Journal of Environmental Management 165 (2016) 280e285

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Journal of Environmental Management

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Research article

Use of MgeAl oxide for boron removal from an aqueous solution in

rotation: Kinetics and equilibrium studies
Tomohito Kameda*, Jumpei Oba, Toshiaki Yoshioka
Graduate School of Environmental Studies, Tohoku University, 6-6-07 Aoba, Aramaki, Aoba-ku, Sendai 980-8579, Japan

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 27 April 2015
Received in revised form
24 September 2015
Accepted 24 September 2015

MgeAl oxide prepared through the thermal treatment of CO3 2
intercalated MgeAl layered double
hydroxides (CO3$MgeAl LDH) was found to remove boron (B) from an aqueous solution. B was removed
by the rehydration of MgeAl oxide accompanied by combination with BOH4
. When using twice the
stoichiometric quantity of MgeAl oxide for Mg/Al 4, the residual concentration of B dropped from 100
to 2.8 mg/L in 480 min, and for Mg/Al 2, it decreased from 100 to 2.5 mg/L in 240 min. In both cases,
the residual concentration of B was highlighted to be lower than the current Japanese efuent standards
(10 mg/L). The removal of B can be explained by way of pseudo-rst-order reaction kinetics. The
apparent activation energy of 63.5 kJ mol
1, calculated from the Arrhenius plot indicating that a chemical
reaction dominates the removal of B by MgeAl oxide (Mg/Al 2). The adsorption of B acts upon a
Langmuir-type phenomena. The maximum adsorption (qm) and equilibrium adsorption constants (KL)
were 7.4 mmol g
1 and 1.9  103, respectively, for MgeAl oxide (Mg/Al 2). BOH4
in B(OH)4$MgeAl
LDH produced by the removal of B was observed to undergo anion exchange with CO3 2
in solution.
Following regeneration, the MgeAl oxide maintained the ability to remove B from an aqueous solution.
This study has claried the possibility of recycling MgeAl oxide for B removal.
2015 Elsevier Ltd. All rights reserved.

Keywords:
MgeAl oxide
Cyclic usage
Boron
Removal
Kinetics
Equilibrium

1. Introduction
Boron (B) is an essential micronutrient for human beings;
however, it sometimes pollutes drinking water sources, leading to
various environmental and health problems (Wang et al., 2014).
Borate in wastewater is difcult to treat as it does not generate
insoluble compounds with heavy metal ions or alkaline earth
metals. However, when aluminum salts and calcium hydroxide are
added to borate-containing wastewater, the borate concentration
in the treated water decreases to a lesser quantity rather than
maximum permissible Japanese efuent standard (10 mg/L). This
decrease occurs because of borate adsorption by the produced
calcium aluminate. In Japan, this method is widely used for
wastewater treatment; however, the method results in vast
amounts of sludge generation caused by the addition of large
amounts of aluminum salts and calcium hydroxide. Therefore, the
development of a new treatment method for borate-containing
wastewater is required. Wang et al. have well reviewed the
removal technology of B dissolved in aqueous solutions (Wang

et al., 2014). It includes adsorption process using chelating resin

and inorganic materials; membrane process using ion-exchange
membranes, reverse osmosis, and electrocoagulation; and hybrid
process using polymer-enhanced ultraltration and adsorptionmembrane ltration. In case of inorganic materials, e.g., y ash
and calcined magnesite have the capacity to take up B in an
aqueous solution. However, these materials are reported to be
nonrecyclable. In this study, for aqueous H3BO3, a new treatment
method is proposed for removing B using MgeAl oxide through the
production of MgeAl layered double hydroxides (MgeAl LDHs), as
presented in Fig. 1.
The formula of MgeAl LDH are typically denoted as
[Mg21
xAl3x(OH)2](An
)x/n$mH2O, the signicance of x is the
molar ratio of Al3/(Mg2 Al3) (0.20  x  0.33), An
is anion, for
example CO3 2
or Cl
(Cavani et al., 1991; Ingram and Taylor, 1967;
Allmann, 1968; Mills et al., 2012). By calcination at 450 e800  C,
the CO3 2
intercalated MgeAl LDH (CO3$MgeAl LDH) can be converted to MgeAl oxide, expressed as eq1:
Mg1
xAlx(OH)2(CO3)x/2 / Mg1
xAlxO1x/2 x/2CO2 H2O

* Corresponding author.
E-mail address: kameda@env.che.tohoku.ac.jp (T. Kameda).
http://dx.doi.org/10.1016/j.jenvman.2015.09.035
0301-4797/ 2015 Elsevier Ltd. All rights reserved.

(1)

The MgeAl oxide is able to incorporate water molecules

T. Kameda et al. / Journal of Environmental Management 165 (2016) 280e285

281

calculated in function to neutralize the brucite-like octahedral

layers positive charge when Mg was replaced by Al at Mg/Al molar
ratio either 4 or 2.

1
xMg2 xAl3 x=2CO3 2
2OH

/ Mg1
x Alx OH2 CO3 x=2
(3)

Fig. 1. Scheme for the proposed treatment method of aqueous H3BO3 by MgeAl oxide.

(rehydration) and anions, resulting in the reconstruction of the

structure of LDH:
Mg1
xAlxO1x/2 x/n An
(1 x/2)H2O
/ Mg1
xAlx(OH)2Ax/n xOH

(2)

Recently, LDH and MgeAl oxide have been examined to remove

humic acid, various types of oxyanions, arsenic, phosphate, benzopurpurine 4B, acid phosphatase, acid red G dye, acid green 68:1,
thiosulfate, iodide, ClO

4 , and chromium(VI) from an aqueous solution (Gasser et al., 2008; Goh et al., 2008, 2009; Goh and Lim,
2010; Hosni and Srasra, 2010; Setti et al., 2010; Zhu et al., 2010;
Wu et al., 2011; Tong et al., 2012; Santos et al., 2013; Geng et al.,
2013; Wu et al., 2013; Iglesias et al., 2014; Lin et al., 2014; Song
and Wu, 2014).
MgeAl oxide can also be used for the treatment of B in order to
produce MgeAl LDH intercalated with BOH4
(B(OH)4$MgeAl
LDH). B(OH)4$MgeAl LDH is treated with CO3 2
in an aqueous
solution, allowing anion exchange between BOH4
in MgeAl LDH
and CO3 2
to regenerate CO3$MgeAl LDH. CO3$MgeAl LDH is
calcined to regenerate MgeAl oxide, which can be reused for the
remediation of aqueous H3BO3. MgeAl oxide has previously been
shown to remove B from an aqueous solution (Yoshioka et al., 2007;
Paez et al., 2014); however, these studies have not considered the
treatment of the complex after B removal. In the current study, we
used MgeAl oxide to remove B from aqueous solution, also
examined the effect of the Mg/Al molar ratio, amount of MgeAl
oxide and temperature. In addition, kinetics and equilibrium
studies were performed, and the adsorption behavior was considered. Furthermore, the effect of coexistent Cl
, NO3
, and SO4 2
on
the removal of B was examined. The B desorption from the produced B(OH)4$MgeAl LDH was also investigated using Na2CO3 solution, and the reproduced CO3$MgeAl LDH was calcined to
regenerate MgeAl oxide, which was further examined for its uptake of B in an aqueous solution.
2. Experimental
Only reagent grade chemicals were used without any additional
purication.
2.1. Preparation of MgeAl oxide

The preparation of CO3$MgeAl LDH was followed as added

MgeAl solution dropwise to Na2CO3 solution and maintained pH
10.5 throughout the reaction. The MgeAl nitrate solutions
comprised with 0.40 M Mg(NO3)2$6H2O and 0.10 M Al(NO3)3$9H2O
or 0.33 M Mg(NO3)2$6H2O and 0.17 M Al(NO3)3$9H2O was added to
deionized water to obtain Mg/Al molar ratio 4 and 2 respectively.
The MgeAl nitrate solution (500 mL) was added dropwise to
0.1 M Na2CO3 solution (500 mL), the reaction condition was
maintained 30  C temperature and 15 mL min
1 addition rate with
agitate mildly. A pH of 10.5 was retained by adding appropriate
amounts of 1.25 M NaOH solution. The successive suspension were
kept for settling down for 1 h at 30  C temperature and ltered
followed by washing with deionized water repeatedly. The resultant precipitate was proceeded to drying for 40 h at 40  C under
reduced pressure (133 Pa) The obtained products were conrmed
to be CO3$MgeAl LDH, as presented in Fig. S1. The obtained
CO3$MgeAl LDH was calcined to get MgeAl oxide at 500  C for 2 h,
as expressed by eq4.
Mg1
xAlx(OH)2(CO3)x/2 / Mg1
xAlxO1x/2 (x/2)CO2 H2O

(4)

The MgeAl oxides prepared via thermal treatment of

CO3$MgeAl LDHs with an initial Mg/Al molar ratio of 4 and 2 are
hereafter called MgeAl oxide (Mg/Al 4) and MgeAl oxide (Mg/
Al 2), respectively. Fig. S2 presents the XRD patterns for (a)
MgeAl oxide (Mg/Al 4) and (b) MgeAl oxide (Mg/Al 2). In both
cases, the products were conrmed to be MgeAl oxide. Table 1
exhibits the elemental compositions of various MgeAl oxides. A
proximate value of the experimental Mg/Al molar ratio with the
initial, indicating CO3$MgeAl LDH preparation and MgeAl oxide
formation according to Eqs. (3) and (4).

2.2. Removal procedure of boron from an aqueous solution

H3BO3 was dissolved in deionized water to prepare H3BO3 solution. The MgeAl oxides were added to the 500 mL of 100 mg/L
H3BO3 solutions. The successive suspensions were stirred at
10 Ce60  C for 840 min with continuous bubbling of N2 during the
procedure. pH was monitored throughout the experiment. Samples
of the suspension were collected at specic time periods and
instantly ltered passing through a membrane lter (0.45 mm). The
residual B, dissolved Mg2 and Al3 was estimated from the ltrates. The quantity of the MgeAl oxide required for borate removal
was 1e2 times the stoichiometric quantities shown in eq5 and is
indicated using the notation eq1eeq2.

Mg1
x Alx O1x=2 xBOH4
1 x=2H2 O

/Mg1
x Alx OH2 BOH4

x

xOH

(5)

MgeAl oxide was obtained through the thermal treatment of

2

MgeAl LDH intercalated with CO3

(CO3$MgeAl LDH). The
coprecipitation reaction for CO3$MgeAl LDH can be explained by
eq3. In the present study, x values of 0.20 and 0.33 were used. The
stoichiometric coefcients of 0.20 and 0.33 for CO3 2
were

The adsorption isotherm study of B with MgeAl oxide was

conducted, therefore, a mixed 20 mL 0.01e0.06 M H3BO3 solution
and 0.1 g MgeAl oxide was shaken at 30  C for a week using 50 mL
screw-top tubes.
To examine the effect of coexistent anions on B removal, NaCl,
NaNO3, or Na2SO4 was added to the H3BO3 solution. The amount of

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T. Kameda et al. / Journal of Environmental Management 165 (2016) 280e285

Table 1
Elemental compositions of various MgeAl oxides.
wt%

MgeAl oxide (Mg/Al 4)

MgeAl oxide (Mg/Al 2)

(a)
(b)

Molar ratio

Mg2

Al3

Mg/Al

16.8
13.6

5.2
7.8

3.6
1.9

Cl
, NO3
, or SO4 2
is 0.5e10 times the molar equivalents of B,

expressed as 0.5e10 mol.eq.
2.3. Desorption of boron from MgeAl LDH
During the treatment of H3BO3 solution by MgeAl oxide,
BOH4
intercalated MgeAl LDH was formed as (B(OH)4$MgeAl
LDH). The desorption of B from B(OH)4$MgeAl LDH in Na2CO3 solution was examined. The theoretical equation is expressed as:

Mg1
x Alx OH2 BOH4

x

x=2CO3 2

/Mg1
x Alx OH2 CO3 x=2 xBOH4

(6)
B(OH)4$MgeAl LDH was formed by contact with MgeAl oxide
(Mg/Al 2) suspension and H3BO3 solution at 30  C for 8 h at eq1.
B(OH)4$MgeAl LDH contained 3.3 wt% of B. A mixed 20 mL
0.01e1 M Na2CO3 solution and 0.1 g B(OH)4$MgeAl LDH was
shaken at 30  C for 120 min using 50 mL screw-top tubes.

Fig. 2. Change in the concentration of B over time in the MgeAl oxide (Mg/Al 4)
suspension in H3BO3 solution at various stoichiometric quantities (eqs.) at 30  C.

2.4. Procedure for removing boron by regenerated MgeAl oxide

from an aqueous solution
The MgeAl oxide (Mg/Al 2) was regenerated from
B(OH)4$MgeAl LDH in 0.05 M Na2CO3 solution at 30  C for 120 min,
followed by calcination at 500  C for 2 h. The regenerated MgeAl
oxide (Mg/Al 2) was suspended in H3BO3 solution at 30  C at eq1.
2.5. Characterization methods
The materials were analyzed using X-ray diffraction (XRD)
conditioned with Cu Ka radiation at 40 kV and 20 mA (scanning
rate: 2 /min, step size: 0.02). The concentration of B, dissolved
Mg2 and Al3 were estimated from the ltrates using inductively
coupled plasma atomic emission spectroscopy (ICP-AES). Furthermore, anions concentration in the ltrates were measured by a
Dionex DX-120 ion chromatograph (IC), Dionex model AS-12A
column condition maintained as eluent: 2.7 mM Na2CO3 and
0.3 mM NaHCO3; 1.3 mL min
1 of ow rate.

Fig. 3. Change in the concentration of B over time in the MgeAl oxide (Mg/Al 2)
suspension in H3BO3 solution at various stoichiometric quantities (eqs.) at 30  C.

3. Results and discussion

3.1. Removal status of boron from an aqueous solution
Figs. 2 and 3 show the change in the concentration of B over
time in the MgeAl oxide (Mg/Al 4) and the MgeAl oxide (Mg/
Al 2) suspensions in H3BO3 solution at various stoichiometric
quantities (eqs.) at 30  C. In all cases, the B concentration was
decreased with increasing time. In both MgeAl oxides, the B concentration was decreased as the stoichiometric quantity increased.
For the MgeAl oxide (Mg/Al 4) at eq2, the residual B was
observed lesser concentration than the maximum permissible
Japanese efuent standards (10 mg/L) after 120 min, and the lowest
residual concentration of B was 2.8 mg/L at 480 min. For the MgeAl
oxide (Mg/Al 2) at eq2, the residual B was observed lesser concentration than the maximum permissible Japanese efuent

standards (10 mg/L) after 120 min, and the lowest residual concentration of B was 2.5 mg/L at 240 min Figs. S3 and S4 show the
change in the pH over time in the MgeAl oxide (Mg/Al 4) and
MgeAl oxide (Mg/Al 2) suspensions in H3BO3 solution at various
stoichiometric quantities (eqs.) at 30  C. In all cases, the pH showed
an initial rapid increase but slowed to a more gradual increase with
time. For the MgeAl oxide (Mg/Al 4), the pH reached ~10.5 and
11.5 at eq1 and eq2, respectively. For the MgeAl oxide (Mg/Al 2),
the pH reached ~9.5 and 10.0 at eq1 and eq2, respectively. The
hydrolysis reaction of boric acid is shown in eq7.

H3 BO3 H2 O % H BOH4

(7)

The acid dissociation constant (pKa) of boric acid is 9.2

T. Kameda et al. / Journal of Environmental Management 165 (2016) 280e285

(Pourbaix, 1974). In the suspension, more B is considered to be

present as BOH4
than boric acid. Hence, the B removal using
MgeAl oxide is characterized to the rehydration and combination
with BOH4
, according to eq5. On the other hand, B could not be
effectively removed by both MgeAl oxides at eq1. This is attributed
to the intercalation of OH
, as shown in to eq8.
Mg1
xAlxO1x/2 xOH
(1 x/2)H2O
/ Mg1
xAlx(OH)2(OH)x xOH
(8)
Figs. S5 and S6 show the change in Mg2 dissolved over time in
the MgeAl oxide (Mg/Al 4) and MgeAl oxide (Mg/Al 2) suspensions in the H3BO3 solution at various stoichiometric quantities
(eqs.) at 30  C. In this case, the dissolved Al3 was not observed
because of the property of amphoteric metal. In both Mg/Al 4 and
2, the dissolved Mg2 once increased and then gradually decreased.
Although Mg2 was rst dissolved from the solid, Mg2 was then
precipitated. This is attributed to the buffer action of Mg2, leading
to the nal pH of 9.5e11.5. The nal dissolved Mg2 was around 5%
at the maximum, indicating the high stability of MgeAl LDH in the
present experimental conditions.
Figs. S7 and S8 indicates the XRD patterns for products produced
from the contact with MgeAl oxide (Mg/Al 4) and MgeAl oxide
(Mg/Al 2) suspensions in H3BO3 solution at eq1 and eq2 at 30  C.
The XRD peaks could be attributed to hydrotalcite (JCPDS card
22e700) for all products, which indicates the formation of LDH
structure after B removal. This supports that the BOH4
intercalated MgeAl LDH was reconstructed from MgeAl oxide, as shown
in eq5.
Figs. 2 and 3, recommended that at the initial period of the reaction (~60 min) B removal by MgeAl oxide (Mg/Al 2) was
observed to be faster than that by MgeAl oxide (Mg/Al 4). A
higher positive layer charge density of the reconstructed MgeAl
LDH with Mg/Al 2 than Mg/Al 4 is due to more Mg2 is replaced
with Al3, leading to a stronger electrostatic attractive force for
BOH4
. Therefore, the next kinetic study was conducted using the
MgeAl oxide (Mg/Al 2).
Fig. 4 shows the change in the amount of B removed over time
by a suspension of MgeAl oxide (Mg/Al 2) in H3BO3 solution at
various temperatures. The acceleration of B removal increased,
which occurs at higher temperatures and suggests that a chemical
reaction dominates in this phenomena. The reaction kinetics of B
with MgeAl oxide (Mg/Al 2) was studied. First-order kinetics (Ho

Fig. 4. Change in the amount of B removed over time by a suspension of MgeAl oxide
(Mg/Al 2) in H3BO3 solution at various temperatures. A stoichiometric quantity (eq1)
of the MgeAl oxide was used.

283

et al., 2000), which depend on the concentration of B, are expressed

by
eln(1
x) kt,

(9)

where x degree of B removal, t reaction time (min), and k rate

constant for B removal (min
1). Fig. 5 shows the pseudo-rst-order
plot for removing B using the suspension of MgeAl oxide (Mg/
Al 2) in H3BO3 solution at various temperatures. Consistent
linearity was observed at all temperatures, indicating that pseudorst-order kinetics can be better to represent B removal phenomena. B removal can be represented by pseudo-rst-order reaction
kinetics. The apparent rate constants at 10  C, 30  C, and 60  C were
1.0  10
3, 7.2  10
3, and 5.8  10
2 min
1, respectively. Therefore, as increasing temperature, the rate constant increased
apparently. The apparent activation energy for removing B by
MgeAl oxide (Mg/Al 2) was observed 63.5 kJ mol
1 which was
calculated from the Arrhenius plot shown in Fig. S9. The result
recommends that a chemical reaction dominates the removal of B
by MgeAl oxide (Mg/Al 2).
Fig. S10 shows the adsorption isotherms for the adsorption of B
by MgeAl oxide (Mg/Al 2). An increasing trend was observed for
the equilibrium adsorption amount with equilibrium concentration. The adsorption isotherms displayed a Langmuir-type phenomena, validated by arranging the data obtained from this
experiment in terms of the Langmuir equation (Langmuir, 1918),
expressed as follows:
qe CeqmKL/(1 CeKL),

(10)

where qe equilibrium adsorption (mmol g
1), Ce equilibrium

concentration (mM), qm maximum adsorption (mmol g
1), and
KL equilibrium adsorption constant. The eq10 can be represented
as
Ce/qe 1/qmKL Ce/qm.

(11)

Fig. 6 shows the Ce/qe versus Ce plot of the adsorption isotherms

for the adsorption of B by MgeAl oxide (Mg/Al 2). A good linear
plot with acceptable correlation coefcient was obtained, which
indicates that the adsorption of B with MgeAl oxide (Mg/Al 2)
followed Langmuir-type phenomena. The qm and KL value calculated from the slope and intercept of the linear t of the data given

Fig. 5. Pseudo-rst-order plot for removing B by MgeAl oxide (Mg/Al 2) in H3BO3

solution at various temperatures. A stoichiometric quantity (eq1) of the MgeAl oxide
was used.

284

T. Kameda et al. / Journal of Environmental Management 165 (2016) 280e285

Fig. 6. Ce/qe versus Ce plot for the adsorption isotherms of the adsorption of B by
MgeAl oxide (Mg/Al 2). MgeAl oxide quantity: 0.1 g; initial B concentration:
0.01e0.06 M; temperature: 30  C; time: 1 week.

in Fig. 6, were 7.4 mmol g
1 and 1.9  103, respectively.

Wang et al. have reviewed the capacity of some adsorbents to
remove B (Wang et al., 2014). The imino-bis-propanediol and
amine-functional copolymer and chitosan are known to have a high
capacity for B removal of 4.0 mmol g
1 and 3.3 mmol g
1, respectively. This study shows that MgeAl oxide (Mg/Al 2) has a higher
capacity for B removal than the above adsorbents.

2

Fig. S11 shows the effect of coexistent Cl , NO3 , and SO4 on

the change in the concentration of B over time in the MgeAl oxide
(Mg/Al 2) suspension in H3BO3 solution at 30  C. In the presence
of 1 mol.eq. of either Cl
or NO3
, the concentration of B only
increased by 10 mg/L compared with those without co-anion,
which were 40 mg/L at 480 min Fig. S12 shows that ~50% of
either Cl
or NO3
(1 mol.eq.) was removed by the MgeAl oxide
(Mg/Al 2) at any time. These result suggest that MgeAl oxide
(Mg/Al 2) can simultaneously uptake Cl
or NO3
with BOH4
.
Although the Cl
and NO3
concentrations increased from 1 to
10 mol.eq., the remaining B concentration decreased from 100 to
~60 mg/L after 120 min. This recommends that MgeAl oxide (Mg/
Al 2) can preferentially take up BOH4
over Cl
or NO3
. The
most likely explanation for this preferential uptake is that the
BOH4
contains higher charge density than Cl
or NO3
. In the
presence of SO4 2
at 0.5 and 5 mol.eq., the concentration of B was
much higher than that without any co-anion at any time. Even at
0.5 mol.eq. of SO4 2
, the concentration of B did not decrease below
80 mg/L. In this case, the SO4 2
removal was ~80% after 120 min, as
shown in Fig. S12. Therefore, the prevention of the removal of B by
MgeAl oxide (Mg/Al 2) under coexistent SO4 2
can be characterized to the removal of SO4 2
. MgeAl oxide (Mg/Al 2) can
preferentially take up SO4 2
over BOH4
in solution, as the higher

charge density of SO4 2
than BOH4
.

Fig. S13 shows the change in the B desorption over time in
B(OH)4$MgeAl LDH in Na2CO3 solution at 30  C. The B desorption
increased rapidly with time and eventually remained constant for
all the concentrations. The B desorption was nally 80%e90% at all
concentrations after 120 min. BOH4
in B(OH)4$MgeAl LDH was
found to undergo anion exchange with CO3 2
in solution, according
to eq6. B could be sufciently desorbed from B(OH)4$MgeAl LDH
using Na2CO3 solution.
Fig. S14 shows the change in the concentration of B over time in

MgeAl oxide (Mg/Al 2) before and after regeneration in H3BO3

solution at 30  C. A stoichiometric quantity (eq1) of the MgeAl
oxide was used to clarify the difference of the remaining B concentration. If eq2 of MgeAl oxide is used, the difference may be
little. You may not be able to understand the performance of MgeAl
oxide after regeneration. Similar to the original MgeAl oxide (Mg/
Al 2), the concentration of B showed an initial rapid decrease but
slowed to a more gradual decrease with time using the regenerated
MgeAl oxide (Mg/Al 2). The concentration of B at 480 min was
32.3 and 62.1 mg/L before and after regeneration, respectively;
thus, the performance of the regenerated MgeAl oxide (Mg/Al 2)
for B removal worsened. Fig. S15 exhibits the XRD patterns for
MgeAl oxide (Mg/Al 2) and its reactant. Fig. S15(c) indicates the
remaining LDH structure after B desorption. However, the lower
crystallinity of the regenerated MgeAl oxide (Mg/Al 2)
(Fig. S15(d)) was observed than the original MgeAl oxide (Mg/
Al 2) (Fig. S15(a)). Similarly, the crystallinity of the reproduced
B(OH)4$MgeAl LDH (Fig. S15(e)) was observed to be lower than
that of the original B(OH)4$MgeAl LDH (Fig. S15(b)). This suggests
that regeneration destroys the LDH structure. The low performance
of MgeAl oxide (Mg/Al 2) for B removal after regeneration is
attributed to the decrease in its crystallinity and the small amount
of B remaining in MgeAl LDHs. However, the regenerated MgeAl
oxide (Mg/Al 2) maintained the ability to remove B from an
aqueous solution.
In summary, this study has claried the probability of recycling
MgeAl oxide to remove B, as shown in Fig. 1.
4. Conclusions
MgeAl oxide was demonstrated its ability to uptake B from
aqueous solutions. B was removed through the rehydration of
MgeAl oxide accompanied by combination with BOH4
. For the
MgeAl oxide (Mg/Al 4) at eq2, the residual B was observed lesser
concentration than the Japanese efuent standards (10 mg/L) after
120 min, and the lowest residual concentration of B was 2.8 mg/L at
480 min. For the MgeAl oxide (Mg/Al 2) at eq2, the residual B was
observed lesser concentration than the Japanese efuent standards
(10 mg/L) after 120 min, and the lowest residual concentration of B
was 2.5 mg/L at 240 min. B removal can be explained by pseudorst-order reaction kinetics. For MgeAl oxide (Mg/Al 2), the
apparent rate constants at 10  C, 30  C, and 60  C were 1.0  10
3,
7.2  10
3, and 5.8  10
2 min
1, respectively. The apparent activation energy of 63.5 kJ mol
1, calculated from the Arrhenius plot
indicating that a chemical reaction dominates the removal of B by
MgeAl oxide (Mg/Al 2). The adsorption of B by MgeAl oxide (Mg/
Al 2) follows a Langmuir-type adsorption. For MgeAl oxide (Mg/
Al 2), the maximum adsorption was 7.4 mmol g
1, while the
equilibrium adsorption constant was 1.9  103. MgeAl oxide (Mg/
Al 2) showed preferential uptake of BOH4
over Cl
or NO3
;
however, it also showed preferential uptake of SO4 2
over BOH4

in solution. BOH4
in B(OH)4$MgeAl LDH was found to undergo

anion exchange with CO3 2
in solution. The regenerated MgeAl

oxide (Mg/Al 2) maintained the ability to remove B from an
aqueous solution. In summary, this study has claried the possibility of recycling MgeAl oxide for B removal, as shown in Fig. 1.
Because the previous paper on B removal by MgeAl oxide had not
considered the treatment of the complex after B removal, the
recycle use of MgeAl oxide as mentioned above is very useful to
reduce the amount of sludge.
Acknowledgments
This research was supported by the Environment Research and

T. Kameda et al. / Journal of Environmental Management 165 (2016) 280e285

Technology Development Fund (5RFb-1201) of the Ministry of

Environment, Japan.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jenvman.2015.09.035.
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