Journal of Hazardous Materials 342 (2018) 446–453

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Application of ozone micro-nano-bubbles to groundwater

remediation
Liming Hu ∗ , Zhiran Xia
State Key Laboratory of Hydro-Science and Engineering, Department of Hydraulic Engineering, Tsinghua University, Beijing 100084, China

h i g h l i g h t s

• This paper presents the high efficiency of gas supply and mass transfer in water using MNBs.
• The ozone MNBs technique was applied for in situ groundwater remediation of an organics-contaminated site.
• Ozone MNBs show considerable advantages in contaminant cleanup and time efficiency.
• Ozone MNBs potentially represent an innovative technology for in situ remediation of organics-contaminated groundwater.

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

Article history: Ozone is widely used for water treatment because of its strong oxidation ability. However, the effi-
Received 25 February 2017 ciency of ozone in groundwater remediation is limited because of its relatively low solubility and rapid
Received in revised form 3 July 2017 decomposition in the aqueous phase. Methods for increasing the stability of ozone within the subsur-
Accepted 12 August 2017
face are drawing increasing attention. Micro-nano-bubbles (MNBs), with diameters ranging from tens of
Available online 18 August 2017
nanometres to tens of micrometres, present rapid mass transfer rates, persist for a relatively long time in
water, and transport with groundwater flow, which significantly improve gas concentration and provide
Keywords:
a continuous gas supply. Therefore, MNBs show a considerable potential for application in groundwa-
Micro- nano-bubbles (MNBs)
Ozone
ter remediation. In this study, the characteristics of ozone MNBs were examined, including their size
Groundwater remediation distribution, bubble quantity, and zeta potential. The mass transfer rate of ozone MNBs was experimen-
Mass transfer tally investigated. Ozone MNBs were then used to treat organics-contaminated water, and they showed
Field test remarkable cleanup efficiency. Column tests were also conducted to study the efficiency of ozone MNBs
for organics-contaminated groundwater remediation. Based on the laboratory tests, field monitoring
was conducted on a trichloroethylene (TCE)-contaminated site. The results showed that ozone MNBs can
greatly improve remediation efficiency and represent an innovative technology for in situ remediation
of organics-contaminated groundwater.
© 2017 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Soil and groundwater contamination are major environmen-
tal problems; thus, numerous technologies have been developed
to remediate such contaminants [1]. In situ chemical oxidation is
one method commonly used to remediate polluted sites. Oxidants
such as Fenton’s reagent, peroxydisulfate, and permanganate show
remarkable efficiency in the oxidation of organic contaminants and
are generally used for site remediation [2]. However, the efficiency
of the Fenton process is strongly dependent on the pH [3]. A con-
siderable amount of oxygen is formed during the Fenton process,
∗ Corresponding author.
E-mail address: gehu@tsinghua.edu.cn (L. Hu).
which may cause the blockage of pore channels and can limit the
area affected by Fenton’s reagent [2]. Peroxydisulfate tends to be
relatively stable at ambient temperatures (∼20 ◦ C) and must be
activated to be used in site remediation [4]. A large amount of
sulfate is produced as a by-product [5], however, which results in
secondary contamination. In situ chemical oxidation with perman-
ganate produces MnO2 , which also may result in pore plugging and
can lower the remediation efficiency [6].
Ozone is widely used for oxidation of pharmaceuticals in drink-
ing water [7,8]. Because of its strong oxidation ability, ozone also
has high potential in the treatment of wastewater [9,10]. Hydrogen
peroxide can be used to accelerate the oxidation of contaminants by
ozone [11,12]. However, the efficiency of ozone oxidation is limited
by the rapid decomposition rate of dissolved ozone in water, which
is much faster than that in the gas phase. Methods used to prolong

http://dx.doi.org/10.1016/j.jhazmat.2017.08.030
0304-3894/© 2017 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/
4.0/).
 L. Hu, Z. Xia / Journal of Hazardous Materials 342 (2018) 446–453
the reactivity of aqueous-phase ozone are thus urgently needed,
and some stabilisers have been used to increase the stability of
ozone in groundwater [13].
Micro-nano-bubbles (MNBs) are tiny bubbles with diameters
ranging from tens of nanometres to several tens of micrometres
[14,15]. Owing to their small diameter, MNBs present high inter-
nal pressures and rapid mass transfer rates, which can significantly
improve gas solubility. Compared with normal bubbles, MNBs have
lower rising velocity in the liquid phase. Nano-bubbles can persist
in water for long periods [16,17]. Those with radii of 150–200 nm
have been shown to remain stable for two weeks [18], and clusters
of nano-bubbles could further increase their stability [19]. Owing
to their long existence in water, MNBs can migrate with the water
flow and provide continuous gas supply for the dissolution phase.
In our previous work, the properties and mass transfer efficiency of
MNBs were studied [20–22]. One remarkable proven characteristic
of MNBs is that their large specific surface area leads to a con-
siderable capacity for pollutant adsorption on the bubble surface
[23]. In recent years, the potential application of MNBs in envi-
ronmental engineering has become a research focus [24–27]. Such
studies include the use of MNBs in surface water treatment owing
to their special characteristics of large specific surface area, nega-
tively charged surface, and high mass transfer efficiency [28–30].
Although the MNB technique has remarkable advantages in envi-
ronmental cleanup, its application to groundwater remediation has
not been systematically investigated thus far [20–22].
The purpose of this study is to investigate the feasibility and
efficiency of applying ozone MNBs to groundwater remediation.
The physic-chemical characteristics of ozone MNBs, such as the
size distribution and zeta potential, were studied experimentally,
and the mass transfer behaviour was investigated by model tests.
The remediation efficiency for contaminated water and ground-
water was examined under laboratory conditions using methyl
orange as a representative organic contaminant. A field test on a
trichloroethylene (TCE)-contaminated site was also conducted to
study the efficiency of in situ remediation by ozone MNBs.
2. Methods and materials
2.1. Experimental facilities
2.1.1. Micro-nano-bubble generator
The MNBs used in this research were produced by a spiral liquid
flow-type [31] MNB generator (Eco-20, Taikohgiken Ltd., Nishi-ku,
Kumamoto, Japan). Water was pumped into the generator, and a
maelstrom-like cavity was formed by the high-speed rotation of the
liquid flow. Gas was injected into the generator and was reduced to
MNBs by the centrifugation effect. The MNB size is affected by the
injection rates of water and gas. During the generation of MNBs,
a generator was placed inside the water, and a pipe was used to
inject gas. In this research, the flow rates of ozone and water were
4 L/min and 270 L/min, respectively.
2.1.2. Millimetre-bubble generation facility
A millimetre-bubble generation facility was used to generate
millimetre bubbles for ozone mass transfer tests and treatment effi-
ciency tests. Ozone was generated by the ozone generator and was
injected into the water by the air compressor through a pipe having
a diameter of 7 mm. A gas flow meter was used to control the flow
rate of the ozone.
2.1.3. Ozone generators
Two ozone generators were used in this research. Both are based
on the corona discharge method, and oxygen was transformed into
ozone by high-voltage discharge. In this study, the output rate of
447
gas was 4 L/min. The generator (RQ-30, Ruiqing Ltd., Jinan, Shan-
dong, China) which was used to produce ozone for all laboratory
tests including size distribution, gas mass transfer, and treatment of
methyl orange; the supplied ozone had a concentration of approx-
imately 50 mg/L. As a result, the mass percentages of ozone and
oxygen in the supplied gas were 3.5% and 96.5%, respectively. A
second generator (S4-R02, Ecodesign Inc., Ogawa, Saitama, Japan),
which was used to produce ozone in the field tests, supplied ozone
with a concentration of approximately 100 mg/L. The mass percent-
ages of ozone and oxygen in the generated gas were 6.8% and 93.2%,
respectively.
2.1.4. Size distribution analyser
The size distribution and number of the ozone MNBs were
measured by a nanoparticle tracking analyser (NanoSight LM-
10, Malvern Instruments Ltd., Malvern, Worcestershire, UK). For
nanoparticles in liquids, the rate of Brownian motion was not
affected by the particle density and was related only to the viscos-
ity and temperature. MNBs in liquid were illuminated by a laser,
and the analyser used a charge-coupled device to capture the MNB
movement. The nanoparticle size was calculated according to the
rate of nanoparticle movement by using the Stokes–Einstein equa-
tion. The measurement range for the size distribution was from 10
to 1000 nm, and the measurement range for the number of MNBs
was 106 –109 bubbles per mL.
2.1.5. Zeta potential analyser
The zeta potential of ozone MNBs in solution was measured
by using a zeta potential analyser (Delsa-nano C, Beckman Coulter
Inc., Brea, California, US). The interfacial charge characteristics of
the ozone MNBs were measured by calculating the electrophoretic
mobility. The measurement range of the zeta potential was from
−200 mV to +200 mV.
2.1.6. Dissolved ozone monitor
The concentration of dissolved ozone in water was measured by
a dissolved ozone monitor (Q45H/64, Analytical Technology Inc.,
Collegeville, Pennsylvania, US). The monitor used a polarographic
membrane sensor to accurately determine the concentration
of the dissolved ozone. The display range of the monitor was
0–20.00 mg/L, and the accuracy was ±0.1 mg/L.
2.1.7. UV spectrophotometer
The concentration of methyl orange was measured by UV spec-
trophotometry (DR5000, Hach, Loveland, Colorado, US). Based on
the Beer-Lambert law, at a wavelength of 462 nm, the intensity
of light absorbed by the methyl orange solution was measured to
determine the concentration of methyl orange.
2.1.8. Gas chromatograph
The concentration of TCE was measured by a gas chromatograph
(GC-310C, SRI Instruments, Torrance, California, US). Samples were
heated in a water bath, and the TCE in the headspace was mea-
sured to determine the TCE concentration in the samples. Each of
the groundwater samples was measured at least twice, and the
deviation was less than 0.005 mg/L.
2.2. Setup of laboratory tests
2.2.1. Size distribution and zeta potential analysis tests
A Perspex tank with internal dimensions of 0.8 m
(length) × 0.2 m (height) × 0.2 m (width) was used to perform
the experiments. The MNB generator was placed inside 20 L of
deionised water to generate ozone MNBs under 20 ◦ C. Ozone MNBs
were generated for 30 min, and water samples were then taken
to measure the MNB size distribution and quantity over time
448 L. Hu, Z. Xia / Journal of Hazardous Materials 342 (2018) 446–453
Fig. 1. Column tests setup.
with the size distribution analyser. The effect of salinity on size
distribution and zeta potential was also studied. Sodium chloride
was used to adjust the salinity of the deionised water, and the size
distribution and zeta potential of ozone MNBs generated under
different salinity conditions were measured. For this analysis,
filtration equipment was used to remove bubbles larger than 1 ␮m
because micro-bubbles significantly affect the measurement of
nano-bubbles.
2.2.2. Gas mass transfer tests
The gas mass transfer efficiency of bubbles was studied by
measuring the dissolved ozone concentration. The MNB genera-
tor was placed inside the tank with 20 L of deionised water to
generate ozone MNBs. For comparison, the millimetre-bubble gen-
eration facility was used to generate millimetre bubbles in 20 L of
deionised water. The dissolved ozone concentration was measured
during and after the generation process. The ozone MNB tests were
divided into four groups, in which ozone MNBs were generated for
8 min, 12 min, 17 min, 30 min, respectively. Millimetre-sized bub-
bles were generated for 30 min. Each test was conducted twice to
ensure the repeatability of the data.
2.2.3. Organics-contaminated water treatment tests
The treatment efficiency of ozone MNBs was studied. Methyl
orange, a commercial dye which can be degraded by ozone [32],
was used as the target contaminant to investigate the treatment
efficiency by ozone MNBs. 20 L of methyl orange solution at a
concentration of 10 mg/L was treated by ozone MNBs, ozone mil-
limetre bubbles, and oxygen MNBs, respectively. The ozone used in
MNB tests and millimetre-bubble tests was controlled to the same
amount to study whether MNBs can increase the treatment effi-
ciency by ozone. Because the collapse of MNBs may produce free
radicals to react with methyl orange [33], oxygen MNBs were used
to show the effects for comparison. Each test was conducted twice
to ensure the repeatability of the data.
2.2.4. Column tests
Column tests were conducted in a Perspex cylinder (Fig. 1)
with an internal diameter of 12 cm to study the treatment of
organics-contaminated groundwater by ozone MNBs. Glass beads
Fig. 2. Relative locations of wells.
were mixed with methyl orange solution at an initial concentration
of 10 mg/L to simulate organics-contaminated soil and groundwa-
ter. The specific gravity of the glass beads was 2.43, the average
diameter was 60 ␮m, and the dry density was 1.43 g/cm3 . The
hydraulic conductivity was 1.3 × 10−4 m/s because the glass beads
were poorly graded, which represents medium sand. The height of
the soil sample was 76 cm, and four sampling ports #1, #2, #3, and
#4 were distributed at 16 cm, 32 cm, 48 cm, and 64 cm from the bot-
tom, respectively. Ozone MNBs were generated in deionised water
continuously to ensure that the quantity of ozone MNBs was main-
tained at the peak value. Water containing ozone MNBs was fed
upwards to the column from the bottom with a hydraulic gradient
i of 0.368; deionised water without MNBs was used for comparison
testing. Each test was conducted twice to ensure the repeatability
of the data.
2.3. Setup of field tests
2.3.1. Site condition
The field tests were conducted at an organics-contaminated site
in Niiza, Japan. The contaminated site, which is the former loca-
tion of an electronic components factory, has an area of 1100 m2 .
The main contaminant was TCE, which according to the Japanese
standard has a concentration limit of 0.03 mg/L in groundwater.
The groundwater at this site is mainly distributed in a confined
sandy aquifer at depths of 12 m to 16 m, and the maximum con-
centration of TCE in the groundwater is approximately 10 mg/L.
The hydraulic conductivity of the sandy aquifer is approximately
10−6 m/s, whereas the upper and lower strata of the aquifer are clay
layers with a hydraulic conductivity of approximately 10−8 m/s. The
groundwater level is 6.5 m below the ground surface.
2.3.2. Extracted groundwater treatment
Experiments were conducted onsite to study the effect of H2 O2
on the treatment efficiency of ozone MNBs. 100 L of groundwa-
ter was extracted and stored in an airtight reaction tank having a
capacity of 500 L. Ozone MNBs, H2 O2 , and ozone MNBs plus H2 O2
were used to treat the TCE-contaminated water. H2 O2 reagent was
added during the generation of ozone MNBs at a mass ratio of
ozone:H2 O2 of 1:1. The concentration of TCE during the treatment
was measured.
2.3.3. Wells
One extraction well, one injection well, and five monitoring
wells, the locations of which are shown in Fig. 2, were used for
in situ remediation. The initial groundwater flow direction was
from the injection well to the extraction well. The depth of each
well was 16 m, and the screened intervals were from 12 m to 16 m.
The diameter of the extraction well was 25 cm, and a pump with an
extraction rate of 36 L/min was placed inside the well at a depth of
15 m. The diameter of the injection well and the monitoring wells
was 5 cm. The injection well was connected to the injection unit,
and the injection rate was 15 L/min. Because the injection rate was
limited by site and facility conditions, a high extraction rate was
applied to create stronger groundwater flow. The residual water
was treated and discharged far from the tested area. Groundwater
 L. Hu, Z. Xia / Journal of Hazardous Materials 342 (2018) 446–453 449

Fig. 3. In situ remediation facility.

samplers were installed in the monitoring wells to collect samples

at a depth of 15 m.

2.3.4. In situ remediation

Fig. 4. Ozone MNBs size distribution.
An in situ remediation facility (Fig. 3) was developed for the field
test. The remediation system contained three parts: the extrac-
tion unit, the reaction unit, and the injection unit. Contaminated
groundwater was extracted from the site and was filtered to remove
soil particles. After filtration, the groundwater was treated by an
air sparging facility to remove the TCE. Subsequently, the treated
groundwater was injected into the reaction tank. The MNB gener-
ator was located inside the tank to generate in situ ozone MNBs.
H2 O2 reagent was added during the generation of ozone MNBs at
a mass ratio of ozone:H2 O2 of 1:1. After the ozone MNBs and H2 O2
were added, the water was injected back into the ground by the
injection unit. The flow rate from reaction tank to the injection
unit was 15 L/min, and the residence time was 33.3 min in order to
achieve the best MNB generation. In situ groundwater remediation
was conducted for six days from 09:00 to 18:00 local time each day.
Groundwater was sampled to monitor the TCE concentration.

3. Results and discussions

Knowledge of the physic-chemical characteristics of ozone

MNBs and gas mass transfer is essential for designing a system for
Fig. 5. Zeta-potential of MNBs under various salinity conditions.
site remediation.

3.1. Size distribution and zeta-potential of ozone MNBs
The size and concentration of MNBs are main factors affecting
the mass transfer efficiency. Smaller bubbles present larger spe-
cific surface area and higher inner pressure, which result in higher
mass transfer efficiency. The MNB concentration affects the influ-
encing area of each bubble and therefore affects the concentration
of dissolved ozone and the remediation efficiency. Zeta potential
describes the charge characteristics of MNBs and affects their dis-
persion [20]. High absolute value of zeta potential prevents MNBs
from coalescence and improves their stability.
The size distribution of ozone MNBs generated in deionised
water for 30 min is shown in Fig. 4. The diameters of the ozone
MNBs mainly ranged from 32 nm to 460 nm, and the Sauter mean
diameter was 247 ± 9 nm.
The quantity of ozone MNBs was measured continuously after
the generation was stopped; the results are shown in Table 1.
Despite fluctuation caused by measurement error, the quantity
of ozone MNBs showed no significant decrease within 3 h; thus, it
is reasonable to conclude that ozone MNBs remain stable in water.
Therefore, ozone MNBs can stay relatively stable and can contin-
uously provide dissolved ozone when injected into groundwater.
The migration ability of ozone MNBs will be studied further through
column tests.
The zeta potential and Sauter mean diameter of ozone MNBs
under various salinity conditions are shown in Fig. 5 and Table 2,
respectively.
The salinity showed a slight effect on the zeta potential, and the
ozone MNBs remained negatively charged under various salinity
conditions; however, the salinity showed no obvious effect on the
diameter of ozone MNBs. Thus, the ozone MNBs are stable and can
be applied for remediation of groundwater with various salinity
levels.
3.2. Gas mass transfer and fate of MNBs
MNBs have a high internal pressure and a large specific sur-
face area, which greatly enhances the ozone mass transfer. The gas
mass transfer characteristics of ozone MNBs determine the treat-
ment efficiency of organic contaminants in both surface water and
groundwater.
The dissolved ozone concentration during and after the gen-
eration process is shown in Fig. 6. For the group in which ozone
MNBs were generated for 30 min, the dissolved ozone concentra-
tion reached a peak value of 10.09 ± 0.09 mg/L at 22 min. For the
millimetre-bubbles test, millimetre-sized bubbles were generated
for 30 min, and a peak value of 0.64 ± 0.00 mg/L was reached at
6 min.
450 L. Hu, Z. Xia / Journal of Hazardous Materials 342 (2018) 446–453

Table 1
Quantity of ozone MNBs.

Time after generation was stopped (h) 0 1 2 3

Quantity in 1 mL (107 bubbles) 4.55 ± 0.23 4.63 ± 0.27 4.44 ± 0.27 4.35 ± 0.18

Fig. 6. Mass transfer process for ozone MNBs and millimetre bubbles. Fig. 7. Degradation rates of methyl orange in laboratory tests. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

Table 2 3.3. Contaminated water treatment efficiency by ozone MNBs

Sauter mean diameter of ozone MNBs under various salinity conditions.

Salinity (mg/L) 0 9
Sauter mean diameter (nm) 247 ± 9 226 ± 25
The mass transfer tests results are shown in Table 3. The average
increasing rate of dissolved ozone concentration from the begin-
ning of generation to the first achievement of the peak value was
used to evaluate the dissolved ozone provision ability. Compared
with the millimetre bubbles, the MNBs significantly enhanced the
dissolution process of ozone. The high internal pressure and large
specific area of MNBs significantly improved the increasing rate.
Ozone MNBs can persist in water and can reach high concentra-
tion levels, which greatly increase the peak value of the dissolved
ozone concentration. Similar results were reported by Li et al. [21],
who showed that MNBs significantly increased the mass transfer
efficiency of oxygen.
After the generation was stopped, the decrease of dissolved
ozone obeyed the first-order reaction model, and the half-life
time of the dissolved ozone was calculated. The average half-life
time for the MNB system was 10.51 min, whereas that for the
millimetre-bubble system was 0.70 min. Compared with the mil-
limetre bubbles, MNBs can persist in water for long periods and
can provide ozone constantly, thereby significantly prolonging the
active time of the ozone.
18 Methyl orange was treated by ozone MNBs and millimetre bub-
265 ± 27 bles for 30 min to study whether MNBs can increase the treatment
efficiency by ozone. The tests were conducted twice, and the devi-
ation was less than 0.03 mg/L. The concentration of methyl orange
after the treatment is shown in Table 4, and the degradation rates
over time are shown in Fig. 7.
Oxygen MNBs were not shown to oxidise methyl orange, which
means that free radicals produced through the collapse of MNBs
had little effect on methyl orange in this case. After treatment
for 30 min, the concentration of methyl orange in ozone MNBs
and millimetre-bubble tests decreased to 0.16 mg/L and 9.08 mg/L,
respectively. The MNBs greatly enhanced the decomposition effi-
ciency of methyl orange by ozone. At 10 min, 2.25% methyl orange
was degraded in the ozone millimetre-bubble test, whereas 92.95%
methyl orange was degraded in the ozone MNBs test. The treat-
ment efficiency of the MNBs was 40 times faster than that of the
millimetre bubbles. After 10 min of treatment, the degradation
rate of methyl orange slowed obviously because its concentra-
tion decreased. Similar results were reported by Chen [32], in
which the concentration of methyl orange decreased to a mini-
mum of 0.5 mg/L and remained unchanged during further injection
of ozone. In the present study, the concentration of methyl orange
further decreased to 0.18 mg/L after the 30 min treatment by MNBs.
The high concentration of dissolved ozone by the MNBs was spec-
ulated to be the main reason.
Furthermore, methyl orange is a non-volatile compound. For
volatile organic compounds, it can be inferred that the contami-

Table 3
Mass transfer tests results.

Bubble type MNBs MNBs MNBs MNBs Millimetre bubbles

Generation duration (min) 30 17 12 8 30

Peak value of dissolved ozone concentration (mg/L) 10.09 ± 0.09 8.38 ± 0.07 6.95 ± 0.08 5.33 ± 0.06 0.64 ± 0.00
Increasing rate of dissolved ozone concentration (mg/L min) 0.46 0.49 0.58 0.67 0.11
Half-life time of dissolved ozone (min) 10.61 10.62 10.70 10.12 0.70
R2 for dissolved ozone half-life time 0.980 0.978 0.983 0.972 0.980
 L. Hu, Z. Xia / Journal of Hazardous Materials 342 (2018) 446–453 451

Table 4
Concentration of methyl orange after 30 min of treatment.

Bubble type Ozone MNBs Ozone millimetre bubbles Oxygen MNBs

Concentration of methyl orange after 30 min treatment (mg/L) 0.18 ± 0.02 9.10 ± 0.02 9.99 ± 0.01

Fig. 9. Concentrations of TCE during treatment of ozone MNBs, hydrogen peroxide,

Fig. 8. Concentrations of methyl orange in column tests over time. (For interpre- and ozone MNBs plus hydrogen peroxide.
tation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)

nants can transfer into MNBs and react with ozone in the gas phase.
As a result, the treatment efficiency of ozone MNBs will be further
increased.

3.4. Column tests of ozone MNBs

In the organics-contaminated water treatment tests, ozone

MNBs showed remarkable treatment efficiency. It was reported
by Li et al. [20] that water with MNBs presented nearly the
same hydraulic conductivity as water without MNBs. Column tests
were conducted to study the treatment of organics-contaminated
groundwater by ozone MNBs.
The concentrations of methyl orange at the sampling ports
are shown in Fig. 8. For all the sampling ports, the concentration
of methyl orange in the ozone MNBs test decreased significantly
faster than that in the deionised water tests. The transport of
MNBs in groundwater can be described as colloid transport [21];
it can be inferred that the dispersion of ozone MNBs significantly
increased the migration velocity. In contaminated sites, dispersion
with groundwater flow can expand the influencing area of ozone
MNBs.
When the concentration of methyl orange decreased from
10 mg/L to 1 mg/L, ozone MNBs were 64% faster than deionised
water; when it decreased from 1 mg/L to 0.2 mg/L, the ozone MNBs
were 82% faster. Methyl orange was slightly adsorbed by soil. At
low concentrations, the removal of methyl orange by deionised
water slowed, whereas ozone MNBs remained more efficient.
Ozone MNBs showed strong potential for application in organics-
contaminated groundwater remediation.
3.5. Field test of ozone MNBs
Based on the laboratory tests, field tests were conducted at a
TCE-contaminated site to study the remediation ability of ozone
MNBs in groundwater.
Ozone is a practical decontamination method for TCE, and
hydrogen peroxide can significantly accelerate the oxidation [11].
Fig. 10. TCE concentrations in monitoring wells over time.
Experiments were conducted to study the effect of H2 O2 on the
treatment of TCE by ozone. The concentration of TCE during the
treatment is shown in Fig. 9. Hydrogen peroxide alone showed low
treatment efficiency for TCE, although it improved the treatment
efficiency by ozone MNBs by a factor of approximately 3. There-
fore, the combination of ozone and H2 O2 was used for the field
tests.
In situ remediation of organics-contaminated groundwater was
conducted; the initial and final TCE concentrations in the ground-
water are shown in Table 5.
During the in situ remediation by MNBs, the TCE concentration
in the monitoring wells showed remarkable decrease; an overall
removal rate of 99% was reached. The final TCE concentration in
the entire treated area decreased to less than 0.03 mg/L, which is
the standard limit in Japan. The concentration of TCE over time is
shown in Fig. 10. Ozone MNBs migrated with the groundwater for
a constant supply of dissolved ozone. Previous research indicated
that an ozone–peroxide system forms OH radicals, which presents
high treatment efficiency on TCE; moreover, TCE can be treated also
452 L. Hu, Z. Xia / Journal of Hazardous Materials 342 (2018) 446–453
Table 5
Initial and final TCE concentrations in groundwater.
Well Number #1
Initial TCE concentration (mg/L) 3.529 ± 0.002
Final TCE concentration (mg/L) 0.010 ± 0.004
by direct reaction with ozone [11]. The reaction between ozone
plus H2 O2 and TCE was described by pseudo-first-order kinetics, in
which the decreasing rate of TCE was related to the concentrations
of ozone and H2 O2 [11].
For monitoring wells #1, #2, #3, and #5, 90% of TCE was removed
during the first three or four days, and the decreasing rate from high
to low occurred in #3, #2, #5, and #1. Well #3 was in closest prox-
imity to the injection well and presented the highest concentration
of oxidants, which resulted in the fastest decrease of TCE. In the
field tests, the groundwater flow was affected by the injection and
extraction wells. Well #2, located along the injection-extraction
direction, with groundwater presented a higher flow rate; thus,
the concentration of oxidants at #2 was higher than at #5. Well
#1, located farthest from the injection well, presented the lowest
oxidants concentration and resulted in the slowest decreasing rate
of TCE.
The initial concentration of monitoring well #4 was 0.26 mg/L,
which is lower than that in other areas. However, the concentra-
tion of TCE showed apparent decreases during the treatment, which
indicates that ozone MNBs are still effective for treating groundwa-
ter with relatively low concentrations of contaminants.
During the first three or four days, the decreasing rate of TCE
increased over time, which indicates that the concentration of oxi-
dants in the site increased during the remediation. According to
the results of extracted groundwater treatment, the degradation of
TCE was attributed mainly to ozone. It can be concluded that ozone
MNBs are stable in groundwater and that the constant injection
increased the concentration of ozone MNBs at the site. When the
concentration of TCE was lower than 0.01 mg/L, its degradation rate
obviously slowed. Similar results were obtained in the treatment
of methyl orange; thus, it can be assumed that the low concentra-
tion of organics-contaminant was the main reason for the limited
remediation efficiency.
4. Conclusion
In this study, the characteristics of ozone MNBs were studied.
MNBs can reach a high unit quantity and remain stable in water for
long periods. Ozone MNBs stay negatively charged under varied
salinities, which means that they are stable and can be applied in
the remediation of groundwater with varying salinities.
MNBs significantly increase the mass transfer efficiency of ozone
and can remain stable in water to constantly supply ozone. The
half-life of ozone in the MNB system is significantly longer than
that in the millimetre-bubble system. Under laboratory conditions,
ozone had a significant effect on organics-contaminants in the sur-
face water and groundwater, and the MNBs greatly enhanced the
treatment efficiency. An in situ remediation facility was developed,
and field tests were performed in a TCE-contaminated site in Japan.
An overall removal rate of 99% was reached after six days of treat-
ment. Ozone MNBs showed a sound effect on the remediation of
TCE-contaminated groundwater and potentially represent an inno-
vative technology for in situ remediation of organics-contaminated
groundwater.
Novelty statement
As a widely used oxidant, the application of ozone in ground-
water remediation is limited by its migration ability. The purpose
#2 #3 #4 #5
4.502 ± 0.005 10.130 ± 0.004 0.264 ± 0.002 2.129 ± 0.004
0.003 ± 0.001 0.018 ± 0.014 0.007 ± 0.002 0.003 ± 0.000
of this manuscript is to study the feasibility and efficiency of
applying ozone to groundwater remediation in the form of micro-
nano bubbles (MNBs). Basic characteristics and mass transfer
behaviour of ozone MNBs were studied, and the remediation effi-
ciency of organics-contaminants by ozone MNBs were studied
through laboratory and field tests. Ozone MNBs represent an inno-
vative technology for in-situ remediation of organics-contaminated
groundwater, and this manuscript will surely attract attention
of geo-environmental engineers interested in technologies for
organics-contaminated groundwater remediation.
Acknowledgements
The financial support from National Natural Science Founda-
tion of China (Project No. 41372352, 51323014, 51661165015)
and Tsinghua University (Project No. 2015THZ02-2-20161080101,
2015THZ01-1-20161080079) are gratefully acknowledged. The
support for the testing facility from State Key Laboratory of Hydro
Science and Engineering (SKLHSE-2016-d-03) is also acknowl-
edged. The authors thank the assistance of Dr. D Song at IS Solution
Company for field monitoring on MNB remediation. The two anony-
mous reviewers are also thanked for giving valuable comments that
improved the overall quality of this paper.
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