Accepted Manuscript

Micro and nanobubble technologies as a new horizon for water-

treatment techniques: A review

Tatek Temesgen, Thi Thuy Bui, Mooyoung Han, Tschung-il Kim,

Hyunju Park

PII: S0001-8686(17)30171-9
DOI: doi: 10.1016/j.cis.2017.06.011
Reference: CIS 1782
To appear in: Advances in Colloid and Interface Science
Revised date: ###REVISEDDATE###
Accepted date: ###ACCEPTEDDATE###

Please cite this article as: Tatek Temesgen, Thi Thuy Bui, Mooyoung Han, Tschung-il
Kim, Hyunju Park , Micro and nanobubble technologies as a new horizon for water-
treatment techniques: A review, Advances in Colloid and Interface Science (2017), doi:
10.1016/j.cis.2017.06.011

This is a PDF file of an unedited manuscript that has been accepted for publication. As
a service to our customers we are providing this early version of the manuscript. The
manuscript will undergo copyediting, typesetting, and review of the resulting proof before
it is published in its final form. Please note that during the production process errors may
be discovered which could affect the content, and all legal disclaimers that apply to the
journal pertain.
 ACCEPTED MANUSCRIPT

Micro and nanobubble technologies as a new horizon for water-treatment

techniques: A review

Tatek Temesgena,*, Thi Thuy Buia,*, Mooyoung Hana,**, Tschung-il Kimb, Hyunju Parkb

a
Department of Civil and Environmental Engineering, Seoul National University, Seoul 151-

744, South Korea

PT
Institute of Construction and Environmental Engineering, Seoul National University, 599

Gwanak-ro, Gwanak-gu, Seoul 151-744, South Korea

RI
SC
*
Co-first author: Tatek Temesgen Terfasa
NU (tate95et@gmail.com), Thi Thuy Bui

(thuyngoxda@gmail.com) Tel: +82-2-880-7375; Fax: +82-2-885-7376;

**
Corresponding author: Tel: +82-2-880-7375; Fax: +82-2-885-7376; E-mail: myhan@snu.ac.kr
MA

(Mooyoung Han)
D

Word count: 6263

TE

Number of Figures: 4
P

Number of Tables: 2
CE
AC

1
 ACCEPTED MANUSCRIPT

Abstract
This review article organizes the studies conducted on the areas of microbubbles and nanobubbles

with a special emphasis on water treatment. The basic definitions of bubble types and their size ranges are

also presented based on the explanations of different researchers. The characterization parameters with

state-of-the-art measuring and analysis techniques of microbubble and nanobubble technologies are

summarized. Some major applications of these technologies in water-treatment processes are reviewed and

T
IP
briefly discussed. Based on the reviews, various potential areas for research and bubble application gaps in

water and wastewater treatment technologies are identified for further study. The article is prepared in such

CR
a way that it provides a step-by-step acquaintance to the subject matter with the objective of focusing on

US
the application of microbubbles and nanobubbles in water-treatment technology.

Keywords: Nano bubble, microbubble, bubble technology, bubble property, bubble application
AN
Contents
1. Introduction ........................................................................................................................................ 3
M

2. Definition and classification of bubbles............................................................................................ 4

3. Bubble generation .............................................................................................................................. 7
ED

4. Properties of MBs and NBs ............................................................................................................... 9

4.1. Bubble size and size distribution ............................................................................................. 9
PT

4.1.1. Measurement technique .............................................................................................. 9

4.1.2. Bubble size under various design and operation conditions .................................. 10
CE

4.1.3. Bubble sized dependence on frothers and electrolyte solutions ............................. 11

4.2. Bubble rising velocity ............................................................................................................. 13
4.3. Zeta potential .......................................................................................................................... 15
AC

4.4. Mass transfer Properties ........................................................................................................ 19

4.4.1 Volumetric mass transfer coefficient ........................................................................ 20
4.4.2 Surface area to volume ratio ...................................................................................... 21
4.4.3 Gas holdup................................................................................................................... 21
5. Applications of MBs and NBs in water-treatment technology ..................................................... 22
5.1. Overview .................................................................................................................................. 22
5.2. Aeration ................................................................................................................................... 22
5.3. Flotation................................................................................................................................... 24
5.4. Disinfection.............................................................................................................................. 25

2
 ACCEPTED MANUSCRIPT

1. Introduction
Operations that involve phase changes are largely applicable in environmental, agricultural,

healthcare, chemical or industrial and energy fields. Among the phase-related processes, gasliquid

operations are often applied in wastewater and water treatment technologies, aquatic system restoration,

food processing industries, aqua farming, and chemical as well as petrochemical industries. The efficiency

of most gasliquid processes are affected by different design and operational parameters, types of

T
IP
contacting operations, and the properties of contacting fluids. In the basic theoretical phase mass-transfer

theories, an increase in the contact-surface area is one of the major factors that contribute towards an

CR
improvement in the process performance. Moreover, mixer design, packing column materials, tray and

US
baffle type structures, spray methods, injection nozzles, and sparger-type designs, are other parameters that

play an important role in enhancing either the heat and mass transfer or reaction-surface areas between the
AN
contacting phases.

In the past two decades, many researchers have been focusing on microbubbles (MBs) and
M

nanobubbles (NBs) as a way of improving the efficiency of gasliquid phase processes. Most studies
ED

focused on the generation methods, measuring techniques, and characterization of fine and ultrafine bubble

categories. Recently, few studies revealed the possibility of scale-up and application of MB and NB
PT

application at industrial levels. Based on some preliminary results, most researchers suggested that MB and

NB applications in water-treatment technologies have great potential.

CE

Limited efforts have been made on collecting and preparing a well-organized, comprehensive
AC

report of the researches done in the areas of MBs and NBs with respect to water-treatment technologies. In

addition, existing studies have some discrepancies and vague boundaries, particularly in defining the range

of bubble category. In this comprehensive review, extensive effort was made to reduce such discrepancies

and provide concise information regarding the current condition of MB and NB applications in water

treatment. In the review, a stepwise approach was followed while addressing general to specific issues of

MB and NB applications in water-treatment technologies. Different types of bubbles are defined, and a

range of bubble sizes is proposed for each type based on the common properties presented in different

3
 ACCEPTED MANUSCRIPT

studies. The general MB and NB generation techniques that were previously proposed are summarized to

discuss the major bubble characterization parameters, existing measurement methods and characterization

techniques. The focus of this review is to extensively summarize the current status of MBs and NBs in

water-treatment technologies, reveal existing research gaps and address future application scope of this

technology in the field.

T
2. Definition and classification of bubbles

IP
Studies pertaining to bubbles in bulk-liquid mediums have been conducted for more than half a

CR
century. However, the types and classifications of bubbles were hardly defined in a clear and comprehensive

manner. Instead the flow regimes in bubble columns are better explained and categorized in to three definite

US
types. These flow regime classifications are characterized by the superficial velocity and bubble column

diameters as homogeneous (bubbly), heterogeneous (churn-turbulent) and slug flow regimes [1]. The
AN
bubbly flow regime is characterized by small bubbles having gentle mixing compared to the churn turbulent

flow which is characterized by vigorous mixing and a range of bubble sizes [2]. Usually, sluggish flow is
M

observed in laboratory columns of small diameter while the churn flow is observed in large industrial size
ED

systems [2]. Bubbly flows normally follow cluster flow of bubbles and further subdivided in to disperse

bubble flow regime that exist at very low superficial velocities followed by turbulent flow at higher
PT

superficial gas velocities and vertical-spiral flow with a unique flow pattern [2]. Bubbly flows can be
CE

affected by superficial gas and liquid flow rates, diffuser and/or mixer type and design, surfactants and

frother types as well as impurities and water contaminants. The effect of these in bubbles under bubbly flow
AC

generation and application systems will be discussed in later sections.

Researchers attempted to classify bubbles in bubbly flows based on different bubble characteristics.

The most frequently studied factors are bubble size, surface nature, and the residence time of the bubbles

[3]. [4] found that most of these factors depend on the size distribution of the bubbles. Hence, many

researchers frequently employed the bubble sizes as a basis for categorization. Bubbles were categorized

on the differences in their sizes. Based on these categories, various studies defined the bubbles as macro

bubbles, MBs, and sub-micro or NBs for conventional or big bubbles, fine bubbles, and ultrafine bubbles,

4
 ACCEPTED MANUSCRIPT

respectively [5-12]. However, the researchers defined the range of the sizes differently. [8] employed the

term conventional bubbles to describe the bubbles with sizes ranging between 6002500 m, whereas [7]

categorized them vaguely as large bubbles in comparison to MBs. In another study, [13]labeled the

conventional bubbles with diameters in the range of 25 mm as macrobubbles, representing those

commonly used in fermenters, gasliquid reactors, and ore-flotation equipment. In addition, [5] grouped

the ellipsoidal-shaped conventional bubbles with diameters in the range 110 mm as large bubbles.

T
IP
Similarly, [14] considered conventional industrially applicable bubbles to be in the range of 17 mm for

CR
their research on scale-up of bubble column reactors. Based on these studies, the conventional bubbles size

range usually falls between 0.610 mm, and the bubbles with diameters greater than 10 mm are assumed

US
to have different shapes and flow characteristics. [5] showed that these conventional bubbles exhibit a

change in their shape from spherical to elliptical with an increase in their sizes. For the bubbles with
AN
diameters greater than 10 mm, the individual bubbles take the shape of a spherical cup, and the flow regime

changes to churn flow rather than bubbly flow.

M

MBs or fine bubbles are defined by [6] as tiny bubbles having sizes in the range of 1050 m,
ED

whereas [15] categorized these types of bubbles as having diameters less than 50 m. In another study,

[10]classified these bubble types as small bubbles with sizes in the range of 1060 m based on their field
PT

of application in a study of physiological activity, whereas the bubbles in the range of few hundreds of
CE

nanometers to 10 m were observed in the field of fluid physics. Similarly, [5] categorized the bubbles

under the size of several 100 m and less, as small bubbles having a rigid spherical shape. [8] classified
AC

MBs in the range of 30100 m. Likewise, [16] considered MBs as bubbles in the range of 10-50 m.

Although the researchers disagree on the size boundaries of the MBs, most of them suggested a minimum

size of approximately 10 m, while the maximum size suggested was 100 m.

The presence and stability of NBs has been a controversial issue since the proposal of their

contribution to the attraction between hydrophobic surfaces in water [17-19]. Since then, many researchers

investigated their presence using different techniques [4, 18]. Similar to the case of the MBs, the researchers

5
 ACCEPTED MANUSCRIPT

did not arrive at a consensus regarding the definition of the NBs; moreover, some of the definitions exclude

a range of bubble sizes that is not between the minimum size proposed for the MBs and the maximum for

the NBs. [6] did not classify the bubbles that fall in the range between 200 nm and 10 m. Based on their

definition, the diameters below 200 nm represent the NBs. To define this range, [6] presented the names

micro-nano bubbles (MNBs) based on the suggestion from [20], which shows the confusion and lack of

T
a clear category for ultrafine bubbles. In addition, Wu et al. (2012) defined the NBs or sub-micron bubbles

IP
as bubbles having sizes less than a micron and categorized the bubbles they generated with a size less than

CR
500 nm as sub-MBs or NBs. Moreover, recently, [21] defined the NBs as bubbles having a diameter less

than few hundreds of a nanometer, which is vague and controversial. By summarizing the upper limit of

US
the bubbles that different researchers considered for NBs, bubbles less than a micron was found reasonable

to categorize them under ultrafine bubbles/NBs based on their measured size and shared similarity of
AN
properties.

The bubble categorization proposed in the previous studies do not only depend on size but also on
M

the shared characteristics and behaviors of the bubbles in a bulk-liquid medium. Fig. 1 shows the summary
ED

of the size category based on the most agreed size ranges for the different bubbles with their major

properties. For the bubbles ranging in between 110 m, we propose the name sub-MBs because the
PT

properties of these bubbles, which will be discussed later in this manuscript, falls in between the MBs and
CE

NBs.

Although the researchers agree on the characteristics of the MBs, the agreement on clear size
AC

boundary for the different bubble types is not yet standardized. Given this fact, our proposal, shown in Fig.

1, can be adopted as a basis for standardization based on the perspectives of the reviewed articles as well

as the common properties shared by the bubbles with sizes categorized under the respective groups.

6
 ACCEPTED MANUSCRIPT

Bubble Diameter (m)

T
IP
CR
US
AN
Figure 1. Proposed range of the bubble sizes and major properties
M

3. Bubble generation
ED

Bubble formation is considered as a static or quasi-static process. It is followed by the dynamic

processes, namely, coalescence and break up. [6] defined these overall process of bubble formation, growth,
PT

and collapse process of bubbles as cavitation. Based on the content of the bubble, cavitation is classified as

a vaporous cavitation and gaseous cavitation. It is different from boiling by its generating mechanism
CE

mainly caused by a reduction of pressure below a certain critical value at constant temperature. It thus
AC

seems similar to boiling, except the driving mechanism is not a temperature change but a pressure change

[22] [23]. Coalescence and break up are two opposite states of the fine bubbles. In the case of coalescence,

fine bubbles combine to form bigger bubbles, whereas the possibility of further breakup favors the

formation of ultrafine bubble generation and/or collapse. Different studies applied different techniques of

fine and ultrafine generation: hydrodynamic cavitation and particle cavitation [6], acoustic or sonication [6,

7, 24], electrochemical cavitation [9], and mechanical agitation [7]. In all these techniques the physics

behind the generation of bubbles is related to reduction of pressure using surface tension and energy deposit.

7
 ACCEPTED MANUSCRIPT

There are two techniques to create cavitation by reducing the pressure below a certain critical value. One

is the hydrodynamic cavitation where the pressure variation is achieved by a flowing fluid causing a velocity

variation and the other is by applying an acoustic field. The cavitation by local energy deposit can be either

induced by photons of leaser light or by other elementary particles [25]. The hydrodynamic cavitation

is the most frequently applied system in water-treatment technologies and it can be achieved by pressurized

T
saturation, bubble shearing, splitting, and mechanical agitation [3, 4, 10, 11, 16, 26-29]. [10] discussed

IP
some of the MB generators in detail including the spiral liquid-flow type, Venturi type, ejector type, and

CR
pressure dissolution type, which use hydrodynamic-cavitation mechanism based on the liquid and gas flow.

In all these systems the pressure is reduced below its vapor pressure due to high velocity inside the flow

US
path. According to [25] the hydrodynamic cavitation was well described by Bernoullis equation given as:
1
+ 2 2 = () (1)
AN
Rearranging equation 1
2 2
2 +
M

=
(2)

Where, V is the water flow velocity, P is the pressure, and is the liquid density. From equation 2
ED

it is clear that the negative pressure due to the flowing fluid that can create cavitation could occur when
PT

2
the flow velocity exceeds .

CE

On top of this, the hydrodynamic bubble splitter system apply a plug flow big bubble shearing and bubble

cavitation technique to reduce bubble sizes [27]. The acoustic or sonication system employs the ultrasonic
AC

waves either by using an ultrasonic probe [7] inside the bulk liquid or external ultrasonic wave generator

[24]. Cavitation in this case occur when a sufficiently energetic acoustic wave produces periods of high

negative pressure exceeding the ambient hydrostatic pressure [30]. There are two possibilities for this

technique to create cavitation. The first is called homogeneous nucleation where the liquid ruptures when

the tensile stress due to the acoustic wave exceeds the intermolecular cohesion forces. The energy needed

for this to happen is much larger than found in practical situations. Because of the inhomogeneities in the

8
 ACCEPTED MANUSCRIPT

liquid distribution of bubbles may appear, seemingly from out of nowhere. The second type of cavitation

caused is classified as heterogeneous nucleation. In this case negative pressure is determined by the weakest

link which in this case is a preexisting minute volume of gases due to lack of diffusive stability [31]. The

electrochemical systems employ an electrical current on a given surface, which is immersed into a given

solution to generate surface nucleated bubbles [9]. The mechanical cavitation is a technique that employs

T
high speed agitation by using mechanical mixers to a given volume of bulk liquid with a limited amount of

IP
gas [12] this technic applies the same physics behind hydrodynamic cavitation.

CR
4. Properties of MBs and NBs
4.1. Bubble size and size distribution

US
4.1.1. Measurement technique

Several techniques have been used for measuring the size and size distribution of the MBs and NBs.
AN
Among the measurement methods applied, the laser-diffraction particle-size analyzer [6, 15, 32-38] atomic

force microscope [39], and image analysis [27, 29, 40] are considered as the most typical tools. Each
M

measurement method has its own merits and limitations. For example, the image analysis and atomic force
ED

microscope methods could report the average diameter with a visible image; however, these methods

require considerable time for provision of a meaningful size because of lack of obtaining enough focused
PT

bubble images in few snapshots for meaningful size determination. Studies show that Image analysis can
CE

be used for bubble sizes of the minimum size of 0.8m, which is relatively higher compared to the other

measuring techniques [27]. Moreover atomic force microscopy technique has shortcomings in the case of
AC

measuring homogeneous bubbles surrounded by only the bulk fluid. Laser-diffraction particle-size analyzer

is a simple tool that can be used to obtain the average size of a large number of bubbles without a visible

image. It employs bubble size measurement technique based on their light-scattering properties. It is

applicable to measure sizes ranging from approximately 0.1m to 3 mm. [41] proposed another technique

for determination of ultrafine bubbles using resonant mass measurement method. It is assumed to solve the

drawbacks of other conventional techniques in differentiating particles from NBs with the size range of

9
 ACCEPTED MANUSCRIPT

100-200 nm. It is capable of distinguishing positively buoyant particles (bubbles) from negatively buoyant

particles. Because the NBs exist in water for a considerable duration of time, along with its stability [4], the

need of a simple and field adaptive method is highly needed.

4.1.2. Bubble size under various design and operation conditions

Several studies show the effects of design and operation conditions on the size and/or distribution

T
of the MBs and NBs. For instance, it was demonstrated that the size and fraction of the MBs mainly depend

IP
on the pressure differences across the nozzle system. Higher pressure would produce smaller bubbles

CR
because of an increase in air density and at pressures above approximately 3.5 atm, the sizes of the MBs

were almost constant [40, 42-44]. For the case of the NBs, the pressure [27, 40, 44], sonic power [37], and

US
other operation conditions, such as the length, diameter, and type of hose [27] are introduced as relatively

major factors affecting the size. [4] indicated that different types of gases used in bubble creation; such as
AN
oxygen and air, resulted in NBs with similar, common average sizes (measured using particle analyzer) of

137 nm and 140 nm, respectively. But for macro size and relatively bigger size MBs using higher molecular
M

weight gas increases the density leading to smaller bubble generation [45]. Table 1 summarize some of
ED

the studies on the size dependency of the MBs and NBs on the aforementioned factors.
PT

Table 1 MBs and NBs sized dependence of design and operation parameters
CE

Affecting parameters Size range Average size References

AC

2 20 130 m* 71 m* [44, 46]

Pressures (atm) 3 10 110 m* 41 m * [46-48]

3.5 15 - 85 m* 30 m * [46, 48]

Sonic power 50 - 750 nm

[37]
(W) 100 - 935 nm

10
 ACCEPTED MANUSCRIPT

150 - 921 nm

200 - 965 nm

Hose diameter 8 - 2.65 m

(mm) 10 - 3.61 m [27]

10 - 3.19 m

T
20 - 2.90 m

IP
Hose length (m) 30 - 2.56 m [27]

CR
40 - 2.61 m

50 - 2.61 m

US
Braid
- 3.26 m
Teflon
AN
Hose type - 2.93 m [27]
Wrinkle
- 2.49 m
pipe
M

*
Bubble size is measured using laser-diffraction particle-size analyzer method;
ED

Other results: bubble size is measured using image analysis method.

4.1.3. Bubble sized dependence on frothers and electrolyte solutions

PT

Frothers are chemical additives used in flotation processes to facilitate generation of fine bubbles
CE

and reduce bubble coalescence. It also interact with collectors to enhance the particle to bubble collusion

interaction. Many studies are done to confirm the effect of frothers on bubble size reduction. Studies
AC

comparing the effect of effect of electrolyte solutions containing NaCl and other salt ions, and effect of

commercial frothers on synthetic sea water was tested along with the influence of air flow rate and impeller

speed as two other main operation variables on relatively large size MB generation systems [49, 50]. As

results, at a lower impeller speed of 4.2 m/s or a higher gas velocity of 0.5 cm/s bubble size of the synthesis

sea salt solution was about of 850 ??m which is higher than that of all the sizes found for synthetic frother

solutions (~ 650 700 ??m) [51]. This result supports the discussion on the effect of frothers for the

11
 ACCEPTED MANUSCRIPT

reduction of bubble size in the sea water solution [52, 53]. Furthermore, a comprehensive study on a single

impeller speed and gas flow rate was conducted for a detailed explanation on the interaction between

frothers and salts. [51] concluded that in the absence of frother (i.e. Methyl isobutyl carbinol MIBC),

bubbles formed in the 0.5 M NaCl and synthesis sea salt solution were smaller than in deionized water. The

study also provided the range of frother concentration added into the solution. It was found that by adding

small amount of frother (as 1 10 ppm of MIBC) bubble created in 0.5 M NaCl solution increased its size

T
IP
in comparison to a frotherless NaCl solution. And at above 10 ppm of MIBC, all electrolyte solutions

CR
produced bubbles with similar size. More results on difference in bubble size of each solution in the

presence of frother are summerized in table 2.

US
Table 2. Bubble size of the frother-electrolyte solutions at different concentration**
AN
Average bubble size Frother (MIBC) concentration (ppm)

(??m) 0 1 2 3 4 5 6 10 15 20 50
M

Deionized water 3700 2800 2500 2300 2200 1800 1450 1000 900 900 850
ED

0.5 M NaCl 750 760 800 800 780 800 850 1000 900 900 850

Sea salt solution 1200 950 850 850 800 850 850 870 900 900 900
PT

**
adopted from [51] [51, 53, 54]

To discuss the differences in the case of frother absence, ionic strength of electrolyte solution which
CE

related to critical coalescence concentration was attributed [51, 54-56]. The synthesis sea salt solution with

the ionic strength of 0.7 produced larger bubbles compared to NaCl solution with the ionic strength of 0.5.
AC

Also, [54] summanized that the critical coalescence concentration would be extended to saline solutions

with the solutions ionic strength to have an ability to reduce bubble size. When comparing the synthesis

sea salt solution and NaCl solution, [51] indicated that the interactions of the salt ions present in synthesis

sea salt solution, being the cause of the larger bubble size. Regarding to this, many researches had been

conducted, considering NaCl solution as a base and other salt ions (i.e. MgCl2, CaSO4, MgSO4, and KCl)

independently in order to investigate their individual effect on bubble size. As resulted, 0.5 M NaCl created

12
 ACCEPTED MANUSCRIPT

the smallest bubble in the absence of the frother while the addition of MgCl 2, CaSO4, and KCl to NaCl

solution had an insignificant effect on the bubble sized difference. In contrast, a mixtures of frotherless

MgSO4 and NaCl generated larger bubbles [51, 53, 54]. For inorganic salts some inhibits coalescence and

others do not. In this perspective, the authors attributed that Mg2+ and SO42- contribute towards bubble

coalescence. It was also assumed that at 0.5 M NaCl, the coalescence inhibition had been maximized and

T
the changes in bubble size could be due to the break-up phenomena [53, 54]. This breakage has a relation

IP
to the local stress on the air/water interface after frother is added into the solution [51, 57]. The role of

CR
frother in bubble break-up with a proposed mechanism of inducing surface tension gradient to increase the

instability between air and water interface was summarized by [57]. In summary, different studies suggest

US
the role of frothers in playing a dual role in generation of fine bubble during bubble formation and stabilize

their size by preventing coalescence after generation. But the justifications given by previous researches on
AN
the effect of frothers during bubble breakage is not satisfactory and needs further work in the future.

4.2. Bubble rising velocity

M

Rising velocity is a key parameter affecting the behavior of the bubbles in water and liquid solution
ED

[58]. Several studies mention the theoretical approach for determining the terminal velocity of a single,

sphere bubble that could be expressed with Stokes law and/or HadmardRybczynskis equation (HR
PT

equation) at a Reynolds number of zero [59]. Based on these principles, the diameter of the bubble and

liquid viscosity are concluded as factors affecting the rising velocity.

CE

For experimental verification, the rising velocities of the MBs and NBs are measured with a system
AC

that uses an optical microscope via a very high-speed camera, a measuring cell, and an image analysis

software [27, 58, 60]. Figure 2 summarize the results of the rising-velocity measurements of the MBs,

which were conducted by different researchers. For larger sizes of the bubble (Figure 2), the rising velocity

increases. This tendency is consistent with the Stokes law and HR equation.

13
 ACCEPTED MANUSCRIPT

T
IP
CR
US
Figure 2. Rising velocities of the MBs according to size; data points show single bubble
AN
Bubbles generated from various gases (i.e., CO2, air, He, and N2) showed different behavior with

the theoretical approaches confirming the effect of gas molecular weight on rising velocity. For example,
M

rising velocity has an excellent agreement with the H-R equation for the MBs generated by N2; whereas, a

slip has occurred in the cases of the MBs generated by air and He, and it exceeds the values predicted by
ED

the HR equation [59]. Similarly for the case of MBs generated by CO2, an exceeding terminal velocity has
PT

been resulted since the enhancement of CO2 solubility could form a diffusion boundary layer surrounding

the bubbles.
CE

In relation to bubble size, [61] has observed the relationship between gas holdup and bubble rising

velocity. The author reported a decrease in bubble rising velocity is highly associated with a decrease in
AC

bubble size resulting in a continuous increase in gas holdup. In addition, frother type and concentration is

also observed to have an effect on bubble rising velocity since it is highly related with the size of the bubble

formed and bubble surface properties. For instance, at equal gas holdup, small bubbles in a pentanol solution

rise the same velocity as bubbles about double the size in a polyglycol frother solution. Considering the

binding of the frothers on the amounts of water to a bubble, [62-64] suggested a variation level of interaction

14
 ACCEPTED MANUSCRIPT

with the water due to the frother hydrophilic groups; providing a dependence of frother properties on surface

viscosity that could influence bubble rising velocity by influencing the surface drag forces [63, 64].

4.3. Zeta potential

4.3.1. Principle of measurement

Zeta-potential is the electrical potential at the slipping plane between the bulk liquid and bulk

liquid[65]. A fundamental zeta-potential calculation method for the MBs and NBs is the application of the

T
IP
Smulochowskis equation [4, 27, 37, 65-69]. In many studies, zeta potential analyzers (such as

zetaphoremeter IIIShephy, France; zetaplusBrookhaven Instruments Co., New York; zeta potential

CR
analyzerZeecom MicroTech Co. Ltd, Japan, etc.) are widely used [4, 27, 37]. This system detects the

US
electrophoretic mobility (horizontal speed in the recorded image) of the bubble at the stationary plane in

the measurement cell, and the zeta potential is then calculated from the recorded speed. In addition, in many
AN
cases, an electrophoretic system that have an electrophoretic cell (measurement cell), a video camera, and

a video image analysis software is applied to measure the value of the zeta potential [48, 65-72]. Figure 3
M

shows a typical zeta-potential-measurement system with the movement of a bubble in the electrolyte
ED

solution, which is originally set by [66], and later well-applied in several studies [40, 48, 71].

4.3.2. Shifting of zeta potential in electrolyte and surfactant solution

PT

Zeta potential of bubble is a function of electrolyte properties, chemical surfactants of the solution

and pH [37, 73-75]. Generally, both the NBs and MBs are negatively charged in the pH range of 212. At
CE

a neutral pH, the negativity of the zeta potential was shown in several studies, with approximately -50 mV
AC

[76], approximately -40 mV [37, 77] and approximately -30 to -20 mV [48, 66, 75, 78, 79]. The negative

zeta potential of the MBs and NBs in water is related to OH- ions adsorption to the interface of the bubbles

from the water molecules. Basically, two explanations are proposed on the mechanism of the negative zeta-

potential of bubbles in relation to OH- ions. These mechanisms that induce selective adsorption of OH- ions

are based on the hydration energies of H+ and OH- and the water molecular dipole orientation at the

interface[80-82]. The hydration energies of H+ and OH- are -1127 and -489kJ/mol respectively[65].

15
 ACCEPTED MANUSCRIPT

T
IP
CR
a US b
AN
Figure 3. a) Measurement system of the zeta potential (adopted from [66]) and b) the images of a single
M

bubble captured in the electrolyte solution with respect to time (adopted from [48])

Therefore, the tendency of the H+ ions to stay in the bulk water phase is high exposing the OH- ions
ED

to the gas phase. The other justification is that an electric double layer is formed because of the structural
PT

orientation of water dipole at the interface with hydrogen pointing to the bulk water phase and oxygen

atoms pointing towards the gas phase.

CE

For divalent coagulant additions, such as Mg2+ and Ca2+, the zeta potential of the MBs yielded negative

results, varying from approximately -45 to -20 mV (Figure 4a) [67, 69]. But for a certain dose of trivalent
AC

coagulant with Al3+, the zeta potential shifted from negative to positive value, i.e., from approximately -27

mV to approximately 20 mV for Al3+ dose of above 5 mg/L ( Figure 4b) [48, 71]. It was explained that

trivalent metal ions can rapidly adsorb onto the bubbles, creating a positive electric potential at the interface,

thereby yielding a positive value of zeta potential [71]. In other research [65] explained the tendency of

higher valence ions of increasing the zeta-potential of a bubble in relation to the force of attraction. Since

the force of attraction depends on the valency of counterions, in this case the metal ions, the ion with higher

16
 ACCEPTED MANUSCRIPT

valence tend to be attracted to the negative interface more strongly than ions with lower valency. Therefore

trivalent ions have more tendency of making positive bubbles compared to divalent and monovalent ions.

T
IP
CR
a US b
AN
Figure 4. Zeta potential of MBs and NBs in the presence of various coagulants (a - adopted from [67,
M

69]; and of Al3+ (b adopted from [44, 48]

In pure water the surface charge on the negativity of Micro and NBs highly depend on pH values.
ED

But researches indicated that addition of surfactants also affect zeta potential of Micro and NBs by
PT

modifying the electro-kinetic properties of gas-liquid interface caused by adsorption of anions and/or

desorption of cations [65, 83-85]. Regarding to this, [83] focused on the certain flotation collectors and
CE

study the effect of primary amines, and fatty acids. Later, [84] investigated the response of cationic

surfactant tetradecyltrimethylammonium bromide (TTAB, Fluka, purity higher than 98%), anionic
AC

surfactant (hexadecylbenzenesulfonate), and nonionic surfactants (decaoxyethylene octylphenol (EO10OP,

Gaf) and ethylene dodecanol (EO6DD, Nikko) on their effect on changing zeta potential of air bubble

under pH from 5 to 8. Furthermore, [75] and [86] have indicated that the charge on the NBs depends on

the surfactant solution and its ionization properties at different pH values. In all researches findings show

that cationic surfactants such as as CTAB and/or DAH can change the electrical charge of the bubble being

adsorbed onto bubble interface producing a positive electrical charge. It was abstracted that the charge on

17
 ACCEPTED MANUSCRIPT

the NBs was positive in CTAB [86] and DAH [87] at pH < 12 [75]. [84] has mentioned the reflection of

the anionic surfactant on the negativity of microspheres electrophoretic mobility due to the adsorption

ability of the negative groups of anionic molecules on the microspheres. Following this research, more

contributions on surface charge of the NBs have been performed, showing the negatively charged for all

pH values in pure water, AG [86], and SDS solutions [75, 86]. In conclusion, the possibility of the

T
adsorption and surface ionization of surfactants on MBs and NBs surface are the typical mechanism related

IP
to the shifting of zeta potential [73, 88] [86]. As a result, cationic surfactant produces positive bubble

CR
meanwhile anionic and non-ionic surfactant promote production of negatively charged bubbles [73, 86, 88]

In summary, table 3 gives the dependency of the surface charge of the NBs on the surfactant solutions For

US
the mechanism of zeta-potential shifting, [78] proposed a model (Figure 5) for the mechanism of positive

bubble formation as it is a result of selective adsorption of specific metal ion on the bubble interface and/or
AN
due to precipitation of metal hydroxide on the bubble interface.

Table 2. Average zeta potential of the NBs (mV) in different surfactant solutions at various pH
M

pH SDSa, b AGb Pure watera CTABb DAHa

ED

2 ~ -39 N/A N/A N/A ~ +70

PT

3 ~ -60 ~ -1.30 -0.27 ~ +47 ~ +50

CE

4 ~ -55 N/A N/A N/A ~ +58

5.5 ~ -64 N/A ~ -4.21 N/A ~ + 49

AC

7 ~ -70 ~ 8.12 ~ -15.68 ~ +43 ~ +54

11 N/A N/A ~ -26.73 ~ +39 ~ +5

12 ~ -73 ~ -26.86 N/A ~ +38 ~ -9

a
Adopted from [75]
b
Adopted from [86]

18
 ACCEPTED MANUSCRIPT

T
IP
CR
US
Figure 5. Proposed mechanism of bubble charge reversal (modified from [78])
AN
4.4. Mass transfer Properties
M

In many applications involving gasliquid phase operations, bubble columns and stirred tank

reactors are commonly used as contacting process units [87, 89, 90]. The rate of gas-to-liquid phase transfer
ED

often controls the process efficiency; hence, it is a critical design criterion [91-95]. The mass-transfer

efficiency of the bubble columns depends on the size distribution of the bubbles, rising velocity of the
PT

bubbles, surface area to volume ratio, coalescence and breakup, gasliquid hydrodynamics, phase mixing,
CE

and physical properties [93, 96, 97]. According to the classical two-film theory of gas absorption, the rate

of mass transfer between two phases depends on the gas and liquid phase mass-transfer coefficient, mass-
AC

transfer surface area to volume ratio, and the concentration gradient between the two phases [93, 98]. The

mass transfer rate " (mol/m3s) in a given gasliquid reactor is calculated using the unsteady state method

[10, 21, 87, 93, 99]:

= ( ) (3)

19
 ACCEPTED MANUSCRIPT

where " " is the liquid-side mass transfer in (m/s), "" is the gasliquid interfacial area in (m2/m3), " " is

the liquid saturation concentration in (mol/m3), and (mol/m3) is the gas concentration in the liquid phase

at any given time t in (s).

4.4.1 Volumetric mass transfer coefficient

In the gasliquid reactors, mass transfer can be characterized by measuring the volumetric mass

transfer coefficient, as it is an important parameter for evaluating the performance of the reactor [99]. It is

T
the product of the liquid mass-transfer coefficient " " and the interfacial surface area "". The liquid mass-

IP
transfer coefficient is a function of the turbulence and liquid parameters affecting the liquid film renewal.

CR
The interfacial area depends on the size distribution of the bubbles, which is a function of the gas flow rate,

sparger and nozzle design, shear rate, fluid properties like (liquid viscosity and gas density) and other

US
design and operating parameters. Different correlations have been proposed for estimation the mass transfer
AN
coefficient for conventional and MBs with respect to different factors based on mathematical modeling and

experimental studies. One of the major problems of the experimental studies is the divergence of the
M

proposed correlations mainly because of the difference in the system size and the measuring methods [99].
ED

Although the gasliquid mass transfer depends on the bubble size and several investigations of mass transfer

on conventional bubbles are conducted, models that relate the size of the bubble with the rate of the mass
PT

transfer for MBs and NBs are limited. For the conventional bubbles, [99] attempted to relate the mass-

transfer coefficient with the bubble size in dual-impeller-agitated reactors for average bubble sizes ranging
CE

from 36 mm. Similarly, [100] investigated the dependence of mass transfer on the diameter of the bubble

for the gasliquid mass transfer in air lift contactors under the influence of salinity using the Grashof
AC

number. The investigated bubbles had a bimodal distribution curve for bubbles in the range of 110 mm.

Moreover, [100] related the bubble size and the coefficient of mass transfer with the average bubble

size for a bubble distribution in the range 0.910 mm. On the contrary, studies on the MBs are limited;

among these, [101] followed a dynamic model that relates the mass-transfer coefficient with many factors

including the shrinkage in the bubble size for a single MB and solved it numerically for a bubble size in the

order of 25 m. To enhance the mass transfer using the MBs, [102] developed a model that relates the rate

20
 ACCEPTED MANUSCRIPT

of CO2 mass transfer based on the size of the bubble. Recently, [26] studied the stirred reactor using the

MBs of approximately 50 m and revealed that circulating a portion of the bulk liquid through a MB

generator increased the temperature in the bulk liquid, which affected the gas solubility, particularly for

relatively small volume of the bulk liquid. Hence, they employed a temperature correction factor to

determine at 20 oC for comparison purpose referring to the study by [103], expressed in equation (4).

( )

T
( )200 = 0 (4)
20

IP
where is the temperature correlation factor with a reported value in the range 1.0081.054. They selected

CR
0.975 as the correlation factor by fitting the curve between Vs T. By employing the temperature-

adjusted value, they developed a relation of with respect to the total power consumption and superficial

US
velocity of the gas. The models developed so far have different approaches based on the system, application,
AN
and modeling methods followed. So far, studies on the mass transfer using the ultrafine bubbles are limited.

Experimental methods of determining volumetric mass-transfer coefficient in a gasliquid phase processes

M

irrespective of bubble size is well summarized in the review paper of [104]. In most of these reviewed
ED

articles, dynamic method, CO2 absorption method and Sodium sulfite oxidation method are applied for

determination of for fine bubble processes [26, 101, 104, 105].

PT

4.4.2 Surface area to volume ratio

The other key parameter in determining the rate of mass transfer in a gasliquid system is the
CE

interfacial area to volume ratio ". In most of the developed mass-transfer models in the aforementioned

studies, the rate of mass transfer is related to the bubble size through the interfacial area using the relation
AC

given in equation (5) based on the common assumption that bubbles have a simple, spherical shape with

one representative diameter and the dependence of gas holdup on the size of the bubble [6, 100, 102, 106].
6
= (5)
(1 )

4.4.3 Gas holdup

Gas holdup () is defined as the volume fraction occupied by the bubble or gas in the entire gas

liquid dispersion, usually given by equation (6) [6, 93, 95]. It is determined by the volume expansion

21
 ACCEPTED MANUSCRIPT

method [95] and calculated by measuring either the bulk liquid table depth/pressure change or volume

change before and after aeration/de-aeration.

=
=
=
(6)

where is the volume of the gas, = is the final volume of the gasliquid solution, is the initial

volume of the liquid before bubbling, is the final water table head of the gasliquid solution, and is

T
the initial water table head of the bulk liquid.

IP
5. Applications of MBs and NBs in water-treatment technology

CR
5.1. Overview
Application of MBs and NBs in water-treatment technology has been recently gaining attention

US
[24]. It has been reported that MBs and NBs can detoxify contaminated water by catalyzing the reactions

of chemicals, thereby improving the efficiency of the chemical treatment process [6, 107]. According to
AN
several studies, bubbles generated from air and nitrogen could enhance the activities of microorganisms
M

and/or bacteria in both anaerobic and aerobic conditions, in defouling solid surface and membranes [6, 108,

109]. In different literatures, MBs and NBs have been applied in typical treatment processes [33, 109, 110],
ED

flotation, and disinfection [24, 111-114]. The most commonly known processes applied in water treatment

utilizing bubble technology are floatation, aeration, disinfection and advanced oxidation processes. In most
PT

of the researches done, the main objectives of applying MB and NB technologies are to downsize the
CE

facilities, to reduce operation time and reduce operation and maintenance cost of water-treatment plants,

with a greater contaminant removal efficiency.

AC

5.2. Aeration
In natural water restoration and water treatment, aeration plays a major role in delivering oxygen,

which is an important life-sustaining component for aquatic lives and biochemical reaction substrate in

aerobic treatment. Moreover, fluid therapy is one of the most common intervention areas in cell biology

and healthcare [115]. Many studies have been conducted on the effect of aeration processes in biological

water and wastewater treatment, ground water remediation as well as agriculture. The main target objectives

of most studies are improving the aeration efficiency to improve biological matter degradation, microbial

22
 ACCEPTED MANUSCRIPT

growth rate, seed germination, and growth rates. In the previous studies, the main concern is optimizing the

efficiency of the mass-transfer rate-limiting factor. In the conventional aerobic systems, dissolved oxygen

is a critical factor to consider in efficiency [116]. In these conventional systems, the mass-transfer rate of

oxygen is very important because most contacting equipment utilize the mechanical aerators or diffusers,

which require high electrical input and mechanical part maintenance resulting in high operating costs [117].

T
The attention of most of the aeration researches more focused on the design of aerators and optimization of

IP
operating parameters for conventional bubbles.

CR
Recently application of MBs and NBs received attention in the processes stated earlier to improve

mass transfer in the area of aeration. But, researches in the application of this bubble types at the industrial

US
scale is not yet well developed. [26] studied the dispersion and gasliquid mass-transfer characteristics of

the MBs for aeration in stirred-tank reactors and concluded that a higher impeller speed does not always
AN
mean a greater , and proposed that the MB aeration was more suitable for bioreactors. [118] investigated

the impact of the MB aeration on the fermentation of Trichoderma reesei, which is highly affected by the
M

limited mass-transfer rate of oxygen. Their study concluded that, by applying the MB aeration, the dissolved
ED

oxygen concentration was above the critical concentration at low agitation rates and the cell mass

concentration increases very rapidly during the fast growth stage with the mass productivity increment from
PT

0.1 to 0.18 g/lh in comparison to the conventional bubbling. In another research [58] studied the oxidative
CE

capacity of the NB aeration of seeds and its effects on germination. Their result concluded that the seed

germination was improved by using the NB aerated water in comparison to those submerged in distilled
AC

water. Similarly, [119] investigated the effect of the MB aeration on the growth of leaf lettuce (Lactuca

sativa) and found that fresh and dry weights of the MB aerated lettuce are 2.1 and 1.7 times greater than the

macro bubble aerated lettuce, respectively. In both studies, the researchers speculated that the resulted

germination and growth improvement was because of the high specific-surface area of Micro-NBs and the

ability of attracting positive ions owing to their high negative electronic charges. However, the effect of

MBs and NBs on nitrifying bacteria and other useful bacteria growth was overlooked. [120] studied the

aeration possibility of ground water by micro-NBs and found that the hydraulic conductivity of the sand

23
 ACCEPTED MANUSCRIPT

was not affected by the micro-NBs inside the pore water. Moreover, the mass transfer rate of oxygen to the

water was found to be 125 times faster than the macro bubbled water which was 16 times less dissolved

oxygen enhancement durability compared to micro-nano bubbled water. Based on the outcome of the study,

they suggested that the applications of MBs and NBs can predictably facilitate the aerobic biodegradation

process for ground-water contaminant removal. Considering the limitation of Micro-NBs application

T
studies in wastewater treatment the authors of this paper performed research on the utilization of NBs for

IP
aerobic waste degradation. The results show that the oxygen utilization rate and the volumetric mass

CR
transfer coefficient in the NB aerated synthetic wastewater treatment unit is almost double compared to a

conventional bubble aerated one. The organic waste degradation in the NB aerated unit took less than half

US
of the retention time used for the conventional system. Similarly, the biomass system in the NB aerator unit

showed higher growth and decay rates [121]. Based on the experience of our results it is highly
AN
recommended to work on further tests and researches in this area.

5.3. Flotation
M

Floatation had been one of the basic separation processes in water treatment for many decades [122,
ED

123]. Most of the target substances to be separated by floatation include powders, chemicals, metal ions,

oils and organic (Rubio et al, 2002). The need in reduction of bubble size in floatation processes is highly
PT

related to improving separation efficiency. [124] explained the possibility of optimizing the efficiency of

floatation by modification of bubble characteristics mainly size and surface charge in addition to particle
CE

properties. From the perspective of flotation, both the MBs and NBs are widely used to remove the
AC

contaminants in water with a better efficiency. There is a large body of experimental evidence showing that

bubbleparticle collection efficiency [125]. [126] investigated the effect of bubble size reduction to MB on

the rate of fine particles. The bubble size was controlled by varying impeller speed. They found out that the

floatation rate was strongly affected by bubble size to the extent of one hundred fold for a bubble size

reduction from 655 m to 75 m. Similarly, [127] reported the need of bubble size reduction in froth

floatation is highly related to increasing the collusion probability of small particles with fine gangue.

According to the study the probability of collusion increases as the bubble size decreases improving the

24
 ACCEPTED MANUSCRIPT

separation efficiency. Surface charge and size of particles as well as small bubbles play an important role

in flotation [48, 71, 128]. It has been provided that positively charged MBs could efficiently separate algae

from freshwater, with approximately 90% of cell number removal and 92% of chlorophyll a reduction [48,

71, 129]. For organic matter, i.e., total organic carbon and dissolved organic carbon and other

aliphatic/aromatic compounds, a removal rate greater than 30% could be achieved in the application of the

T
MBs [15, 71]. The principle for removal mechanism of the contaminants in water is attributed to the similar

IP
size and opposite charge between the bubbles and fine particles, which leads to better collision of bubbles

CR
and contaminated particles, making it easy to float [66, 70, 78, 130]. Increase in concentration of NB in

froth floatation increases the stability of MB suspension reducing rising velocity creating favorable

US
condition for froth flotation of coarse particles or hard-to-float particles that require a relatively long slide

time [25]. In another study [131]studied the effect of NB on floatation. It has been found that the presence
AN
of NB widen floatation particle size range and increased particle surface hydrophobicity and improved froth

floatation efficiency. Furthermore, negatively charged NB flotation with coagulation/flocculation process

M

(PAC as coagulant) is concluded as to be a cost-effective treatment for chemical, mechanical polishing of

ED

wastewater. The conductivity experiments performed in the lab and the pilot scales conducted by [132]

reported an increase of 40% of wastewater clarification efficiency with a good removal of approximately
PT

95% for the turbidity, total solids, and total silica. Moreover, the cost and performance of the NB flotation
CE

technology with coagulation/flocculation is found to be considerably lesser than the conventional processes.

For a field scale application, the operation needs to be optimized to demonstrate the feasibility of the NB
AC

flotation technology.

5.4. Disinfection
Oxidation of pollutants and disinfection of pathogens using ozone is a promising method for

treatment of drinking water and wastewater [133, 134]. Ozone gas bubbles have been applied for water

treatment because of its powerful disinfection ability under low concentration and short contact time. Its

disinfection efficiency increased its preference for the disinfection application of chemical resistance spore

forming bacteria like Bacillus subtilis and Cryptosporidium parvum [133, 135-138]. Further improvement

25
 ACCEPTED MANUSCRIPT

of its efficiency was achieved by applying MB. The observation of disinfection kinetic for E. Coli by

illustrated a faster reduction rate (approximately 99.99% of inactivation), a smaller tank size, and a lower

ozone requirement for application of MBs in comparison to the conventional ozonation disinfection process

[113]. Another study on stopping multiplication of E. Coli by cavitation of MB resulted in 75% reduction

within 3 min at an energy input of 490 W/L [114]. Similar results of the hydrodynamic cavitation reported

T
in several studies convincingly prove the effectiveness of a non-reagent technique, such as MB and NB

IP
technologies, for water disinfection [111, 112]. The generation of OH and shock waves from collapsing

CR
MBs are discussed as the main cause of E. Coli inactivation; however, the deactivation level of each

influence factor still requires further research.

US
The inlet ozone concentration for the generation of MBs affected the removal of Bacillus subtilis

spores, resulting in a greater log reduction at higher ozone concentration (i.e., 5-log reduction for 140 mg/L,
AN
1.6-log reduction for 110 mg/L, and 0.3-log reduction for 40 mg/L with a contact time of 2 min) [133]. To

achieve a 5-log reduction of Bacillus subtilis spores at a concentration of 40 mg/L of ozone, the time
M

requirement is longer, found to be 5 min [133]. This study concludes that high inlet-ozone concentration
ED

would enhance the log reduction of Bacillus subtilis because the dissolved zone rises during the disinfection.

In addition, it has significant influence on reducing the cost of the process.

PT

An analysis on deactivation for differing bacteria in a continuous test using the MBs indicated the
CE

effect of the bursting force of the bubble on the disinfection efficiency [24]. The investigation revealed that

E. Coli was not detected [70, 79, 139]after 30 min of MB generation. Moreover, the disinfection level of
AC

other bacteria is very high, more than 90% [24]. In addition, the optimum conditions for increasing the

disinfection are reported to be smaller size and larger volume of the bubble and the bursting of the bubbles

in the presence of bacteria at or near the water surface. In the application of NBs for bathing pools, [140]

observed a high prevention of pathogen growth. In this study, two circulation systems are applied to connect

the bathing pool with a reservoir, and the range of the sizes of the NBs were 1020 nm. It has been found

that subsequent burst of the NBs would provide a greater disinfection and cleaning in both the bath and

reservoir pools compared to that of the traditional ultrasonic vibrator.

26
 ACCEPTED MANUSCRIPT

The application of ozone MB is not only limited to disinfection as mentioned earlier. Recent

researches revealed that reduction of bubble size also improved the oxidation of different pollutants by

improving the formation of hydroxyl radical for advanced oxidation [134]. In wastewater treatment,

advanced oxidation process (AOPs) are known to have the capacity of converting most organic

compounds in to carbon dioxide, water and mineral acids or salts. This mineralization process is

T
achieved by an elevated amount of radicals generated in the system. Among AOPs O3 based

IP
systems have been showing better efficiency in water treatment. In O3 based AOP processes the

CR
predominant radical species are the hydroxyl radicals (OH) [141-143]. In such systems, the

oxidation of any compound could occur via either through the oxidation of compounds via O3

US
molecule (direct reaction) or the oxidation through the reaction of the compound with the hydroxyl
AN
radicals formed from O3 (indirect reaction) [134, 143]. Since the standard oxidation potential of O3

(2.07V) is lower than the hydroxyl radical (2.80V), the indirect oxidation of water pollutants via
M

OH generation is highly reactive and non-selective to almost all kinds of organic pollutants.
ED

Therefore the oxidation reaction with the pollutants is better accelerated by the indirect reactions

[142]. But to improve the overall disinfection efficiency improving both reaction mechanisms is
PT

important. Different studies explained that ozonation and ozone based AOP is affected by water
CE

properties like; pH, alkalinity, concentration and type of organic matter as well as temperature

[135, 144-147]. The pH of water is very important because the decomposition of O3 is accelerated
AC

by an increase in pH or concentration of OH [146, 148, 149]. In conventional bubbling systems

generation of OH is not detected in acidic pH [15]. Similarly,[141] studied the degradation of

organic substances in winery wastewater, and observed that reduction of chemical oxygen demand

(COD) under the action of O3 for acidic pH is negligible and more accelerated in neutral and

alkaline pH by the fast OH formation. Similar phenomenon has been observed by [150, 151]. But

[134] claimed that during the application of microbubbles the O3 concentration and OH exposure

27
 ACCEPTED MANUSCRIPT

in the acidic media is higher than at the basic pH. This result probably contradict with the result of

previous researchers findings of less COD reduction in acidic pH. At this state it is recommended

top further check the ambiguity in this aspect. But the existence of OH radicals in the acidic

medium could be explained by the zeta-potential properties of MBs. It is known that microbubbles

have a negative zeta-potential because of accumulation of OH ions at their interface. As it is

T
proposed by [152], the interior ozone gas of the microbubbles encounter these OH ions

IP
surrounding the microbubbles while dissolving to the surrounding water. This accumulation of

CR
OH ions acts almost as the same situation for ozone as being dissolved in a high pH even at low

pH solutions. By this mechanism the MBs can improve the OH leading to efficient degradation

US
of organic matters even in acidic pH. Despite the advantages of MBs in increasing the
AN
concentration of O3 and OH, which of course improves disinfection and waste degradation,

studies are not yet done on the effect MBs on the formation of disinfection byproducts. Similar
M

investigations are needed to confirm if the same situation happens for NBs. Further works are
ED

needed on the effect of micro NBs in O3 utilization efficiency, reactor optimization, and reduction

of temperature effect as well as efficiency improvement test of specific pollutants for different pH.
PT

6. Future scope of MB and NB technologies

CE

Micro/Nano bubble technologies are theoretically and experimentally known to be less chemical

consuming and considerable tendency of reducing size of the treatment facility. Hence, they have
AC

significant potential for design and operational cost reduction on top of their contribution as an environment

friendly technique. With this regard, its application has a significant importance and future in water

treatment because of the ability of the bubbles high mass transfer efficiency, relatively lower rising velocity,

easily tailored surface charge, free radical generation ability and improved collusion efficiency. Wide

applications of MB and NB for particle separation, disinfection and organic-matter reduction have been

anticipated via the high floatability of the bubble-particle aggregate, improvement of ozone mass transfer

28
 ACCEPTED MANUSCRIPT

and contact time, upgrading of aeration efficiency in biological wastewater treatment using bacteria, as well

as enhancement of OH radical formation for advanced oxidation. Moreover, free radical generation in the

absence of chemicals makes the future applicability of oxygen and/or ozone MB and NB for the use of

contaminant oxidation in water systems more attractive. The bursting energy of MB and improved aeration

potential of NB have also a future in membrane de-fouling by improving surface scouring and reduction of

T
sludge formation in membrane bio-reactors. Finally, it can be stated that the use of both the MBs and NBs

IP
as an efficient and low-cost technology in different water treatment processes is yet the coming challenge

CR
considering the scaling up of the systems to industrial scale. This review presented the current scope of MB

and NB definition, technology and research status in different water treatment applications. The present

US
status depicts its potential future and need of further research and engineering development to industrial

scale.
AN
Acknowledgements: This research was supported by Development of Nano-Micro bubble dual system

for restoration of self-purification and sustainable management in lake project (Project number: ERL
M

2016000200007) funded by Republic of Korea Ministry of Environment as well as the support from the
ED

Institute of Construction and Environmental engineering at Seoul National University.

PT

Reference
CE

1. Khan, K.I., Fluid dynamic modelling of bubble colum reactors, in Department of Applied Science
and Technology. 2014, Polytechnic university of Turin: Turin, Italy p. 122.
2. Hyndman, C.L., F. Larachi, and C. Guy, Understanding gas-phase hydrodynamics in bubble columns:
a convective model based on kinetic theory. Chemical Engineering Science, 1997. 52(1): p. 63-77.
AC

3. Shu, L., et al., Effect of micro-bubbles on coagulation flotation process of dyeing wastewater.
Separation and Purification Technology, 2010. 71(3): p. 337-346.
4. Ushikubo, F.Y., et al., Evidence of the existence and the stability of nano-bubbles in water. Colloids
and Surfaces A: Physicochemical and Engineering Aspects, 2010. 361(13): p. 31-37.
5. Edzwald, J.K., Dissolved air flotation and me. Water Research, 2010. 44(7): p. 2077-2106.
6. Agarwal, A., W.J. Ng, and Y. Liu, Principle and applications of microbubble and nanobubble
technology for water treatment. Chemosphere, 2011. 84(9): p. 1175-1180.
7. Xu, Q., et al., A comparative study of microbubble generation by mechanical agitation and
sonication. Innovative Food Science & Emerging Technologies, 2008. 9(4): p. 489-494.
8. Prez-Garibay, R., E. Martnez-Ramos, and J. Rubio, Gas dispersion measurements in microbubble
flotation systems. Minerals Engineering, 2012. 26: p. 34-40.

29
 ACCEPTED MANUSCRIPT

9. Wu, Z., et al., Cleaning using nanobubbles: Defouling by electrochemical generation of bubbles.
Journal of Colloid and Interface Science, 2008. 328(1): p. 10-14.
10. Terasaka, K., et al., Development of microbubble aerator for waste water treatment using aerobic
activated sludge. Chemical Engineering Science, 2011. 66(14): p. 3172-3179.
11. Ohgaki, K., et al., Physicochemical approach to nanobubble solutions. Chemical Engineering
Science, 2010. 65(3): p. 1296-1300.
12. Wu, C., et al., Generation and characterization of submicron size bubbles. Advances in Colloid and
Interface Science, 2012. 179182: p. 123-132.
13. Khuntia, S., K. Majumder Subrata, and P. Ghosh, Microbubble-aided water and wastewater
purification: a review. 2012. p. 191.

T
14. Krishna, R. and J.M. Van Baten, Scaling up Bubble Column Reactors with the Aid of CFD. Chemical

IP
Engineering Research and Design, 2001. 79(3): p. 283-309.
15. Takahashi, M., K. Chiba, and P. Li, Free-Radical Generation from Collapsing Microbubbles in the
Absence of a Dynamic Stimulus. The Journal of Physical Chemistry B, 2007. 111(6): p. 1343-1347.

CR
16. Ebina, K., et al., Oxygen and Air Nanobubble Water Solution Promote the Growth of Plants, Fishes,
and Mice. PLoS ONE, 2013. 8(6): p. e65339.
17. Parker, J.L., P.M. Claesson, and P. Attard, Bubbles, cavities, and the long-ranged attraction

US
between hydrophobic surfaces. The Journal of Physical Chemistry, 1994. 98(34): p. 8468-8480.
18. Walczyk, W. and H. Schnherr, Characterization of the Interaction between AFM Tips and Surface
Nanobubbles. Langmuir, 2014. 30(24): p. 7112-7126.
AN
19. Berkelaar, R.P., H.J.W. Zandvliet, and D. Lohse, Covering Surface Nanobubbles with a NaCl
Nanoblanket. Langmuir, 2013. 29(36): p. 11337-11343.
20. Tsuge, H., Fundamentals of microbubbles and nanobubbles. Bulletin of the society of sea water
science, 2010. 64: p. 4-10.
M

21. Parmar, R. and S.K. Majumder, Microbubble generation and microbubble-aided transport process
intensificationA state-of-the-art report. Chemical Engineering and Processing: Process
ED

Intensification, 2013. 64: p. 79-97.

22. Michel, J.-P.F.J.-M., Fundamentals of Cavitation Fluid mechanics and its applications ed. R.
Moreau. Vol. 76. 2005, United States of America: Springer Science + Business Media, Inc.
PT

23. Maoming, F., et al., Nanobubble generation and its application in froth flotation (part I):
nanobubble generation and its effects on properties of microbubble and millimeter scale bubble
solutions. Mining Science and Technology, 2010. 20: p. 1-19.
CE

24. Kim, T.-i. and M. Han, Analysis of bubble potential energy and its disinfection application and oil
washing, in Civil and Environmental Engineering Department. 2010, Seoul National University. p.
196.
25. Fan, M., et al., Nanobubble generation and its application in froth flotation (part I): nanobubble
AC

generation and its effects on properties of microbubble and millimeter scale bubble solutions.
Mining Science and Technology (China), 2010. 20(1): p. 1-19.
26. Li, X., et al., Gas-Liquid Mass Transfer Characteristics with Microbubble Aeration I. Standard
Stirred Tank. Chemical Engineering & Technology, 2016. 39(5): p. 945-952.
27. Kim, H. and M. Han, A study on the development of sub-micron bubble generator and
characterization of sub-micron bubble, in Civil and Environmental Engineering Department 2014,
Seoul National University p. 133.
28. AWWA, A.W.W.A., Water quality and Treatment. 5th ed. 1999, United States of America:
McGraw-Hill. 1163.
29. Kim, T.-i. and M. Han, Analysis of bubble potential energy and its application to disinfection and
oil washing, in Civil and Environmental Engineering 2010, Seoul National University:
Environmental Engineering Research Group.

30
 ACCEPTED MANUSCRIPT

30. Besancon, R., The Encyclopedia of Physics. 2013: Springer US.

31. Zijlstra, A.G., Acoustic surface cavitation in Physics of fluid group. 2011, Faculty of science and
technology of Twente Netherlands.
32. Kukizaki, M. and M. Goto, Size control of nanobubbles generated from Shirasu-porous-glass (SPG)
membranes. Journal of Membrane Science, 2006. 281(12): p. 386-396.
33. Tasaki, T., et al., Degradation of methyl orange using short-wavelength UV irradiation with oxygen
microbubbles. Journal of Hazardous Materials, 2009. 162(23): p. 1103-1110.
34. Yoshida, H., et al., Particle size measurement with an improved sedimentation balance method
and microscopic method together with computer simulation of necessary sample size. Advanced
Powder Technology, 2001. 12(1): p. 79-94.

T
35. Yoshida, H., et al., Particle size measurement of standard reference particle candidates with

IP
improved size measurement devices. Advanced Powder Technology, 2003. 14(1): p. 17-31.
36. Han, M., T.-i. Kim, and D. Kwak, Measurement of bubble bed depth in dissolved air flotation using
a particle counter. Journal of Water Supply: Research and Technology - Aqua, 2009. 58(1): p. 57-

CR
63.
37. Cho, S.-H., et al., Ultrasonic formation of nanobubbles and their zeta-potentials in aqueous
electrolyte and surfactant solutions. Colloids and Surfaces A: Physicochemical and Engineering

US
Aspects, 2005. 269(13): p. 28-34.
38. Xiong, Y. and F. Peng, Optimization of cavitation venturi tube design for pico and nano bubbles
generation. International Journal of Mining Science and Technology, 2015. 25(4): p. 523-529.
AN
39. Binnig, G., C.F. Quate, and C. Gerber, Atomic Force Microscope. Physical Review Letters, 1986.
56(9): p. 930-933.
40. Kim, T.I., Y.H. Kim, and M. Han, Development of novel oil washing process using bubble potential
energy. Marine Pollution Bulletin, 2012. 64(11): p. 2325-2332.
M

41. Kobayashi, H., et al. Measurement and identification of ultrafine bubbles by resonant mass
measurement method. 2014.
ED

42. Han, M.Y., Modeling of DAF: the effect of particle and bubble characteristics. Journal of Water
Supply: Research and Technology - Aqua, 2002. 51(1): p. 27-34.
43. Bui, T.T. and M. Han, Removal of Phormidium sp. by positively charged bubble flotation. Minerals
PT

Engineering, 2015. 72(Complete): p. 108-114.

44. de Rijk, S.E., G. Jaap H.J.M. aivan der, and J.G. den Blanken, Bubble size in flotation thickening.
Water Research, 1994. 28(2): p. 465-473.
CE

45. Kulkarni, A.A. and J.B. Joshi, Bubble Formation and Bubble Rise Velocity in GasLiquid Systems: A
Review. Industrial & Engineering Chemistry Research, 2005. 44(16): p. 5873-5931.
46. Han, M., et al., Effect of pressure on bubble size in dissolved air flotation. Water Science and
Technology: Water Supply, 2002. 2(5-6): p. 41-46.
AC

47. Kim, T.-i., Y.-h. Kim, and M. Han, Development of novel oil washing process using bubble potential
energy. Marine Pollution Bulletin, 2012. 64(11): p. 2325-2332.
48. Bui, T.T. and M. Han, Removal of Phormidium sp. by positively charged bubble flotation. Minerals
Engineering, 2015. 72: p. 108-114.
49. Castro, S., et al., Effect of frothers on bubble coalescence and foaming in electrolyte solutions and
seawater. International Journal of Mineral Processing, 2013. 124: p. 8-14.
50. O'Connor, C.T., E.W. Randall, and C.M. Goodall, Measurement of the effects of physical and
chemical variables on bubble size. International Journal of Mineral Processing, 1990. 28(1): p. 139-
149.
51. Sovechles, J., M., Lepage, M., R., Johnson, B., Waters, K., E., Effect of gas rate and impeller speed
on bubble size in frother-electrolyte solution. Minerals Engineering, 2016. 99: p. 133-141.

31
 ACCEPTED MANUSCRIPT

52. Laskowski, J., S., Cho, Y., S., Ding, K., Effect of frothers on bubble size and foamstability in potash
ore flotation systems. Canada Journal of chemical engineering, 2003. 81: p. 63-69.
53. Quinn, J., J., Sovechles, J., M., Finch, J., A., Waters, K., E., Critical coalesence concentration of
inorganic salt solution. Minerals Engineering, 2014. 58: p. 1-6.
54. Sovechles, J., M., Waters, K., E., Effect of ionic strength on bubble coalescence in inorganic salt
and seawater solutions. AlChE Journal, 2015. 61(8): p. 2489-2496.
55. O'connor, C., T., Randall, E., W., Goodall, C., M., Measurement of the effects of physical and
chemical variables on bubble size. International Journal of Mineral Processing, 1990. 28: p. 139-
149.
56. Castro, S., Miranda, C., Tolero, P., Laskowski, J., S., Effect of frothers on bubble colescence and

T
foaming in electrolyte solutions and seawater. International Journal of Mineral Processing, 2013.

IP
124: p. 8-14.
57. Chu, P., Waters, K., E., Finch, J., A., Break-up in formation of small bubbles: break-up in a confined
volume. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2016. 503: p. 88-93.

CR
58. Liu, S., et al., Oxidative Capacity of Nanobubbles and Its Effect on Seed Germination. ACS
Sustainable Chemistry & Engineering, 2016. 4(3): p. 1347-1353.
59. Parkinson, L., et al., The terminal rise velocity of 10100 m diameter bubbles in water. Journal of

US
Colloid and Interface Science, 2008. 322(1): p. 168-172.
60. Tomiyama, A., et al., Terminal velocity of single bubbles in surface tension force dominant regime.
International Journal of Multiphase Flow, 2002. 28(9): p. 1497-1519.
AN
61. Azgomi, F., Gomez, C., O., Finch, J., A., Correspondence of gas holdup and bubble size in presence
of different frothers. International Journal of Mineral Processing, 2007. 83: p. 1-11.
62. Finch, J., A., Glinas, S., Moyo, P., Frother-related research at McGill University. Minerals
Engineering, 2006. 19: p. 726733.
M

63. Zhou, Z., A., Egiebor, N., O., Plitt, L., R., Frother effect on bubble motion in a water column.
Canadian Metallurgical Quarterly 1992. 31: p. 11 16.
ED

64. Zhou, Z., A., Egiebor, N., O., Plitt, L., R., Frother effects on bubblemotion in a swarm. Canadian
Metallurgical Quarterly, 1993. 32: p. 89 96.
65. Takahashi, M., Potential of Microbubbles in Aqueous Solutions: Electrical Properties of the
PT

GasWater Interface. The Journal of Physical Chemistry B, 2005. 109(46): p. 21858-21864.

66. Han, M. and S. Dockko, Zeta potential measurement of bubbles in DAF process and its effect on
the removal efficiency. KSCE Journal of Civil Engineering, 1998. 2(4): p. 461-466.
CE

67. Yang, C., et al., Measurement of the Zeta Potential of Gas Bubbles in Aqueous Solutions by
Microelectrophoresis Method. Journal of Colloid and Interface Science, 2001. 243(1): p. 128-135.
68. Spanos, N. and P.G. Koutsoukos, Calculation of Zeta Potential from Electrokinetic Measurements
on Titania Plugs. Journal of Colloid and Interface Science, 1999. 214(1): p. 85-90.
AC

69. Han, M.Y., et al., The effect of divalent metal ions on the zeta potential of bubbles. Water Science
and Technology, 2004. 50(8): p. 49-56.
70. Han, M., W. Kim, and S. Dockko, Collision efficiency factor of bubble and particle (alpha bp) in DAF:
theory and experimental verification. Water Sci Technol, 2001. 43(8): p. 139-44.
71. Bui, T.T., S.-N. Nam, and M. Han, Micro-Bubble Flotation of Freshwater Algae: A Comparative
Study of Differing Shapes and Sizes. Separation Science and Technology, 2015. 50(7): p. 1066-1072.
72. Graciaa, A., et al., The -Potential of Gas Bubbles. Journal of Colloid and Interface Science, 1995.
172(1): p. 131-136.
73. Elmahdy, A., M., Mirnezami, M., Finch, J., A., Zeta potential of air bubble in presence of frothers.
International Journal of Mineral Processing, 2008. 89: p. 40-43.

32
 ACCEPTED MANUSCRIPT

74. Bueno-Tokunaga, A., Prez-Garibay, R., Matinez-Carrillo, D., Zeta potential of air bubbles
conditioned with typical froth flotation reagents. International Journal of Mineral Processing, 2015.
140: p. 50-57.
75. Najafi, A.S., et al., A novel method of measuring electrophoretic mobility of gas bubbles. Journal
of Colloid and Interface Science, 2007. 308(2): p. 344-350.
76. Okada, K., et al., Analysis of particle trajectories of small particles in flotation when the particles
and bubbles are both charged. The Canadian Journal of Chemical Engineering, 1990. 68(4): p. 614-
621.
77. Kubota, K. and G.J. Jameson, A Study of the Electrophoretic Mobility of a Very Small Inert Gas
Bubble Suspended in Aqueous Inorganic Electrolyte and Cationic Surfactant Solutions. JOURNAL

T
OF CHEMICAL ENGINEERING OF JAPAN, 1993. 26(1): p. 7-12.

IP
78. Han, M.Y., M.K. Kim, and M.S. Shin, Generation of a positively charged bubble and its possible
mechanism of formation. Journal of Water Supply: Research and Technology - Aqua, 2006. 55(7-
8): p. 471-478.

CR
79. Han, M.Y., M.K. Kim, and H.J. Ahn, Effects of surface charge, micro-bubble size and particle size on
removal efficiency of electro-flotation. Water Science and Technology, 2006. 53(7): p. 127-132.
80. Currie, B., W., Alty, T., Adsorption at awater surface. Part I. Proceedings of the Royal Society of

US
London, Series A, 1929. 122(790): p. 622-633.
81. Karraker, K., A., Radke, C., J., Disjoining pressures, zeta potentials and surface tensions of aqueous
non-ionic surfactant/electrolyte solutions: theory and comparison to experiment. Advances in
AN
Colloid and Interface Science, 2002. 96(1-3): p. 231-264.
82. Liu, S., et al., Effects of nanobubbles on the physicochemical properties of water: The basis for
peculiar properties of water containing nanobubbles. Chemical Engineering Science, 2013. 93: p.
250-256.
M

83. Laskowski, J., S., Yordan, J., L., Yoon, R., H., Electrokinetic potential of microbubbles generated in
aqueous solutions of weak electrolyte type surfactants. Langmuir, 1989. 5: p. 373-376.
ED

84. Saulnier, P., Lachaise, J., Morel, G., Graciaa, A., Zeta potential of air bubbles in surfactant solutions.
Journal Colloid Interface Science, 1996. 182(2): p. 395-399.
85. Graciaa, A., Morel, G., Saulner, P., Lachaise, J., Schechter, R., S., The zeta-potential of gas bubbles.
PT

Journal of Colloid and Interface Science, 1995. 172: p. 131-136.

86. Kim, J.Y.S., M.-G. Song, and J.-D. Kim, Zeta Potential of Nanobubbles Generated by Ultrasonication
in Aqueous Alkyl Polyglycoside Solutions. Journal of Colloid and Interface Science, 2000. 223(2): p.
CE

285-291.
87. Han, L. and M.H. Al-Dahhan, Gasliquid mass transfer in a high pressure bubble column reactor
with different sparger designs. Chemical Engineering Science, 2007. 62(12): p. 131-139.
88. Cho, S., H., Kim, J., Y., Chun, J., H., Kim, J., D., Ultrasonic formation of nanobubbles and their zeta-
AC

potential in aqueous electrolyte and surfactant solutions. Colloids and Surfaces A: Physicochemical
and Engineering Aspects, 2005. 269: p. 28-34.
89. Hecht, K., et al., Effect of Gas Density on Gas Holdup in Bubble Columns. Chemie Ingenieur Technik,
2015. 87(6): p. 762-772.
90. Lueske, J., et al., Power Draw and Gas-Liquid Mass Transfer Characteristics of a Stirred-Tank
Reactor with Draft Tube Configuration. Chemical Engineering & Technology, 2015. 38(11): p.
1993-2001.
91. Prince, M.J. and H.W. Blanch, Bubble coalescence and break-up in air-sparged bubble columns.
AIChE Journal, 1990. 36(10): p. 1485-1499.
92. Weiguo, Y., W. Jinfu, and J. Yong, Gas-liquid mass transfer in a slurry bubble column reactor under
high temperature and high pressure. Chinese Journal of Chemical Engineering, 2001. 9(3): p. 253-
257.

33
 ACCEPTED MANUSCRIPT

93. Bouaifi, M., et al., A comparative study of gas hold-up, bubble size, interfacial area and mass
transfer coefficients in stirred gasliquid reactors and bubble columns. Chemical Engineering and
Processing: Process Intensification, 2001. 40(2): p. 97-111.
94. Linek, V., M. Korda, and T. Moucha, Mechanism of mass transfer from bubbles in dispersions:
Part II: Mass transfer coefficients in stirred gasliquid reactor and bubble column. Chemical
Engineering and Processing: Process Intensification, 2005. 44(1): p. 121-130.
95. Wongsuchoto, P., T. Charinpanitkul, and P. Pavasant, Bubble size distribution and gasliquid mass
transfer in airlift contactors. Chemical Engineering Journal, 2003. 92(13): p. 81-90.
96. Camacho Rubio, F., et al., Mixing in bubble columns: a new approach for characterizing dispersion
coefficients. Chemical Engineering Science, 2004. 59(20): p. 4369-4376.

T
97. Wilkinson, P.M. and L.L. v. Dierendonck, Pressure and gas density effects on bubble break-up and

IP
gas hold-up in bubble columns. Chemical Engineering Science, 1990. 45(8): p. 2309-2315.
98. Whitman, W.G., The two film theory of gas absorption. International Journal of Heat and Mass
Transfer, 1962. 5(5): p. 429-433.

CR
99. Bouaifi, M. and M. Roustan, Bubble size and mass transfer coefficients in dual-impeller agitated
reactors. The Canadian Journal of Chemical Engineering, 1998. 76(3): p. 390-397.
100. Akita, K. and F. Yoshida, Bubble Size, Interfacial Area, and Liquid-Phase Mass Transfer Coefficient

US
in Bubble Columns. Industrial & Engineering Chemistry Process Design and Development, 1974.
13(1): p. 84-91.
101. Worden, R.M. and M.D. Bredwell, Mass-Transfer Properties of Microbubbles. 2. Analysis Using a
AN
Dynamic Model. Biotechnology Progress, 1998. 14(1): p. 39-46.
102. Ying, K., et al., Enhanced Mass Transfer in Microbubble Driven Airlift Bioreactor for Microalgal
Culture Engineering, 2013. 5: p. 735-743.
103. Stenstrom, M.K. and R.G. Gilbert, Effects of alpha, beta and theta factor upon the design,
M

specification and operation of aeration systems. Water Research, 1981. 15(6): p. 643-654.
104. Garcia-Ochoa, F. and E. Gomez, Bioreactor scale-up and oxygen transfer rate in microbial
ED

processes: An overview. Biotechnology Advances, 2009. 27(2): p. 153-176.

105. Ying, K., et al., Enhanced Mass Transfer in Microbubble Driven Airlift Bioreactor for Microalgal
Culture. Engineering, 2013. 5(9).
PT

106. Ruen-ngam, D., et al., Influence of salinity on bubble size distribution and gas-liquid mass transfer
in airlift contactors. Chemical Engineering Journal, 2008. 141(1-3): p. 222-232.
107. Takahashi, M., Base and technological application of micro-bubble and nanobubble. Material
CE

Integration 2009. 22: p. 2-19.

108. Ghadimkhani, A., W. Zhang, and T. Marhaba, Ceramic membrane defouling (cleaning) by air Nano
Bubbles. Chemosphere, 2016. 146: p. 379-384.
109. Yamasaki, K., K. Uda, and K. Chuhjoh, Wastewater Treatment Equipment and Method of
AC

Wastewater Treatment, U. patent, Editor, Editor. 2009: USA.

110. Yamasaki, K., K. Sakata, and K. Chuhjoh, Wastewater Treatment Method and WaterTreatment
System, U. patent, Editor, Editor. 2010: USA.
111. Jyoti, K.K. and A.B. Pandit, Water disinfection by acoustic and hydrodynamic cavitation.
Biochemical Engineering Journal, 2001. 7(3): p. 201-212.
112. Jyoti, K.K. and A.B. Pandit, Hybrid cavitation methods for water disinfection: simultaneous use of
chemicals with cavitation. Ultrasonics Sonochemistry, 2003. 10(45): p. 255-264.
113. Sumikura, M., et al., Ozone micro-bubble disinfection method for wastewater reuse system. Water
Science and Technology, 2007. 56(5): p. 53-61.
114. Mezule, L., et al., A simple technique for water disinfection with hydrodynamic cavitation: Effect
on survival of Escherichia coli. Desalination, 2009. 248(13): p. 152-159.

34
 ACCEPTED MANUSCRIPT

115. Matsuki, N., et al., Oxygen supersaturated fluid using fine micro/nanobubbles. International
Journal of Nanomedicine, 2014. 9: p. 4495-4505.
116. Tang, C.-C., et al., Effect of aeration rate on performance and stability of algal-bacterial symbiosis
system to treat domestic wastewater in sequencing batch reactors. Bioresource Technology, 2016.
222: p. 156-164.
117. El-Zahaby, A.M. and A.S. El-Gendy, Passive aeration of wastewater treated by an anaerobic
processA design approach. Journal of Environmental Chemical Engineering, 2016. 4(4, Part A):
p. 4565-4573.
118. Weber, J. and F. Agblevor, Microbubble fermentation of Trichoderma reesei for cellulase
production. Process Biochemistry, 2005. 40(2): p. 669-676.

T
119. Park, J.-S. and K. Kurata, Application of microbubbles to hydroponics solution promotes lettuce

IP
growth. HortTechnology, 2009. 19(1): p. 212-215.
120. Li, H., et al., Subsurface Transport Behavior of Micro-Nano Bubbles and Potential Applications for
Groundwater Remediation. International Journal of Environmental Research and Public Health,

CR
2014. 11(1): p. 473.
121. Temesgen, T., Enhancing gas-liquid mass transfer and (bio) chemical reactivity using
ultrafine/nanobubble in water and waste water treatments, in Civil and Environmental

US
Engineering. 2017, Seoul national university: Seoul, Korea.
122. Hopper, S.H. and M.C. McCowen, A floatation process for water purification. Journal of American
Water Works Association, 1952. 44(8): p. 719-726.
AN
123. Rubio, J., M.L. Souza, and R.W. Smith, Overview of flotation as a wastewater treatment technique.
Minerals Engineering, 2002. 15(3): p. 139-155.
124. Dockko, S. and M.Y. Han, Fundamental characteristics of bubbles and ramifications for the
flotation process. Water Science and Technology, 2004. 50(12): p. 207-214.
M

125. Miettinen, T., J. Ralston, and D. Fornasiero, The limits of fine particle flotation. Minerals
Engineering, 2010. 23(5): p. 420-437.
ED

126. Ahmed, N. and G.J. Jameson, The effect of bubble size on the rate of flotation of fine particles.
International Journal of Mineral Processing, 1985. 14(3): p. 195-215.
127. Yoon, R.H., Microbubble flotation. Minerals Engineering, 1993. 6(6): p. 619-630.
PT

128. Collins, G.L. and G.J. Jameson, Experiments on the flotation of fine particles: The influence of
particle size and charge. Chemical Engineering Science, 1976. 31(11): p. 985-991.
129. Teixeira, M.R., V. Sousa, and M.J. Rosa, Investigating dissolved air flotation performance with
CE

cyanobacterial cells and filaments. Water Research, 2010. 44(11): p. 3337-3344.

130. Haarhoff, J. and J.K. Edzwald, Modelling of floc-bubble aggregate rise rates in dissolved air
flotation. Water Science and Technology, 2001. 43(8): p. 175-184.
131. Fan, M., et al., Nanobubble generation and its applications in froth flotation (part II): fundamental
AC

study and theoretical analysis. Mining Science and Technology (China), 2010. 20(2): p. 159-177.
132. Tsai, J.-C., et al., Nano-bubble flotation technology with coagulation process for the cost-effective
treatment of chemical mechanical polishing wastewater. Separation and Purification Technology,
2007. 58(1): p. 61-67.
133. Zhang, F., et al., Effect of inlet ozone concentration on the performance of a micro-bubble
ozonation system for inactivation of Bacillus subtilis spores. Separation and Purification
Technology, 2013. 114: p. 126-133.
134. Khuntia, S., S.K. Majumder, and P. Ghosh, Quantitative prediction of generation of hydroxyl
radicals from ozone microbubbles. Chemical Engineering Research and Design, 2015. 98: p. 231-
239.

35
 ACCEPTED MANUSCRIPT

135. kim, J.-H., G.U. Von, and B. J.Martin, Simultaneous Prediction of Cryptosporidium parvum Oocyst
Inactivation and Bromate Formation during Ozonation of Synthetic Waters. Environmental
Science and Technology, 2004. 38: p. 2232-2241.
136. Kim, J.-H., et al., Modeling Cryptosporidium parvum oocyst inactivation and bromate in a flow-
through ozone contactor treating natural water. Water Research, 2007. 41(2): p. 467-475.
137. Larson, M.A. and B.J. Marias, Inactivation of Bacillus subtilis spores with ozone and
monochloramine. Water Research, 2003. 37(4): p. 833-844.
138. Aydogan, A. and M.D. Gurol, Application of Gaseous Ozone for Inactivation of Bacillus subtilis
Spores. Journal of the Air & Waste Management Association, 2012. 56(2): p. 179-185.
139. Han, M., W. Kim, and S. Dockko, Collision efficiency factor of bubble and particle (abp) in DAF:

T
theory and experimental verification. Water Science and Technology, 2001. 43(8): p. 139-144.

IP
140. Chen, K.K., Bathing Pool Assembly with Water Full of Nano-Scale Ozone Bubbles for Rehabilitation,
U.S. Patent, Editor. 2009: USA.
141. Lucas, M.S., et al., Ozonation kinetics of winery wastewater in a pilot-scale bubble column reactor.

CR
Water Research, 2009. 43(6): p. 1523-1532.
142. Lucas, M.S., J.A. Peres, and G. Li Puma, Treatment of winery wastewater by ozone-based advanced
oxidation processes (O3, O3/UV and O3/UV/H2O2) in a pilot-scale bubble column reactor and

US
process economics. Separation and Purification Technology, 2010. 72(3): p. 235-241.
143. Sievers, M., 4.13 - Advanced Oxidation Processes A2 - Wilderer, Peter, in Treatise on Water Science.
2011, Elsevier: Oxford. p. 377-408.
AN
144. GLAZE, W., H. WEINBERG, and J. CAVANAGH, Evaluating the formation of brominated DBPs during
ozonation. Journal-American Water Works Association, 1993. 85(1): p. 96-103.
145. Siddiqui, M.S. and G.L. Amy, Factors affecting DBP formation during ozone-bromide reactions.
Journal of the American Water Works Association, 1993: p. 63-72.
M

146. von Gunten, U., Ozonation of drinking water: Part I. Oxidation kinetics and product formation.
Water Research, 2003. 37(7): p. 1443-1467.
ED

147. Tang, G., et al., Modeling Cryptosporidium parvum Oocyst Inactivation and Bromate Formation in
a Full-Scale Ozone Contactor. Environmental Science & Technology, 2005. 23(39): p. 9343-9350.
148. Tomiyasu, H., H. Fukutomi, and G. Gordon, Kinetics and mechanism of ozone decomposition in
PT

basic aqueous solution. Inorganic Chemistry, 1985. 24(19): p. 2962-2966.

149. Sehested, K., et al., The primary reaction in the decomposition of ozone in acidic aqueous solutions.
Environmental Science & Technology, 1991. 25(9): p. 1589-1596.
CE

150. Poznyak, T., et al., Effect of pH to the Decomposition of Aqueous Phenols Mixture by Ozone. Journal
of the Mexican Chemical Society, 2006. 50(1).
151. Yang, D.-m., et al., Effects and mechanism of ozonation for degradation of sodium acetate in
aqueous solution. Water Science and Engineering, 2012. 5(2): p. 155-163.
AC

152. Takahashi, M., et al., Effect of Microbubbles on Ozonized Water for Photoresist Removal Journal
of Photopolymer Science and Technology 2015. 28(2).

36
 ACCEPTED MANUSCRIPT

Graphical abstract

T
IP
CR
US
AN
M
ED
PT
CE
AC

37
 ACCEPTED MANUSCRIPT

Highlights
Recent developments trends and future prospects in the bubble technology.
Basic properties of bubble and their high dependence on bubble size variation.
Micro and nano bubble application in aeration, flotation & disinfection processes.

T
IP
CR
US
AN
M
ED
PT
CE
AC

38