Journal of Environmental Management 253 (2020) 109655

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Journal of Environmental Management

journal homepage: http://www.elsevier.com/locate/jenvman

Research article

Ozone combined with ceramic membranes for water treatment: Impact on

HO� radical formation and mitigation of bromate
Khaled Ibn Abdul Hamid a, b, Peter J. Scales c, Sebastien Allard d, Jean-Philippe Croue d,
Shobha Muthukumaran a, b, Mikel Duke a, *
a
Institute for Sustainable Industries & Liveable Cities, Victoria University, PO Box 14428, Melbourne, VIC, 8001, Australia
b
College of Engineering and Science, Victoria University, PO Box 14428, Melbourne, VIC, 8001, Australia
c
Department of Chemical Engineering, The University of Melbourne, Parkville, VIC, 3010, Australia
d
Curtin Water Quality Research Centre, Curtin University, GPO Box U1987, Perth, WA, 6845, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: The beneficial effect of combining ozone with ceramic membrane filtration (CMF) to enhance membrane flux
Ceramic membrane performances during water treatment (e.g., wastewater and drinking water) could be related to the formation of
Ozone hydroxyl (HO�) radicals from the interaction of ozone with ceramic membrane. To explore this effect, para-
pCBA
chlorobenzoic acid was used to probe HO� radical activity during a combined ozone/CMF process using a
Hydroxyl radical
Bromate formation
0.1 μm pore size membrane supplied by Metawater, Japan. Tests were then extended to explore the impact on
bromate formation downstream CMF, a well-known undesirable by-product from ozone use in water treatment.
Ozone reduction by the membrane and its module appeared to be more associated with physical degassing, but a
noticeable formation of HO� radicals was observed during the interaction of ozone with the ceramic membrane.
CMF treatment of ozonated potable water containing bromide showed a reduced bromate formation of 50%
when the water was recirculated to the filtration module containing the ceramic membrane, compared to the
experiment performed with an empty module. Single pass experiments showed bromate mitigation of around
10%. The mitigation of bromate formation was attributed to reduced overall ozone exposure by deagassing ef­
fect, but also potentially from suppression of the oxidation of Br and HOBr/BrO to BrO3 due to the catalytic
degradation of ozone via a HO� radical pathway.

1. Introduction preceded by more aggressive oxidative environments such as ozone

Most applications of membrane filtration utilise polymeric mem­
branes. They are very reliable and cost effective. However, some ap­
plications require a more chemically resilient, longer life and high
physical integrity membrane and ceramic membranes are useful to this
need (Hausmann et al., 2013). The material robustness of ceramic
membranes permits operation under high pressure, temperature and
operating flux whilst still retaining polymeric style rejection character­
istics (Lehman and Liu, 2009). However, like any membrane process,
ceramic membrane performances are improved with
suitable pre-treatment in order to manage fouling and maintain long
term operation. For water treatment applications, ceramic membranes
may be used in conjunction with conventional pre-treatments such as
coagulation, but the uniquely inert material structure allows them to be
(Karnik et al., 2005). Ozone oxidizes electron-rich compounds con­
taining carbon-carbon double bonds, activated aromatic systems and
non-protonated amines (von Gunten, 2003a). This in turn has a powerful
effect to remove colour, taste and odor in drinking water production.
The widespread application of ozone to secondary effluent (SE) is more
limited (Oneby et al., 2010).
The chemical action of ozone on water is well known to be compli­
mentary to physical separation on membranes whereby the combined
process of ozonation and ceramic membranes has been shown to offer
a several advantages. Schlichter et al. (2004) found that a minimum
concentration of 0.05 mg O3/L led to stable high permeate fluxes during
ceramic microfiltration (MF) and ultrafiltration (UF) of river water
without back-flushing (Schlichter et al., 2004). For wastewater recy­
cling, ozone and coagulation were also observed to lead to higher

* Corresponding author.
E-mail addresses: Khaled.ibnabdulhamid@live.vu.edu.au (K. Ibn Abdul Hamid), peterjs@unimelb.edu.au (P.J. Scales), S.Allard@curtin.edu.au (S. Allard), Jean-
Philippe.Croue@curtin.edu.au (J.-P. Croue), Shobha.muthukumaran@vu.edu.au (S. Muthukumaran), Mikel.duke@vu.edu.au (M. Duke).

https://doi.org/10.1016/j.jenvman.2019.109655
Received 2 September 2018; Received in revised form 18 September 2019; Accepted 28 September 2019
Available online 22 October 2019
0301-4797/© 2019 Published by Elsevier Ltd.
K. Ibn Abdul Hamid et al.
sustainable ceramic MF fluxes when considered as a pre-treatment to
RO, where further benefits such as reduced RO biofouling were observed
(Myat et al., 2018). Kim et al. (2008) showed that their hybrid ozona­
tion–ceramic membrane system significantly reduced membrane fouling
and fouling behaviour was strongly dependent upon ozone concentra­
tion and hydrodynamic conditions (Kim et al., 2008). Park et al. (2012)
investigated the characteristics of natural organic matter (NOM) treated
by a hybrid ozone/ceramic membrane process. Changes in permeate flux
against filtration time were observed for a cross flow membrane filtra­
tion system at a flux of 44 L/m2⋅h. A noticeable flux increase (25%) was
observed after ozone pre-treatment. The reduction in fouling was
attributed to the reaction of molecular ozone and/or HO� radicals
generated by ozone decomposition with NOM (Park et al., 2012). Karnik
et al. (2005) investigated samples taken from Lake Lansing (Haslett,
Michigan). The permeate flux through a titania coated ceramic mem­
brane was found to be significantly affected by both ozonation and the
pH of the feed water in the system. The effect of ozone was attributed to
the formation of HO� or other radicals at the membrane surface that
reduced the extent of membrane fouling. Lehman and Liu (2009) studied
the effect of ozonation and ceramic membrane on the SE of a pilot plant
located in Chino, California. They found that ozone treatment was
effective in degrading colloidal NOM which was likely responsible for
the majority of membrane fouling (Lehman and Liu, 2009).
Recently, Wei et al. (2016) investigated the hybrid process of in-situ
ozonation with ceramic UF membrane for the treatment of algal-rich
water (Wei et al., 2016). It was observed that in-situ ozonation can
effectively mitigate membrane fouling by forming a more porous and
thinner cake layer. Moreover, in-situ ozonation can alleviate membrane
pore blocking by inducing accelerated organics degradation within the
membrane pores. Song et al. (2017) compared the pre-ozonation and
in-situ ozonation on mitigation of ceramic UF membrane fouling caused
by alginate (Song et al., 2017). It was concluded that, in-situ ozonation
with ceramic membrane catalyzed ozone decomposition with increased
generation of HO� radicals resulting in alleviated reversible and irre­
versible fouling. These findings separately conclude that, the low fouling
and high flux effect of ozone on ceramic membranes was either due to a
catalytic effect by the membrane or altered fouling layer chemistries on
the membrane surface (Dow et al., 2013). Some are reporting that
ceramic materials are responsible for formation of hydroxyl radicals via
catalytic decomposition (Zhu et al., 2011). However, it has been re­
ported in some other studies (Ikhlaq et al., 2015; Nawrocki and Fijołek,
2013) that, aluminium oxide (the major component of ceramic mem­
brane) is not a catalyst of ozone decomposition in water. Despite these
observations and viable explanations of the unique and positive per­
formance effects when ozone and ceramic membranes are combined, the
actual mechanism of ozone on the membrane has not been confirmed in
a dedicated study (Nawrocki and Kasprzyk-Hordern, 2010). Therefore,
investigating the catalytic effect of ozone on a well-known commercial
water treatment ceramic membrane from Metawater would be highly
significant.
Moreover, when ozone is applied to bromide-containing waters,
bromate is generated (Han et al., 2014; Moslemi et al., 2011; Ozekin
et al., 1998; Pinkernell and von Gunten, 2001; von Gunten and Hoigne,
1994; von Gunten and Oliveras, 1998; Zhao et al., 2013). Bromate is
declared as a potential human carcinogen as it was found to be a gen­
otoxic carcinogen inducing compound (e.g., renal cell tumors in rats)
(Kurokawa et al., 1990; Moslemi et al., 2012a). The guideline value of
bromate issued by the World Health Organization (WHO) is 25 μg/L. A
maximum contaminant level of 10 μg/L bromate is established by both
the European Union (EU) and the United States Environmental Protec­
tion Agency (USEPA) (USEPA, 2002; WHO, 1996). Therefore, an un­
derstanding of bromate formation in the unique ozone-ceramic
membrane process is highly significant. In natural waters, bromide
levels are highly variable with a range of 10–1000 μg/L (von Gunten,
2003b). Bromide itself is not toxic (WHO, 2009), but the formation of
bromate can become a serious issue for bromide concentrations above
2
Journal of Environmental Management 253 (2020) 109655
100 μg/L (von Gunten, 2003b). The formation of bromate is a result of
the oxidation of bromide through a combination of ozone and HO�
radical reactions (Elovitz and von Gunten, 1999).
The goal of this study was to acquire a better understanding of ozone
interaction with a ceramic membrane. The project also aimed to inves­
tigate the mechanism of catalytic ozone decomposition into HO� radicals
in combined ozone and ceramic membrane treatment process. Subse­
quent experiments with bromide-containing water were also investi­
gated to elucidate the impact of ozone/ceramic MF (CMF) on the
formation of bromate.
2. Theory and reaction mechanism
It is well-known that the material used to make ceramic membranes
can catalyse the breakdown of ozone to HO� radicals (Gracia et al.,
2000a; Gracia et al., 2000b; Karnik et al., 2005; Legube and Karpel Vel
Leitner, 1999; Munter, 2001). However, tracking HO� radical formation
during continuous CMF would provide new insights into the ozone/CMF
chemistry. HO� radical formation and kinetics can be extracted using
pseudo-first order kinetics. Due to difficulties in directly measure HO�
radicals, the transient concentration of HO� radicals during ozonation
can be calculated using an ozone resistant probe, para-chlorobenzoic
acid (pCBA). pCBA reacts primarily with HO� radicals (kHO�,
9 1 1
pCBA ¼ 5 � 10 M s ) (Neta and Dorfman, 1968), and insignificantly
with O3 (kO3,pCBA < 0.15 M 1 s 1) (David Yao and Haag, 1991) with the
concentration of HO� radicals extracted by measuring the pCBA con­
centration (Elovitz and von Gunten, 1999). Tert-butanol can be used to
study the reactivity of ozone alone since it is an effective scavenger of
HO� radicals. The reaction rate constants between tert-butanol and
either HO� or O3 have been reported as kHO� ¼ 5.9 � 108 M 1 s 1 and
kO3 ¼ 3.0 � 10 3 M 1 s 1, respectively (de Vera et al., 2015; Hoign�
e and
Bader, 1983; Ma and Graham, 2000; Staehelin and Hoigne, 1985; von
Gunten and Hoigne, 1994).
Elovitz and von Gunten (Elovitz and von Gunten, 1999) proposed the
Rct concept, which was defined as the ratio of HO� radical exposure vs.
ozone exposure shown in Equation (1).
(1)
where the time-integrated ozone concentration, ʃ[O3]dt is the ozone
exposure. The ozone exposure can be calculated from the integral of the
‘ozone concentration vs. time’ data. By following the ozone exposure and
the decay of pCBA, the Rct value can be obtained using Equation (2).
(2)
When the pCBA concentration is plotted with respect to O3 exposure
(product of ozone concentration and time) the slope is then Rct � kHO�,
9 1 1
pCBA. Since kHO ,pCBA is reported as 5 � 10 M s (Elovitz and von
�
Gunten, 1999), the Rct value can also be obtained from the slope. As the
ozone concentration can be easily measured, the Rct value allows the
calculation of the HO� concentration in the ozonation process. The
concept of tracking Rct has become beneficial to model the degradation
of micro-pollutants during the treatment of natural water or wastewater
by ozonation (Elovitz and von Gunten, 1999). Since Rct is a useful tool to
indirectly quantify the relative contribution of HO� radicals in ozonation
system, the catalytic effect of combined ozonation and CMF to generate
HO� radicals during the treatment of SE can be explored using the same
concept.
3. Materials and methods
3.1. Membrane and materials
A multi-channel ceramic membrane was provided by Metawater Co.,
Ltd. The 100 nm membrane is a scaled down version of the Metawater
K. Ibn Abdul Hamid et al.
commercial unit that is commonly operated for full scale water treat­
ment applications. The 10-cm long membrane had 55 channels, each
with 2.5 mm channel diameter and is mostly made of aluminium oxide.
The total filtration surface area of the membrane was 0.04 m2. The
characteristics of the membrane are given in Table 1 pCBA was pur­
chased from Supelco. Tert-butanol and potassium indigo-trisulfonate
were purchased from Sigma Aldrich. Bromide and bromate standards
were prepared using potassium bromide (KBr, MERCK Pty Limited) and
sodium bromate (NaBrO3, Merck Pty Limited).
3.2. Experimental setup
The schematic diagram of the experimental setup is shown in Fig. 1.
The membrane was inserted in a custom made stainless steel module
(also provided by Metawater), and was held in a vertical position with
clamps at its two ends. The feed was pumped using a low speed piston
pump (Fluid Metering, Inc, QG 150) at a flow rate of 48 mL/min.
Stainless steel fittings (Swagelok) and high pressure nylon tubes were
used for connecting the membrane rig. An ozone generator (American
Ozone Systems Inc.) was used to generate a stock ozone solution. Stock
solutions were prepared by continuously bubbling the generated ozone
into ice-cooled ultra-pure water through a Dreschel bottle as described
by Bader and Hoign�e (1981) (Bader and Hoign�e, 1981). The concen­
tration of the stock solutions was approximately 50 mg-O3/L, which
were standardised by measurement of the UV absorbance (ε258
1 subtracted from that of an ozone free blank. The absorbance at 600 nm
nm ¼ 3000 M cm 1). Glass feed beakers and syringes for injecting stock
solution were used to avoid ozone decomposition.
3.3. Experimental procedure
A fixed volume (200 mL and 1000 mL for the recirculating sample
and single pass test, respectively) of tap water (Dissolved Organic Car­
bon ¼ 0.29 mg/L; Conductivity ¼ 220 μS/cm; Turbidity ¼ 0.34 NTU)
was added to the glass beaker (1200 mL). pCBA and bromide was spiked
at 0.5 μM and 6.25 μM, respectively. The measured pH value was always
7.5 (�0.1). The beaker was covered with Parafilm and placed on a
magnetic stirrer. First, the solution was stirred vigorously for 10 s to
ensure good homogeneity. Then, the stirring was lowered and an aliquot
of the stock ozone solution was spiked into the beaker using a glass
syringe so that the effective ozone concentration in the beaker reached
approximately 10 mg O3/L. The ozone decomposition in the beaker was
used as the background data. For the tests, when ozone was spiked into
the beaker, the pump was turned on immediately. After each specified
reaction time, recirculated samples (3 mL) were collected into a tube
containing buffered indigo trisulphonate to quench the ozone reaction.
After 15 min, a sample (3.5 mL) was collected for bromate analysis.
In order to investigate ozone stability in the membrane module, the
filtration unit was filled up with fresh ozonized water before the pump
was stopped and the ozone decay was measured after a certain period of
time. This was done for four different contact times (1 min, 3 min, 5 min
and 7 min) over the course of a single ozonized water feed run. In a
similar experiment, the solution containing pCBA was replaced by a
solution containing 50 mM tert-butanol. After each specified reaction
time, samples (11 mL) from the feed beaker and the permeate outlet
were collected into a test tube containing buffered indigo trisulphonate.
Table 1
Properties of the multi-channel ceramic membrane.
Properties of membrane
Manufacturer Metawater Co., Ltd.
Length (cm) 10
Outer diameter (mm) 30
Channel diameter (mm) 2.5
Number of channels 55
Membrane surface area (m2) 0.04
3
Journal of Environmental Management 253 (2020) 109655
The samples taken from the beaker was used as background data for
comparison. To ensure that the recovered sample volume was repre­
sentative of the solution in contact with the ceramic membrane, sample
was discarded for the first 40 s before collecting it into the reagent tube.
This 40 s delay was obtained by calculating the breakthrough of indigo
solution from the ceramic membrane. The breakthrough of indigo was
calculated by pumping diluted indigo solution into the module until a
complete fill of the membrane and module was ensured. Ultra-pure
water was then pumped through the module. The displacement of the
indigo solution contained within the membrane module was observed
by measuring the UV absorbance of the permeate at 600 nm. Samples
were taken from the feed beaker and the membrane permeates for
bromate analysis. After each set of experiments, the ceramic membrane
was rinsed thoroughly with ultra-pure water.
3.4. Analytical methods
3.4.1. Ozone concentration
The concentration of dissolved ozone in solution was determined by
the Indigo Method (Bader and Hoign�e, 1981). The method is based on
decolourization of the indigo reagent by ozone, where the loss of colour
is directly proportional to the ozone concentration. High purity indigo
trisulfonate (>80%) with a molar absorptivity of about 20,
000 M 1 cm 1 at 600 nm was used. To measure the residual ozone, the
absorbance of indigo trisulfonate after reaction with the sample was
was measured using a UV mini-1240 UV–vis spectrophotometer
(Shimadzu).
3.4.2. pCBA concentration
pCBA was quantified by high performance liquid chromatography
(HPLC) (Agilent Technologies 1200 Series) with UV detection at
240 nm. The flow rate and eluent were 0.7 mL/min of 70% methanol
and 30% 10 mM phosphoric acid, respectively. The column was a
4.6 mm � 250 mm Kinetex XB-C18 (Phenomenex) 5 μm particle size,
with a pre-column attachment. A low detection limit of about 0.025 μM
(4 mg/L) can be achieved by HPLC.
3.4.3. Bromate concentration
Bromate was measured via ion chromatography using a Dionex
ICS3000 (AG9HC/AS9HC) followed by a post-column reaction, ac­
cording to the standard operating procedure from an existing method
previously reported by Salhi and von Gunten (1999) (Salhi and von
Gunten, 1999). All samples were measured in duplicate and blank an­
alyses were performed. The limits of detection (LODs) were calculated
for every analytical batch. The average LOD for bromate was 4 nM
(0.5 μgL 1).
4. Results and discussion
4.1. Ozone decay and HO� radical formation
Fig. 2 shows the residual ozone concentration in tap water solution
recirculated through the ceramic membrane (fitted inside the module),
the empty module, and in the stirred feed beaker. The residual ozone
concentration was similar in all compartments for the first 2 min of
testing. However, after 3 min, the residual ozone concentration in the
empty module and the module containing the membrane declined at a
faster rate. The decrease in ozone concentration started after 2 min and
10 s which corresponded to the time needed to receive recirculated
permeate to the feed beaker. After 13 min (Fig. 2), the residual ozone
concentration for the membrane and empty module were much lower
than for the stirred feed beaker. During the experiments, the sample was
recirculating through the membrane and the module. The water was
passed through the pump and piping to the membrane and or module
and then discharged from the permeate side of the module. While
K. Ibn Abdul Hamid et al.
Fig. 1. Generation of ozone stock solution (a) and schematic of the experimental setup for investigating HO� radical formation across the CMF membrane (b).
Fig. 2. Comparison of residual ozone concentration in recirculating water so­
lution in a beaker, passing through membrane and empty module (0.5 μM
pCBA; 6.25 μM bromide; applied ozone: 10 mg/L; pump flow rate: 48 mL/min;
flux: 72 L m 2⋅h 1; temperature: 22 � 1 � C; pH 7.5).
leaving via the permeate, the tap water was exposed to air before
returning to the feed beaker. Moreover, flowing water through a pump
and tubing sufficiently agitated the solution to cause ozone degassing
from solution. The differences in ozone consumption between the
beaker and the experiments carried with the module might be due to
reaction with tubing material or the module itself and degassing of
ozone. Looking more closely at specific times, between 2 and 8 min in
Fig. 2, the residual ozone concentration through the membrane is
noticeably lower than in the empty module. As the differences in re­
sidual ozone concentration for the empty module and membrane is
significant between 2 and 8 min, the first order linear reaction rate
constants and Rct were calculated using data collected during this time
frame.
Table 2 shows the first order linear reaction rate constants for the
beaker, empty module and membrane. The differences observed for the
empty module and the membrane may be due to additional consumption
4
Journal of Environmental Management 253 (2020) 109655
of ozone via formation of HO� radicals and/or simply degassing of ozone
as it depressurises (7 kPa) when exiting the membrane. These observa­
tions imply there is an important effect of degassing from both the
membrane and its module, however, quantification of the ozone losses
due to degassing is subject of further study. Therefore, the HO� radical
behaviour must be indirectly measured by pCBA as a probe to isolate the
unique effect of the membrane itself. The behaviour of HO� radical via
single pass tests will be examined later in this paper.
The Rct values (ratio of HO� radical exposure vs. ozone exposure)
calculated using the samples from 3 min and onwards for the beaker,
empty module and membrane are also shown in Table 2. For reference,
the original concentration data for pCBA over time is shown in Fig. A1
from the Supplementary Material. Under standard ozonation conditions
and ozone-based advanced oxidation processes, Rct values between 10 7
– 10 10 have been calculated (de Vera et al., 2017; Elovitz et al., 2000).
As expected, samples collected from the stirred feed beaker have the
lowest Rct value compared to either the empty module or membrane.
The lower rate of ozone decomposition in the stirred feed beaker
compared to the empty module and membrane are correlated to a lower
Rct value in the stirred feed beaker samples. However, the Rct value for
the membrane was slightly higher than that of the empty module. This is
due to the enhanced HO� radical formation by the ceramic membrane,
indicating the catalytic degradation of ozone to HO� radicals.
However, the calculated decay rates of ozone for the membrane and
empty module in Table 2 are not representative of the decomposition of
ozone across the membrane/module alone. Since the ozonized tap water
solution is recirculated to the feed beaker, the decay rates in Table 2 are
representative of the combination of natural decomposition of ozone in
the stirred feed beaker along with the decomposition of ozone across the
membrane/module. Agitation and repeated contact with air is a likely
factor in the loss of ozone. McClurkin et al. (2013) determined the
half-life of ozone as a function of air flow in an airtight cylinder
(McClurkin et al., 2013). Three fans were used inside the cylinder to
Table 2
First order reaction rate constants k and Rct in water solution in a beaker, passing
through the membrane and empty module (0.5 μM pCBA: 6.25 μM bromide;
applied ozone: 10 mg/L; pump flow rate: 48 mL/min, pH 7.5, temperature:
22 � 1� C).
Test k (s 1) Rct
Stirred feed beaker 0.47 � 10 3
1.09 � 10 9
3 9
Empty module 2.56 � 10 1.82 � 10
3 9
Metawater membrane 2.75 � 10 2.16 � 10
K. Ibn Abdul Hamid et al.
obtain different flow rates of air. It was observed that the half-life
decreased exponentially as the air flow was increased by increasing
fan speed. Moreover, the experiments herein were conducted in such a
way that the membrane permeate was recirculated back to the feed
beaker and depressurised prior to feeding back to the membrane.
Therefore, to avoid agitation and to isolate the effect of the mem­
brane/module on the decomposition of ozone, single pass experiments
were conducted with tap water. This reduced the contact of the ozonized
sample with air and ensured adequate reaction time with the membrane
without active flow (agitation or pressure).
Table 3 shows an example of ozone decomposition for a holding time
inside the module with and without membrane of 1 min with an addi­
tional 40 s (1.6 min). This 40 s was determined by calibrating against the
breakthrough of the contents contained within the membrane as
described in Section 3.3. The results show that running the feed solution
through the empty module led to a lower concentration of ozone
compared to the expected decay in the beaker. Although, this drop in
ozone concentration was similar to when the membrane was installed,
indicating small differences in the effect on ozone decay between the
empty module and the membrane (Table 3). Meanwhile, the decrease in
ozone concentration with pCBA while being held with the membrane
was larger compared to the decrease in ozone with tert-butanol
(Table 3). This gives further evidence that catalytic decomposition of
ozone occurred with the ceramic membrane via a HO� radical reaction.
More tests for comparing the ozone decomposition through the empty
module with tert-butanol would be helpful to investigate this further.
4.2. Kinetic analysis of ozone decay
To investigate the mechanisms of ozone decay more closely, the re­
sults of ozone decay shown in Table 3 are analysed here. The first order
kinetic rate constants k were determined. The total ozone decomposition
rate during each contact time can be expressed by,
kTot ¼ kB þ kMemþMod (3)
where, kB and kMemþMod are the first order reaction rate constants (s 1) of
ozone inside the beaker and membrane (installed in its module)
respectively. kB was calculated from the experiments (the natural
decomposition of ozone in beaker). kTot can be calculated from the
membrane decay results. Ozone decomposition across the membrane,
kMemþMod can be determined by rearranging Equation (3). The calculated
kMemþMod can be defined as the effective rate constant of the ceramic
membrane in its module.
Fig. 3 shows the calculated effective rate constants (kMemþMod) of
ozone decomposition for 1, 3, 5 and 7 min holding time. The rate con­
stant of ozone decomposition in the tert-butanol and pCBA solution
through the membrane decreased for 1 min, 3 min, 5 min and 7 min
contact times. Fig. 3 also showed that the rate of ozone depletion was
higher in the experiments carried out with pCBA compared to the ex­
periments with tert-butanol. This result confirms the observation shown
Table 3
Comparison of residual ozone concentration in the feed beaker, the empty
module and the membrane for 1 min holding time. (Tap water with 6.25 μM
bromide, 0.5 μM pCBA and 50 mM tert-butanol; pump flow rate: 48 mL/min;
flux: 72 L m 2⋅h 1; temperature: 22 � 1 � C; pH 7.5).
Test Residual ozone % reduction
concentration
5 min 6 min
40 s
Beaker 8.88 8.60 3.2
Tap water with pCBA through empty module 8.87 8.04 9.4
Tap water with tert-butanol through 8.88 7.78 12.4
membrane
Tap water with pCBA through membrane 8.88 7.41 16.6
5
Journal of Environmental Management 253 (2020) 109655
Fig. 3. Impact on ozone decomposition induced by the ceramic membrane for
different holding times shown by effective rate constants of ozone decomposi­
tion in pCBA (0.5 μM) and tert-Butanol (50 mM) (6.25 μM bromide; flux:
72 L m 2⋅h 1; applied ozone: 10 mg/L; pump flow rate: 48 mL/min; tempera­
ture: 22 � 1 � C; pH 7.5).
in Tables 3 and i.e., ozone decomposition was slightly enhanced by HO�
radical generation due to the catalytic effect of membrane (Staehelin
and Hoigne, 1985). Moreover, the differences between the pCBA and
tert-butanol rate constant decreased with increasing holding time (or
contact time with the membrane) and for a contact time of 7 min, no
differences were observed between the pCBA and tert-butanol experi­
ment. This is because, ozone decomposition is faster at higher
concentration.
4.3. Bromate formation
In order to investigate the impact of CMF on bromate formation,
bromide was added to the feed solution. Fig. 4 shows bromate forma­
tions for an experiment performed with permeate recirculation to the
feed beaker for 15 min.
As per Fig. 4, the bromate concentrations measured in the samples
taken at 15 min for the stirred beaker test (Fig. 2), empty module and
membrane were 4.38 μM, 1.63 μM and 0.8 μM, respectively. The amount
of bromate formed in the stirred beaker test was much higher compared
to either the membrane and module tests, since the ozone was more
stable in the beaker test. Therefore, the exposure to bromide was higher
and a higher bromate formation was observed. However, the formation
of bromate in the membrane test was found to be lower (50%) than that
of the empty module. The results therefore suggested that, bromate
formation can be minimized using ceramic membranes. In previous
work by Ciba et al. (1995), it was found that the addition of a hetero­
geneous catalyst (TiO2) to ozone minimized the formation of bromate
from brominated surface waters (Ciba et al., 1995). The results in this
study have identified possible effects including a slight ozone reduction
by catalysis and degassing, but these were very small relative to re­
actions with ozone in bulk. The reduced bromate formation observed in
our study may be due to a lower ozone exposure with bromide. The
lower ozone exposure may also be due to the small catalytic formation of
HO� radical at the surface of the membrane which in turn leads to a
lower formation of HOBr (Fischbacher et al., 2015). Further study on
this was conducted with samples collected in the single-pass tests
(Table 3).
Fig. 5 shows the corresponding bromate concentration results during
K. Ibn Abdul Hamid et al.
Fig. 4. Bromate concentration during ozonation of a water sample passing
through ceramic membrane and empty module (0.5 μM pCBA; 6.25 μM bro­
mide; applied ozone: 10 mg/L; pump flow rate: 48 mL/min; pH 7.5; flux:
72 L m 2⋅h 1; temperature: 22 � 1 � C, 15 min).
the single-pass tests. The concentration of bromate formed in the
membrane and empty module are compared with the concentration of
bromate formed in the feed water. It is interesting to observe that the
concentrations of bromate in the permeate of the membrane is reduced
by 10 μg/L to 50 μg/L for every holding time. Whereas, the concentra­
tion of bromate at the outlet of the empty module is essentially equal to
that of the feed. The membrane therefore, appeared to slightly mitigate
the formation of bromate.
The reduction of bromate formation could also be explained by the
surface property of the ceramic membrane that causes the attraction and
repulsion of ions. The surface of ceramic membranes is typically
charged. This is due to the amphoteric nature of the surface hydroxyl
groups on the metal oxide surface of the ceramic membrane (Tsuru,
2001). Previous studies have shown that due to their surface charge,
ceramic UF membranes can reject ions, even though the pore size of the
membrane is much larger than the size of the ions (Combe et al., 1997;
Fig. 5. Bromate formation during ozonation of water sample passing through the ceramic membrane (a) and the empty module (b) (0.5 μM pCBA; 6.25 μM (500 μg/
L) bromide; applied ozone: 10 mg/L, pump flow rate: 48 mL/min; flux: 72 L m 2⋅h 1; temperature: 22 � 1 � C; pH 7.5).
6
Journal of Environmental Management 253 (2020) 109655
Fievet et al., 2002; Labbez et al., 2003; Skluzacek et al., 2006). If a
charged membrane is in contact with an electrolyte solution, electro­
static repulsion will result in a lower concentration of ions with the same
charge as the membrane (referred to as co-ions) near the membrane
surface and within the membrane pores. On the other hand,
counter-ions, which have an opposite charge to that of the membrane
surface, are attracted to the membrane and the concentration of these
ions within the membrane and at its surface is higher than that in bulk
solution (Moslemi et al., 2012b). To exhibit a beneficial effect on
bromate removal by such mechanism, rejection of up to 68% has been
reported with a 5 kDa ceramic UF membranes having estimated pore
size of 0.004 μm (Moslemi et al., 2012b). However this dropped to
13.3% and lower in the presence of Ca2þ with concentrations starting at
0.4 mg/L. While Ca2þ ion influence on bromate rejection was subject of
their study, it was also acknowledged that minerals in general (including
the more dominant Naþ present in water supplies) will have similar
influence in shielding the surface and reducing the rejection effect on
bromate. Considering our test water had a mineral content
(EC ¼ 220 μS/cm) and a 25-fold larger pore size, we don’t expect the
membrane to participate in rejecting bromate by the charge repulsion
mechanism. Meanwhile the fundamentals effects of the surface proper­
ties of ceramic membrane (ion interactions with the surface and
zeta-potential) play an important role and is a worthy topic to explore
any further beneficial bromate removal effects in detail.
This work attempted to identify the formation of HO� radicals during
ozonation of CMF. This has enabled to identify whether HO� radicals are
formed and relative to how much ozone is present, and any potential
influence on other mechanisms such as disinfection by-products. As the
degassing effect was a finding as part of the work, another dedicated
work would be needed to isolate the effect of ozone degassing over other
ozone removal mechanisms such as chemical reaction including HO�
radical formation. It would need close examination of the equipment
used, and likely better undertaken on a pilot scale membrane system
which uses realistic pumps, valves, piping and tanks.
5. Conclusions
Ceramic membranes are known to benefit from a pre-treatment of
the feed water with ozone. However, the mechanism of ozone on the
membrane surface is not well understood. This work found that a
commercial ceramic membrane provided by Metawater led to an in­
crease of HO� radicals formation that induced an increased ozone decay.
The contact of pipes and pump of the membrane rig and air exposure
K. Ibn Abdul Hamid et al.
significantly reduced the residual ozone concentration. Meanwhile, an
effective reduction of bromate formation by using ozonation followed by
the CMF was demonstrated. When ozonized water was recirculated to
the membrane module, bromate formation was reduced by 50%
compared to the experiment conducted with an empty module. When
single pass experiments were performed, bromate mitigation was
around 10%. The mechanism responsible for the mitigation of bromate
was the suppression of the oxidation of Br and HOBr/BrO to BrO3 due
to the decomposition of ozone and therefore lower O3 exposure. From a
practical point of view for application to water treatment, it can be
concluded that although HO� radicals might react with organics present
in the raw water, subtle effects such as reduction of bromate, could be
useful features of the unique catalytic effect of ceramic membranes. The
application of pCBA played a significant role in identifying HO� radical
formation during ozone-CMF interaction, however further work is
needed to identify where the HO� radicals are formed (e.g. inside the
pores).
Acknowledgement
The authors are grateful to the Collaborative Research Network
(CRN), Australia and National Centre of Excellence in Desalination,
Australia (NCEDA) for providing financial support of this project. The
membrane was generously supplied by Metawater, Japan. The experi­
ments were conducted in the Curtin Water Quality Research Centre
(CWQRC) at Curtin University. The authors are thankful for all these
contributions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jenvman.2019.109655.
References
Bader, H., Hoign�e, J., 1981. Determination of ozone in water by the indigo method.
Water Res. 15, 449–456.
Ciba, N., Allemane, H., Prados, M.J., Luck, F., 1995. The impact of catalytic ozonation on
bromate formation. In: Proceedings of the 12th Ozone World Congress, 1,
pp. 585–594.
Combe, C., Guizard, C.G., Aimar, P., Sanchez, V., 1997. Experimental determination of
four characteristics used to predict the retention of a ceramic nanofiltration
membrane. J. Membr. Sci. 129, 147–160.
David Yao, C.C., Haag, W.R., 1991. Rate constants for direct reactions of ozone with
several drinking water contaminants. Water Res. 25, 761–773.
de Vera, G.A., Stalter, D., Gernjak, W., Weinberg, H.S., Keller, J., Farre, M.J., 2015.
Towards reducing DBP formation potential of drinking water by favouring direct
ozone over hydroxyl radical reactions during ozonation. Water Res. 87, 49–58.
de Vera, G.A., Gernjak, W., Weinberg, H., Farr�e, M.J., Keller, J., von Gunten, U., 2017.
Kinetics and mechanisms of nitrate and ammonium formation during ozonation of
dissolved organic nitrogen. Water Res. 108, 451–461.
Dow, N., Murphy, D., Clement, J., Duke, M., 2013. Outcomes of the australian ozone/
ceramic membrane trial on secondary effluent. Water (AWA) 40, 7.
Elovitz, M.S., von Gunten, U., 1999. Hydroxyl radical/ozone ratios during ozonation
processes. I. The Rct concept. Ozone: Sci. Eng. 21, 239–260.
Elovitz, M.S., von Gunten, U., Kaiser, H.-P., 2000. Hydroxyl radical/ozone ratios during
ozonation processes. II. The effect of temperature, pH, alkalinity, and DOM
properties. Ozone Sci. Eng. 22, 123–150.
Fievet, P., Labbez, C., Szymczyk, A., Vidonne, A., Foissy, A.A., Pagetti, J., 2002.
Electrolyte transport through amphoteric nanofiltration membranes. Chem. Eng. Sci.
57, 2921–2931.
Fischbacher, A., L€oppenberg, K., von Sonntag, C., Schmidt, T.C., 2015. A new reaction
pathway for bromite to bromate in the ozonation of bromide. Environ. Sci. Technol.
49, 11714–11720.
Gracia, R.d., Cortes, S., Sarasa, J., Ormad, M.P., Ovelleiro, J.L., 2000. Heterogeneous
catalytic ozonation with supported titanium dioxide in model and natural waters.
Ozone Sci. Eng. 22, 461–471.
Gracia, R.d., Cort�es, S., Sarasa, J., Ormad, P., Ovelleiro, J.L., 2000. Catalytic ozonation
with supported titanium dioxide. The stability of catalyst in water. Ozone Sci. Eng.
22, 185–193.
Han, Q., Wang, H., Dong, W., Liu, T., Yin, Y., 2014. Suppression of bromate formation in
ozonation process by using ferrate(VI): batch study. Chem. Eng. J. 236, 110–120.
Hausmann, A., Duke, M.C., Demmer, T., 2013. Principles of Membrane Filtration,
Membrane Processing. Blackwell Publishing Ltd., pp. 17–51
7
Journal of Environmental Management 253 (2020) 109655
Hoign�e, J., Bader, H., 1983. Rate constants of reactions of ozone with organic and
inorganic compounds in water-I. Non-dissociating organic compounds. Water Res.
17, 173–183.
Ikhlaq, A., Brown, D.R., Kasprzyk-Hordern, B., 2015. Catalytic ozonation for the removal
of organic contaminants in water on alumina. Appl. Catal. B Environ. 165, 408–418.
Karnik, B.S., Davies, S.H.R., Chen, K.-C., Jaglowski, D.R., Baumann, M.J., Masten, S.J.,
2005. Effects of ozonation on the permeate flux of nanocrystalline ceramic
membranes. Water Res. 39, 728–734.
Kim, J., Davies, S.H.R., Baumann, M.J., Tarabara, V.V., Masten, S.J., 2008. Effect of
ozone dosage and hydrodynamic conditions on the permeate flux in a hybrid
ozonation–ceramic ultrafiltration system treating natural waters. J. Membr. Sci. 311,
165–172.
Kurokawa, Y., Maekawa, A., Takahashi, M., Hayashi, Y., 1990. Toxicity and
carcinogenicity of potassium bromate–a new renal carcinogen. Environ. Health
Perspect. 87, 309–335.
Labbez, C., Fievet, P., Thomas, F., Szymczyk, A., Vidonne, A., Foissy, A.A., Pagetti, P.,
2003. Evaluation of the "DSPM" model on a titania membrane: measurements of
charged and uncharged solute retention, electrokinetic charge, pore size, and water
permeability. J. Colloid Interface Sci. 262, 200–211.
Legube, B., Karpel Vel Leitner, N., 1999. Catalytic ozonation: a promising advanced
oxidation technology for water treatment. Catal. Today 53, 61–72.
Lehman, S.G., Liu, L., 2009. Application of ceramic membranes with pre-ozonation for
treatment of secondary wastewater effluent. Water Res. 43, 2020–2028.
Ma, J., Graham, N.J.D., 2000. Degradation of atrazine by manganese-catalysed
ozonation - influence of radical scavengers. Water Res. 34, 3822–3828.
McClurkin, J.D., Maier, D.E., Ileleji, K.E., 2013. Half-life time of ozone as a function of air
movement and conditions in a sealed container. J. Stored Prod. Res. 55, 41–47.
Moslemi, M., Davies, S.H.R., Masten, S.J., 2011. Bromate formation in a hybrid
ozonation-ceramic membrane filtration system. Water Res. 45, 5529–5534.
Moslemi, M., Davies, S.H., Masten, S.J., 2012. Empirical modeling of bromate formation
during drinking water treatment using hybrid ozonation membrane filtration.
Desalination 292, 113–118.
Moslemi, M., Davies, S.H., Masten, S.J., 2012. Rejection of bromide and bromate ions by
a ceramic membrane. Environ. Eng. Sci. 29, 1092–1096.
Munter, R., 2001. Advanced oxidation processes - current status and prospects. Proc.
Estonian Acad. Sci. Chem.
Myat, D.T., Roddick, F., Puspita, P., Skillman, L.C., Charrois, J.W.A., Kristiana, I.,
Uhl, W., Vasyukova, E.V., Roeszler, G., Chan, A., Zhu, B., Muthukumaran, S.,
Gray, S., Duke, M., 2018. Effect of oxidation with coagulation and ceramic
microfiltration pre-treatment on reverse osmosis for desalination of recycled
wastewater. Desalination 431, 106–118.
Nawrocki, J., Fijołek, L., 2013. Effect of aluminium oxide contaminants on the process of
ozone decomposition in water. Appl. Catal. B Environ. 142–143, 533–537.
Nawrocki, J., Kasprzyk-Hordern, B., 2010. The efficiency and mechanisms of catalytic
ozonation. Appl. Catal. B Environ. 99, 27–42.
Neta, P., Dorfman, L.M., 1968. Pulse radiolysis studies. XIII. Rate constants for the
reaction of hydroxyl radicals with aromatic compounds in aqueous solutions. Adv.
Chem. Ser. 81, 222–230.
Oneby, M.A., Bromley, C.O., Borchardt, J.H., Harrison, D.S., 2010. Ozone treatment of
secondary effluent at U.S. municipal wastewater treatment plants. Ozone Sci. Eng.
32, 43–55.
Ozekin, K., Westerhoff, P., Amy, G.L., Siddiqui, M., 1998. Molecular ozone and radical
pathways of bromate formation during ozonation. J. Environ. Eng. 124, 456–462.
Park, H., Kim, Y., An, B., Choi, H., 2012. Characterization of natural organic matter
treated by iron oxide nanoparticle incorporated ceramic membrane-ozonation
process. Water Res. 46, 5861–5870.
Pinkernell, U., von Gunten, U., 2001. Bromate minimization during ozonation:
mechanistic considerations. Environ. Sci. Technol. 35, 2525–2531.
Salhi, E., von Gunten, U., 1999. Simultaneous determination of bromide, bromate and
nitrite in low μg l 1 levels by ion chromatography without sample pretreatment.
Water Res. 33, 3239–3244.
Schlichter, B., Mavrov, V.D., Chmiel, H., 2004. Study of a hybrid process combining
ozonation and microfiltration/ultrafiltration for drinking water production from
surface water. Desalination 168, 307–317.
Skluzacek, J.M., Isabel Tejedor, M., Anderson, M.A., 2006. An iron-modified silica
nanofiltration membrane: effect of solution composition on salt rejection.
Microporous Mesoporous Mater. 94, 288–294.
Song, J., Zhang, Z., Zhang, X., 2017. A comparative study of pre-ozonation and in-situ
ozonation on mitigation of ceramic UF membrane fouling caused by alginate.
J. Membr. Sci. 538, 50–57.
Staehelin, J.N., Hoigne, J., 1985. Decomposition of ozone in water in the presence of
organic solutes acting as promoters and inhibitors of radical chain reactions.
Environ. Sci. Technol. 19, 1206–1213.
Tsuru, T., 2001. Inorganic porous membranes for liquid phase separation. Separ. Purif.
Methods 30, 191–220.
USEPA, 2002. National primary drinking water regulations: long term 1 enhanced
surface water treatment rule. Final Rule. Fed Regist 67, 1811–1844.
von Gunten, U., 2003. Ozonation of drinking water: Part I. Oxidation kinetics and
product formation. Water Res. 37, 1443–1467.
von Gunten, U., 2003. Ozonation of drinking water: Part II. Disinfection and by-product
formation in presence of bromide, iodide or chlorine. Water Res. 37, 1469–1487.
von Gunten, U., Hoigne, J., 1994. Bromate formation during ozonization of bromide-
containing waters: interaction of ozone and hydroxyl radical reactions. Environ. Sci.
Technol. 28, 1234–1242.
von Gunten, U., Oliveras, Y., 1998. Advanced oxidation of bromide-containing waters:
bromate formation mechanisms. Environ. Sci. Technol. 32, 63–70.
K. Ibn Abdul Hamid et al.
Wei, D., Tao, Y., Zhang, Z., Liu, L., Zhang, X., 2016. Effect of in-situ ozonation on ceramic
UF membrane fouling mitigation in algal-rich water treatment. J. Membr. Sci. 498,
116–124.
WHO, 1996. Guidelines for Drinking-Water Quality, Health Criteria and Other
Supporting Information. World Health Organization, Geneva.
WHO, 2009. Bromide in drinking-water. Guidelines Drink. Water Qual. 15.
Journal of Environmental Management 253 (2020) 109655
Zhao, G., Lu, X., Zhou, Y., Gu, Q., 2013. Simultaneous humic acid removal and bromate
control by O3 and UV/O3 processes. Chem. Eng. J. 232, 74–80.
Zhu, B., Hu, Y., Kennedy, S., Milne, N., Morris, G., Jin, W., Gray, S., Duke, M., 2011. Dual
function filtration and catalytic breakdown of organic pollutants in wastewater using
ozonation with titania and alumina membranes. J. Membr. Sci. 378, 61–72.