Ind. Eng. Chem. Res.

2002, 41, 6149-6155 6149

Arsenic Removal Using Iron Oxide Loaded Alginate Beads

Anastasios I. Zouboulis* and Ioannis A. Katsoyiannis
Division of Chemical Technology, Department of Chemistry, Aristotle University,
Thessaloniki GR-54124, Greece

The application of biopolymers (alginate), as sorbent supports, for the removal of arsenic from
contaminated water has been investigated in the present study. Calcium alginate beads were
placed in a column to form a fixed bed and treated (doped/coated) with hydrous ferric oxides.
Three different types of modified alginate beads were examined for the removal of arsenic; the
most efficient type was found to be doped with alginate and subsequently coated with iron oxides,
whereas the other two types were calcium alginate beads doped or coated with iron oxides. The
total amount of iron loaded on this material was found to be 3.9 mg of Fe/g of wet alginate bead.
Approximately 230 bed volumes of a 50 µg/L As(V) solution were treated before the breakthrough
point was reached, whereas the removal of As(III) was not as efficient, reaching the breakthrough
point after the treatment of only 45 bed volumes. The results were modeled using the bed depth
service time and empty bed residence time models.

Introduction sand,12-14 but other materials have been also examined,

Arsenic is considered as a naturally occurring con-
taminant of drinking water supplies, causing adverse
effects on human health. Chronic exposure to arsenic
concentrations above 100 µg/L can cause vascular
disorders, such as dermal pigments (blackfoot disease)
and skin and lung cancer.1,2 Since 1993, the World
Health Organization has recommended a maximum
contaminant level (MCL) for arsenic in drinking water
of 10 µg/L.3 In 1998, under EC directive 98/83 related
to water intended for human consumption, the Euro-
pean Commission adopted the same value as the MCL,
and by 2003, all European countries will have to comply
with this limit.4 Recently, the same limit has been
adopted by the United States, and the date by which
water treatment systems must comply with the new
standard is January 2006.5 Therefore, the arsenic
problem is of primary concern in many countries and
research into the development of cost-competitive tech-
nologies for arsenic removal from water sources is
urgent.
Arsenic is present in natural waters mainly in its
inorganic oxyanionic forms of arsenate (HAsO42-) and
arsenite (H3AsO3). As(V) predominates in oxygenated
waters (e.g., surface water), whereas under anoxic
conditions (e.g., anaerobic groundwaters), As(III) com-
prises the main form.6 The main treatment methods
used for arsenic removal from contaminated waters fall
into the following categories: (a) precipitation-coagula-
tion processes, such as coagulation with iron or alumi-
num salts or lime softening; (b) membrane processes,
such as reverse osmosis, nanofiltration, or electrodialy-
sis; and (c) adsorption processes, such as adsorption on
activated alumina or on iron oxides.7-11
A modification of the last category is “adsorptive
filtration”. This technique is based on the coating of the
filter medium with adsorbents, resulting in modified
media that can act simultaneously as a filter and as an
adsorbent. The most widely used filter medium in
adsorbing filtration technique is iron oxide coated
* Corresponding author. Tel./fax: +30 310-997794. E-
mail: zoubouli@chem.auth.gr.
10.1021/ie0203835 CCC: $22.00 © 2002 American Chemical Society
Published on Web 10/29/2002
such as coated catalysts15 and coated olivine.16 In the
present study, alginate gel beads have been applied as
a support matrix for the immobilization of hydrous ferric
oxides.
Alginate is a biopolymer, extracted mainly from
brown seaweed. It is a linear polysaccharide of (1 f 4)-
linked R-L-guluronate (G) and β-D-mannuronate (M)
residues arranged in a nonregular, block-wise pattern
along the linear chain.17,18 Monovalent salts of alginic
acid have generally been considered as being the water-
soluble species of alginate. With divalent cations, algi-
nate acid produces thermally irreversible gels that are
insoluble in water. Calcium is the cation mostly used
in the preparation of alginate beads.19
Alginate is one of the most widely used carriers for
the immobilization of enzymes and proteins, as well as
for the controlled release of drugs. Furthermore, algi-
nate has been applied as a biosorbent material for the
removal of cationic metals, such as Pb2+, Zn2+, Cd2+,
and Ni2+ from aqueous solutions.18 Regarding the
removal of oxyanionic compounds, modified alginate
beads have found application in the removal of chro-
mium and selenium,20 whereas for the removal of
arsenic, only one citation can be found in the litera-
ture.21 In the latter study (batch experiments), promis-
ing results were reported regarding the sorption of
pentavalent arsenic on modified alginate beads. In the
present study, the modified medium was examined
under continuous-operation (fixed-bed) mode.
The objective of this research was to examine the
efficiency of alginate beads as possible supports for
hydrous ferric oxides and to apply the modified filter
medium in the adsorbing filtration processes for the
removal of arsenic from contaminated water sources,
to achieve a residual arsenic concentration below the
concentration limit of 10 µg/L. The aim is not for this
particular modified medium to replace other adsorptive
or ion-exchange materials already applied in arsenic
removal processes, such as activated alumina or granu-
lar ferric hydroxide (GFH), but rather for more informa-
tion to be obtained regarding the application of this
material in the treatment of arsenic-contaminated
6150 Ind. Eng. Chem. Res., Vol. 41, No. 24, 2002
groundwaters where soluble iron might also coexist.
Iron is usually removed from groundwaters by oxidation
and subsequent filtration. The oxidation of iron and
subsequent filtration result in a natural coating of the
filter medium. Iron-oxidizing bacteria can then attach
and grow on the medium surface, accelerating the
overall process. Subsequently, arsenic can be removed
by sorption on the naturally produced iron oxides, and
possible As(III) oxidation by bacteria might enhance the
overall treatment efficiency.22
The obtained results were modeled by the application
of the bed depth service time (BDST) and empty bed
residence time (EBRT) models.23,24
Materials and Methods
Reagents and Stock Solutions. All chemicals used
were reagent-grade, and all glassware was acid-washed
and rinsed with deionized water. Alginate beads were
prepared from sodium alginate (Parneac), which was
used without further purification. Arsenate and arsenite
stock solutions were prepared from sodium arsenate
heptahydrate (Na2HAsO4‚7H2O, Parneak) and arsenic
trioxide (As2O3, AnalaR), respectively, dissolved in
deionized water. Working solutions were prepared by
dilution of certain amounts of stock solutions with tap
water. The final concentration of the working solutions
for both arsenate and arsenite experiments was 50 µg/
L, i.e., the previous limit for arsenic in drinking water.
Calcium solutions, used in the gel synthesis, were
prepared from CaCl2‚2H2O (Merck) dissolved in deion-
ized water. Hydrous ferric oxide (HFO) suspensions
used for gel activation were prepared from Fe(NO3)3‚
9H2O (Merck) dissolved in deionized water with adjust-
ment of the pH to 5.0 using NaOH solution.
Alginate Bead Synthesis. The biopolymer powder
(2 g) was dispersed in 100 mL of deionized water to give
a 2% w/v alginate solution; this solution was mixed with
a mechanic stirrer until a transparent, viscous solution
was obtained.
Calcium alginate beads were prepared by dropping
sodium alginate aqueous solution into a continuously
stirred calcium chloride solution. This technique enabled
the formation of spherical droplets, which after being
dispersed in CaCl2 solution, would result in the forma-
tion of spherical particles. Approximately one drop of
polymer solution was dispensed per second into 500 mL
of CaCl2 solution under gentle stirring (60 rpm) during
formation of the gel beads, because the beads were
reported to be susceptible to hydrodynamic forces.18
A glass tube was used to dispense the polymer
solution. A pipet tip (3-mm diameter) was positioned
approximately 6 cm above the surface of the calcium
solution used in the gel formation. It has been reported
that this is the optimum distance, as smaller distances
lead to the formation of beads with short tails whereas
longer distances result in deformation of the obtained
particles.18 The beads were allowed to cure in Ca2+
solution and then removed and rinsed twice with
deionized water. The concentration of the CaCl2 solution
and the contact time of the alginate beads within this
solution were selected after preliminary experiments.
For the preparation of Ca-Fe-doped beads, biopoly-
mer powder (2 g of sodium alginate) was dispersed in
100 mL of various concentrations of HFO suspensions
at pH 5.0.; then, the aforementioned procedure was
followed.
Experimental Setup and Conditions for Adsorp-
tion Experiments. A glass column (40-cm height, 2.86-
cm inner diameter) was filled with calcium alginate or
Ca-Fe-immobilized alginate beads (of mean diameter
3.6 mm, with approximate bed porosity 0.33). For the
preparation of Fe-coated beads, alginate beads were
treated with an Fe(NO3)3 suspension (of various initial
concentrations) at pH 5.0, where ferric oxides are
practically insoluble. The preformed iron oxide suspen-
sion was passed through the column in upflow mode
under recirculation to coat the surface of filtration
media. The bed was subsequently washed with deion-
ized water to remove iron oxides residuals that were
not coated on the surface of filter media. This washing
action was finished when no iron could be detected in
the outlet stream. It should be noted that, in the present
research, the artificial coating of beads by ferric oxides
has been examined, whereas natural coating might also
find application under certain conditions (i.e., treatment
of iron-rich groundwaters).
Following bed modification, aqueous solutions spiked
with arsenic entered the treatment column in upflow
mode and passed once through the modified medium,
and samples were collected from the exit of the column.
After the treatment of several bed volumes, the break-
through point was reached. Breakthrough was defined
as the point at which the effluent arsenic concentration
was over the permissible maximum concentration limit
of 10 µg/L.
Analytical Determinations. The determination of
total arsenic in the collected samples was performed by
hydride-generation atomic absorption spectrophotom-
etry (HG-AAS, Perkin-Elmer MHS 10, Perkin-Elmer
2380). The method is based on the conversion of soluble
arsenic in the respective volatile arsines, which are
subsequently determined by atomic flame absorption.
The reduction of arsenic was performed by KI addition
(10% w/v), and the pretreatment of the samples also
involved the addition of HCl (32% v/v). Following this
procedure, the samples were reacted with Na(BH4), and
the produced arsines were determined by means of the
respective calibration curve. The calibration curve
enables the determination of arsenic in the concentra-
tion range from 1 to 20 µg/L. To measure separately the
trivalent arsenic (speciation), samples were pretreated
only with acetic acid (0.05 M), to avoid the reduction of
pentavalent arsenic. Following pretreatment, samples
were also analyzed by hydride generation atomic ab-
sorption spectrophotometry.25
The samples were also analyzed for iron by flame
atomic absorption spectrometry. To determine the
amount of iron loaded on the calcium alginate beads,
10 g of modified beads was treated with (1 M) HCl acid.
In this way, iron was dissolved in the acid solution.
Results and Discussion
Alginate Bead Characterization. The concentra-
tion of cationic solution (CaCl2), as well as the duration
of incubation (curing) in this solution, was determined
on the basis of preliminary experiments. Alginate bead
characterization was performed by scanning electron
microscopy (SEM JSM-840A, JEOL scanning micro-
scope). It was found that the contact time in CaCl2
solution, as well as the CaCl2 concentration, affects the
structure and the mechanical properties of the beads.
The most appropriate beads for sorption experiments
in column operation were those formed by incubation

Figure 1. As(V) removal by alginate beads doped with iron oxides
(conditions: linear velocity, 1.16 m/h; bed volume, 50 mL; pH 7.0).
in CaCl2 solution (0.3 M) for 24 h. Following this
procedure, calcium alginate beads were modified by iron
oxides suspension, either doped or coated. Previous
investigations have shown that calcium alginate beads
(unmodified) have a minimal tendency to adsorb ar-
senic;21 therefore, they were not further examined in
this study.
Arsenic Removal by Calcium Alginate Beads
Doped with Iron Oxides. Iron oxides were doped into
the calcium alginate network during the preparation of
beads as previously described. Two kinds of calcium-
iron alginate beads were prepared, depending on the
concentration of the Fe(NO3)3 suspension used for iron
doping, and tested against the removal of As(V). The
results are presented in Figure 1.
It can be noticed that the removal of arsenic was
greatly affected by the Fe(NO3)3 concentration used for
the creation and doping of iron oxides. Because adsorp-
tion processes are greatly dependent on the available
amount of adsorbent,12 the extent of arsenic removal
was increased when 0.05 M doped iron concentration
([Fe]dop) was used, as compared to the experiments
performed with 0.025 M [Fe]dop. The amounts of doped
iron oxides were 2.8 and 1.4 mg of Fe/g of wet alginate
bead, respectively. In the first case, the breakthrough
point was reached after the treatment of around 80 bed
volumes. It has been reported that, for calcium-iron
alginate beads (batch experiments), the retention of
arsenic was around 1.7 µg of As/g of wet alginate bead
when incubated for 2 h, which increased to 6.5 µg of
As/g of wet bead when the incubation time was 24 h.21
In this study, the retention of arsenic up to the
breakthrough point was found to be 4.75 µg of As/g of
wet alginate bead or 1.75 µg of As/mg of Fe doped.
These results can be considered satisfactory, because,
in contrast to previously published results (batch equi-
librium experiments), the solution passes only once
through the sorptive bed during column operation,
resulting in a short residence time (5.5 min). Further-
more, the results from continuous column experiments
cannot be directly compared with those from batch
experiments, because, in the first case, the operation
terminates when the breakthrough point is reached and,
in this case, it terminated when the effluent concentra-
tion exceeded 10 µg/L, rather than when the bed reached
its maximum sorptive capacity.
Arsenic Removal by Calcium Alginate Beads
Coated with Iron Oxides. Apart from Ca-Fe-doped
alginate beads, calcium alginate beads coated with iron
oxides were also examined for the removal of arsenic.
Ind. Eng. Chem. Res., Vol. 41, No. 24, 2002 6151
Figure 2. As(V) removal by alginate beads coated with iron oxides
(conditions: linear velocity, 1.16 m/h; bed volume, 50 mL; pH, 7.0;
[As]o, 50 µg/L).
Figure 3. As(V) removal by alginate beads coated with iron
oxides: influence of coating duration (conditions: linear velocity,
1.16 m/h; bed volume, 50 mL; pH, 7.0; [As]o, 50 µg/L; [Fe]coat, 0.3
M).
The preparation of this material was previously de-
scribed, and it was performed after the placement of the
calcium alginate beads in the column. During the
coating procedure, most of the adsorbent was loaded
onto the surface of the material, probably as a result of
ion exchange between calcium and iron.21
When the coating was performed with the 0.3 M Fe-
(NO3)3 suspension, the amount of iron coated per gram
of wet alginate bead corresponded to 0.63 mg of Fe/g of
wet alginate bead, whereas when 0.025 or 0.1 M Fe-
(NO3)3 was used, the amounts of iron coated were 0.24
and 0.44 mg of Fe/g of wet alginate bead, respectively.
The pronounced effect of the adsorbent quantity on the
sorption efficiency was also confirmed by the results
displayed in Figure 2. Arsenic removal was found to be
more efficient when the coating was performed with the
more concentrated iron oxide suspension, and the
breakthrough point was reached after the treatment of
almost 45 bed volumes. The maximum amount of
arsenic sorbed onto the alginate beads was found to be
2.6 µg of As/g of wet alginate bead, or 4.4 µg of As/mg
of Fe.
During these experiments, the duration of the coating
procedure was 3 h. To investigate the kinetics of iron
coating onto the calcium alginate beads and the sequen-
tial effect on arsenic removal, the coating procedure was
also performed for 24 and 96 h, and the results are
presented in Figure 3. It can be noticed that, when the
coating was performed for 24 h, the removal of arsenic
6152 Ind. Eng. Chem. Res., Vol. 41, No. 24, 2002
Figure 4. As(V) removal by different types of modified alginate
beads (conditions: linear velocity, 1.16 m/h; bed volume, 50 mL;
pH, 7.0; [As]o, 50 µg/L).
was more efficient, in comparison with the 3-h coating
duration; however, it was found to be almost equal to
the results obtained when the coating was performed
for 96 h. This finding can be directly correlated with
the amount of iron oxide coated onto the surface of the
calcium alginate beads, which was found to be almost
equal for 24- and 96-h coatings (1.13 and 1.145 mg of
Fe/g of alginate, respectively).
From the obtained results, it was obvious that the
sorption of arsenic could occur on both the interior and
the exterior surface of the alginate beads, if this
material were modified appropriately. Therefore, the
best conditions for preparing modified alginate beads
would be to use calcium alginate beads doped with Fe
([Fe]dop ) 0.05 M) and, after placing them in the
operating column, to treat them with Fe [at an iron
coating concentration ([Fe]coat) of 0.3 M for 24 h] to allow
sufficient coating to occur.
Arsenic Removal by Calcium Alginate Beads
Doped and Coated with Iron Oxides. Arsenic re-
moval was examined using alginate beads prepared by
a combination of doping and coating with iron oxides
and was compared with previous results (Figure 4). The
removal of arsenic was found to be more efficient. The
adsorbing agents (iron oxides) were immobilized on both
the interior and exterior surfaces of the beads. The
deposition of iron oxides onto a greater area contributes
to the extension of the active surface for sorption.
Subsequently, more efficient utilization of the respective
adsorption sites can be achieved by the adsorbates. The
amount of iron loaded onto this combined (doped and
coated) material was found to be 3.9 mg of Fe/g of wet
alginate bead, comparable to the amount of iron coated
on sand (2-10 mg of Fe/g of sand, although efficient
coating requires temperatures over 200 °C).14 The
increased amount of loaded iron had a direct conse-
quence on the efficiency of the sorption process, as the
breakthrough point was reached after 120 treated bed
volumes, which corresponds to 7.2 µg of As/g of wet
alginate bead or 1.8 µg of As/mg of Fe loaded on the
bead, which is comparable to previous findings.21
Further investigations regarding treatment efficiency
included an examination of the residence time of the
solution in the filtration bed. The residence time is a
critical parameter in adsorption experiments are carried
out, as the removal efficiency depends strongly on the
contact time between the adsorbent (iron hydroxides)
and the adsorbate (arsenic). The effect of residence time
Figure 5. Effect of linear velocity on As(V) removal by alginate
beads doped and coated with iron oxides (conditions: bed volume,
50 mL; pH, 7.0; [As]o, 50 µg/L).
was investigated by applying different values of linear
velocity, and the results are presented in Figure 5. As
expected, the extent of adsorption decreased as the
linear velocity was increased because of the resulting
lower contact times. The contact time, or empty bed
residence time (EBRT) is the time required for the liquid
to fill the empty column: EBRT ) bed volume/volumet-
ric flow rate of the liquid.23
The best results were obtained when the linear
velocity was lowest examined, i.e., 0.6 m/h, with a
corresponding residence time 10 min. In this case, the
breakthrough point was reached after the treatment of
almost 230 bed volumes, or if expressed in pore volumes,
the breakthrough point was reached after the treatment
of almost 700 pore volumes. The amount of arsenic
sorbed was also found to increase and reached 13.8 µg
of As/g of wet alginate bead.
The increase in sorption capacity with increasing
residence time indicates that the sorption process is
controlled by intraparticle mass transfer, rather than
by external mass transfer,23 thus the critical stage in
the arsenic removal kinetics is the diffusion of liquid
into the bed porosity. However, the main mechanism
responsible for arsenic removal is the chemical reaction
between iron and arsenic. As(V) is known to form stable
coordination compounds with iron oxides, by specific
adsorption, through the following reaction26
M-FeOH + H3AsO4 f M-Fe-H2AsO4 + H2O
The product of this reaction is ferric arsenate, which
has a very low solubility product (10-20 mol/L).8 These
results can be considered as satisfactory regarding the
applicability of the method, as they were obtained
without any pretreatment of the solution (i.e., pH
adjustment). Additionally, because no studies regarding
the application of modified alginate beads in fixed beds
for the removal of arsenic from contaminated water
could be found in the literature, the direct comparison
of the obtained results with other literature findings was
not possible.
Previous investigations regarding arsenic removal by
adsorptive filtration have been performed by applying
conventional iron oxide coated sand.12 These results
were equally efficient regarding the number of bed
volumes treated before the breakthrough point (200-
250 bed volumes), although the pH of the treated
solution was adjusted to 3.5, which certainly is not
typical of natural waters. It is well-documented that

Figure 6. Comparison between As(V) and As(III) removal by
alginate beads doped and coated with iron oxides (conditions:
linear velocity, 0.6 m/h; bed volume, 50 mL; pH, 7.0; [As]o, 50 µg/
L).
As(V) tends to be more strongly adsorbed at lower
solution pH, because the extent of complex formation
between arsenates and iron depends on the ratio of the
concentration of arsenates to the concentration of
OH-.27 The log K values (affinity constants) of hydrous
ferric oxide and ferric arsenate are 3827 and 20.2,28
respectively, which indicates that OH- has a stronger
affinity for Fe(III) than does arsenate, as both anions
compete with Fe(III) for the same adsorption sites.
Thus, by decreasing the pH, the tendency of the arsen-
ate ions to enter the coordination sheath of the Fe(III)
ions will increase. Therefore, if the pH value in the
present study were adjusted to 5.0, the results could be
further improved, but the applicability of this method
would also be restricted, because the pH values typically
encountered fall in the range 6-8.
However, the efficiency of alginate was found to be
equal to or greater than that of other polymeric materi-
als applied in the adsorbing filtration process.29 Under
similar conditions, the use of iron oxide coated polysty-
rene beads was found to reach breakthrough after the
treatment of 60 bed volumes, and iron-coated polymer-
ized high internal phase emulsion (poly HIPE) produced
similar results. In this study, the effect of other con-
stituents of natural waters was also examined. It was
found that phosphates inhibit the sorption of arsenic
on iron-coated polymeric beads, whereas other anions,
such as chlorides, nitrates, and bicarbonates, have a
smaller effect on arsenic removal. These results were
consistent with the findings of previous studies,30 and
it was considered that similar results would be obtained
in the present study.
The aforementioned results refer to the removal of
pentavalent arsenic anions. The other main inorganic
form of arsenic that is usually present in aquatic
environments is trivalent arsenic (AsIII), which is
mainly present under mildly anaerobic or anoxic condi-
tions, such as those found in groundwaters.6 This fact
aggravates the overall problem of arsenic removal,
because trivalent arsenic anions are far more toxic than
pentavalent ones.1 Therefore, experiments were also
performed by spiking the samples with trivalent arsenic,
to investigate the removal of As(III) separately using
the same modified alginate beads (Figure 6).
It was found that As(V) was removed from the
aqueous stream more efficiently, whereas the removal
of trivalent arsenic was not significant, reaching the
breakthrough point after the treatment of only 45 bed
Ind. Eng. Chem. Res., Vol. 41, No. 24, 2002 6153
Figure 7. Breakthrough curves of As(V) for different sorbent
quantities (40, 80, or 160 g of alginate beads doped and coated
with iron oxides) (conditions: linear velocity, 0.6 m/h; pH, 7.0;
[As]o, 50 µg/L).
volumes. This difference in removal efficiencies of
inorganic arsenic forms could be attributed to the
speciation of inorganic arsenic in natural waters. Pen-
tavalent arsenic in the pH range of interest for drinking
water is present in its anionic forms of H2AsO4- and
HAsO42- (pKa ) 2.19, pKb ) 6.94).31 Thus, it can be
adsorbed more easily on iron oxides, which, in this pH
range, are mainly present with the cationic monomeric
form [Fe(OH)2+],32 because adsorption is facilitated by
Coulombic interactions.
In contrast, trivalent arsenic in the same pH range
is mainly present in its nonionic form of arsenious acid
(H3AsO3, pKa ) 9.22).31 Therefore, at pH 7, it is not
dissociated. Although specific chemical interactions
between Fe(III) and As(III) can occur, Coulombic inter-
actions are unfavorable, and thus, sorption is decreased.
These results indicate that, when both forms of inor-
ganic arsenic are present in an aqueous stream, a
preoxidation step is essential to achieve maximum
overall arsenic removal. This oxidation step can be
performed by the application of chemical reagents, such
as ozone, hydrogen peroxide, chlorine, etc.,8,33,34 and
biological processes could also be used to catalyze
trivalent arsenic oxidation.22
Modeling Fixed-Bed (Column) Operation by the
Application of the Bed Depth Service Time (BDST)
Model. During operation of a fixed-bed adsorption
column, the service time of the system can be related
to the bed depth for a given set of experimental
conditions.23 The main consideration when sizing ad-
sorptive columns is to predict the service time until the
effluent exceeds a predefined pollutant concentration.
The BDST model relates the service time of a fixed bed
to the height of the adsorbent material in the bed and,
hence, to its total quantity, as it is directly proportional
to the bed height for a specific column size. Therefore,
sorbent quantity is used in preference to bed height
(Figure 7).24 The BDST model was found to be suf-
ficiently described by the equation
( )
qo Co
1
t) M- ln - 1 ) RM + b (1)
CoV kCo Ct
where t is the service time (h), qo is the adsorption
capacity (µg/g), Co is the initial concentration of adsor-
bate (µg/L), V is the applied flow rate (L/h), M is the
quantity of sorbent inside the column (g), and Ct is the
6154 Ind. Eng. Chem. Res., Vol. 41, No. 24, 2002
Table 1. Calculated Constants of Bed-Depth Service Time Equation for Adsorption of As(V) on Alginate Beads Doped
and Coated with Iron Oxides
k qo
pH of breakthrough (10-3 L
influent species (%) min mol-1)
-1
7 As(V) 10 11.7
20 2.91
30 1.6
Figure 8. Iso-removal lines for As(V) sorption on alginate beads
doped and coated with iron oxides at 10, 20, and 30% breakthrough
(conditions: linear velocity, 0.6 m/h; pH, 7.0; [As]o, 50 µg/L).
Definition of percent breakthrough (e.g., 10%): the point when
the effluent has a concentration equal to 10% of the influent
concentration.
Figure 9. Operating line plot for fixed-bed alginate exhaustion
rate vs minimum residence time for As(V) removal for 20% total
breakthrough (conditions: pH, 7.0; [As]o, 50 µg/L; quantity of
sorbent, 40 g; material, alginate beads doped and coated with iron
oxides).
respective effluent concentration of adsorbate at time
t. From the iso-removal lines (plots of t versus M)
(Figure 8), regarding column operation under constant
experimental conditions (except sorbent quantity), the
main parameters of the BDST model can be calculated.
Subsequently, from the slope (R) of the respective lines,
the adsorption capacity (qo) can be calculated, and from
the intercept (b), the rate constant of adsorption (k) can
be found. Table 1 contains the summarized results of
these calculations.
The application of the BDST model describing the
sorption of arsenic onto (modified) alginate beads or onto
iron oxides has not previously been reported. Therefore,
the direct comparison of the obtained results with other
related experimental work is not possible. Nevertheless,
the calculated parameters regarding the theoretical
qo
(µg of As/ (µg of As/ correlation
g of alginate) mg of Fe) coefficient, r2
7.79 1.99 0.99
13.75 2.91 0.99
22.6 5.79 0.99
amount of arsenic sorbed onto the modified alginate
beads was found to be in good agreement with the
experimental results. The amount of arsenic sorbed for
20% breakthrough was calculated as 13.75 µg of As/g
of wet alginate bead, whereas the experimental calcula-
tions for the corresponding experimental conditions
produced a sorptive capacity equal to 13.8 µg of As/g of
wet alginate bead. The application of different flow rates
of contaminated water through the column can be also
calculated by multiplying the original slope (R) by the
ratio between the original and the new flow rate,
because a linear change in flow rate is not expected to
have any effect on the intercept (b). The influence of
the feed concentration of the metal from Co to a new
value Cn can be determined by performing the following
correcting calculations
()
Co
Rnew ) Rold (2)
Cn
and
bnew ) bold ( )[
Co ln(Cn - 1)
Cn ln(Co - 1) ] (3)
Fixed-Bed Operational Optimization Using the
Empty Bed Residence Time (EBRT) Model. The two
major parameters in the design of an adsorber unit are
the contact time (or empty bed residence time) and the
adsorbent exhaustion rate. The definition of EBRT was
mentioned earlier. The adsorption exhaustion rate is the
mass of adsorbent used per volume of liquid treated at
the breakthrough point.23 The EBRT model enables the
calculation of two basic parameters in the design of
fixed-bed columns: (a) the minimum EBRT required to
achieve the desired effluent concentration at infinitely
high adsorption exhaustion rate and (b) the minimum
adsorbent exhaustion rate, which occurs when the
EBRT is large enough, so that the exhausted adsorbent
is in equilibrium with the influent and the total volume
treated at breakthrough will not increase with increas-
ing EBRT. These two parameters can be calculated by
plotting the EBRT versus the adsorbent exhaustion rate
for the preselected breakthrough concentration and for
different flow rates, which provides different EBRTs for
the same amount of adsorbent (Figure 9). This plot
produces the so-called “operating line” of the process,
from which the aforementioned parameters can be
obtained from the respective intercepts.23
This study was directed toward removing arsenic from
contaminated water, so the breakthrough concentration
of 10 µg/L was selected. Therefore, the operating line of
the modified alginate system was designed for 20%
breakthrough for an initial As(V) concentration of 50
µg/L. From the data presented in Figure 9, it was found
that the minimum EBRT required to achieve an effluent
concentration of 10 µg/L was 76 s (for an adsorbent
exhaustion rate 4.3 kg of modified alginate/dm3), and

the minimum adsorption exhaustion rate after which
the influent was in equilibrium with the exhausted
adsorbent was 0.45 kg of modified alginate/dm3.
Conclusions
Alginate beads were applied in fixed beds as supports
for hydrous ferric oxides and examined in the removal
of arsenic from contaminated water. The operation was
found to be controlled by intraparticle mass transfer,
as, when the residence time was increased, the extent
of adsorption also increased. For a residence time of 10
min, 230 bed volumes of As(V) solution were treated
before the breakthrough point of 10 µg/L was reached.
In comparison, when As(III) solution was used, only 45
bed volumes were treated before the breakthrough
point, indicating the need for preoxidation when As(III)
is also present in the aqueous stream.
The results were further elaborated using the bed
depth service time model, and it was found that, for 20%
breakthrough, the theoretical bed sorptive capacity was
13.75 µg of As/g wet alginate bead or 2.91 µg of As/mg
of Fe. The application of the EBRT model enabled the
calculation of two basic parameters for the design of
column operations. The minimum EBRT required for
achieving a predefined effluent concentration (i.e., 10
µg/L) was 76 s, and the minimum adsorbent exhaustion
rate after which the volume treated at breakthrough
will not increase further with increasing EBRT was
determined to be 0.45 kg of alginate/dm3.
Acknowledgment
This work was part of the Doctoral Dissertation of
Mr. Katsoyiannis, which was financially supported by
the Greek State Scholarship Foundation. Thanks are
also due to Ms. F. Kiachidou (Chemist) for experimental
collaboration.
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Received for review May 23, 2002
Revised manuscript received September 9, 2002
Accepted September 14, 2002
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