Journal of Chemical Engineering of Japan, Vol. 53, No. 11, pp.

722–728, 2020 Research Paper

Acceleration of Bromine Oxyacid Generation and

Organic Compound Decomposition by O3 Fine Bubble Injection
into an Aqueous Solution Containing Bromide Ions
Yoshinari Wada1, Kaoru Onoe2 and Masakazu Matsumoto1
1
College of Industrial Technology, Nihon University, 2-11-1 Shinei Narashino-shi, Chiba 275-8576, Japan
2
Faculty of Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino-shi,
Chiba 275-0016, Japan

Keywords: Fine Bubbles, Bromine, Ozone, Tertiary Butyl Alcohol, Water Purification

To achieve the rapid decomposition of refractory organic compounds for water purification, an effective technique for
the generation of bromine oxyacids by O3 fine bubble injection and bromide addition was developed. When O3 bubbles
are micronized in the liquid phase, the absorption of O3 is accelerated, and OH· generation is promoted because of the
increased contact probability between the dissolved O3 and accumulated OH− at the minute gas–liquid interface. Ad-
ditionally, when O3 fine bubbles are supplied into a liquid phase containing Br−, further improvement in the oxidation
potential of the liquid phase can be expected because of the increased HOBr/BrO− generation with OH· generation.
At 298 K, O3 bubbles with an average diameter (dbbl) of 50 or 2000 µm were supplied into NaBr aqueous solutions with
different initial NaBr concentrations ((CNaBr)0). The rate of generation of total oxygen species and the constant value of
concentration of total oxygen species (C*OS) increased with the acceleration of the bromine oxyacid generation, induced
by the decrease in dbbl and the increase in (CNaBr)0. Furthermore, the decomposition of tert-butyl alcohol (TBA) by O3
fine bubble injection at various (CNaBr)0 values was carried out. Consequently, the rate constant of TBA decomposition
showed a maximum value at C*OS of 0.54 mmol/L because of the conversion of HOBr/BrO− with a high oxidation potential
to BrO− − −
3 with a low oxidation potential, caused by the excess oxidation of Br . Hence, the generation of HOBr/BrO with
O3 fine bubble injection and bromide addition is effective for achieving enhanced decomposition of refractory organic
compounds.

that of hypochlorous acid (HOCl) and is suitable for water

Introduction
The demand for bromine-based products is increasing
annually because bromine is an essential element in fine
chemicals, agricultural products, pharmaceuticals, inorganic
chemicals, and catalysts (Wanklyn and Erlenmeyer, 1863;
Scott et al., 1963; Bajpai, 2015). In particular, in sterilization
processes, the bromine oxyacids obtained by the oxidation
of bromide are effective against waterborne viruses, such as
poliovirus and rotaviruses. Bromine oxyacids are powerful
disinfectants that have the ability to kill the cells of many
pathogens; consequently, they have been widely and fre-
quently used (Floyd et al., 1976; Williams et al., 1988; Yang
et al., 2015). However, bromine oxyacids have various forms
depending on the degree of oxidation, and each form has
different properties, such as the oxidation potential (Hoigne
and Bader, 2008; Buxton et al., 1988; von Gunten and Oli-
veras, 1998). In particular, hypobromous acid (HOBr) has
the highest oxidation potential among bromine oxyacids,
and it can be utilized as a water purification reagent because
of its excellent decolorizing activity and disinfectant proper-
ties (Bajpai, 2015). In addition, HOBr has a pKa higher than
Received on August 12, 2020; accepted on October 7, 2020
DOI: 10.1252/jcej.20we164
Correspondence concerning this article should be addressed to M.
Matsumoto (E-mail address: matsumoto.masakazu@nihon-u.ac.jp).
purification at a relatively high pH (Haag and Hoigne, 1983;
Jung et al., 2013, 2017). Therefore, the enhanced generation
of HOBr could be exploited for the effective decomposition
of refractory organic compounds for water purification. In
this study, to generate HOBr in an aqueous solution effec-
tively, a technique based on the formation of fine bubbles of
O3 and the addition of bromide, which results in the genera-
tion of hydroxyl radicals (OH·) at the gas–liquid interfaces
of fine bubbles and the rapid oxidation of bromide anions,
was developed for the decomposition of organic compounds
in aqueous solutions. In general, reducing the bubble di-
ameter in gas–liquid systems has the following effects: 1)
the acceleration of mass transfer and reactant absorption
with the increase in the gas–liquid interfacial area; 2) the
increase in the average residence time of the bubbles with a
decrease in buoyancy; and 3) the formation of interactions
at the gas–liquid interface caused by charge accumulation
on the surfaces of the fine bubbles (Matsumoto et al., 2009;
Matsumoto et al., 2010; Matsumoto et al., 2013; Matsumoto
et al., 2015). The leading cause of the negative charge on
bubble surfaces in water is the adsorption of OH− at the
gas–liquid interface (Takahashi, 2005). Accordingly, the fine
bubbles with a negative surface potential can remain in the
liquid phase for a long period, and the local regions near the
gas–liquid interfaces are available as novel reaction fields.
As mentioned, when O3 fine bubbles are supplied into the

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of Chemical
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Engineers,
of Japan
liquid phase, the absorption of O3 gas is accelerated by the
increase in the gas–liquid interfacial area and residence
time of the bubbles, and the generation of active oxygen
species is enhanced by the increased contact probability
between the dissolved O3 and accumulated OH− around
the fine bubble surfaces. Moreover, in the case where O3
fine bubbles are supplied into an aqueous phase containing
Cl− or Br−, further improvement of the oxidation potential
of the liquid phase should occur because of the enhanced
halogen oxyacid generation with OH·. Thus, an increase in
the organic compound decomposition because of increased
OH· generation with the injection of O3 fine bubbles and its
accompanying bromine oxyacid generation can be expected.
In this paper, we report the effects of the average diam-
eter (dbbl) of O3 bubbles and the initial NaBr concentration
((CNaBr)0) on the concentration of the total oxygen species,
which is used as an index for the oxidation potential in the
liquid phase. Furthermore, the decomposition of tert-butyl
alcohol (TBA), which has poor chemical reactivity toward
O3 (Hoigne and Bader, 1983; Chen et al., 2019), by injection
of O3 fine bubbles into NaBr/TBA aqueous solution at vari-
ous (CNaBr)0 was investigated.
1. Experimental Apparatus and Procedure
1.1 O3 fine bubble generator
Our experimental apparatus for the organic compound
decomposition comprised a gas flow controller (FCC-
3000-G1, KOFLOC Co.), a dielectric barrier discharge
(DBD) reactor (SHOWA KANKYO SYSTEM Co., Ltd.), a
transformer, a pH meter (S220, METTLER TOLEDO, Swit-
zerland), a self-supporting bubble generator (TECH Ind.), a
dispersion-type bubble generator (501G No. 1, KINOSHITA
RIKA KOGYO Co.), and a reaction vessel. The O2 flow rate
(FO2) was controlled at 2.23 mmol/min, and O2 was convert-
ed to O3 in the DBD reactor at atmospheric temperature and
pressure. At a primary voltage of 80 V and a secondary volt-
age of approximately 7.2 kV, the conversion ratio from O2
to O3 remained almost constant at 5 mol%. O3 fine bubbles
with a dbbl value of 50 µm and a variation coefficient of 0.45
were generated using a self-supporting bubble generator
functioning with the impeller shear and negative pressure
induced by a high rotation speed (Matsumoto et al., 2010;
Matsumoto et al., 2013; Tsuchiya et al., 2017) with the rota-
tion rate maintained at 1,500 min–1 and constant FO2. Bub-
bles with dbbl of 2,000 µm were obtained using a dispersing-
type generator (hole size of dispersing plate: 100–120 µm) at
a FO2 of 2.23 mmol/min for comparison. The agitation rate
was set to 800 min−1 using a propeller-type mixer with 4
blades. The dbbl and variation coefficient were determined
from the bubble size distribution measured with a laser
particle size analyzer (LA-920, HORIBA, Ltd., Japan) and by
image analysis of microscopy data (VH-5000, KEYENCE,
Co., Japan).
Vol. 53  No. 11  2020
1.2 Measurement of the concentration of the total
oxygen species for the evaluation of the oxidation
potential of the liquid phase
1.2.1 Effects of minimizing the bubble diameter and the
presence of NaBr on the concentration of the total oxygen
species in an NaBr aqueous solution At a solution temper-
ature (TS) of 298 K, O3 bubbles with a dbbl of 50 or 2,000 µm
were continuously supplied to 800 mL of an NaBr aqueous
solution at a (CNaBr)0 of 3.0 mmol/L with a bubble injection
time (tb) of 90 min. For comparison, O3 bubbles with dbbl
values of 50 or 2,000 µm were also fed into ion-exchanged
water, i.e., (CNaBr)0 was 0.0 mmol/L. After the injection of O3
fine bubbles for different tb values, 5 mL of the solution was
sampled, and the concentration of the total oxygen species
(COS) was determined by a colorimetric method using O3
test reagent and a colorimeter (O3-3F, KASAHARA Chemi-
cal Instruments Co., Ltd.). The colorimetric method was
used to measure COS because the O3 test reagent reacts with
O3, free radicals such as OH·, OOH·, and ·O− 2 , and bromine
oxyacids such as HOBr and HBrO3. In addition, COS was
corrected for the presence of Br− anions arising from the
use of the NaBr aqueous solution because the O3 test reagent
also reacts with Br−.
1.2.2 Effects of NaBr concentration on the concentra-
tion of the total oxygen species during the injection of O3
fine bubbles To thoroughly investigate the effects of Br−
ions on the concentration of the total oxygen species during
the injection of O3 fine bubbles, O3 fine bubbles with a dbbl of
50 µm were supplied to 800 mL of NaBr aqueous solution in
the (CNaBr)0 range of 0.0–5.0 mmol/L within a t of 180 min at
a TS of 298 K. COS was determined by a colorimetric method,
as described above. The initial generation rate of the total
oxygen species ((rOS)0) was calculated from the initial gradi-
ent of the time changes in COS at a tb of 10 min. Additionally,
the constant value of COS (C*OS) was defined using the time
profiles of COS as an index to evaluate the influence of the
active oxygen species generated by the decomposition of
refractory organic compounds during O3 fine bubble injec-
tion.
1.3 Decomposition of refractory organic compounds
during the injection of O3 fine bubbles into an
aqueous solution containing NaBr
To confirm the effects of the increasing oxidation poten-
tial of the liquid phase in the presence of Br− on the decom-
position of the refractory organic compounds, commercial-
grade TBA (99.0% purity, Wako Pure Chemical Industries,
Ltd., Japan) was added to 800 mL of the NaBr aqueous solu-
tion in the (CNaBr)0 range of 1.0–5.0 mmol/L and was decom-
posed by the injection of O3 fine bubbles within 180 min at a
TS of 298 K. The initial TBA concentration ((CTBA)0) was set
to 6.0 mmol/L. For comparison, a similar process was also
performed in the TBA aqueous solution without Br−. The
TBA concentration (CTBA) during the O3 bubbled-induced
decomposition was determined using a high-performance
liquid chromatography system (HPLC, LaChrom Elite,
Hitachi High-Tech Science Co.) equipped with an RSpak
723
DE-413 column (3 µm, 4.6ϕ×150 mm; SHOWA DENKO
K.K.) and a refractive index (RI) detector. The chromato-
graphic separation was carried out using 1 vol% H3PO4
aqueous solution as the mobile phase.
2. Results and Discussion
2.1 Change in the oxidation potential of the liquid phase
with injection of O3 fine bubbles and addition of NaBr
2.1.1 Effects of bubble size minimization and coexist-
ing NaBr on the concentration of the total oxygen spe-
cies The improvement of the oxidation potential in the
liquid phase with the injection of O3 fine bubbles and the
addition of NaBr was investigated, and the effects of dbbl and
coexisting Br− on COS were determined. Figure 1 shows
the change in COS with time when O3 fine bubbles with a
dbbl of 50 or 2000 µm were supplied into an NaBr aqueous
solution or ion-exchanged water within 90 min. The COS in
ion-exchanged water increased as dbbl decreased from 2,000
to 50 µm. Further, the increase in COS in the presence of
Br− at a dbbl of 50 µm was significantly greater than that at
2,000 µm. At a tb of 90 min, the COS value at a dbbl of 50 µm
increased by 8.7 times with NaBr addition, although the COS
value at a dbbl of 2,000 µm in the NaBr aqueous solution was
3.4 times greater than that in ion-exchanged water.
With minimizing the bubble diameter in the gas–liquid
systems, the following effects were observed. In the case
where a gas with a constant volume (Vgas) segregates into
bubbles whose dbbl is 50 µm or 2,000 µm, the interfacial area
based on the unit gas volume of bubbles (Abbl/Vgas) is ob-
tained by Eq. (1), and Abbl/Vgas at a dbbl of 50 µm is generally
40 times higher than that at dbbl of 2,000 µm (Tsuge, 2014).
Abbl /Vgas = 6/dbbl (1)
Additionally, the inner pressure of bubbles increases with
minimizing the bubble diameter, in order to balance the
Fig. 1 Time changes in COS at various dbbl values in NaBr aqueous
solution or ion-exchanged water
724
compressive action of surface tension (Aogaki et al., 2009).
When the pressure differences between the inside and the
outside of the bubble (∆P) are calculated by Young–Laplace
equation (Eq. (2)), the inner pressure of the fine bubbles
with a dbbl of 50 µm increases to 5.8×103 Pa in comparison
with the surrounding pressure of the fine bubbles (Tsuge,
2014).
ΔP = 4σ /dbbl (2)
where ∆P is the pressure difference between the inside and
the outside of the bubble, σ is the surface tension. The mass
transfer from the bubbles per unit time to the liquid phase
(N) is shown in Eq. (3), when the mass-transfer resistance in
the gas phase was negligible (Tsuge, 2014).
N = kL Abbl ( p − p∗)/H (3)
where kL is the liquid-phase mass-transfer coefficient, p is
the partial pressure of dissolved component in the bubble,
p* is the partial pressure, and H is the Henry constant. N
increases 2.1×103 times for the case where dbbl is reduced
from 2,000 to 50 µm (Tsuge, 2014). Moreover, when the
flotation rate of spherical bubbles is followed by Stokes law
under conditions with the Reynolds number <1, the flota-
tion rate of the bubbles (Ubbl) is represented by Eq. (4).
2
U bbl = ρ g dbbl /18μ (4)
where ρ is the liquid density, g is the gravitational accelera-
tion, and µ is the liquid viscosity. Ubbl at dbbl of 50 µm in the
water decreases to 6.3×10−4, while the mass transfer per
unit flotation distance increases to 3.4×106, in comparison
to the mass transfer at 2,000 µm (Tsuge, 2014; Tsuchiya
et al., 2017). Therefore, O3, which had poor solubility in
water, is effectively dissolved into the liquid phase with the
minimization of the O3 bubble diameter. Furthermore, to
understand the differences in the interactions depending on
the action of OH− at the gas–liquid interfaces, the surface
charges on the fine bubbles were determined when the fine
bubbles were supplied to aqueous solutions with various
OH− concentrations (COH−). The zeta potentials of the fine
bubbles were negative in the dbbl range of 10–30 µm, and the
absolute value of the zeta potential increased with increas-
ing COH−. Takahashi (2005) observed similar changes in the
zeta potential of fine bubbles with an increase in the solution
pH and reported that the main contributor to the negative
charge on the fine bubble surfaces was the specific adsorp-
tion of OH− at the gas–liquid interface. These findings sug-
gest that highly concentrated regions of OH− occur locally
near the gas–liquid interfaces of the fine bubbles. Moreover,
the dissolved O3 in water is decomposed following a radi-
cal chain mechanism, which is initiated by the reaction
between O3 and OH− (Staehelin and Hoigne, 1985; Langlais
et al., 1991; Selcuk, 2005; Khuntia et al., 2015; Venkatesh
et al., 2017), and active oxygen species (OH·, hydroperoxyl
radicals (OOH·), and superoxide radicals (O− 2 ·) etc.) are
generated. In our previous publication (Tsuge, 2014), O3
bubbles with different dbbl values were continuously supplied
into water, and the effects of dbbl on COS were assessed using
Journal of Chemical Engineering of Japan
 Fig. 3 Relationship between (CNaBr)0 and (rOS)0 or COS*

Fig. 2 Stepwise reaction from Br− to BrO−

3 via HOBr/BrO with O3
−

or OH·

a colorimetric method to confirm the increased generation

of OH· from O3. The reduction of the size of the O3 bubbles
allowed the acceleration of O3 dissolution and the enhance-
ment of OH· generation owing to the increase in the contact
probability between the dissolved O3 and OH− caused by
the accumulation of OH− at the minute gas–liquid interface.
Furthermore, when aqueous solutions containing Br− were
used, the consecutive reaction from Br− to BrO− 3 through
HOBr/BrO− proceeds by oxidation with either O3 or OH·.
Asami and Aizawa (1999) proposed that the oxidation of
Br− with O3 or OH· follows a stepwise reaction pathway, as
shown in Figure 2. According to the kinetic studies of sev-
eral research groups (Hoigne and Bader, 2008; Buxton et al.,
1988; Song et al., 1996; von Gunten and Oliveras, 1998), the
rate of the consecutive reaction from Br− to BrO− 3 with OH·
is greater than that with O3. In addition, the O3 test reagent Fig. 4 Relationship between the standing time and COS after O3 fine
bubble injection at various (CNaBr)0 values
for colorimetry reacts with O3 and OH·, as well as bromine
oxyacids, such as HOBr and HBrO3. Therefore, the minimi-
zation of the O3 bubble diameter in NaBr aqueous solution the time changes in COS. The relationships between (CNaBr)0
resulted in the acceleration of bromine oxyacid generation and (rOS)0 and C*OSown in Figure 3. Both (rOS)0 and C*OS
with OH· generation at the minute gas–liquid interface, increased with an increase in (CNaBr)0, and C*OS at (CNaBr)0
which is effective in increasing the oxidation potential of the of 5.0 mmol/L was 4.9 times greater than that at (CNaBr)0 of
liquid phase. 1.0 mmol/L. In addition, to evaluate the residence time of
2.1.2 Effects of NaBr concentration on the initial gen- the generated bromine oxyacids in the liquid phase, aque-
eration rate of the total oxygen species and the constant ous solutions with (CNaBr)0 of 0.0 or 1.0 mmol/L were left to
concentration of total oxygen species To thoroughly ex- stand for 1,500 min after O3 fine bubble injection. Figure 4
amine the effects of coexisting Br− on the enhanced oxida- shows the relationship between the standing time and COS.
tion potential in the liquid phase due to bromine oxyacid Although the value of COS in the aqueous solution without
generation caused by the injection of O3 fine bubbles and Br− after 80 min reduced to half the initial value, in the pres-
the NaBr addition, (CNaBr)0 was varied as the operational ence of Br−, COS was maintained constant at approximately
parameter. When O3 fine bubbles were supplied to the 0.4 mmol/L within the standing time of 1,500 min. The ob-
NaBr aqueous solution within 120 min for a (CNaBr)0 range tained results indicate that the lifetime of the generated
of 0.0–5.0 mmol/L, COS increased with increasing t, and the bromine oxyacid was longer than that of OH·. Similar find-
values of COS were constant after a tb of 60 min at all values ings regarding the lifetime of bromine oxyacids and OH·
of (CNaBr)0. In addition, a clear increasing trend in COS with have been reported by Ono and Oda (2003). Further, when
tb was apparent with an increase in (CNaBr)0. The initial oxidizable substances, such as organic compounds, are not
rate of generation of oxygen species, including bromine present in the liquid phase, OH· cannot remain in the liq-
oxyacids, (rOS)0, was calculated from the initial gradient uid phase for long because of the formation of H2O2 via the
of the time changes in COS, and C*OS was defined based on coupling reaction between OH· (Lu et al., 2015). Therefore,

Vol. 53  No. 11  2020 725

the improvement of the oxidation potential in the liquid
phase can be maintained for long periods by promoting the
generation of bromine oxyacids with long lifetimes in the
aqueous solution.
2.2 Enhanced refractory organic decomposition with
an increase in the oxidation potential of the liquid
phase during the injection of O3 fine bubbles into
aqueous solutions of bromide ions
2.2.1 Changes in TBA concentration during the injec-
tion of O3 fine bubbles into NaBr/TBA aqueous solution at
various NaBr concentrations To ascertain whether the in-
crease in the oxidation potential in the liquid phase contain-
ing Br− promotes the decomposition of organic compounds
in aqueous solutions, O3 fine bubbles were supplied to the
NaBr/TBA aqueous solution at various (CNaBr)0 values, and
TBA was decomposed. Figure 5(a) shows the changes with
time in CTBA during the injection of O3 fine bubbles when
(CNaBr)0 was varied between 0.0 and 5.0 mmol/L at a (CTBA)0
of 6.0 mmol/L. The value of CTBA in the TBA aqueous so-
lution without NaBr was nearly constant at 6.0 mmol/L.
However, CTBA remarkably reduced when (CNaBr)0 was in-
creased from 0.00 to 1.00 mmol/L. In the case where (CNaBr)0
Fig. 5 Time changes in a) CTBA and b) the solution pH during the in-
jection of O3 fine bubbles into the NaBr/TBA aqueous solution
726
exceeded 2.00 mmol/L, TBA decomposition was inhibited
by increasing (CNaBr)0. The time changes in solution pH dur-
ing TBA decomposition are also shown in Figure 5(b). At a
(CNaBr)0 of 0.00 mmol/L, the solution pH was almost main-
tained at 6.0. In the (CNaBr)0 range of 0.50–1.00 mmol/L, the
solution pH increased rapidly to approximately 9.5 within
a tb of 10 min and decreased gradually after 10 min. At
(CNaBr)0 >3.00 mmol/L, the solution pH was constant near
9.5. It was found that the reduction in the solution pH with
an increase in tb reflects the reduction in CTBA. Since the
increase in the solution pH is induced by the generation
of HOBr/BrO− in an aqueous solution (Bajpai, 2015), the
relationship between the decrease in CTBA and the change
in the solution pH in our experiments suggests that the
HOBr/BrO− produced by the reaction of Br− and O3 or OH·
was consumed in the decomposition of TBA.
2.2.2 Relationship between the constant concentration
of total oxygen species and the TBA decomposition rate
constant To clarify the effects of the improved oxidation
potential in the liquid phase on TBA decomposition, the
rate constant of TBA decomposition (kTBA) was plotted
against C*OS, as shown in Figure 6. kTBA was determined
by assuming that CTBA was proportional to tb in the ze-
roth order. kTBA showed a maximum value of approxi-
mately 0.012 mmol/(L·min) at a C*OS of 0.54 mmol/L. In the
C*OS range of 0.39–0.54 mmol/L, i.e., in the (CNaBr)0 range
of 0.0–1.0 mmol/L, TBA decomposition was promoted by
the enhanced HOBr/BrO− generation with an increase in
(CNaBr)0 during the injection of O3 fine bubbles into the
NaBr/TBA aqueous solution. In addition, when C*OS in-
creased to over 0.54 mmol/L, i.e., (CNaBr)0 increased beyond
1.0 mmol/L, the TBA decomposition rate was slower than
that at a (CNaBr)0 of 1.0 mmol/L. Thus, for the enhanced
decomposition of refractory organic compounds using
Br− and micronized O3 bubbles, the generation of bromine
oxyacids must be increased, and their oxidation must be
controlled. To validate the effects of each type of bromine
Fig. 6 Relationship between C*OS and kTBA
Journal of Chemical Engineering of Japan

Fig. 7 Changes in CTBA with the reaction time during TBA decompo-
sition with the addition of bromide or bromine oxyacids
oxyacid on TBA decomposition during the injection of O3
fine bubbles into the NaBr/TBA aqueous solution, TBA was
decomposed in the presence of NaBr, NaBrO, or NaBrO3
without O3 fine bubble injection within 60 min. Figure 7
shows the changes in CTBA with the reaction time. For com-
parison, the values of CTBA during the injection of O3 fine
bubbles into TBA aqueous solution without bromide or bro-
mine oxyacids are also shown in Figure 7. The CTBA profile
in the NaBr/TBA aqueous solution without O3 fine bubble
injection was almost the same that in the TBA aqueous solu-
tion with bubble injection alone. When NaBrO3 was added
to the TBA aqueous solution, CTBA slightly decreased within
60 min. Further, the decreasing trend in CTBA was most
evident in the case of NaBrO addition. Thus, TBA reacted
negligibly with BrO− 3 , although the O3 test reagent used for
COS measurement reacted with O3, OH·, and HOBr, as well
as BrO− 3 . Consequently, the decomposition of TBA with the
injection of O3 fine bubbles into an aqueous solution con-
taining Br− is enhanced because of the increased generation
of HOBr/BrO− induced by the increased generation of OH·
at the gas–liquid interfaces around O3 fine bubbles.
Conclusions
In this study, a technique based on O3 fine bubble forma-
tion and the addition of bromide, which allows the effective
generation of bromine oxyacids with the accelerations of
the O3 dissolution and OH· generation at the gas–liquid
interfaces, was applied for the decomposition of refractory
organic compounds. The effects of reducing dbbl and the co-
existence of Br− on COS, which is an index for the oxidation
potential in the liquid phase, were evaluated during the
injection of O3 bubbles with a dbbl of 50 or 2,000 µm in an
NaBr aqueous solution at various (CNaBr)0 values from 0.0 to
5.0 mmol/L. The following results were obtained:
Vol. 53  No. 11  2020
1) The value of COS in an aqueous solution containing Br− is
greater than that without Br− at all dbbl values, and COS
markedly increased with the decrease in the size of O3
bubbles in the aqueous solutions containing Br−.
2) When (CNaBr)0 increased from 0.0 to 5.0 mmol/L during
the O3 fine bubble injection into the NaBr aqueous solu-
tion, (rOS)0 and C*OS increased due to the acceleration of
bromine oxyacid generation.
To verify the enhanced decomposition of refractory or-
ganic compounds with enhanced bromine oxyacid gener-
ation, TBA was decomposed by injecting O3 fine bubbles
with a dbbl of 50 µm into an NaBr/TBA aqueous solution
at different (CNaBr)0 values. The results are as follows:
3) kTBA had a maximum value at a C*OS value of 0.54 mmol/
(L·min), i.e., at a (CNaBr)0 value of 1.0 mmol/L, because
of the conversion of HOBr/BrO− with a high oxidation
potential to BrO− 3 with a low oxidation potential, caused
by the excess oxidation of Br− with the injection of O3
fine bubbles.
4) The generation of HOBr/BrO− with the micronization
of O3 bubbles in the presence of Br− is effective for the
accelerated decomposition of refractory organic com-
pounds.
Acknowledgement
This work was financially supported by the Salt Science Research
Foundation (Nos. 17A4, 18A4, and 19A4), Japan.
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