Chemical Engineering Journal 187 (2012) 63–68

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Chemical Engineering Journal

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Bromate removal from aqueous solutions by nano crystalline akaganeite

(␤-FeOOH)-coated quartz sand (CACQS)
Chunhua Xu, Junjun Shi, Weizhi Zhou ∗ , Baoyu Gao, Qinyan Yue, Xiaohong Wang
School of Environmental Science and Engineering, Shandong University, Shandong Key Laboratory of Water Pollution Control and Resource Reuse; Jinan, 250100, China

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

Article history: We investigated the feasibility of nano crystalline akaganeite (␤-FeOOH)-coated quartz sand (CACQS) for
Received 28 October 2011 bromate removal from aqueous solutions. Batch experiments were carried out as a function of various
Received in revised form 18 January 2012 operational conditions such as adsorbent dosage (20–160 g/L), initial pH (3–12), contact time (1–240 min),
Accepted 19 January 2012
initial bromate concentration (0.6–10 mg/L) and temperature (288 K, 298 K and 308 K). The uptake rate of
bromate was rapid and the adsorption was almost saturated within 20 min. The adsorption kinetics can be
Keywords:
described by the pseudo-second-order equation. The maximum adsorption capacity of the adsorbent for
␤-FeOOH-coated quartz sand (CACQS)
bromate removal was 37.8 ␮g/g at 298 K. The data fit well with the Langmuir model. Optimum bromate
Bromate
Adsorption
removal was observed between pH 3 and 10. Analysis of the adsorption thermodynamics showed that
Isotherm the adsorption of bromate by CACQS was spontaneous, exothermic and occurred due to physisorption.
Kinetics © 2012 Elsevier B.V. All rights reserved.

1. Introduction
BrO3 − does not occur in natural waters, but it is formed during
ozonation which is commonly used in water treatment because of
the presence of bromide (Br− ) and ammonia ion (NH4 + ) [1]. Kishi-
moto and Matsuda [2] reported that the formation mechanisms of
bromate are quite complex, in which molecular ozone (O3 ) and/or
hydroxyl radical (OH• ) oxidize Br− into hypobromous acid (HOBr)
and/or hypobromite radical (BrO• ) and then further oxidize it into
BrO3 − . During ozonation and/or disinfection of drinking water with
ozone, bromate ion is formed at levels ranging from 3 to 50 ␮g/L
[1]. BrO3 − has been classified by the United States Environmental
Protection Agency [3] as a possible human carcinogen by the oral
route of exposure, and the specified maximum contaminant level
(MCL) is 10 ␮g/L for drinking water [4]. In China, MCL of bromate
is also 10 ␮g/L in drinking water sanitary standard (GB 5749-2006)
and drinking natural mineral water (GB 8537-2008). It has also been
classed as a Group 2B carcinogen by the World Health Organization
(WHO) [5]. The WHO has estimated that the BrO3 − concentrations
in drinking water that correspond to a cancer risk of 10−4 , 10−5 , and
10−6 (life-time exposure) are 30, 3, 0.3 ␮g/L, respectively [6]. Butler
et al. [7] have summarized the toxicity of BrO3 − ; the acute toxicity
symptoms of BrO3 − in humans may include severe gastrointestinal
∗ Corresponding author. Tel.: +86 531 88361383; fax: +86 531 88364513.
E-mail addresses: xuchunhua@sdu.edu.cn (C. Xu), shijunjun165@163.com
(J. Shi), wzzhou@sdu.edu.cn (W. Zhou), bygao@sdu.edu.cn (B. Gao),
qyyue@sdu.edu.cn (Q. Yue), lmj15848247414@163.com (X. Wang).
irritation, depression of the central nervous system, and renal fail-
ure.
For the high solubility and stability in water, bromate is difficult
to remove using conventional treatment technologies [7]. The risks
related to bromate attract the interests to explore effective treat-
ment methods. Recently, several chemical and physical methods
have been used for the removal of bromate from drinking water
such as adsorption [8], reduction using zero-valent iron (Fe0 ) [9],
Fe2+ [10,11], and SO3 2− [10], fixed-film bioreactor [5], ion exchange
[12,13], filtering through a reverse osmosis membrane [14] and
ultraviolet (UV) irradiation [15,16]. Among all the methods, adsorp-
tion seems to be the most attractive owing to its economy and
easy accessibility. Several adsorbents have been tested for bro-
mate removal, including activated carbon [17,18], granular ferric
hydroxide [19] and organo-montmorillonite [8]. BrO3 − removal by
granulated activated carbon (GAC) was also effective for reduc-
ing BrO3 − to Br− [6,18,20,21]. But Asami et al. [20] and Huang
and Chen [22] showed that the BrO3 − removal rate substantially
decreased with the transition from fresh GAC to biological activated
carbon. Iron oxides are promising sorbent materials as they are
characterized by low-cost, high efficiency and free from environ-
ment pollution [23]. Among the iron oxides, akaganeite (␤-FeOOH)
has attracted much interest because of its unique sorption, ion
exchange, and catalytic properties and it is synthesized by a sim-
ple and readily reproduced method under laboratory conditions
[24–26]. Akaganeite has already been tested as an adsorbent of
Cr(VI) [27], As(V) [26,28], arsenites [29], antimony [28], phos-
phate [30], Cd ions [31], U(VI) [32] and bromate [33]. However, the
occurrence of akaganeite in fine powdery forms limits their appli-
cation. So akaganeite can be incorporated with other materials to

1385-8947/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.01.087
64 C. Xu et al. / Chemical Engineering Journal 187 (2012) 63–68
Table 1
The physical advantages of the material before and after coating.
Quartz sand
Specific surface area (m2 /g) 0.38
Surface iron content (mg Fe/g) 0.52
Mechanical oscillation dissolved quantity (%) – 1.2
Acid dissolved quantity (%) – 2.3
Alkali dissolved quantity (%) – 4.7
overcome their disadvantages of loose structure and easy hydroly-
sis [34].
In China, quartz sand is widely used as a filter in water treatment.
It is a stable silicate mineral and its configuration and the surface
holes which are formed by mechanical action make it easy to coat
with akaganeite. Coating akaganeite on the surface of quartz sand
can change the physical and chemical properties of the sand, espe-
cially in increasing the surface area and adsorption capacity, which
may enhance its use as a filter medium to remove bromate from
the water [34]. According to our survey, few researches have been
done to coat akaganeite onto quartz sand for bromate removal.
In this paper, ␤-FeOOH-coated quartz sand (CACQS) was pre-
pared based on the process illustrated in our previous study [34]
and used as a sorbent for removing BrO3 − from water. The objective
of this study is to investigate the application of CACQS for bro-
mate removal from aqueous solution. The role of adsorbent dosage,
initial pH, contact time, initial bromate concentrations and temper-
ature on bromate removal were assessed. The adsorption process is
described by different isotherm and kinetic models to identify the
adsorption mechanism. The results give us a better understanding
of bromate removal by CACQS.
2. Materials and methods
2.1. Materials
Nano crystalline akaganeite (␤-FeOOH)-coated quartz sand
(CACQS) was prepared following the procedure in our previous
study, and the characteristics and important properties of CACQS
compared with quartz sand are listed in Table 1 [34].
2.2. Analytical methods
Bromate was measured with a single-column ion chromato-
graph (IC1010, Shanghai Tianmei Science Instrument Co., Ltd.,
China) with a low-conductivity mobile phase. A 3.6 mmol/L sodium
carbonate solution was used as the effluent at a flow rate of
0.8 mL/min. The sample was injected through a built-in needle
port in the panel of the ion chromatography with six-port sam-
ple injection valve. The separation column (Shodex IC SI-52 4E,
4.0 mm ID × 250 mm) was operated at 40 ◦ C. The data acquisi-
tion was performed using a D-1010 chromatography workstation
V1.08 program. The pH of the solutions was measured with a pH
meter (pHS-3C, Shanghai Precision & Scientific Instrument Co., Ltd.,
China).
2.3. Bromate adsorption experiments
NaBrO3 was purchased from Tianjin Kermel Chemical Reagent
Co., Ltd., China. Bromate stock solutions were prepared from
reagent-grade chemicals using deionized water and stored at 4 ◦ C
and the desired concentrations were obtained by diluting the
stock solution when needed. All adsorption experiments were
carried out with 100 mL of bromate solutions of known initial
concentrations and ␤-FeOOH-coated quartz sand in 250 ml capped
conical flasks with agitation on a thermostated rotary shaker
60
CACQS 50
1.83
removal efficiency (%)
6.70
40
30
20
10
removal efficiency
0
0 40 80 120 160 200
adsorbentdose(g/L)
Fig. 1. Effect of sorbent dose on bromate removal by CACQS. Reaction conditions:
initial bromate concentration 200 ␮g/L, reacted for 12 h at 150 rpm and 298 K.
(SHZ-82, Jintan Medical Instrument Factory, Jiangsu, China) at
150 rpm. After equilibrium, samples were filtered using 0.22 ␮m
disposable membrane filters (Shanghai Mili membrane separation
technology Co., Ltd., China) and the concentration of bromate was
analyzed by ion chromatography.
A series of batch experiments were performed to investigate
the influence of adsorbent dosage, pH, contact time, initial bromate
concentration and temperature on bromate removal. The effect of
adsorbent dosage was tested by varying the adsorbent mass (2–16 g
dry matter) at constant solution volume (0.1 L), using a constant
initial bromate concentration (200 ␮g/L), temperature (298 K), and
contact time (12 h). The effect of pH was investigated by adjusting
solution pH from 3 to 12 using 0.1 M hydrochloric acid (HCl) or 0.1 M
sodium hydroxide (NaOH) under an initial bromate concentration
of 200 ␮g/L, adsorbent dosage of 100 g/L and reaction time 12 h at
298 K. The pH was measured before and after the experiments. The
kinetics studies were done with changing initial bromate concen-
trations (100, 200, 400 ␮g/L) or temperatures (288, 298, 308 K) with
contact time ranging from 1 to 240 min, and samples for bromate
analysis were taken at regular intervals from the reaction solution.
The adsorption isotherm was studied by varying the initial bro-
mate concentration from 0.6 to 10 mg/L at 288 K, 298 K and 308 K.
The concentration retained in the adsorbent phase (qe , ␮g/g) was
calculated using the following equation:
(C0 − Ct )V
qe = (1)
W
where C0 (␮g/L) is the initial bromate concentration, Ct (␮g/L) is the
bromate concentration at any time, t, V (L) is the volume of solution
and W (g) is the mass of the adsorbent.
3. Results and discussion
3.1. Effect of adsorbent dosage
Adsorbent dosage is an important parameter because it deter-
mines the capacity of an adsorbent. Fig. 1 displays the effect of
adsorbent dose on bromate uptake at a fixed initial concentration of
bromate (200 ␮g/L). The results showed that adsorption efficiency
increases rapidly with an increase in adsorbent dose from 20 to
100 g/L. The sharp decreases in BrO3 − concentrations at adsorbent
doses ranging from 20 to 100 g/L are probably due to the strong
binding of BrO3 − in the tunnel sites [33]. The increase in the effi-
ciency of removal may be attributed to the fact that with an increase
in the adsorbent dose, more adsorption sites are available for the
 C. Xu et al. / Chemical Engineering Journal 187 (2012) 63–68 65

2.0 3.2

Amount adsorbed 12
2.8
Equilibrium pH

Amount adsorbed (µg/g)

Amount adsorbed (μg/g)

1.5 10 2.4

Equilibrium pH
2.0 100 μg/L
8 200 μg/L
1.0 1.6 400 μg/L

6 1.2

0.5 (Stable pH zone)

0.8
4
0.4

0.0 2 0.0
2 4 6 8 10 12 0 60 120 180 240
Initial pH Time (min)

Fig. 2. Effect of pH on bromate adsorption onto CACQS. Reaction conditions: initial Fig. 3. Effect of contact time and initial concentration for bromate adsorption onto
bromate concentration 200 ␮g/L, adsorbent dosage 10 g, reacted for 12 h at 150 rpm CACQS. Reaction conditions: adsorbent dosage 10 g, reacted at 150 rpm and 298 K.
and 298 K.

solute to be adsorbed [35]. However, it was noticed that after a

dosage of 100 g/L, there was no significant change in the removal
percentage of bromate. So an adsorbent dose of 100 g/L of CACQS
was selected for further experiments.
3.2. Effect of pH
In order to determine the optimum pH for BrO3 − removal on
CACQS, the bromate adsorption was studied as a function of ini-
tial pH. Fig. 2 presents the adsorption results of an initial solution
of 200 ␮g/L bromate adsorbed onto CACQS, where changes in the
initial and equilibrium pH causes corresponding changes in the
reaction solution. As can be seen, the maximum adsorption of
bromate is about 1.5 ␮g/g in the pH range from 3.0 to 10.0 and
decreases sharply at pHs over 10.0. The lower adsorption at higher
pH is probably due to the competition for anion exchange with
Cl− by the increasing number of OH− ions and the electrostatic
repulsion of bromate ions by the negatively charged surface of the
adsorbing material at high pH [33,36]. A similar trend was also
found in the case of bromate adsorption onto granulated ferric
hydroxide [19].
The results also show that at the initial pH 3–10, after addition
of the adsorbing material the pH dropped to about 3–4. This implies
OH− /Cl− ion-exchange occurs to a certain extent during the BrO3 −
adsorption process [33]. The high removal efficiency of bromate
occurred even at an initial pH of 10.0. This may be due to the high
protonation of ␤-FeOOH at the equilibrium pH of 4.0, which con-
trols the point of zero charge while reacting with bromate [37].
A similar result was also found in adsorption of humic acid onto
nanoscale zerovalent iron [38].
The relationship between the initial and equilibrium pH of bro-
mate adsorption onto CACQS is also shown in Fig. 2. At an initial
pH of around 3.0–10.0, a stable pH zone was observed, where the
equilibrium pH was in the range of 2.9–4.0 and the adsorption
capacities were stable. This may be due to continuous protona-
tion under acidic conditions. When the initial pH was above 10,
the equilibrium pH became alkaline during the adsorption process
and the results showed a noticeable fall in bromate adsorption.
Nevertheless, the optimum bromate removal was observed over
a wide pH range of 3–10, suggesting that the CACQS can be suc-
cessfully utilized in drinking water processes and the pH does not
need adjustment.
3.3. Effect of contact time and bromate initial concentration
Fig. 3 shows the effect of contact time and initial bromate
concentration on adsorption of bromate by CACQS. The results
showed that the adsorption capacity of bromate increased with
time and attained a constant value at 10 min. After that, it remained
unchanged indicating that no further bromate was removed from
the solution (Fig. 3). The equilibrium time was around 10 min but
the adsorption experiments were still run for 240 min for compar-
ison with the literature. It was also found that the adsorption of
bromate onto CACQS was strongly dependent on the initial bro-
mate concentration. For initial concentrations of bromate of 100,
200 and 400 ␮g/L, the amounts absorbed at 10 min were 0.78, 1.27
and 2.72 ␮g/g respectively (Fig. 3). This may be attributed to an
increase in the driving force of the concentration gradient with
the increase in the initial bromate concentration, which overcomes
the mass transfer resistance between the aqueous and solid phases
[39]. Therefore, higher initial bromate concentration may increase
the adsorption capacity.

Table 2
Kinetics parameters for adsorption of bromate.

Parameters qe(exp) (␮g/g) Pseudo-first-order model Pseudo-second-order model

k1 (min−1 ) qe(cal) (␮g/g) R2 k2 (g/␮g min) qe(cal) (␮g/g) R2

C0 (␮g/L)
100 0.82 0.09 0.26 0.5215 1.50 0.80 0.9976
200 1.31 0.24 1.03 0.8773 0.21 1.52 0.9693
400 3.00 0.10 1.28 0.5247 0.60 3.02 0.9906

T (K)
288 1.39 0.17 0.94 0.9604 0.26 1.53 0.9860
298 1.31 0.24 1.03 0.8773 0.21 1.52 0.9693
308 1.10 0.10 0.67 0.9295 0.35 1.11 0.9952
66 C. Xu et al. / Chemical Engineering Journal 187 (2012) 63–68

1.6

Amount adsorbed (μg/g)

50

40 1.2
Amount adsorbed (μg/g)

Amount adsorbed (μg/g)

30
Equilibrium concentration (μg/L)

0.8
20

288K
288K 298K
10 0.4
298K
308K
308K

0 0 60 120 180 240

0 2000 4000 6000 8000 10000
Time (min)
Equilibrium concentration (μg/L)
Fig. 5. Effect of contact time and reaction temperature for bromate adsorption onto
Fig. 4. Effect of initial concentration and reaction temperature for bromate adsorp-
CACQS. Reaction conditions: the initial bromate concentration 200 ␮g/L, adsorbent
tion onto CACQS. Reaction conditions: adsorbent dosage 10 g, reacted for 12 h at
dosage 10 g, shaken at 150 rpm.
150 rpm.

3.5.1. Pseudo-first-order model

3.4. Effect of temperature The linear form of the pseudo-first-order equation is given as
follows:
The effects of temperature on bromate adsorption onto CACQS at
different initial concentrations and contact time were studied. Fig. 4 ln(qe − qt ) = ln qe − k1 t (2)
depicts the effects of different initial concentrations and temper- where k1 is the rate constant of first-order adsorption (min−1 ), qe
ature on the adsorption of bromate on CACQS; experiments were and qt (␮g/g) denote the amounts adsorbed at equilibrium and
performed at 288 K, 298 K and 308 K. As seen in the inset of Fig. 4, at time t (min), respectively. In a pseudo-first-order process ln qe
the equilibrium was not achieved in the low bromate concentra- should be equal to the intercept of a plot of ln(qe − qt ) against t.
tion range (initial bromate concentration 50–400 ␮g/L), therefore Values of the parameters of the pseudo-first-order kinetic model
higher concentrations (0.6–10 mg/L) of bromate were chosen to at three concentrations and temperatures are listed in Table 2.
study the bromate maximum adsorption potential on CACQS. The
results showed that adsorption capacity decreased with increasing
3.5.2. Pseudo-second-order model
temperature and adsorption capacities 47.3, 37.8, 21.7 ␮g/g were
A linear form of the pseudo-second-order model is shown in Eq.
observed at 288 K, 298 K, 308 K, respectively. Therefore, the adsorp-
(3):
tion process is exothermic. Fig. 4 also shows that the adsorption of
bromate depends on the initial concentration of bromate. The ini- t 1 t
tial bromate concentration provides the necessary driving force to = + (3)
qt k2 q2e qe
overcome the resistance to the mass transfer of bromate between
the aqueous and solid phases [40]. where qe and qt have the same meaning as above, and k2 is the
Fig. 5 shows the effect of different contact time on the adsorp- rate constant for the pseudo-second order kinetics. The plots of t/qt
tion of bromate on CACQS at 288, 298 and 308 K. The adsorption versus t with different concentrations or temperatures are depicted
efficiency increased rapidly with an increase in contact time up to and the values of qe(cal) and k2 were determined from the slope and
20 min, and a maximum removal efficiency of more than 60% was intercept of the plot and are compiled in Table 2.
achieved at each temperature and remained nearly constant up to Table 2 shows that the pseudo-second-order model describes
the end of the experiment (240 min). Both Figs. 5 and 3 show that the experimental data well. The values of the correlation coefficient
the adsorption occurred quickly and the time required to achieve (R2 ) vary from 0.9693 to 0.9976. The higher correlation coefficients
equilibrium is independent of the low initial bromate concentration (R2 ) confirmed that the adsorption of bromate onto CACQS was well
and reaction temperature. represented by the pseudo-second-order model in the first 20 min
of adsorption. The calculated adsorption capacities (qe(cal) ) obtained
from the pseudo-second-order model and the experimental values
3.5. Adsorption kinetics (qe(exp) ) are very close, which also support this conclusion.

Adsorption kinetics is important to evaluate the adsorption pro-

3.6. Adsorption isotherm and adsorption thermodynamics
cess; not only can it predict the adsorption rate but also lead to
suitable rate expressions characteristic of possible reaction mech-
Adsorption equilibrium between an adsorbent and an adsorbate
anisms. Two kinetic models, namely the pseudo-first-order and
is described by adsorption isotherms. Two adsorption isotherm
pseudo-second-order, are used to examine the adsorption process
models were used in this research, namely the Langmuir model
in this study. The experimental data for the first 20 min on the
and the Freundlich model [41,42]. The applicability of the isotherm
effect of contact time and different initial concentration and the
models to the adsorption was judged by comparing the correlation
effect of contact time and different reaction temperature were used
coefficients.
to evaluate the adsorption kinetics of bromate from solution onto
The Langmuir model is presented by the following equation:
CACQS. The applicability of the two models was judged by compar-
ing the correlation coefficients (R2 ) and the equilibrium adsorption 1 1 1
= + (4)
capacity, which was compared with the experimental values. qe qm qm bCe
 C. Xu et al. / Chemical Engineering Journal 187 (2012) 63–68 67

0.25 1.8
(A) (B)
0.20 1.5

0.15

log qe
1/qe 1.2

0.10
288K 0.9 288K
298K 298K
0.05 308K 308K

0.6
0.00
0.000 0.001 0.002 0.003 0.004 2.4 2.8 3.2 3.6 4.0
1/Ce log Ce

Fig. 6. Isotherm for bromate adsorption onto CACQS at different temperatures. (A) Langmuir isotherm and (B) Freundlich isotherm.

where qe and Ce express the same meaning as mentioned above, Table 4

Thermodynamic parameters for bromate removal with CACQS.
qm represents the maximum monolayer adsorption capacity and b
is the Langmuir constant related to bonding energy. The Langmuir T (K) K (L/mol) G◦ (kJ/mol) S◦ (J/mol K) H◦ (kJ/mol)
model is valid for monolayer adsorption onto a surface [41]. 288 6.68 × 104
−26.60
The Freundlich model, which is indicative of sorption onto a 298 6.51 × 104 −27.46 69.73 −6.57
heterogeneous surface, is described by the following equation [42]: 308 5.59 × 104 −27.99

1
log qe = log KF + log Ce (5)
n
G◦ = H ◦ − TS ◦ (8)
where qe is the amount adsorbed at equilibrium; Ce is the equilib-
rium concentration; KF and n are Freundlich constants, concerning
where R is the universal gas constant (8.314 J/mol K), T is the abso-
adsorption capacity and adsorption intensity, respectively.
lute temperature and K is the equilibrium constant (L/mol) related
The adsorption isotherms for the adsorption of bromate were
to the Langmuir constant ‘b’. The results are summarized in Table 4.
achieved by varying the initial bromate concentration at 288 K,
The exothermic nature of adsorption is indicated by an increase
298 K and 308 K. The results are shown in Fig. 6. For the Langmuir
in the K values with a drop in temperature [44]. The negative G◦
model, the values of monolayer capacity (qm ) and Langmuir con-
values indicate that the adsorption process is spontaneous and fea-
stant (b) were evaluated from the intercept and slope of Fig. 6(A).
sible. The value of H◦ for bromate adsorption is −6.57 kJ/mol,
And the Freundlich constants were obtained from the slope and
which is negative and lower than 40 kJ/mol, suggesting that inter-
intercept of the linear plots of Fig. 6(B). The theoretical parameters
action between bromate and CACQS is exothermic and that the
along with the regression coefficients were calculated from the two
adsorption can be described as a physical process. This result is the
models and are given in Table 3.
same as the conclusion obtained from the isotherm calculations.
As Table 3 shows, the greater correlation coefficients (>0.99)
The positive S◦ value may be due to the affinity of the adsorbent
at all the temperatures indicated the Langmuir model fit the data
for bromate.
better than the Freundlich model in the present study. This suggests
that a bromate monolayer is adsorbed on CACQS. The magnitude
of n indicates the favorability of adsorption. Values of n (Table 3) 4. Conclusion
greater than 1 suggest that the process of bromate adsorption by
this adsorbent is feasible [43]. The values of qm calculated from The results showed that CACQS could be used for bromate
the Langmuir isotherm accorded well with the experimental values removal. The selected optimum adsorbent dose was 100 g/L at a
(Fig. 6(A)). bromate concentration of 200 ␮g/L. The adsorption capacities of
The amount of bromate adsorbed at equilibrium at 288, 298 CACQS for bromate were 47.3, 37.8 and 21.7 ␮g/g at 288, 298 and
and 308 K was examined to calculate the thermodynamic parame- 308 K, respectively. The Langmuir isotherm model characterized
ters. Three basic thermodynamic parameters: standard free energy the bromate adsorption well, corroborating monolayer adsorption
(G◦ ), standard enthalpy (H◦ ) and standard entropy (S◦ ), were onto the CACQS for the bromate removal. Analysis of the adsorp-
obtained using the following equations: tion kinetics shows that the pseudo-second-order model describes
G◦ = −RT ln K (6) the experimental data well. The optimum bromate removal was

K2 H ◦
1 1
 observed over a wide pH range. The thermodynamic parameters
ln = − (7) showed that the adsorption of bromate was a spontaneous and
K1 R T1 T2 exothermic physical process.

Table 3
Values of the constants of the Freundlich and Langmuir models. Acknowledgments

T Freundlich constants Langmuir constants

(K)
This research was supported by the National Natural Science
n KF (␮g/g) R2 qm (␮g/g) b (L/␮g) R2 Foundation of China (grant no. 51102157 and 51178255), Jinan Sci-
288 1.46 0.13 0.9984 47.39 5.22 × 10−4 0.9906 ence and Technology Bureau (no. 201102042) and Shandong Key
298 1.58 0.17 0.9818 45.75 5.09 × 10−4 0.9947 Scientific and Technological Projects of China (2010G0020606). The
308 1.83 0.19 0.9170 29.07 4.37 × 10−4 0.9923 authors thank Dr. Pamela Holt for proofreading the manuscript.
68 C. Xu et al. / Chemical Engineering Journal 187 (2012) 63–68
References
[1] U. von-Gunten, J. Hoigne, A. Bruchet, Bromate formation during ozonation of
bromide-containing waters, Inter. Water Supply Assoc. 5 (1993) 1–5, 6.
[2] N. Kishimoto, N. Matsuda, Bromate ion removal by electrochemical reduc-
tion using an activated carbon felt electrode, Environ. Sci. Technol. 43 (2009)
2054–2059.
[3] US Environmental Protection Agency, Guidelines for carcinogen risk assess-
ment, Federal Register 51 (1986) 33992–34003.
[4] H.S. Weinberg, C.A. Delcomyn, V. Unnam, Bromate in chlorinated drinking
waters: occurrence and implications for future regulation, Environ. Sci. Tech-
nol. 37 (2003) 3104–3110.
[5] R. Butler, S. Ehrenberg, A.R. Godley, R. Lake, L. Lytton, E. Cartmell, Remediation
of bromate-contaminated groundwater in an ex situ fixed-film bioreactor, Sci.
Total Environ. 366 (2006) 12–20.
[6] M. Siddiqui, W. Zhai, G. Amy, C. Mysore, Bromate ion removal by activated
carbon, Water Res. 30 (1996) 1651–1660.
[7] R. Butler, A. Godley, L. Lytton, E. Cartmell, Bromate environmental contamina-
tion: review of impact and possible treatment, Crit. Rev. Environ. Sci. Technol.
35 (2005) 193–217.
[8] R. Chitrakar, Y. Makita, A. Sonoda, H. Hirotsu, Adsorption of trace levels of
bromate from aqueous solution by organo-montmorillonite, Appl. Clay Sci. 51
(2011) 375–379.
[9] L. Xie, C. Shang, The effects of operational parameters and common anions on
the reactivity of zero-valent iron in bromate reduction, Chemosphere 66 (2007)
1652–1659.
[10] G. Gordon, R.D. Gauw, G.L. Emmert, B.D. Walters, B. Bubnis, Chemical reduction
methods for bromate ion removal, J. Am. Water Works Assoc. 94 (2002) 91–98.
[11] M. Siddiqui, G. Amy, K. Ozekin, W. Zhai, P. Westerhoff, Alternative strategies
for removing bromate, J. Am. Water Works Assoc. 86 (1994) 81–96.
[12] C.J. Johnson, P.C. Singer, Impact of a magnetic ion-exchange resin on ozone
demand and bromate formation during drinking water treatment, Water Res.
38 (2004) 3738–3750.
[13] P.C. Singer, K. Bilyk, Enhanced coagulation using a magnetic ion-exchange resin,
Water Res. 36 (2002) 4009–4022.
[14] V.S. Hatzistavros, P.E. Koulouridakis, I.I. Aretaki, N.G. Kallithrakas-Kontos, Bro-
mate determination in water after membrane complexation and total reflection
X-ray fluorescence analysis, Anal. Chem. 79 (2007) 2827–2832.
[15] H. Noguchi, A. Nakajima, T. Watanabe, K. Hashimoto, Design of a photocatalyst
for bromate decomposition: surface modification of TiO2 by pseudo-boehmite,
Environ. Sci. Technol. 37 (2003) 153–157.
[16] S. Peldszus, S.A. Andrews, R. Souza, F. Smith, I. Douglas, J. Bolton, P.M. Huck,
Effect of medium-pressure UV irradiation on bromate concentrations in drink-
ing water, a pilot-scale study, Water Res. 38 (2004) 211–217.
[17] W.J. Huang, Y.L. Cheng, Effect of characteristics of activated carbon on removal
of bromate, Sep. Purif. Technol. 59 (2008) 101–107.
[18] M.J. Kirisits, V.L. Snoeyink, J.C. Kruithof, The reduction of bromate by granular
activated carbon, Water Res. 34 (2000) 4250–4260.
[19] A. Bhatnagara, Y.H. Choi, Y.J. Yoon, Y. Shin, B.H. Jeon, J.W. Kang, Bromate removal
from water by granular ferric hydroxide (GFH), J. Hazard. Mater. 170 (2009)
134–140.
[20] M. Asami, T. Aizawa, T. Morioka, W. Nishijima, A. Tabata, Y. Magara, Bromate
removal during transition from new granular activated carbon (GAC) to bio-
logical activated carbon (BAC), Water Res. 33 (1999) 2797–2804.
[21] M.L. Bao, O. Griffini, D. Santianni, K. Barbieri, D. Burrini, F. Pantani, Removal of
bromate ion from water using granular activated carbon, Water Res. 33 (1999)
2959–2970.
[22] W.J. Huang, L.Y. Chen, Assessing the effectiveness of ozonation followed by
GAC filtration in removing bromate and assimilable organic carbon, Environ.
Technol. 25 (2004) 403–412.
[23] D.N. Bakoyannakis, E.A. Deliyanni, A.I. Zouboulis, K.A. Matis, L. Nalbandian, Th.
Kehagias, Akaganeite and goethite-type nanocrystals: synthesis and character-
ization, Microporous Mesoporous Mater. 59 (2003) 35–42.
[24] L. Mazeina, S. Deore, A. Navrotsky, Energetics of bulk and nano-akaganeite,
␤-FeOOH: enthalpy of formation, surface enthalpy, and enthalpy of water
adsorption, Chem. Mater. 18 (2006) 1830–1838.
[25] S. Yusan, S.A. Erenturk, Adsorption equilibrium and kinetics of U (VI) on beta
type of akaganeite, Desalination 263 (2010) 233–239.
[26] P.M. Solozhenkin, E.A. Deliyanni, V.N. Bakoyannakis, A.I. Zouboulis, K.A. Matis,
Removal of As(V) ions from solution by akaganeite ␤-FeO(OH) nanocrystals, J.
Min. Sci. 39 (2003) 287–296.
[27] N.K. Lazaridis, D.N. Bakoyannakis, E.A. Deliyanni, Chromium(VI) sorptive
removal from aqueous solutions by nanocrystalline akaganèite, Chemosphere
58 (2005) 65–73.
[28] F. Kolbe, H. Weiss, P. Morgenstern, R. Wennrich, W. Lorenz, K. Schurk, H. Stanjek,
B. Daus, Sorption of aqueous antimony and arsenic species onto akaganeite, J.
Colloid Interface Sci. 357 (2011) 460–465.
[29] E.A. Deliyanni, L. Nalbandian, K.A. Matis, Adsorptive removal of arsenites by a
nanocrystalline hybrid surfactant–akaganeite sorbent, J. Colloid Interface Sci.
302 (2006) 458–466.
[30] R. Chitrakar, S. Tezuka, A. Sonoda, K. Sakane, K. Ooi, T. Hirotsu, Phosphate
adsorption on synthetic goethite and akaganeite, J. Colloid Interface Sci. 298
(2006) 602–608.
[31] E.A. Deliyanni, K.A. Matis, Sorption of Cd ions onto akaganéite-type nanocrys-
tals, Sep. Purif. Technol. 45 (2005) 96–102.
[32] S.D. Yusan, S. Akyil, Sorption of uranium(VI) from aqueous solutions by aka-
ganeite, J. Hazard. Mater. 160 (2008) 388–395.
[33] R. Chitrakar, S. Tezuka, A. Sonoda, K. Sakane, T. Hirotsu, Bromate ion-exchange
properties of crystalline akaganéite, Ind. Eng. Chem. Res. 48 (2009) 2107–2112.
[34] C.H. Xu, D.D., Cheng, B.Y., Gao, Z.L., Yin, Q.Y., Yue, X. Zhao, Preparation and
characterization of ␤-FeOOH-coated sand and its adsorption of Cr(VI) from
aqueous solutions, J. Front. Environ. Sci. Eng. China. (online FirstTM , 31 May
2011).
[35] V.K. Garg, R. Gupta, A.B. Yadav, R. Kumar, Dye removal from aqueous solution
by adsorption on treated sawdust, Bioresour. Technol. 89 (2003) 121–124.
[36] E. Kumar, A. Bhatnagar, M. Ji, W. Jung, S.H. Lee, S.J. Kim, G. Lee, H. Song, J.Y.
Choi, J.S. Yang, B.H. Jeon, Defluoridation from aqueous solutions by granular
ferric hydroxide (GFH), Water Res. 43 (2009) 490–498.
[37] E. Illiés, E. Tombácz, The effect of humic acid adsorption on pH-dependent sur-
face charging and aggregation of magnetite nanoparticles, J. Colloid Interface
Sci. 295 (2006) 115–123.
[38] A.B.M. Giasuddin, S.R. Kanel, H. Choi, Adsorption of humic acid onto nanoscale
zerovalent iron and its effect on arsenic removal, Environ. Sci. Technol. 41
(2007) 2022–2027.
[39] E. Demirbasa, N. Dizgeb, M.T. Sulakb, M. Kobyab, Adsorption kinetics and equi-
librium of copper from aqueous solutions using hazelnut shell activated carbon,
Chem. Eng. J. 148 (2009) 480–487.
[40] P. Luo, Y.F. Zhao, B. Zhang, J.D. Liu, Y. Yang, J.F. Liu, Study on the adsorption of
neutral red from aqueous solution onto halloysite nanotubes, Water Res. 44
(2010) 1489–1497.
[41] V.L. Snoeyink, Adsorption of organic compounds, in: F.W. Pontius (Ed.), Water
Quality and Treatment, McGraw-Hill Inc., New York, 1990, pp. 781–876.
[42] H.M.F. Freundlich, Over the adsorption in solution, J. Phys. Chem. 57 (1996)
385–471.
[43] O. Ajouyed, C. Hurel, M. Amari, L.B. Allal, N. Marmier, Sorption of Cr (VI) onto
natural iron and aluminum (oxy) hydroxides: effects of pH, ionic strength and
initial concentration, J. Hazard. Mater. 174 (2010) 616–622.
[44] X.S. Wang, Z.Z. Li, C. Sun, Removal of Cr(VI) from aqueous solutions by low-cost
biosorbents: marine macroalgae and agricultural by-products, J. Hazard. Mater.
153 (2009) 1176–1184.