Fe Doped TiO

2
Prepared by Microwave-Assisted Hydrothermal
Process for Removal of As(III) and As(V) from Water
Ivan Andjelkovic,*
,
Dalibor Stankovic,

Jelena Nesic,

Jugoslav Krstic,

Predrag Vulic,

Dragan Manojlovic,

and Goran Roglic*

,

Innovation Center of the Faculty of Chemistry,

Institute of Chemistry, Technology and Metallurgy, Department of Catalysis and
Chemical Engineering,

Faculty of Mining and Geology, Department of Crystallography,

Faculty of Chemistry, Chair of Analytical
Chemistry, and

Faculty of Chemistry, Chair of Applied Chemistry, University of Belgrade, Studentski Trg 12-16, 11000 Belgrade,
Serbia
*S Supporting Information
ABSTRACT: Elevated concentrations of arsenic in groundwater, which is used as a source for drinking water, is a worldwide
problem. Use of TiO
2
and iron doped TiO
2
synthesized by a microwave-assisted hydrothermal method for As(III) and As(V)
removal were examined. Synthesized sorbents were characterized with XRD and nitrogen physisorption. Synthesized sorbents
have predominantly anatase structure, and no peaks for iron could be observed. Doping of iron increases the surface area of
synthesized sorbents. Sorption experiments show that increase of iron in sorbents increases the sorption capacity for As(III) and
As(V). Increase of pH from 3 to 11 has no inuence on As(III) sorption but decreases the sorption of As(V). Batch isotherm
studies were performed to determine the binding capacities of As(III) and As(V). As(III) followed the Freundlich isotherm
model, while for As(V) a better t was with the Langmuir isotherm. The results of competition of SO
4
2
and PO
4
3
anions on
adsorption of As(III) indicated that both anions reduced substantially the eciency of adsorption on both adsorbents while for
As(V) only the presence of PO
4
3
anion interfered with adsorption. Testing 10Fe/TiO
2
sorbent with arsenic contaminated
natural water showed that this material could be used for removal of arsenic to the level recommended by WHO without
pretreatment.
1. INTRODUCTION
Pollution of groundwater, as a main source of drinking water,
with arsenic, is a concern of many countries around the world.
Elevated concentrations of arsenic in groundwater were found
in the United States,
13
China,
4
Japan,
5
Vietnam,
6
and
Australia.
7
The most severe problem is in Bangladesh
8
and
West Bengal,
9
where it has been estimated that as many as 100
million people are exposed to high levels of arsenic, exceeding
the World Health Organization (WHO) standard of 10 g/L.
Human beings have a important impact on the concentration
of arsenic in nature through mining activity, combustion of
fossil fuels, use of arsenical pesticides, and use as a additive to
livestock feed. Use of arsenical products has decreased recently,
but the impact on the environment will remain for some years.
The inuence of anthropogenic activity can be monitored and
controlled, but most environmental arsenic problems are a
result of mobilization from soil minerals under natural
conditions which are dicult to control.
Arsenic can occur in the environment in several oxidation
states (3, 0, +3, and +5) but in natural waters is mostly found
in inorganic form as oxyanions of trivalent arsenite As(III) or
pentavalent arsenate As(V). It is generally recognized that the
soluble inorganic arsenicals are more toxic than the organic
ones, and that As(III) compounds are more toxic than As(V)
compounds.
10
The eects of arsenic exposure through drinking water can
manifest through discoloration of skin and intestinal, vascular,
and cardiac problems. The relative toxicity of arsenic depends
mainly on its chemical form and is dictated in part by the
valence state. Trivalent arsenic has a high anity for thiol
groups, as it readily forms kinetically stable bonds to sulfur.
Thus, reaction with As(III) induces enzyme inactivation, as
thiol groups are important to the functions of many enzymes.
Pentavalent arsenic has a poor anity toward thiol groups,
resulting in more rapid excretion from the body. However, it is
a molecular analogue of phosphate and can uncouple
mitochondrial oxidative phosphorylation, resulting in failure
of the energy metabolism system.
11
Adsorption is considered to be one of the best technologies
for arsenic removal because it can be simple in operation, is
cost-eective, and could reduce arsenic concentrations below
10 ppb as is required by water quality standards.
12
Eective
removal of arsenic by adsorption is dependent on many factors
such as the presence of common competing anions, pH, and Eh
which inuence the species of arsenic that are present in water,
reaction kinetics, etc. These factors can inuence that an
adsorbent eective with one type of groundwater may be less
eective with groundwater that has a dierent matrix.
At the near-neutral pH typical for most groundwaters,
As(III) exists as a neutral species (H
3
AsO
3
), whereas As(V)
exists as an anionic species (H
2
AsO
4

or HAsO
4
2
).
13
Thus,
most methods used for arsenic removal exhibit higher anity
for As(V) compared to As(III). In recent years micro and nano
Received: March 5, 2014
Revised: June 5, 2014
Accepted: June 13, 2014
Article
pubs.acs.org/IECR
XXXX American Chemical Society A dx.doi.org/10.1021/ie500849r | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
sized materials were explored for arsenic adsorption.
1416
Also,
metal based adsorbents, especially titanium and iron, have been
extensively examined to remove arsenic from water. Titanium
dioxide is a famous photocatalyst that oers a relatively
inexpensive and environmentally safe way to achieve
oxidation.
1720
Iron oxide minerals are abundant in nature
and are relatively inexpensive. The use of iron oxyhydroxides is
promoted by their amorphous structure which gives high
specic surface area values, and their strong anity and
relatively high selectivity for the most frequently occurring
arsenate species under natural pH values of water.
2123
The
application of composite sorbents containing two or more
metal oxides was extensively investigated in recent years.
2426
FeCe bimetal oxide sorbent demonstrated higher As(V)
sorption capacity than Fe
3
O
4
and CeO
2
oxides prepared with
the same procedure.
27
The objectives of this research were to synthesize TiO
2
nanoparticles doped with two amounts of iron(III) by a
microwavehydrothermal method, characterize them, and
examine their eciency for removal of arsenic from ground-
water. A microwavehydrothermal technique was chosen
because it was superior to the conventional hydrothermal
process, as it allows rapid heating to the required temperature
and extremely rapid rates of crystallization.
28,29
Prepared
materials were characterized with X-ray diraction (XRD)
and nitrogen physisorption measurements at 77 K, and the
point of zero charge was determined. Batch experiments were
conducted to examine sorption characteristics of synthesized
materials.
2. EXPERIMENTAL SECTION
All chemicals used in synthesis were of analytical reagent grade.
Hydrochloric acid and sodium hydroxide were used to adjust
the pH.
Stock solutions containing (1000 ppm) As(V) and As(III)
were prepared by dissolving appropriate quantities of
Na
2
HAsO
4
7H
2
O and NaAsO
2
in deionized water, respectively.
Solutions of required lower concentrations were prepared by
diluting the stock solutions.
2.1. Sorbent Preparation. Sorbents were prepared using
the microwavehydrothermal method. In a typical preparation
procedure, TiCl
4
was added to icy deionized water (TiCl
4
:H
2
O
(v/v) ratio 1:10) and a homogeneous and transparent solution
was obtained. Then, the solution was subjected to precipitation
by the slow addition of NH
4
OH (30%) solution under constant
stirring at room temperature. The hydrolysis was controlled
with the addition of NH
4
OH, until the reaction mixture
attained a pH between 7 and 8. Precipitate was obtained, and
the suspension was transferred into a Teon microwave closed
vessel (digestion system ETHOS 1 Milestone, equipped with a
high pressure rotor, SK-10, Italy), sealed, and heated by
microwave irradiation. The maximum temperature of 423 K
was reached in 10 min, and then this temperature was
maintained for 15 min more for hydrothermal treatment. The
resulting product was separated by centrifugation and washed
repeatedly with deionized water until the precipitate became
free of chloride ion. Finally, it was dried at 353 K for 5 h and
then calcined at 773 K for 10 h. Doped TiO
2
samples were
prepared according to the above procedure including addition
of Fe(III) salt in water to give 4 and 10% dopants.
Both dopant concentrations mentioned in this work are the
weight percent. Adsorbents TiO
2
doped with 4 and 10% iron
were labeled as 4Fe/TiO
2
and 10Fe/TiO
2
, respectively.
2.2. Characterization of Synthesized Adsorbents. X-
ray powder diraction (XRPD) was used for the identication
of crystalline phases, quantitative phase analysis, and estimation
of crystallite size and strain. The XRPD patterns were collected
with a Philips diractometer PW1710 employing Cu K
radiation. Step scanning was performed with 2 ranging from
20 to 100, step size of 0.10, and a xed counting time of 5 s
per step. The XRPD patterns were used to rene the
crystallographic structure and microstructural parameters
using the procedure implemented in the FullProf computer
program.
30
Scanning electron microscopy (SEM) was used to examine
the morphology of synthesized materials. The SEM analysis was
conducted on a JEOL microscope Model JSM-6610LV.
Adsorptiondesorption isotherms were obtained by nitrogen
adsorption at 77 K using a Sorptomatic 1990 Thermo Finnigan
device. Prior to adsorption, the samples were degassed for 1 h
at room temperature under vacuum and additionally 16 h at
383 K at the same residual pressure. The specic surface area of
samples (S
BET
) was calculated by applying the Brunauer
EmmetTeller equation, from the linear part of the adsorption
isotherm.
31
The total pore volumes (V
tot
) were obtained from
the N
2
adsorption, expressed in liquid form, by applying
Gurevitschs rule.
32
Micropore volumes (V
mic
) were estimated
according to the DubininRadushkevich method.
33
Mesopore
volumes (V
mes
) were estimated according to the Barrett, Joyner,
and Halenda (BJH) method from the desorption branch of the
isotherm.
34
The point of zero charge (pH
pzc
) was determined in
accordance with procedure described by Babic et al.
35
2.3. Arsenic Adsorption Experiments. The adsorption
kinetic study for As(III) and As(V) was carried out with 10
mg/L concentration of arsenic in 0.01 M NaCl solution. Plastic
asks with 100 mL of arsenic solutions and 50 mg of adsorbent
were mixed for 30, 60, 120, 240, 360, 720, 1440, and 2880 min
at room temperature (20 2 C). The pH was adjusted at 7.0
0.2 by adding the proper amount of hydrochloric acid and
sodium hydroxide at the beginning of adsorption. No pH
adjustment was conducted in the kinetic study, and the pH
value change was found to be negligible after the treatment.
For the pH study, plastic asks were lled with 100 mL of 10
mg/L As(III) or As(V) in 0.01 M NaCl solution. The required
initial pHs of test solutions were adjusted using HCl or NaOH
solutions. A 50 mg sample of adsorbent was added and the
plastic asks were shaken for 1 h at room temperature.
Adsorption isotherm experiments were conducted at room
temperature at pH 3.0 0.2 by a batch adsorption procedure.
Experiments were performed by adding dierent concen-
trations of As(III) and As(V) in 0.01 M NaCl solution in plastic
asks with 50 mg of adsorbent. The concentrations of arsenic
were in the range 110 mg/L. The volume of solution was 100
mL in all experiments. Plastic asks were shaken for 1 h.
In order to examine the inuence of common anions
(phosphate and sulfate) along with arsenic in water on the
adsorption capabilities of adsorbents, two concentrations of
anions, 1 and 5 mM, in 100 mL of 1 mg/L arsenic solution in
0.01 M NaCl at pH 3 were mixed with 50 mg of sorbent for 1
h. The quantities of adsorbed arsenic with and without these
salts were compared.
The sorption capability of 10Fe/TiO
2
was tested on arsenic
naturally contaminated water samples, taken from the tap water
of the city of Zrenjanin, Serbia. The arsenic concentration was
92 g/L, and the pH value was 8.0. Kinetic experiments were
Industrial & Engineering Chemistry Research Article
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conducted with 0.1, 0.5, and 1.0 g/L adsorbent doses,
respectively.
The samples were ltered through a 0.45 m membrane lter
and arsenic concentrations in supernatant were determined
with inductively coupled plasma atomic emission spectroscopy
(iCap 6500Duo, Thermo Scientic, UK).
3. RESULTS AND DISCUSSION
3.1. Characterization. XRPD analysis showed that the
most intensive diraction peaks for adsorbents can be ascribed
to the anatase crystal structure (JCPDS card 78-2486) (Figure
1). From diractograms of 4Fe/TiO
2
and 10Fe/TiO
2
it can be
seen that no obvious peaks that could be attributed to the
doped Fe are present. The ionic radius of the Fe
3+
ion is close
to the ionic radius of Ti
4+
, and it can be expected that the Fe
3+
ion could be incorporated into the TiO
2
lattice. Because no
corresponding peaks from iron oxide phase were observed,
either Fe
3+
ions are highly dispersed to the TiO
2
structure or
small iron oxide clusters are formed having sizes and/or
concentrations lower than the detection limit of the
diractometer.
Physical parameters of TiO
2
, 4Fe/TiO
2
, and 10Fe/TiO
2
synthesized by the microwavehydrothermal method are
presented in Table 1. Doping TiO
2
with 4% Fe increased the
specic surface area and micropore volume while decreasing the
mesopore volume. Further increase of the amount of doped
iron continued the same trend. The specic surface area and
micropore volume of 10Fe/TiO
2
are twice as big compared to
TiO
2
. A large specic surface area is preferable for providing
large adsorption capacity. Also, the size of the micropores
determines the accessibility of adsorbate molecules to the
adsorption surface, so an increase of these two properties of the
material can be benecial for its sorption properties.
Figures 2, 3, and 4 show SEM images of TiO
2
, 4Fe/TiO
2
,
and 10Fe/TiO
2
, respectively. Comparing images of TiO
2
with
images of Fe doped TiO
2
, we can see dierences in the
morphology and decrease of the average particle size of doped
TiO
2
. Figures 3 and 4 also reveal more porous structures of
4Fe/TiO
2
and 10Fe/TiO
2
compared to TiO
2
which are
benecial for the adsorption of arsenic and are in accordance
with the increase of specic surface area of these materials.
3.2. Kinetics Analysis. In order to have a better picture of
the adsorption capacities of our adsorbents, initial concen-
trations of As(III) and As(V) were higher than the average
concentration of arsenic in groundwater.
From Figures 5 and 6, we can see that adsorbent with higher
percentage of Fe had better adsorption of As(III) and As(V). In
the rst hour, from initial As(III) and As(V) concentrations, 45
and 46% were adsorbed on 10Fe/TiO
2
, respectively. For the
same time, 4Fe/TiO
2
from initial concentrations of As(III) and
As(V) removed 30 and 36%, respectively. A higher specic
surface area of 10Fe/TiO
2
compared to 4Fe/TiO
2
could be
responsible for faster initial adsorption. We can see similarities
in the kinetic behavior of As(III) and As(V) on both
adsorbents. More than 73% of the adsorbed As(III) and
As(V) amounts within 48 h was adsorbed in the rst hour, for
both adsorbents.
The rates of As(III) and As(V) adsorption were evaluated
using pseudo-rst-order and pseudo-second-order kinetic
models. The pseudo-rst-order rate expression of the Lagergren
equation
36
is given as
= Q Q Q k t log( ) log
t e e
1 (1)
where Q
e
and Q
t
are the amounts of arsenate adsorbed (mg/g)
at equilibrium and at time t (min), respectively; k
1
(min
1
) is
the rate constant of the pseudo-rst-order adsorption. The
adsorption rate constant can be determined from the slope of
the linear plot of log(Q
e
Q
t
) versus t.
The pseudo-second-order rate expression is as follows:
37
= +
t
Q Q k
t
Q
1
t e
2
2 t
(2)
where k
2
(g mg
1
min
1
) is the pseudo-second-order rate
constant. k
2
can be calculated from the slope and intercept of
the plot of t/Q
t
versus t.
Kinetics parameters for the pseudo-rst-order and pseudo-
second-order equations are presented in Table 2.
The presented kinetics adsorption data for As(III) and As(V)
on both adsorbents, based on r
2
values, were described better
with the pseudo-second-order model. Close values of k
2
for
As(III) and As(V) on 10Fe/TiO
2
show similar adsorption rates
of these two species. The real test of the validity of the
equations used for the description of the rate of adsorption
arises from a comparison of the experimentally determined Q
e
values and those obtained from the plots of log(Q
e
Q
t
) versus
t and t/Q
t
versus t for the Lagergren and pseudo-second-order
models, respectively.
38
Comparison of Q
e
values, experimentally
determined and obtained from the plots for the pseudo-rst-
order and pseudo-second-order rate models are presented in
Table 3. As we can see from Table 3, the adsorption process
follows a more complex mechanism than the one on the basis
of simple rst-order kinetics and conrms good agreement with
the pseudo-second-order model rate.
The time required for reaching equilibrium was 12 h for
As(III) and As(V) on both adsorbents. For all other batch
Figure 1. XRD diractograms of (a) TiO
2
, (b) 4Fe/TiO
2
, and (c)
10Fe/TiO
2
.
Table 1. Comparison of Physical Properties of TiO
2
, 4Fe/
TiO
2
, and 10Fe/TiO
2
adsorbent
TiO
2
4Fe/TiO
2
10Fe/TiO
2
pore vol (Gurvich) at p/p
0
(cm
3
g
1
) 0.236 0.250 0.257
sp surf. area (m
2
g
1
) 66 84 123
mesopore (BJH) desorption stand.
Lecloux, cumul pore vol, (cm
3
g
1
)
0.306 0.191 0.189
micropore vol (DR) (cm
3
g
1
) 0.019 0.028 0.037
Industrial & Engineering Chemistry Research Article
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experiments 1 h of mixing time was chosen although the
equilibrium time was 12 h because the percentage of As(III)
and As(V) removal after 1 h increases by less than 0.1% per
minute.
3.3. Eect of pH. Arsenic in groundwater mostly occurs in
two common forms: arsenite (AsO
3
3
) and arsenate (AsO
4
3
).
As(V) exists as H
3
AsO
4
at pH <2.1 and as H
2
AsO
4

, HAsO
4
2
,
and/or AsO
4
3
in less acidic, neutral, and alkaline waters. The
Figure 2. (ac) SEM images of TiO
2
at dierent magnications.
Figure 3. (ac) SEM images of 4Fe/TiO
2
at dierent magnications.
Figure 4. (ac) SEM images of 10Fe/TiO
2
at dierent magnications.
Figure 5. Eect of contact time on adsorption of As(III) on 4Fe/TiO
2
and 10Fe/TiO
2
(c
0
= 10 ppm, pH 7, adsorbent dose 0.5 g/L).
Figure 6. Eect of contact time on adsorption of As(V) on 4Fe/TiO
2
and 10Fe/TiO
2
(c
0
= 10 ppm, pH 7, adsorbent dose 0.5 g/L).
Industrial & Engineering Chemistry Research Article
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dominant form of As(III) in the pH range from 0 to 9.2 is
H
3
AsO
3
, and in more alkaline conditions H
2
AsO
3

, HAsO
3
2
,
and AsO
3
3
are dominant. The determined pH
pzc
values were
6.8 0.2 and 6.7 0.2 for 4Fe/TiO
2
and 10Fe/TiO
2
,
respectively. These pH
pzc
values suggest that below pH 7 the
surface of both adsorbents should be predominantly positive.
From pH 3 to 9, the adsorbed amount of As(III) on 10Fe/
TiO
2
slowly increases, reaching a maximum at pH 9. A nearly
50% decrease of adsorbed amount was at pH 3 than at pH 9.
Increasing the pH above 9 resulted in a decrease of As(III)
adsorption. The same trend was observed for As(III)
adsorption on 4Fe/TiO
2
(Figure 7). The decrease of
adsorption of As(III) with increase of pH above 9 could be
due to two factors: the repulsion of the negative surface charge
of adsorbents and H
2
AsO
3

anions which are dominant form

under the mentioned pH and competition of hydroxyl anions
for active sites.
As can be seen in Figure 8, adsorption of As(V) is strongly
dependent on the pH. The greatest adsorption for both
adsorbents occurred at pH 3. At pH 3 the surfaces of
adsorbents are positively charged and could bind negatively
charged H
2
AsO
4

anions. With increase of pH the positive

charge of adsorbent surfaces decreases gradually up to pH
pzc
,
after which they are negatively charged. Decreasing positive
surface charge and increasing electrostatic repulsion between
arsenate anions and the surface could be responsible for the
decrease of adsorption with increase of pH. Also, with the
increase of pH, the concentration of OH

anions increases and

could compete for active sites on the adsorbent.
3.4. Adsorption Isotherms. For determination of the
adsorption capacity of adsorbents, the Freundlich and
Langmuir isotherm models were used.
The expression for the Freundlich isotherm model was given
as
= Q K C
n
f e
1/
(3)
where Q (mg/g) is the amount of adsorbed arsenic per unit of
adsorbent, K
f
is a Freundlich constant related to the adsorption
capacity, C
e
(mg/L) is the equilibrium arsenic concentration,
and n is a dimensionless Freundlich constant which indicates
the intensity of adsorption.
The Langmuir isotherm model is expressed as
= +
C
Q bQ
C
Q
1
e
e m
e
m
(4)
where Q
e
(mg/g) is the amount of adsorbed arsenic per unit of
adsorbent, C
e
(mg/L) is the equilibrium concentration of
arsenic, Q
m
(mg/g) is the amount adsorbed per unit weight of
adsorbent required for monolayer capacity, and b (L/mg) is
Langmuir constant.
Freundlich and Langmuir isotherms do not give any idea
about the adsorption mechanism. In order to understand the
mechanism of adsorption, the equilibrium data were also tted
with the DubininRasdushkevich (DR) isotherm. The DR
isotherm has the following linearized form:
39
= Q Q K ln ln
m
DR
2
(5)
where K
DR
is a constant correlated to the adsorption energy, Q
m
is the adsorption capacity, (Polanyi potential) is [RT ln(1 +
1/C
e
)], R is the gas constant, and T is the temperature.
Table 2. Pseudo-First-Order and Pseudo-Second-Order
Kinetic Parameters for As(III) and As(V) onto 4Fe/TiO
2
and 10Fe/TiO
2
pseudo rst order pseudo second order
adsorbent k
1
(min
1
) r
2
k
2
(g mg
1
min
1
) r
2
As(III) 4Fe/TiO
2
0.0009 0.7918 0.0031 0.9999
As(III) 10Fe/TiO
2
0.0012 0.9933 0.0074 0.9993
As(V) 4Fe/TiO
2
0.0010 0.9883 0.0063 0.9976
As(V) 10Fe/TiO
2
0.0009 0.9940 0.0073 0.9993
Table 3. Comparison of Q
e
Values, Experimentally
Determined and Obtained from the Plots for Pseudo-First-
Order and Pseudo-Second-Order Rate Models, for
Adsorption of As(III) and As(V) onto 4Fe/TiO
2
and 10Fe/
TiO
2
Q
e
(mg/g)
obtained from plot
adsorbent exptl pseudo rst order pseudo second order
As(III) 4Fe/TiO
2
8.286 0.885 8.161
As(V) 4Fe/TiO
2
8.672 3.011 8.566
As(III) 10Fe/TiO
2
11.600 2.898 11.591
As(V) 10Fe/TiO
2
11.952 2.977 11.677
Figure 7. Eect of initial pH on As(III) adsorption onto 4Fe/TiO
2
and 10Fe/TiO
2
(c
0
= 10 ppm, adsorbent dose 0.5 g/L).
Figure 8. Eect of initial pH on As(V) adsorption onto 4Fe/TiO
2
and
10Fe/TiO
2
(c
0
= 10 ppm, adsorbent dose 0.5 g/L).
Industrial & Engineering Chemistry Research Article
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Generally DR is used to distinguish between physical and
chemical adsorption. From the slope and intercept of the plot
ln Q against
2
, the DR isotherm constants K
DR
and Q
m
are
calculated. The mean energy of adsorption (E) is calculated
from the K
DR
value using the following equation:
=

E K (2 )
DR
0.5
(6)
It is known that the magnitude of E can be used to estimate
the type of adsorption. If this value is in the range 816 kJ/
mol, the adsorption type can be explained by chemisorption,
and if E < 8 kJ/mol, then the adsorption type is
physisorption.
40
Correlation coecients (r
2
), K
f
, K
DR
, n, Q
m
, and Q
ml
values
were derived from linear forms of the Freundlich, Langmuir,
and DR models, and are shown in Table 4.
The Freundlich equation is often considered to be an
empirical equation. It assumes multilayer adsorption on an
energetically heterogeneous surface, while the Langmuir model
is based on the assumption that sorption is monolayer on
energetically equivalent sites without interaction between
adsorbed molecules on neighboring sites. For the adsorption
of As(III) on TiO
2
, 4Fe/TiO
2
, and 10Fe/TiO
2
and As(V) on
TiO
2
, correlation coecients were better with the Freundlich
isotherm model suggesting multilayer adsorption. Increase of
the adsorption capacity of doped sorbent is probably because of
the increase of the surface area with doping, which provides
more active sites for sorption. Data for adsorption of As(V) on
both doped adsorbents were better tted with the Langmuir
model than with the Freundlich model. A possible explanation
could be the sorption of As(V) to doped Fe instead of TiO
2
active sites due to the higher anity of As(V) toward Fe
sorption centers. Adsorption capacities, derived from the
Langmuir model, for As(III) and As(V) on 10Fe/TiO
2
were
8.61 and 17.35 mg/g, respectively. Comparing these results
with adsorption capacities of As(III) and As(V) on TiO
2
, we
can see a improvement of the adsorption capacity with the
increase of the amount of Fe doped for TiO
2
. As the adsorption
capacity of the sorbent varies with experimental conditions
(initial arsenic concentration, solution pH, time of agitation), it
may be dicult to compare the values directly. Comparison of
the removal capacity of 10Fe/TiO
2
sorbent with adsorbents
reported in the literature (commercially available and doped
sorbents, with experimental conditions similar to ours) are
presented in Table S1 in the Supporting Information.
For the adsorption of As(III) and As(V) on TiO
2
and As(III)
on both 4Fe/TiO
2
and 10Fe/TiO
2
, the experimental data do
not correlate well with the DR isotherm model (Table 4),
giving low values for r
2
. The reason for the poor-tting results
could be because adsorption occurs mainly on the surface
rather than in the pores and the DR model assumes volume
lling.
41
As(V) adsorption on 4Fe/TiO
2
and 10Fe/TiO
2
gave
good correlation coecients, and calculated E values were 5.86
and 5.68 kJ/mol, respectively. These E values indicate that the
adsorption of As(V) onto both doped adsorbents is
physisorption.
3.5. Competing Anions. The presence of anions, such as
PO
4
3
and SO
4
2
, can inuence arsenic adsorption. These two
anions are common constituents of natural waters, and their
molecular structures are similar to that of arsenic. The results of
a competing anion study are shown in Table 5.
The presence of 1 mM SO
4
2
decreased the adsorption of
As(III) on 4Fe/TiO
2
and 10Fe/TiO
2
by more than 70 and
78%, respectively. Higher concentration of SO
4
2
showed
similar results, suggesting that saturation of active sites was
achieved with 1 mM concentration. Removal of As(III)
decreased in the presence of 1 mM PO
4
3
for 87 and 90%
on 10Fe/TiO
2
and 4Fe/TiO
2
, respectively.
Little decrease of adsorption on both adsorbents occurred
with the presence of 5 mM SO
4
2
while with 1 mM SO
4
2
both
adsorbents eectively removed As(V). With 1 mM PO
4
3
present in solution, 55% decrease of adsorption occurred for
both adsorbents. With an increase of the PO
4
3
concentration
to 5 mM, a more than 83% decrease in adsorption occurred for
both adsorbents. However, the concentrations of PO
4
3
used in
this study were much higher than that likely to be encountered
in groundwater.
The larger decrease of adsorption of As(III) on both
sorbents in the presence of PO
4
3
and SO
4
2
anions suggests a
stronger sorption anity of these two anions for adsorbents
than As(III). As(V) showed stronger anity for adsorption on
both adsorbents compared with SO
4
2
. These results are in
agreement with n constants derived from the Freundlich
isotherm model, which represents the strength of adsorption.
3.6. Arsenic Removal in Natural Water Sample. The
city of Zrenjanin is located in the northeastern part of Serbia, in
Vojvodina, which has an elevated concentration of arsenic in
the groundwater. This groundwater is pumped from wells and
Table 4. Freundlich and Langmuir Adsorption Parameters for As(III) and As(V) Adsorption onto TiO
2
, 4Fe/TiO
2
, and 10Fe/
TiO
2
Freundlich Langmuir DR
adsorbent r
2
n K
f
r
2
Q
ml
(mg/g) r
2
K
DR
(mol
2
/kJ
2
) E (kJ/mol)
As(III) TiO
2
0.9888 3.21 3.66 0.9542 5.52 0.8183 0.0382 3.62
As(V) TiO
2
0.9997 5.63 5.34 0.9941 7.39 0.8407 0.0065 8.77
As(III) 4Fe/TiO
2
0.9982 1.70 1.35 0.9636 6.17 0.7538 0.1954 1.60
As(III) 10Fe/TiO
2
0.9971 1.79 2.28 0.9654 8.61 0.8194 0.1430 1.87
As(V) 4Fe/TiO
2
0.9264 3.58 10.54 0.9969 13.41 0.9773 0.0147 5.83
As(V) 10Fe/TiO
2
0.8421 4.46 16.52 0.9958 17.35 0.9555 0.0155 5.68
Table 5. Eect of PO
4
3
and SO
4
2
Anions on As(III) and
As(V) Adsorption onto 4Fe/TiO
2
and 10Fe/TiO
2
Adsorbents
a
concn of As(III) (ppm)
after adsorption with
concn of As(V) (ppm) after
adsorption with
anion concn 10Fe/TiO
2
4Fe/TiO
2
10Fe/TiO
2
4Fe/TiO
2
0 <0.010 <0.010 <0.010 <0.010
1 mM PO
4
3
0.867 0.901 0.553 0.554
5 mM PO
4
3
0.887 0.926 0.832 0.862
1 mM SO
4
2
0.708 0.786 <0.010 <0.010
5 mM SO
4
2
0.722 0.823 0.036 0.038
a
Initial concentration of arsenic c
0
= 1 mg/L, pH
i
3.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie500849r | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX F
with the addition of chlorine is distributed to taps. The
chemical composition of the water sample is shown in Table S2
in the Supporting Information.
Kinetics experiments with dierent loadings of 10Fe/TiO
2
adsorbent were carried out to investigate the eciency with the
natural water sample. From Figure 9 we can see fast adsorption
of arsenic with all adsorbent dosages. With 1 g/L dosage, after 5
min contact with adsorbent more than 70% of arsenic was
removed. After 60 min contact time, with the same dosage, the
total arsenic concentration was below the WHO limit for
arsenic in drinking water.
4. CONCLUSIONS
A novel TiO
2
doped with 4 and 10% Fe adsorbents for removal
of As(III) and As(V) were synthesized using a microwave-
assisted hydrothermal method. Using this method for doping
TiO
2
with Fe, higher specic surface area and micropore
volume than those of the starting material were achieved. The
pseudo-second-order kinetic model was found to best correlate
with the data for As(III) and As(V) adsorption on both
adsorbents. Both adsorbents showed similar pH dependences
of adsorption. The best results were achieved at pH 3 and pH 9
for As(V) and As(III), respectively. Isotherm studies showed
that the Freundlich model ts the experimental data for As(III)
adsorption while the Langmuir model better describes As(V)
adsorption. The presence of SO
4
2
anions decreased As(III)
adsorption, while it had no inuence on the adsorption of
As(V). Substantial decrease of adsorption on As(III) and As(V)
on both adsorbents occurred in the presence of PO
4
3
anions.
Improvement in the adsorption capabilities for As(III) and
As(V) was achieved with doping TiO
2
with Fe. Better removal
for As(III) and As(V) was achieved with 10Fe/TiO
2
adsorbent.
The maximal adsorption capacities, derived from the Langmuir
isotherm model, were 8.61 and 17.35 mg/g for As(III) and
As(V), respectively. Treatment of a natural water sample that
contained 92 g/L total arsenic with 1.0 g/L 10Fe/TiO
2
adsorbent showed very fast adsorption of arsenic with the
nal concentration below the WHO limit after 60 min of
contact time. Simplicity of synthesis, low cost of sorbent, and
increasing adsorption capability of As(III) and As(V) with
increasing amount of doped Fe recommend further inves-
tigation of this method for synthesis of TiO
2
doped with higher
amounts of Fe, for arsenic removal.

ASSOCIATED CONTENT
*S Supporting Information
Tables comparing adsorption capacities of other sorbents with
our study and water quality data of real water sample (tap water
of city of Zrenjanin, Serbia). This material is available free of
charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION
Corresponding Authors
*E-mail: ivanhem@chem.bg.ac.rs. Tel.: + 381 64 3702462.
*E-mail: groglic@chem.bg.ac.rs. Tel.: +381 64 1718149.
Notes
The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work has been supported by the Ministry of Education
and Science, Republic of Serbia (Project No. 172030).

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