.0001 g, Lumsail Industrial Inc., China) and the solution volume
was maintained at 50 mL. The residual arsenic concentration in
solution was measured by inductively coupled plasma atomic
emission spectroscopy (ICP-AES, the detection limit of 0.003 mg/
L, Intrepid II, Thermosher, USA) or inductively coupled plasma
atomic emission spectroscopy mass spectrometer (ICP-MS, the
detection limit of 0.001 mg/L, ICAP Qc, Thermosher, USA). The
adsorption capacity at equilibrium of the adsorbents for arsenic
was calculated according to the following equation:
q
e

C
o
C
e
V
m
where C
o
and C
e
represent the initial and equilibrium arsenic con-
centrations (mg/L), respectively, V is the volume of the arsenic solu-
tion (mL), and m is the amount of adsorbent (g).
In order to estimate equilibrium adsorption rate for the uptake
of As(III) and As(V) by MICB, time-dependent adsorption studies
were conducted. The kinetics adsorption on the As(III) and As(V)
were both investigated using different initial arsenic concentra-
tions of 2.01 mg/L, 5.20 mg/L and 10.60 mg/L, respectively,
with 1.0 g/L of adsorbent and a total solution volume of 750 mL
As(III) and As (V) solutions immersing in 1000 mL glass vessel.
The pH of the solutions was chosen at 6.8 0.2 for optimal adsorp-
tion. The mixtures were shaken at 140 rpm and approximately
5 mL aliquots were then removed periodically for measuring the
26 J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534
corresponding arsenic concentration, in order to calculate their
time-dependent adsorption capacity.
The effect of dose on As(V) and As(III) removal was conducted at
an initial arsenic concentration of 1 mg/L with an increase of
adsorbent dose from 0.2 g/L to 2.0 g/L at pH 7.0 0.2 and ambient
temperature. Typically, variable dose (0.22.0 g/L) of adsorbent
were immersed in 20 mL initial arsenic concentration of 1 mg/L
As(III) or As(V) solutions by shaking at 140 rpm for 24 h to achieve
equilibrium.
The effect of pH on the arsenic adsorption was investigated
using initial arsenic concentrations of 10.4 mg/L with 1.0 g/L of
adsorbent and a total suspension volume of 100 mL.
The effects of co-existing anions (carbonate, nitrate, chloride,
phosphate and sulfate) on arsenic adsorption were performed with
an adsorbent dose of 1.0 g/L and an initial arsenic concentration of
5 mg/L at pH 6.8 0.2. The co-existing anions were set at four
concentration levels of 0, 0.1, 1, 10 mmol/L, respectively.
The adsorption performance of the regenerated MICB were
evaluated with 20 mL initial arsenic concentration of 1 mg/L
As(V) and As(III) solutions and adsorbent dose of 1 g/L at pH
6.8 0.2 for 24 h. Regeneration of arsenic saturated adsorbents
was achieved using 0.1 mol/L sodium hydroxide solution.
Kinetics adsorption experiments on underground water sample
were carried out in the 750-mL underground water from Inner
Mongolia of China with an increase of the treatment time using
the as-prepared MICB at a loading of 1.0 g/L without any pre-treat-
ment and/or pH adjustment.
2.6. Column adsorption experiments
Dynamic ow adsorption experiments were conducted in a Per-
spex column of about 1.5 cm internal diameter and 30 cm length.
The column was packed with the dried adsorbent. The bed volume
was 30 cm
3
. The experiments were operated at room temperature.
The inuent solution was pumped into the column in an up-ow
direction. A constant ow rate was maintained throughout the
run. The inuent solutions were formed by diluting As(III) standard
solution and Na
3
AsO
4
12H
2
O solution in deionized water, respec-
tively. The pH of the inuent solution was kept at 6.8 0.2 without
adjustment, and the upward ow at a ow rate was 2.5 mL/min.
The efuent was collected from the column end at regular intervals
of time and the concentration of arsenic and metal ions in the
efuent solution were measured by ICP-MS.
3. Results and discussion
3.1. Structural and morphological characteristics of MICB
A solgel templating technique was employed for the fabrica-
tion of MICB. Optical images of undried and dried MICB are shown
in Fig. 1a and b, respectively. It is observed that the brown spher-
ical shape of undried MICB turned into the red brown quasi-sphere
of dried MICB after freeze-drying. This might be due to the conden-
sation reactions and partial oxidation of Fe
3
O
4
nanosphere surface
during freeze-drying process. The dried MICB have an average
diameter of about 2.5 mm as shown in Fig. 1b. The outer and inner
surface morphology of the dried MICB were studied using SEM
after the MICB were sectioned with a scalpel as shown in Fig. 1c
and d, respectively. It can be seen that the MICB illustrated an
interconnected porous network with macropore sizes of a few hun-
dred nanometers, and magnetic particles Fe
3
O
4
@Zr(OH)
4
dispersed
well in the chitosan network, which would facilitate diffusion of
adsorbate moleculars into the system and capture at adsorptive
sites. The BET surface area and total pore volume of MICB was
measured to be 50.20 m
2
/g and 0.052 cm
3
/g, respectively (See
Fig. S1).
The XRD pattern of the dried MICB powder is illustrated in
Fig. 2a. The diffraction peaks at 2h = 30.459, 35.649, 43.472,
53.933, and 63.073 correspond to the primary diffraction of the
(220), (311), (400), (511), and (440) planes of the Fe
3
O
4
(JCPDS
le 19-0629), respectively [26], which indicated that the coating
zirconium hydroxide and chitosan network should be in amor-
phous forms. Such a phenomenon was also reported by other
researchers in the study of metal-impregnated polymeric material
[27].
Fig. 2b shows the FTIR spectrum of the dried MICB. A strong and
broad band in 36003100 cm
1
region is assigned to OH bond
stretching and NH bond stretching. The bands at 2922 and
2876 cm
1
can be assigned to m
as
(CH
2
) in CH
2
OH group and
m(CH) in pyranose ring, respectively. The bands at 1610.20 cm
1
,
1378 cm
1
and 1065.5 cm
1
correspond to OH bending, NH
deformation and CO stretching vibration, respectively [7,28,29].
The bands demonstrate the feature characteristic of chitosan. The
peak at 1358 cm
1
is assigned to the bending vibration of ZrOH
[30]. The band at 580 cm
1
is typical characteristic for FeO [31].
To further understand the elemental information of the MICB,
XPS was used to characterize the surface composition and
electronic state of the sample [32]. Fig. 2c demonstrates the peak
positions of carbon, nitrogen, oxygen, iron, and zirconium through
XPS analysis for the MICB. The C 1s peak was determined at
283.0 eV, and the Zr peak at 183.6 eV. The N 1s peak at 398.0 eV
was attributed the amino groups in chitosan [33].
Additionally, a distinct advantage of the MICB was that it could
readily be isolated from solution by application of an external
magnetic eld. Fig. 2d shows the eld-dependent magnetization
behavior for the MICB at room temperature. The MICB showed
no remanence or coercivity, demonstrating typical superparamag-
netic behavior. The saturation magnetization of the MICB was
found to be 17.14 emu/g, which was enough for magnetic separa-
tion from the suspension with application of a magnet as displayed
in the inset of Fig. 2d.
3.2. Effect of dose of MICB
The inuence of adsorbent dose on As(V) and As(III) removal at
an initial arsenic concentration of 1 mg/L and neutral pH is shown
in Fig. 3. It is noticed that the percentage removal of As(V)
increased from 84% to 99% with an increase of adsorbent dose from
0.2 g/L to 2.0 g/L, while the percentage removal of As(III) increased
from 51% to 99% under the same experimental process, which was
attributed to the increasing active sites/As ratio with the increase
of adsorbent dose. From Fig. 3, it is observed that more than 90%
of As(V) and As(III) were removed with an excess of dosage of
1.0 g/L. Considering the balance between the percentage of arsenic
removal and adsorption capacity, the adsorbent dose of 1.0 g/L was
selected to use in the following adsorption study.
3.3. Effect of pH
pH plays a signicant role in adsorption-based water treatment
processes, because the speciation of arsenic and the surface charge
of the adsorbents are strongly inuenced by the water pH value
[34]. The effect of pH on the adsorption of As(III) and As(V) on
the MICB is shown in Fig. 4. It is noticed that there was no signif-
icant effect of pH on As(III) adsorption over a range of pH 59. This
might be due to the dominant As(III) species as neutral H
3
AsO
3
at
most pH levels (pK
a1
= 9.2, pK
a2
= 12.1, and pK
a3
= 12.7) [18]. The
decrease in As(III) removal was observed at pH >9, because the
amount of negatively charged As(III) species rise, while negatively
charged surface sites of the MICB also increase (pH
pzc
= 6.45, see
Fig. S11), and consequently the repulsion effect enhances. At pH
<5, As(III) adsorption decreased with the decrease of pH value
J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534 27
due to the partial solubility of chitosan at low pH [7]. On the other
hand, As(V) was evidently pH-dependent in a range of pH 311.
As(V) predominantly exists as negatively charged H
2
AsO
4

and
HAsO
4
2
under the pH range of 311 (pK
a1
= 2.3, pK
a2
= 6.9, and
pK
a3
= 11.5) [35]. Acidic solution environment was favorable for
the protonation of the adsorbent surface, which was advantageous
for the adsorption of As(V) on the MICB because of electrostatic
attraction between the adsorbent surface and As(V) anions. But
at low pH, the chitosan polymer is not very stable, which might
affect the adsorption [33]. Under alkaline conditions, the nega-
Fig. 1. (a) and (b) Photograph of undried MICB and dried MICB, respectively. (c) and (d) SEM images of outer surface and inner surface morphology of MICB, respectively.
Fig. 2. (a) XRD pattern, (b) FTIR spectrum, (c) XPS spectrum, and (d) room-temperature eld-dependent magnetization behavior of the dried MICB, respectively. Inset:
Magnetic separation of the MICB in solution.
28 J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534
tively charged sites of the adsorbent surface increased with the
increase of pH value, which led to the decreasing adsorption of
As(V) on the MICB because of the repulsion effect. Similar experi-
mental phenomenon have been reported for adsorption of As(V)
and As(III) by a Zr(IV)-loaded orange waste gel and removal of
As(III) using iron oxide coated cement [36,37]. Considering
practical operating conditions and drinking water standard for
pH, pH 6.8 was selected to use in the entire study.
3.4. Kinetics of adsorption
The adsorption kinetics of arsenic on the MICB at various initial
concentrations was investigated. Fig. 5 shows the change of
adsorbed arsenic as a function of contact time. The adsorption of
As(V) happened more quickly, and needed less time to reach equi-
librium than that of As(III). Over 90% of the equilibrium adsorption
capacity for As(V) was achieved within 1 h, while about 3 h was
needed for As(III) to reach 82% of the equilibrium adsorption
capacity.
To further quantify the changes of arsenic adsorption with time
on the MICB, the pseudo-rst-order and pseudo-second-order
kinetic models were used to simulate the kinetics (Figs. S2 and
S3). The kinetics parameters were obtained by tting the experi-
mental data and are summarized in Table 1. According to the
values of regression coefcients (R
2
), the experimental data tted
the pseudo-second-order model better than the pseudo-rst-order
model for both As(V) and As(III). The rate constant (k
2
) of the
pseudo-second-order equation decreased with increasing initial
arsenic concentration, indicating that arsenic adsorption might
be more favorable at low solute concentration. Meanwhile, the
values of k
2
for As(V) adsorption were higher than those for As(III)
adsorption under the same experimental conditions, conrming
that the removal of As(V) by the MICB was faster than As(III).
3.5. Adsorption isotherms
The adsorption capacities of the MICB toward As(V) and As(III)
were evaluated using the adsorption isotherms with adsorbent
dose of 1 g/L at pH 6.8 0.2 and room temperature (Fig. 6a and
b). In order to understand the adsorption performance and adsorp-
tion mechanism, the Langmuir and Freundlich models were used
to describe the adsorption isotherms (see Figs. S4 and S5), and
the adsorption parameters obtained from the isotherms are
presented in Table 2. As shown in Table 2, the Langmuir model
was more suitable for describing the adsorption behavior of both
As(V) and As(III) on the MICB according to the value of regression
coefcients (R
2
). Maximum adsorption capacities were calculated
from the Langmuir equation to be 35.7 mg/g for As(V), and
35.3 mg/g for As(III), respectively. Although it was difcult to
compare the MICB directly with other adsorbents because of
different applied experimental conditions, the adsorption capacity
for arsenic on the granular MICB was reasonably high compared
with other granular adsorbents (Table 3). These results demon-
strated that the MICB was effective for both As(V) and As(III)
removal. Especially, it showed good adsorption performance for
As(III), as most adsorbents reported previously were effective for
As(V) adsorption, but not for the case of As(III) due to its uncharged
form at most pHs [12,21,38]. This is the advantage of the adsorbent
since As(III) is more toxic and more difcult to remove from water
than As(V).
Arsenic concentration in contaminated natural waters is usually
low. Thus, the adsorption performance of the adsorbent for As(V)
and As(III) at low equilibrium arsenic concentration should be
evaluated. Fig. 6c and d shows the adsorption isotherms at low
equilibrium arsenic concentrations for As(V) and As(III), respec-
tively. At such a low equilibrium arsenic concentration, the As(V)
and As(III) adsorption data were all better tted to the Langmuir
model (Figs. 6c, d, S6 and S7 and Table 2). At an equilibrium arsenic
concentration of 0.01 mg/L (the standard for drinking water), the
adsorption capacities for As(V) and As(III) were about 4.02 mg/g
and 3.17 mg/g, respectively. And a full comparison of adsorption
capacity of the MICB with other materials at low equilibrium
arsenic concentration was listed in Table 3.
3.6. Effect of co-existing ions
Considering the complexity of water source, the presence of
other ions, such as Cl

, NO
3

, SO
4
2
, CO
3
2
and PO
4
3
ions, might
compete with arsenic for active adsorption sites and greatly
Fig. 3. Effect of adsorbent dose on (a) As(V) and (b) As(III) removal, respectively. Initial concentrations: 1 mg/L, pH: 7 0.2, temperature: 25 C.
Fig. 4. Effect of pH on As(V) and As(III) adsorption by the MICB. Initial arsenic
concentration: 10.4 mg/L, adsorbent dose: 1 g /L, temperature: 25 C.
J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534 29
Fig. 5. Kinetics of (a) As(V) and (b) As(III) removal by the MICB at different initial concentrations: 2.01 mg/L, 5.2 mg/L, 10.6 mg/L, respectively. Adsorbent dose: 1 g/L, pH:
6.8 0.2, temperature: 25 C.
Table 1
Kinetics parameters for As(V) and As(III) adsorption on the MICB with various initial arsenic concentrations.
Arsenic species Initial concentration (mg/L) First-order kinetics Second-order kinetics
lnq
e
q
t
lnq
e
k
1
t
t
q
t

1
k2q
2
e

t
q
e
k
1
(1/min) q
e
(mg/g) R
2
k
2
(g/(mg min)) q
e
(mg/g) R
2
As(V) 2.02 0.00447 0.09829 0.923 0.0184 2.03 0.999
5.28 5.37 10
3
2.762 0.786 6.985 10
3
5.229 0.999
10.73 5.82 10
3
3.549 0.648 5.80 10
3
10.619 0.999
As(III) 2.01 0.00937 0.6384 0.886 0.0152 2.03 0.999
5.19 0.00898 3.9759 0.927 6.659 10
3
5.089 0.999
10.58 0.00963 7.9044 0.960 3.07 10
3
9.859 0.999
Note: k
1
is the adsorption rate constant for pseudo-rst order reaction (1/min). k
2
is the rate constant for pseudo-second order reaction (g/(mg min)). q
e
and q
t
are the amounts
of solute adsorbed at equilibrium and at any time t (mg/g), respectively.
Fig. 6. Adsorption isotherms of (a and c) As(V) and (b and d) As(III) at high and low arsenic equilibrium concentrations, respectively, by the MICB with adsorbent dose of 1 g/L
at pH 6.8 0.2 and room temperature. Black solid lines represent the Langmuir model and blue solid lines represent the Freundlich model. The tted parameters are
summarized in Table 2. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
30 J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534
Table 2
Langmuir and Freundlich adsorption isotherm parameters for As(V) and As(III) by the MICB at high and low arsenic equilibrium concentrations, respectively.
Langmuir model Freundlich model
Equations
q
e

q
m
kL Ce
1kL Ce
q
e
kC
1=n
e
Parameter C
e-max
(mg/L) K
L
(L/mg) q
max
(mg/g) R
2
n k R
2
As(V) 1.0 30.06 19.1 0.99 2.64 24.05 0.96
As(III) 0.5 39.07 11.7 0.99 3.01 16.51 0.92
As(V) 16 2.09 35.7 0.99 3.00 16.83 0.96
As(III) 15 0.88 35.3 0.96 1.95 10.12 0.95
Note: C
e-max
is the upper limit of arsenic equilibrium concentration (mg/L); C
e
is the equilibrium concentration of arsenic (mg/L); q
e
is the amount of arsenic adsorbed on per
weight of adsorbent after equilibrium (mg/g); q
m
represents the maximum adsorption capacity of arsenic on per weight of adsorbent (mg/g); k
L
is the Langmuir constant
related to the energy of adsorption (L/mg). The Freundlich constant k is correlated to the relative adsorption capacity of the adsorbent (mg/g), and 1/n is the adsorption
intensity.
Table 3
Comparison of adsorption capacity with different granular adsorbents.
Granular adsorbent C
initial
(mg/L) q
e, max
(mg/g) q
e,0.01
(mg/g) pH Ref.
As(V) As(III) As(V) As(III)
Iron-impregnated chitosan granular 10 22.5 16.1 <0.2 <0.4 7.0 [39]
TiO
2
-impregnated chitosan bead 10 2.05
a
2.10
b
n.a. n.a. 9.2
a
; 7.7
b
[40]
TiO
2
: granular 80 41.4 32.4 <3.0 <2.0 7.0 [41]
Polyaluminum granulate 280 14.85 18.00 <0.07 <0.007 7.5 [42]
Iron oxide coated sponge 5 4.5 3.85 <0.5 <0.4 6.57.3 [43]
Iron oxide coated cement 13.5 n.a 0.689 n.a. <0.003 7.0 [37]
MICB 50 35.7 35.3 4.02 3.17 6.8 Our work
n.a. = not available.
The label
a
and
b
only denote the corresponding relationship.
C
initial
is the initial concentration of arsenic (mg/L); q
e, max
represents the maximum adsorption capacity of arsenic (mg/g); q
e,0.01
(mg/g) is the adsorption capacity of arsenic at
the arsenic equilibrium concentration of 0.01 mg/L.
Fig. 7. Effects of co-existing anions on (a) As(V) and (b) As(III) removal at xed initial arsenic concentration of 5 mg/L. Adsorbent dose: 1 g/L, pH: 6.8 0.2, temperature: 25 C.
Fig. 8. (a) Adsorption efciency of the regenerated MICB for As(V) and As(III) with initial arsenic concentration of 1 mg/L and adsorbent dose of 1 g/L at pH 6.8 0.2 for 5
times. (b) Desorption cycles for As(V) and As(III) adsorbed on the MICB using 0.1 mol/L sodium hydroxide solution.
J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534 31
degrade the arsenic removal performance by the adsorbent. So, the
effect of various co-existing ions at four concentration levels (0,
0.1, 1.0, 10 mM) upon adsorption of arsenic was investigated, and
the results are shown in Fig. 7. It was observed that the presence
of Cl

, NO
3

, SO
4
2
and CO
3
2
ions had no signicant effect on
As(V) and As(III) adsorption in the concentration range of 0.1
10 mmol/L. However, phosphate could cause the greatest decrease
in arsenic adsorption, which might be due to the strong competi-
tion between the phosphate and arsenic for the binding sites of
the adsorbent. Both phosphate element and arsenic element are
located in the same main group, and the molecular structure of
the phosphate ion is very similar to that of the arsenic ion. Thus,
the present phosphate ions strongly competed with arsenic ions
for adsorptive sites on the surfaces of the MICB.
3.7. Reusability of adsorbent
It is desirable that an adsorbent could be regenerated and
reused so that it can be put into cyclic use in a cost effective man-
ner. To study the regeneration, the MICB was rst saturated with
As(V) and As(III) by shaking the adsorbent with initial arsenic con-
centration of 1 mg/L and adsorbent dose of 1 g/L at pH 6.8 0.2 for
24 h. Regeneration of arsenic saturated adsorbents was achieved
using 0.1 mol/L sodium hydroxide solution. In the recycle study,
Fig. 8a shows the adsorption efciency of the regenerated MICB
for As(V) and As(III) with initial arsenic concentration of 1 mg/L
and adsorbent dose of 1 g/L at pH 6.8 0.2 for 5 times. The MICB
maintained 99.5% for As(V) and 97.9% for As(III), respectively, of
original adsorption capacity after one adsorptiondesorption cycle.
And after 5 cycles of reuse, the regenerated MICB still retained
about 88.2% and 76.02%, respectively, of the original adsorption
capacity for As(V) and As(III), indicating the good reusability of
the adsorbent for arsenic removal. Simultaneously, the regenera-
tion study was shown in Fig. 8b. The desorption efciency of
arsenic on the MICB decreased slowly with increasing cycle num-
bers, and the desorption efciency remained more than 80% after
5 regeneration cycles, indicating the arsenic adsorbed MICB could
be regenerated efciently with 0.1 mol/L sodium hydroxide
solution.
3.8. Arsenic removal in natural water samples by the MICB
To examine the arsenic removal ability by the MICB in the nat-
ural water environment, arsenic adsorption studies were con-
ducted using the natural water samples from Tuoketuo County in
Inner Mongolia of China. Table 4 displays the characteristics of
the underground water sample, demonstrating the complexity of
substances in the water and high arsenic concentration exceeding
the limit of safe drinking. Fig. 9 shows the kinetic study of arsenic
adsorption by the adsorbent on the underground water sample.
The arsenic concentration of 0.103 mg/L could be decreased to
below 0.05 mg/L without any pre-treatment within 60 min, and
reduced to less than 0.01 mg/L after 5 h using adsorbent dose of
1 g/L. As a result, over 96% arsenic was removed, and the efuent
quality met the guideline limit of arsenic in drinking water regu-
lated by the WHO.
3.9. Column adsorption
Breakthrough curves for As(V) and As(III) from a bed packed
with the MICB are shown in Fig. 10. With the inuent As(III) and
As(V) concentrations of 0.25 mg/L, pH of 6.8 0.2, ow rate of
2.5 mL/min, the efuent As(III) and As(V) concentrations were
below 0.01 mg/L until 580 and 660 bed volumes (BV) were treated,
respectively. The adsorption bed was considered to be exhausted
when arsenic concentration of the efuent coming out of the
column reached the allowable maximum discharge level
(0.01 mg/L). Metal ions in the efuent including Fe and Zr were
Table 4
Characteristics of the natural water sample from Inner Mongolia of China.
Items Value
F

(mg/L) 2.820
Cl

(mg/L) 119.6
As (mg/L) 0.103
SO
4
2
(mg/L) 4.740
Hg (mg/L) 0.006
Pb (mg/L) 0.003
Mn (mg/L) 0.049
Fe (mg/L) 0.107
Cu (mg/L) 0.003
Na (mg/L) 0.435
Ca (mg/L) 0.008
Mg (mg/L) 0.0213
Total hardness 108.8
UV
254
0.746
pH 8.52
TOC (mg/L) 22.232
Fig. 9. Kinetics adsorption experiment on an underground water sample from Inner
Mongolia with adsorbent dose of 1.0 g/L without any pre-treatment at room
temperature.
Fig. 10. Experimental breakthrough curves for adsorption of As(III) and As(V) on
the MICB. Initial concentration of As(III) and As(V): 0.25 mg/L; ow rate: 2.5 mL/
min; pH: 6.8 0.2; bed volume: 30 mL.
32 J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534
analyzed three times at BV of 10, 200 and 500. The concentrations
of Fe and Zr were all less than 0.01 mg/L, respectively, indicating
that the MICB exhibited good stability during the process of water
treatment.
3.10. Adsorption mechanism
Revealing the adsorption mechanism plays an important role in
understanding the material characteristics and designing the
application purpose of the newadsorbent. To elucidate the changes
in surface functional groups of the adsorbent, FTIR and XPS
analysis were carried out. Fig. S9 presents the FTIR spectra of the
MICB before and after As(III) and As(V) adsorption. It is clearly
showed that the peak at 1358 cm
1
shifted to 1362 cm
1
and
1364 cm
1
, respectively, and the peak intensity decreased, indicat-
ing that the hydroxyl groups on the adsorbent surface were
involved in the arsenic adsorption [44]. Additionally, a new band
emerged at 890 cm
1
after the As(V) adsorption, matching well
with the stretching frequencies of AsO in the H
2
AsO
4

group [39].
Moreover, to further investigate the roles of the surface hydro-
xyl group on the MICB adsorbent, XPS spectra of the adsorbent
before and after As(V) and As(III) adsorption at pH 6.8 were
analyzed. A ne-scan XPS of the As region was performed for the
MICB after adsorption of As(V) and As(III) (Fig. 11a). Only one wide
peak appeared in the As(3d) spectra respectively. The binding
energy of 44.3 should be attributed to As(III)O, and 45.3 eV for
As(V)O [35]. The results demonstrated that the MICB could effec-
tively immobilize As(V) and As(III). Fig. 11bd show the O1s XPS
peak scan over the MICB before and after As(V) and As(III) adsorp-
tion, respectively. Multi-peaks Gaussian tting was carried out to
divide the O1s XPS peak spectrum into four peaks with the center
positions at 529.6 eV, 530.8 eV, 531.8 eV, and 532.4 eV, which
could be assigned to metal oxide (MO), hydroxyl bonded to metal
(MOH), adsorbed water (H
2
O), and hydroxyl in chitosan (COH),
respectively [4446]. It is clearly found that the area ratio of
MOH peak decreased from 24.59% to 14.93% after As(V)
adsorption, and reduced to 12.72% after As(III) adsorption, which
suggested that the MOH groups on the adsorbent surface surely
were involved in arsenic adsorption. And the increase of the area
ratio for the peak at 529.6 eV might be due to the formation of
MOAs groups on the adsorbent surface after arsenic adsorption.
Simultaneously, it is observed that the area ratio of COH peak
changed little before and after arsenic adsorption, indicating that
the hydroxyl groups of chitosan hardly participated in arsenic
adsorption at pH 6.8.
The DubininRadushkevich (DR) isotherm is usually used to
estimate the adsorption energy either physical or chemical adsorp-
tion. The linear form of the DR isotherm equation (Fig. S8) and the
results of various adsorption parameters obtained from the model
are listed in Table S1. The DR isotherm model was a better t at
low equilibrium arsenic concentration based on the R
2
values.
The mean adsorption energy (E) could be estimated from the k
ads
value (DR isotherm model parameter, Table S1) using the follow-
ing equation: E 2k
ads

0:5
. The E values were calculated to be
9.05 and 10.10 kJ mol
1
for As(V) and As(III) adsorbed on the MICB,
respectively, which are in the range of 816 kJ mol
1
, implying
chemical adsorption. These results are in agreement with the FTIR
and XPS analysis.
4. Conclusions
This study demonstrates that magnetic nanoparticles
Fe
3
O
4
@Zr(OH)
4
-impregnated chitosan beads could be prepared
via a template method and could be used as an effective adsorbent
for arsenic removal. The adsorption isotherm could be described
well by the Langmuir model, and the maximum capacity was cal-
culated to be 35.7 mg/g for As(V), and 35.3 mg/g for As(III) at pH
6.8, respectively, which was reasonably good compared with that
of other granular adsorbents reported previously. The adsorption
kinetics followed pseudo-second order kinetic model. And the
Fig. 11. (a) As(3d) spectra of the MICB after adsorption of As(V) and As(III), respectively. (b)(d) The surface O 1s spectra of the MICB before and after adsorption of As(V) and
As(III), respectively.
J. Wang et al. / Chemical Engineering Journal 251 (2014) 2534 33
MICB could retain about 88.2% and 76.02% of the original adsorp-
tion capacity for As(V) and As(III), respectively, after 5 cycles of
reuse. The study of adsorption mechanism indicated that the
hydroxyl groups on the adsorbent surface were involved in arsenic
adsorption based on FTIR and XPS analysis. A eld application of
the adsorbent for removal of arsenic in groundwater demonstrated
that it could be promising for practical drinking water treatment.
Acknowledgements
This work was supported by the National Basic Research
Program of China (2011CB933700), and the Natural Science
Foundation of China (50901073 and 90923033).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2014.04.061.
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