Journal of Hazardous Materials 235236 (2012) 152158

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Journal of Hazardous Materials

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Removal of blue-green algae using the hybrid method of hydrodynamic

cavitation and ozonation
Zhilin Wu a,b,, Haifeng Shen a, Bernd Ondruschka b, Yongchun Zhang a, Weimin Wang a, David H. Bremner c
a

Nanjing Institute of Environmental Sciences of the Ministry of Environmental Protection of China, Jiangwangmiaostr. 8, 210042 Nanjing, China1
Institute for Technical Chemistry and Environmental Chemistry, Friedrich Schiller University of Jena, Lessingstr.12, D-07745 Jena, Germany2
c
School of Contemporary Sciences, University of Abertay Dundee, 40 Bell Street, Dundee DD1 1HG, United Kingdom3

h i g h l i g h t s





Hydrodynamic cavitation was induced by suction and extrusion process.

Synergistic effect of cavitation and ozonation on removal of microalgae was found.
Suction-cavitation signicantly promotes ozonation-removal of blue-green algae.
Ozone utilization is obviously raised to reduce the time and energy consumption.

a r t i c l e

i n f o

Article history:
Received 24 December 2011
Received in revised form 11 July 2012
Accepted 16 July 2012
Available online 25 July 2012
Keywords:
Removal of algae
Microcystis aeruginosa
Hydrodynamic cavitation
Ozonation
Synergistic effect

a b s t r a c t
A suspension of Microcystis aeruginosa (30 g L1 chlorophyll a) was circulated in a hydrodynamic cavitation device and ozone was introduced at the suction side of the pump. The removal of algae over 10 min
using hydrodynamic cavitation alone and ozone alone is less than 15% and 35%, respectively. The destruction of algae rises signicantly from 24% in the absence of the orice to 91% with the optimized orice
on 5 min of processing using hydrodynamic cavitation along with ozone (HC/O3 ) and the utilization of
ozone increases from 32% to 61%. Interestingly, the suction process is more effective than the extrusion
method (positive pressure) and the optimal bulk temperature for algal elimination was found to be 20 C.
Increasing the input concentration of ozone is favorable for the removal of algae but leads to a greater
loss of ozone and a decrease in the utilization of ozone. Under the optimal conditions, the algal cells and
chlorophyll a are completely destroyed in 10 min by use of the hybrid method.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The discharge of excessive nitrogen-containing and phosphatecontaining nutrients into the natural environment has lead to
increased blue-green algal blooms in waterbodies worldwide since
1950. In order to overcome this form of pollution, many technologies have been applied in order to remove nitrogen-containing
and phosphate-containing pollutants at sewage treatment plants.
To date, the quality of most natural waters in many devel-

Corresponding author at: Nanjing Institute of Environmental Sciences of the

Ministry of Environmental Protection of China, Jiangwangmiaostr. 8, 210042 Nanjing, China. Tel.: +86 25 85287116; fax: +86 25 85411611.
E-mail addresses: zhilin.wu@uni-jena.de, wzhilin@hotmail.com (Z. Wu),
d.bremner@abertay.ac.uk (D.H. Bremner).
1
Tel.: +86 25 85287116; fax: +86 25 85411611.
2
Tel: +49 3641 948413; fax: +49 3641 948402.
3
Tel.: +44 1382 308667.
0304-3894/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.07.034

oped countries has been improved from a decidedly eutrophic

to a mesotrophic concentration [1,2]. However, algal blooms are
increasingly severe in many developing countries [3,4] and it is
necessary to remove nutrients, as well as algae, from water courses
to ensure an adequate supply of drinking water, clean water for
shing and for use in industrial production.
The number of eutrophic lakes in China has increased rapidly
over the last 30 years and currently there are many instances of
algal blooms observed in most large Chinese lakes [5]. The severe
algal blooms cover the water surface and prevent photosynthesis and gas exchange in the water bodies and consequently the
concentration of dissolved oxygen in water decreases rapidly. This
not only causes the death of aquatic plants and animals, resulting
in ecological disasters, but also seriously affects the aquaculture,
tourism and the lives of people living around the lakes and causes
huge economic losses [6,7]. Moreover, the harmful algal blooms
often produce higher levels of algal toxins and musty-odorous compounds which pose serious threats to the safety of drinking water
and human health [7,8].

Z. Wu et al. / Journal of Hazardous Materials 235236 (2012) 152158

In theory, algal blooms can be controlled, but it is difcult to

nd a low-cost method which does not produce secondary pollution. Chemical, mechanical, biological, ecological, and occulation
treatment of algal blooms have been explored, with clay coagulation and chemical technology being the most commonly used
techniques. Clay coagulation is based on the occulation principle
and being a low-cost treatment has aroused great interest, but the
efciency of traditional clay coagulation is quite low and requires a
large amount of clay to be effective. For a large area of algal blooms,
hundreds or thousands of tons of clay may be added to the natural
water system [9,10]. In addition, the added occulants or coagulants, e.g. Al2 (SO4 )3 or Al(OH)3 , are potentially harmful to the water
ecology and the process does not deal successfully with removal of
algal toxins. As a result the widespread use of coagulation or occulation methods has not been adopted due to inefciency, ecological
safety, or operating costs.
Chemicals, such as soda-lime, alum, chloramine, chlorine gas,
calcium hypochlorite and copper sulfate along with a combination
of air agitation and mechanical ltration have been used to remove
algae since the 1930s [1113]. However, most of these algaecides
are potentially harmful to the water ecology and application to
large bodies of water is not recommended. Consequently, in order
to avoid negative ecological consequences, ozone was introduced
in the 1980s [1418].
Ozone is a very strong oxidant (2.08 V oxidation potential) [19]
and is a powerful disinfectant resulting in oxidation of organic compounds in the cell membranes of microorganisms, causing rupture
of the membranes and affecting cell viability [20]. Due to damage
of the cell walls during the ozonation of Microcystis aeruginosa cellular cytoplasm, intracellular microcystins and volatile organics are
released from the cells [21]. Moreover, ozonation is very effective
in removing microcystins as well as musty-odorous compounds
[2225]. However, ozone treatments are often limited by the mass
transfer of ozone into water, thus novel diffusors such as micro
bubblers and ejectors were developed [26,27].
Cavitation is the formation and then immediate implosion of
cavities in a liquid, which is subjected to rapid changes of pressure.
Acoustic cavitation is driven by ultrasound while hydrodynamic
cavitation can occur in control valves, pumps, propellers and
impellers. During cavitational collapse, these localized hot spots
have temperatures of roughly 5000 C, pressures of 500 atmospheres and lifetimes of a few microseconds [28] producing potent
oxidants, such as the hydroxyl radical and H2 O2 [29]. Shock waves,
micro-jets and turbulence induced by cavitation enhance the volumetric mass transfer coefcient [26,30,31] and an ejector system
was found to be 9-times more effective than a simple bubble column [26].
In addition to the enhancement of mass transfer, shock waves
from cavitation in liquidsolid slurries produce high-velocity interparticle collisions, the impact of which is sufcient to melt
most metals [28]. Thus, ultrasonic irradiation effectively inhibited
cyanobacterial proliferation [32], rapidly destroyed chlorophyceae
[33] and prevented bloom formation in water [34]. The mechanism
was attributed mainly to the mechanical damage to the cell structures caused by cavitation [32,35]. In addition to disrupting the gas
vesicles, sonication was also found to disturb the cell cycle and cell
division and this growth inhibition by ultrasonic radiation was not
considered to result from free radical production [36]. Also, jet cavitation effectively inhibited the growth of Microcystis aeruginosa
where the inhibition strongly depended on the hydraulic characteristics of the cavitation tube, inlet pressure, cavitation number,
light and different algal concentrations [37]. However, it should
be noted that the cavitational process also caused the release of
microcystins into the water [38,39].
While the physical, chemical and biological effects of a combination of acoustic cavitation and ozonation have been investigated

153

recently, little is known about the consequences of a combination of hydrodynamic cavitation and ozonation (HC/O3 ) which
is a novel process for oxidative degradation of organic pollutants and disinfection of microorganisms. The synergistic processes
of cavitation and ozonation reduced to half or one-third the
required concentration of ozone for disinfection of bore well
water, the toxic by-products were eliminated and the cost
was reduced by decreased ozone usage [20,40]. It was also
found that a turbulent jet ow ozone contactor enhanced the
degree of sludge reduction while consuming less energy [31].
In our previous study, the suction-cavitation process considerably enhanced the ozonation of phenol with rate constants for
the zero-order kinetics of simple ozonation and the combined
method being 0.018 and 0.028 min1 , respectively, and the utilization of ozone was signicantly improved by the suction-cavitation
[41].
Algaecide technology, involving a combination of hydrodynamic
cavitation and ozonation can be considered as a green technology without secondary pollution. Hydrodynamic cavitation alone
produces cavitation bubbles, generating strong turbulence during
the collapsing of bubbles and a large number of small vortices are
induced in the ow eld accompanied by high pressure pulses,
micro jets and shock waves. These mechanical forces affect the
micro-organisms by damaging the cell wall rendering the injured
algae more sensitive to ozone treatment. Additionally, due to the
physical effects caused by cavitation ozone is well dispersed in
water and oxidizing species such as oxygen atoms, OH radicals,
and the dissolved ozone destroy the algal cells. The current work
describes the combined effect of hydrodynamic cavitation and
ozone on the removal of algae from water.
2. Materials and methods
2.1. Cultivation of algae
Microcystis aeruginosa was provided by the Institute of Hydrobiology of the Chinese Academy of Sciences. The Microcystis
aeruginosa suspension was cultured and used in experiments
according to the method of Ichimura [42]. The culture medium
was added to a ask (5 L), which was sealed with cotton wool
and wrapped in brown paper. The culture medium was sterilized
for 30 min at 120 C in an autoclave and after cooling the culture medium was inoculated with Microcystis aeruginosa and was
cultured in a GHP-250 light incubator (Shanghai Scientic Shanfa
Instruments Co., Ltd.) with a light intensity of 3500 lux at 25 C
using a lightdark ratio of 14:10 h and the asks were manually
shaken 34 times each day. The variation in the algal density was
observed using an XSP-8C biomicroscope (Shanghai Precision Scientic Instrument Co., Ltd.)
The algal cells were counted using a hemacytometer [43], which
has 9 large squares in the counting chamber where the middle
square is the eld for counting algal cells. This area is 1 mm2
(1 mm 1 mm), including 400 grids, in which 80 (16 5) grids are
selected to be counting grids and the depth is 0.1 mm. Thus in order
to estimate the number of algal cells it is necessary to multiply by
10 to get content of 1 mm3 . After appropriate dilution, the algal
suspension was added to the counting chamber and the number of
living Microcystis aeruginosa cells was counted using a microscope.
The algal density was calculated from Eq. (1):
=

v
80

400 104 f

(1)

where  is the algal density (cells mL1 );  is the algal counts in 80

counting areas; 400 is the number of grids; 104 is the conversion
factor for the volume; and f is the dilution factor.

154

Z. Wu et al. / Journal of Hazardous Materials 235236 (2012) 152158

2.3. Ozone generation

Ozone was generated using a WH-H-Y5 Ozonizer (Nanjing
Aohuan Science and Technology Industrial Co., Ltd.) controlled by a
JW-5 SKVA electronic AC voltage stabilizer (Suzhou Tongda Instrument Factory). The oxygen ow was set at 0.5 L min1 and any
residual unreacted ozone was absorbed using two wash cylinders
connected in series with 250 mL of 0.1 M solutions of KI in each.
Ozone was passed into the system with the input voltages of 190,
205, and 220 V. The inlet and outlet ozone concentrations were
determined by the iodometric titration procedure as described in
the standard method [44]. The ozone yields with the three voltages
were found to be 1.9, 2.0 and 2.3 mg min1 , respectively.
The utilization of ozone was calculated using Eq. (3):
U=

Q Q 
r
0
Q0

100%

(3)

where U is the percentage utilization of ozone; Qr is the quantity of

ozone in the outlet, and Q0 is the input quantity of ozone.
2.4. Typical runs

Fig. 1. Bench scale device for creating hydrodynamic cavitation.

The percentage removal of algae (R) is calculated according to

Eq. (2):
R=

p p 
t
0
p0

100%

(2)

where t is the algal density after treatment and 0 is the initial

algal density.
Chlorophyll in various forms is bound within living cells of photosynthetic organisms, such as phytoplankton and cyanobacteria
(blue-green algae). Chlorophyll a was detected with a Multiparameter Water Quality Monitor (YSI 6600, Ohio, USA) using
irradiation of 435470 nm. For eld measurements, in situ uorimeters induce chlorophyll to uoresce by shining a beam of light
of the appropriate wavelength into the water and the resulting
higher wavelength light which is emitted is measured.
2.2. Device for creating hydrodynamic cavitation
A bench scale device for creating hydrodynamic cavitation
(HC-device) was constructed and is shown in Fig. 1. The device consists of a centrifugal pump, a suction- or extrusion-orice, a heat
exchanger, a water tank, three manometers, a ow meter and some
connecting pipes. All of the contacting materials are composed of
stainless steel (SS316).
The small 1.5 kW centrifugal pump (SW25-180 with an electric
motor; 2900 rpm, Y90S-2, Nanjing, China) operated at 0.10.6 MPa
with a maximal ow of 1980 L h1 . The working volume with
connection pipes (20 mm ID) of the system was 1.75 L and the temperature of the bulk liquid was kept constant by a cooling circulator
and a heat exchanger. An orice plate (20 mm ID; 1 mm thickness)
with various single-holes (5, 10, or 12 mm) was placed at the inlet
and outlet of the pump as required. The cavitation was induced by
suction or extrusion and the extent of cavitation was controlled by
the orice diameter. The suction, extrusion and downstream pressures were measured by the manometers and the ow rates were
determined using an external ow meter, as shown in Fig. 1.

The suction process: The algal suspension (1.75 L;

1.7 106 cells mL1 Microcystis aeruginosa, and 30 g L1 chlorophyll a) was introduced into the device and was sucked by the
pump through the restriction hole at the suction side (the suction
orice) with velocities of 2.910.2 m s1 controlled by the diameter
of suction orice. The pressures at the suction side of the pump
varied from 0.063 to 0.095 MPa depending on the diameter
of the suction orice. The temperature of the algal suspension
increased from 17 to 20 C within 90 s but then stabilized due to
external cooling.
The extrusion process: an orice plate with various single holes
(5, 10, or 12 mm) was positioned at the pump outlet. The same
algal suspension as above (1.75 L) was circulated by the pump with
velocities of 3.011.0 m s1 controlled by the diameter of extrusion
orices. The upstream pressures at the extrusion orices varied
from 0.118 to 0.284 MPa depending on their diameter and the
downstream pressures were measured at 0.0050.037 MPa.
Ozone-containing gas (0.5 L min1 ; 1.9 mg min1 ozone) was
passed into the algal suspension at 20 C in the HC-device and KI
solutions were used to absorb the excess ozone in the exhaust gases
from the HC-device in order to calculate the utilization of ozone, as
shown in Fig. 1. Identical experiments were carried out by passing
ozone into 4-in-line gas wash cylinders (GWC).
A sample (200 mL) of algal suspension was periodically removed
from the system and the content of chlorophyll a was determined
before being returned to the water tank after a measurement time
of <1 min. Also, aliquots (2 mL) of the processed suspension were
removed with an airtight syringe and the number of living Microcystis aeruginosa cells was determined using the bio-microscope.
The percentage removal was calculated as a function of treatment
time and all data are the average of two separate experiments.
3. Results and discussion
3.1. Optimization of orice plates
Firstly, the effect of orice diameter on the removal of algae
under suction and extrusion conditions was investigated in the
absence of ozone. Orices with diameters of 5, 10 and 12 mm were
used and 1.75 L of algal suspension (1.7 106 cells mL1 Microcystis aeruginosa) was processed at 20 C for 20 min. The percentage
removal of algae showed an increase with the orice diameter and
removal with the same orice was slightly higher under suction
than that under extrusion indicating that the impetuous vortex

Z. Wu et al. / Journal of Hazardous Materials 235236 (2012) 152158

155

1.00

algal density
chlorophyll a

0.80

For algal density: C/C

t

= e -0.4946 t

R2 = 0.9309

Ct /C0

0.60

For chlorophyll a: C t/C 0 = e -0.4917 t

0.40

R2 = 0.9842

0.20

0.00
0.0

2.0

4.0

6.0

8.0

10.0

reaction time [min]

Fig. 2. Removal of algae and chlorophyll a using the combination of ozonation and
hydrodynamic cavitation (1.75 L of 1.7 106 cells mL1 Microcystis aeruginosa suspension, ozone 1.9 mg min1 , 20 C, 12 mm orice, hydrodynamic cavitation driven
by suction).

dominates the process. The highest values of algae removal after

20 min of processing were 20% at 0.063 MPa (by suction) and 13%
at 0.118 MPa (by extrusion) when using the 12 mm orice. Suslick
et al. [45] indicated that the resistance of a turbulent ow to cavitation is given by its cavitation number , which is calculated as
shown in Eq. (4):
=

pd pv
pu pd

(4)

where pd , pu , and pv are the downstream, upstream, and vapor

pressures, respectively.
Cavitation inception generally occurs at  = 1 and there are signicant cavitational effects at  values of less than 1. However,
cavitation can also occur at a higher cavitation number possibly
due to the presence of dissolved gases or some impurities in the
liquid medium [46].
In terms of Eq. (4), the cavitation numbers are calculated to
be 0.03, 0.08, and 0.54 with the 5, 10, and 12 mm orices under
suction conditions and are 0.01, 0.06, and 0.43 under extrusion,
respectively. Regardless of suction or extrusion, some hydrodynamic cavitation occurs with the 5, 10 and 12 mm orices, but
turbulent ow and cycle number are higher with 12 mm orice
so greater removal of algae is seen with this orice. The higher
cavitation number expresses less cavitation intensity and higher
turbulence and so the comparison of cavitation numbers between
the suction and the extrusion process indicates that turbulence
obviously promotes the destruction of algal cells under the suction
process.
Secondly, the algal suspension (1.75 L; 1.7 106 cells mL1
Microcystis aeruginosa) was treated in the presence of ozone
(0.5 L min1 of gas-ow and 1.9 mg min1 ozone input) with the
HC-device at 20 C. As seen in Fig. 2, the removal of algae by
ozonation assisted by hydrodynamic cavitation follows rst-order
kinetics and both of the rate constants for algal density and chlorophyll a are very similar (0.495 and 0.492 min1 ) implying that
chlorophyll a is destroyed at the same time as the algal cells. Consequently, only algal density is used to measure the processing effect
in subsequent studies and the destruction of algae using HC/O3 with
various orice plates and locations for 5 min are shown in Fig. 3.
The percentage removal of algae is much higher on ozonation
than in the absence of ozone. The removal increases with the
orice diameter under both suction and extrusion conditions.
Remarkably, 91% of the algae were destroyed using the HC/O3

Fig. 3. Comparison of removal of algae and utilization of ozone with various orice
plates and positions using the hybrid method for 5 min (1.75 L; 1.7 106 cells mL1
Microcystis aeruginosa suspension, ozone 1.9 mg min1 , 20 C).

system under suction and 63% by extrusion with the 12 mm orice

in 5 min. However, on ozonation in the absence of any orice plate
only 24% of algal removal was observed. At the same time, the
utilization of ozone increases with the higher removal of algae
indicating that hydrodynamic cavitation obviously increased the
destruction of the algae. The enhanced order of effectiveness is
consistent with that seen with hydrodynamic cavitation alone.
As previously discussed, the larger aperture of the 12 mm orice
plate induces higher turbulent ow and cycle number, which leads
to better diffusion and higher solubility of ozone, as well as more
frequent high-velocity collisions among oxidants and algal cells.
In our previous study, suction also enhanced the chemical and
physical effects of hydrodynamic cavitation where the decomposition of chloroform was signicantly better with suction compared
to extrusion with the same pump [47]. The increased effect of
suction-cavitation on the ozonation of phenol has also been demonstrated and the utilization of ozone is signicantly improved by
suction-cavitation [41]. Therefore, it is concluded that the enhanced
effects of HC/O3 on the algal elimination is based on the physicochemical consequences of the combination of hydrodynamic
cavitation and ozone.
3.2. Effect of temperature
The solubility of ozone in water decreases with increasing temperature [48] but the reaction of algae with ozone is enhanced at
higher temperature [49]. More importantly, the temperature of the
bulk liquid also inuences the formation and collapsing intensity
of hydrodynamic cavitation [45], thus affecting the dispersion and
decomposition of ozone in water and the formation of OH radicals.
The effect of temperature on the removal of algae over 5 min using
the 12 mm suction orice with ozonation is shown in Fig. 4 and
it can be seen that the optimal temperature is 20 C although the
differences in destruction are not large.
The percentage removal decreases with increasing temperature
when the temperature is over 20 C, due to the rise in the vapour
pressure of water with the higher temperatures which attenuates the efcacy of cavitational collapse and dispersion of ozone.
Meanwhile, the increasing temperature facilitates the escape of
ozone from the water. However, the removal of algae increases
with higher temperature below 20 C, since the increasing temperature enhances the reaction of algae with ozone. Furthermore, the
amount of ozone used (61%) is highest at 20 C but is only 37% at

Z. Wu et al. / Journal of Hazardous Materials 235236 (2012) 152158

100

120

90

100

removal of algae [%]

percentage [%]

156

80
70
60
50

80
60
40

HC/O3
O3
HC

20

40

removal of algae
utilization of ozone

0
0

30
10

15

20

25

30

35

temperature of algal suspension [C]

Fig. 4. Effect of temperature on removal of algae and utilization of ozone (1.75 L;
1.7 106 cells mL1 Microcystis aeruginosa suspension, with ozone 1.9 mg min1 for
5 min, hydrodynamic cavitation driven by suction).

30 C. Due to the rising temperature, the amount of dissolved ozone

in water decreases, resulting in increased escape of ozone from the
Microcystis aeruginosa suspension resulting in a diminution in the
utilization of ozone.
3.3. Effect of input concentration of ozone
The input voltage of the ozonizer was altered (190, 205, or 220 V)
and consequently the ozone concentration in the input gas was
found to be 1.9, 2.0, 2.3 mg min1 , respectively and the effects of the
various concentrations were investigated with the optimal 12 mm
suction orice. The suspension of Microcystis aeruginosa (1.75 L;
1.7 106 cells mL1 ) was circulated for 5 min at 20 C and over 90%
of algae were destroyed in all of the three cases, but the highest
value was achieved with the 220 V input voltage with the other
two voltages being similar. However, the utilization of ozone was
highest (61%) at the input voltage of 190 V (1.9 mg min1 ozone)
compared with 57% and 51% with 205 V and 220 V. Thus, the optimal conditions for the destruction of algae are at 190 V where the
amount of ozone used is highest.
In short, a higher concentration of ozone is favorable for algal
elimination, but leads to a greater loss and lower utilization of
ozone.
3.4. Synergistic effect of hydrodynamic cavitation and ozonation
A series of 4 gas-wash-cylinders containing suspensions of
Microcystis aeruginosa (450 mL, 450 mL, 450 mL, and 400 mL with
1.7 106 cells mL1 in each) was set up, with a fth cylinder containing a solution of KI (250 mL of 0.1 mol L1 ). In order to overcome
the water pressure caused by the gas wash cylinders, the gas ow
rate was adjusted to 1 L min1 and when with an input voltage of
190 V was used the ozone yield was 3.1 mg min1 . This concentration is considerable higher than the 1.9 mg min1 used when the
gas ow was 0.5 L min1 in the hydrodynamic cavitation device.
The destruction of the algae using the 4-tandem gas wash cylinders
was found to be 35% in 10 min and still only 90% even after 60 min
processing which is much less effective than observed previously
with HC-device, possibly due to the low value (28%) of ozone utilization. Interestingly, the removal of algae is also not ideal with
hydrodynamic cavitation alone where the value achieved was only
31% in 60 min.
In order to investigate the synergistic effect of hydrodynamic
cavitation and ozonation, a comparison of (a) hydrodynamic

20

40

60

80

reaction time [min]

Fig. 5. Synergistic effect of hydrodynamic cavitation and ozonation on removal of
algae (1.75 L of 1.7 106 cells mL1 Microcystis aeruginosa suspension, 20 C, 12 mm
orice). HC, hydrodynamic cavitation driven by suction; O3 , ozonation; and HC/O3 ,
ozonation with hydrodynamic cavitation driven by suction.

cavitation driven by suction alone, (b) ozone treatment using

the 4-tandem gas-wash-cylinders (GWC) and (c) hydrodynamic
cavitation/ozone for the destruction of algae was performed. As
shown in Fig. 5, hydrodynamic cavitation alone and by ozone treatment using the GWC destroyed only 15% and 35%, respectively,
of algae in 10 min but 99% were killed using the combination of
hydrodynamic cavitation and ozone. Furthermore, the amount of
ozone used increased from 28% in the GWC to 61% in the hydrodynamic cavitation device and the treatment time was signicantly
shortened, the HC/O3 method was much more efcient, and a 95%
reduction in ozone usage was observed.
The synergistic effect of ozonation and cavitation along with
ozonation in algal elimination is attributed to the following:
(1) The mass transfer of ozone into aqueous solutions is enhanced
by cavitation [26,30,31] and also increases the rate of penetration of ozone into the microorganisms [50,51].
(2) The formation of more active species, such as OH radicals and
nascent oxygen, by the decomposition of ozone is accelerated
by cavitation processes in aqueous solutions [20,40,5254].
The oxidants formed can attack organic compounds in the cell
membranes of the microorganisms, which result in the rupture
of the membranes, affecting the cell viability and thus disinfection is achieved.
(3) The disaggregation of ocs of microorganisms is promoted by
cavitation so that the cells are more easily ruptured [51].
(4) The cells, injured by ozonation, may be more fragile to the
mechanical stress induced by cavitational collapse and alternatively, cells damaged by cavitation may be more sensitive to
the toxic ozone.
Ozone has a higher efciency for algal elimination compared with other strong oxidants. Treatment of algae with ozone
(3 mg L1 ) showed a 76% destruction in 5 min, while for potassium
permanganate (3 mg L1 ) it was 89% over 30 min and hydrogen peroxide (100 mg L1 ) only showed a 50% reduction in the
same time [55]. In addition, conventional coagulation with alum
[Al2 (SO4 )3 18H2 O] is still the main treatment process for algal
eradication, but the released toxins are still present [56]. The pretreatment with ozone specically enhances the coagulation and
oatation process for the removal of algae and its toxins [14,57,58].
The combination of hydrodynamic cavitation and ozonation has
produced excellent results for algal elimination and this process is
a promising technology for algal removal with high efciency.

Z. Wu et al. / Journal of Hazardous Materials 235236 (2012) 152158

4. Conclusion
In summary, the enhanced effects of hydrodynamic cavitation
in conjunction with ozone for the removal of Microcystis aeruginosa
have been demonstrated and the optimum diameters and positions
of the restriction orice, the input concentration of ozone and temperature have been established. Compared to less than 15% removal
of algae by hydrodynamic cavitation and 35% on ozone treatment,
the destruction of algae reached 99% using the combined method of
hydrodynamic cavitation and ozonation over the same time period
and the utilization of ozone increased exponentially. Thus, as a
result of the considerable reduction of ozone usage and treatment
time, and the algaecide efciency of the combined HC/O3 method
this new hybrid process is a major improvement on conventional
ozonation systems. Future, work will try to establish the synergistic mechanisms of hydrodynamic cavitation and ozonation on the
destruction of algae.
Acknowledgements
This work was supported by the Ministry of Science and Technology of China as part of the International Scientic and Technical
Cooperation Program (2010DFB93700) and by the Federal Ministry
of Education and Research of Germany (BMBF) as part of the International Cooperation in Education and Research (CHN09/013).
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