Chemosphere 279 (2021) 130642

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Performance of microbubble ozonation on treated tropical peat water:

Effects on THM4 and HAA5 precursor formation based on DOM
hydrophobicity fractions
Muammar Qadafi a, *, Suprihanto Notodarmojo b, c, Yuniati Zevi b, c
a
Environmental Engineering Program, Institut Teknologi Bandung, Jalan Ganesha No. 10, Bandung, 40132, Indonesia
b
Department of Environmental Engineering, Institut Teknologi Bandung, Jalan Ganesha No. 10, Bandung, 40132, Indonesia
c
Water and Wastewater Engineering Research Group, Faculty of Civil and Environmental Engineering, Institut Teknologi Bandung, Jalan. Ganesha 10,
Bandung, 40132, Indonesia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Microbubble ozonation was con-

ducted prior to final chlorination
process.

DAX-8, XAD-4, and IRA-958 resin
were used to isolate the DOM
fractions.

Microbubble ozonation reduced the
THM4 and HAA5 formation below
USEPA standard.

The TPH fraction decreased during
the microbubble ozonation as C-DBPs
precursor.

The hydrophilic fractions were found
to be B-DBPs precursors.

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

Article history: The hydrophobicity properties of dissolved organic matter (DOM) found in tropical peat water has an
Received 23 December 2020 impact on the formation of carcinogenic DBPs such as trihalomethanes-4 (THM4) and haloacetic acids-5
Received in revised form (HAA5). This study was conducted to determine the effect of microbubble ozonation on changes in DOM
31 March 2021
fraction and its effect on the formation of THM4 and HAA5. Alum coagulation and activated carbon
Accepted 18 April 2021
adsorption were carried out to reduce the DOM concentration before microbubble ozonation. Micro-
Available online 21 April 2021
bubble ozonation was carried out at acidic (pH 5.5), neutral (pH 7) and alkaline (pH 8.5) conditions to
Handling Editor: Junfeng Niu determine the effect of pH. Coagulation and adsorption of activated carbon were successful in reducing
the presence of the hydrophobic acid fraction (HPOA) in peat water completely, but the transphilic (TPH),
Keywords: charged hydrophilic (HPIC) and neutral hydrophilic (HPIN) fractions remained in the water. Microbubble
Microbubble ozonation ozonation succeeded in decreasing the presence of TPH fraction but increased the formation of HPIC and
Tropical peat water HPIN. The degradation of the TPH fraction resulted in reduced formation of chlorinated THM4 and HAA5
DOM fraction (C-THM4 and C-HAA5). On the other hand, the formation of HPIC and HPIN fractions increased the
Trihalomethanes
formation of brominated THM4 and HAA5 (B-THM4 and B-HAA5) after the final chlorination process.
Haloacetic acids
© 2021 Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail addresses: muammar.qadafi@students.itb.ac.id, qadafim.mq@gmail.com
(M. Qadafi).

https://doi.org/10.1016/j.chemosphere.2021.130642
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
M. Qadafi, S. Notodarmojo and Y. Zevi
1. Introduction
Disinfection is an important process in water treatment to
protect human health from aquatic diseases (Siddique et al., 2015;
Wang et al., 2019) such as cholera, dysentery, leptospirosis, etc.
(Postigo et al., 2018). The chlorine disinfection process in water
containing natural organic matter (NOM) triggers the formation of
carcinogenic DBPs such as THM and HAA (Qadafi et al., 202a). The
United States Environmental Agency (USEPA) determines the
contaminant limits for THM4 (chloroform/TCM, bromodichloro-
methane/BDCM, chlorodibromomethane/CBDM, and bromoform/
TBM). Including the limit for HAA5 (Chloroacetic acid/MCAA,
dichloroacetic acid/DCAA, trichloroacetic acid/TCAA, bromoacetic
acid/MBAA, and dibromoacetic acid/DBAA) in drinking water of
80 mg/L and 60 mg/L respectively, due to the carcinogenic properties
(USEPA, 1998).
Natural peat water has been reported to contain very high dis-
solved organic matter (DOM) in the form of humic acid with hy-
drophobic acid (HPOA) properties, therefore producing a brownish
color and acidic pH in water (Mahmud et al., 2013; Sudoh et al.,
2015; Zulfikar et al., 2016). Generally, the high DOM concentra-
tion in tropical peat water triggers high DBPs formation during the
disinfection process using chlorine. It is also reported to contain
other DOM fractions such as TPH, HPIC, and HPIN (Mahmud et al.,
2013). Our previous research reported that the process of alum
coagulation and activated carbon adsorption was unable to reduce
the formation of THM4 and HAA5 below the USEPA standards
(Qadafi et al., 2020a), hence additional treatment is needed. Usu-
ally, the coagulation by using alum only reduces the hydrophobic
fraction in water (Edzwald and Tobiason, 1999; Sudoh et al., 2015),
but activated carbon adsorption adsorbs NOM selectively based on
molecular weight (Park et al., 2019).
DOM can be categorized into several fractions’ types including
hydrophobicity, and molecular weight (Bing-zhi et al., 2007). Its
hydrophobicity fraction is determined using a resin column, for
example, XAD. The DOM hydrophobicity property has different
characteristics as a THM4 and HAA5 precursor (Bond et al., 2012).
Previous research (Bing-zhi et al., 2007; Mahmud et al., 2013)
categorized DOM in natural water-based on fractions, namely Hy-
drophobic acid (HPOA), weak hydrophobic/transphilic (TPH),
hydrophilic-charged (HPIC), and hydrophilic neutral (HPIN). Also,
the THM4 formation potential (THMF4P) and HAA5 formation po-
tential (HAA5FP) depend on THM4 and HAA5 precursors found in
each DOM fraction (He et al., 2018; Navalon et al., 2010).
Ozone has the ability to degrade high molecular weight organic
compounds (i.e., humic acid) to smaller sizes which are usually
hydrophilic (Hua and Reckhow, 2013; Zhong et al., 2017a). Recent
studies reported that the ozonation process could reduce the for-
mation of THMs and HAAs (Yiran et al., 2014; Fan et al., 2015;
Deeudomwongsa et al., 2017; Yaman et al., 2017; Chen et al., 2018;
Gao et al., 2020). Ozonation using microbubble has been widely
used in water and wastewater treatment to reduce various pollut-
ants concentrations (Khuntia et al., 2014; Li et al., 2018a; Deng et al.,
2021). The reactive ozone properties and microbubble that is
capable of optimizing ozone mass transfer (Li et al., 2018; Zeng
et al., 2020) is the right combination to degrade or oxidize the
pollutants mentioned (Deng et al., 2021; Khuntia et al., 2014). The
effect of microbubble ozonation on organic pollutant removal has
been studied recently (Wu et al., 2019; Deng et al., 2021; Jabesa and
Ghosh, 2021; Jothinathan et al., 2021). Jabesa and Ghosh (2021)
reported the same result in removal efficiency of dimethyl sulf-
oxide (DMSO), although ozone microbubbles have higher ozone
consumption than ozone milibubbles. The high reaction rate con-
stant in organic removal also reported by Deng et al. (2021) and
Jothinathan et al. (2021) in wastewater treatment using catalyzed
2
Chemosphere 279 (2021) 130642
microbubble ozonation.
Although microbubble ozonation has been reported successfully
reducing organic pollutants, the research regarding the effect of
microbubble ozonation on DBPs precursor formation is still limited.
Li et al. (2018) reported that microbubble ozonation could promote
the formation of bromo-organic DBPs and bromate precursors in
bromide-containing water. Compared to conventional bubble
ozonation, microbubble ozonation also reported has higher effi-
ciency on the removal of aromatic compounds such as phenol and
nitrobenzene (Wu et al., 2019) which precursors to THMs and HAAs
(Bond et al., 2012). Then, Sun et al. (2021) also reported that
microbubble ozonation could reduce the protein-like compound
that was an important precursor to THMs (Bond et al., 2012). Our
previous research (Qadafi et al., 2020a) reported that microbubble
pre-ozonation has successfully reduced the total formation of
THM4 and HAA5 in tropical peat water treatment below the USEPA
standards.
Considering the fact that the effect of microbubble as the final
step before chlorine disinfection and the mechanism for THM4 and
HAA5 formation based on its precursors in tropical peat water
treatment were still unknown. This research aims to determine the
effect of microbubble ozonation as a treatment before the chlori-
nation process towards changes in the hydrophobicity properties of
DOM fractions and their relationship to the THM4 and HAA5 for-
mation. Based on these results, it is expected that the mechanism of
changes in the DOM fraction resulting THM4 and HAA5 reduction
in tropical peat water treatment using alum coagulation, activated
carbon adsorption, and microbubble ozonation can be explained.
Finally, it is possible to determine the precursor properties of THM4
and HAA5 compounds from each tropical peat water DOM fraction
and suggesting better treatment methods for reducing these two
classes of DBPs.
2. Materials and methods
2.1. Samples and chemicals
Samples were taken from the peat river found in Indragiri Hilir
Regency’s peatland, Riau Province, Indonesia. All fractionation
resins (Superlite DAX-8, Amberlite XAD-4, and Amberlite IR-958),
were purchased from Sigma Aldrich (USA). The fractionation
chemicals (hydrochloric acid, sodium hydroxide, sodium chloride,
sodium sulfite, and methanol), and phosphate buffer were pur-
chased from Merck (Germany). Aluminum sulfate and powdered
activated carbon (1000 mesh; iodine number, 1000 mg/g) were
purchased from Bratachem (Local). The THM4 and HAA5 standards
and extraction reagents were based on our latest research (Qadafi
et al., 2020a, 2020b). Chlorine solution (sodium hypochlorite 25%)
was purchased from Pudak Scientific (local). All solutions were
diluted into mili-Q grade water.
2.2. Experimental procedures
Fig. S1 shows the schematic diagram of the laboratory-scale peat
water treatment including DOM fraction analysis. Alum coagulation
followed by sedimentation was used as pre-treatment to remove
the hydrophobic fraction of DOM. The coagulated peat water was
again treated by powdered activated carbon adsorption placed in a
mechanical shaker for 2 h. Then, Microbubble ozonation was con-
ducted to the treated water in pH 5.5, 7, and 8.5 for acidic, neutral,
and alkaline conditions. The water samples in all sections were
fractionated using fractionation resin and chlorinated to determine
DOM fractions fraction characteristic and THM4 and HAA5 forma-
tion. The same process of microbubble ozonation was also applied
to raw peat water as a control.
M. Qadafi, S. Notodarmojo and Y. Zevi
2.2.1. Coagulation, activated carbon adsorption, and chlorination
The coagulation jar test activated carbon and chlorines dosing
was described elsewhere (Qadafi et al., 2020a). Prior coagulation
process, 150 mg/L of sodium carbonate to increase peat water
alkalinity. The peat water was coagulated using 40.8 mg/L Al2O3 of
Aluminum sulfate. Then, the coagulated peat water was placed in a
mechanical shaker for 2 h activated carbon adsorption using
250 mg/L powdered activated carbon dose. The treated peat water
was filtered using a 2.5 mm ashless filter (Whatman Grade 42)
before placing on a microbubble ozonation reactor. Each sample
was chlorinated for 24 h and stored in the dark at 25  C using
10 mg/L chlorine content of sodium hypochlorite.
2.2.2. Microbubble ozonation
The microbubble ozonation process was carried out based on
our previous research (Qadafi et al., 2020a). Ozone microbubbles
were injected to 9 L of coagulated and activated carbon adsorbed
tropical peat water in a cylindrical Plexiglas reactor with 15 cm
diameter and 60 cm height using a vortex microbubble diffuser. The
ozone flow was maintained at 0.5 L/h with a 3 g/h ozone rate
produced by an ozone generator (Hypro, China) using dehumidified
air as an oxygen source. The water inlet was maintained at 12 L/min
producing a pump pressure of 0.4 MPa. This maintained condition
can produce ozone microbubbles with a 59.6 mm average diameter.
These microbubbles’ size was agreed by the statement of Temesgen
et al. (2017) which states the microbubbles have a tiny diameter
between 10 mm and 100 mm. The water pH was adjusted to 5.5, 7,
and 8.5 for acidic, neutral, and alkaline conditions using hydro-
chloric acid and sodium hydroxide solution. The water was circu-
lated through the reactor, pump, and buffer tank for 60 min
microbubble ozonation time. About 250 mL water was sampled
from the rector every 10 min for analysis. The experiment was
conducted in triplicate for data accuracy.
2.2.3. DOM fractionation
The fractionation of natural dissolved organic matter (DOM) was
conducted according to the previous research (Bing-zhi et al., 2007;
Vieira et al., 2012; Mahmud et al., 2013). Peat water was filtered
using a 0.45 mm membrane to remove suspended particles. Samples
were adjusted to pH 2 then fed onto a Superlite DAX-8 resin, which
absorbs HPOA fraction. The unabsorbed fraction was fed onto an
Amberlite XAD-4 resin, which absorbs the TPH fraction. The
absorbed HPOA and TPH fractions were eluted with sodium hy-
droxide. The unabsorbed, which passed the XAD-4, was fed onto an
anion exchange Amberlite IRA-958 resin, which absorbs HPIC
fraction. This was then eluted with a mixture of sodium hydroxide
and sodium chloride. The remaining effluent of XAD-4 was HPIN
fraction that was not retained by any of the resins. Each of the
processes was conducted in triplicate for data accuracy.
2.3. Analytical methods
The analytical method was conducted based on our latest re-
searches (Qadafi et al., 2020a, 2020b). UVeVis Spectrophotometer
(Shimadzu UV-1700) was used for analyzing UVeVis absorbance,
color (AHPA 8025), and bromide (APHA 4500 BreB) (APHA, 1998).
Argentometric (APHA 4500 CleB) and DPD colorimetric (APHA
4500 Cl-G) methods were used to determine chloride and free re-
sidual oxidant (APHA, 1998). EPA 415.3 method (USEPA, 2003) was
employed to analyze DOC using TOC Analyzer (Shimadzu TOC
VCSH). Gas Chromatography (GC) Agilent 7890 A and Agilent 5975C
Mass Selective Detector (MSD) were used to analyze THM4 and
HAA5. The sample extraction procedure was performed based on
the EPA 551.1 method (USEPA, 1995a), with a modification for GC-
MS (Liu et al., 2015). The THM4 was analyzed using the EPA 552.2
3
Chemosphere 279 (2021) 130642
method (USEPA, 1995b), in which GC-MS (Xie, 2001) was modified
for HAA5 analysis. Agilent 7693 Series Automatic Liquid Sampling
was used for sample injection. The Agilent MSD ChemStation
software was used in the data processing.
3. Results and discussions
3.1. Peat water characteristics
Table 1 showed the natural peat water characteristics as samples
in this research. Natural peat water has a high organic content as
indicated by the high DOC concentration and UV254 absorption (a
measurement of the amount of light absorbed by organic com-
pounds in water). The DOC concentration was intermediate
compared to Borneo Island (Kalimantan) peat water reported by
other researchers (Mahmud et al., 2013; Sudoh et al., 2015) that
reach 20 mg.C/L and 33 mg.C/L respectively. Also, a high SUVA254
value that is greater than 4 and 5.4 indicates that tropical peat
water has a highly hydrophobic DOM (Edzwald and Tobiason,
1999). An acidic pH from natural peat water indicates that the
DOM was found in the form of humic acid and is strongly
hydrophobic.
The chloride content of tropical peat water is categorized as
moderate due to the sea’s tidal influence. However, the bromide
concentration of tropical peat water is relatively high and the same
as the standard seawater bromide concentration reported by other
research (Ged and Boyer, 2014). The high concentration of hydro-
phobic DOM added with the presence of bromide in water requires
adequate treatment, hence the formation of brominated DBPs in
the final chlorination process is controllable.
3.2. Coagulation and activated carbon adsorption
Table S1 showed the effect of alum coagulation, activated carbon
adsorption, and coagulation followed by activated carbon adsorp-
tion on DOM removal. Alum coagulation standalone was successful
in significantly reducing UV254 absorption and dissolved organic
carbon (DOC) concentration. The decrease in DOC concentration by
59.08% caused the SUVA254 value to drop below 4, which indicated
that the coagulation process has succeeded in removing the pre-
dominant hydrophobic DOM (humic and fulvic acid) content
(Edzwald and Tobiason, 1999; Ghernaout, 2014). Since the SUVA254
value between 2 and 4 indicates the mixture of hydrophobic and
hydrophilic DOM (Edzwald and Tobiason, 1999; Matilainen et al.,
2010), it was concluded that the coagulation process could not
remove all the hydrophobic fraction. Same as coagulation stand-
alone, activated carbon standalone could remove DOC concentra-
tion significantly by 50.83%, but the SUVA254 value still higher than
4. Activated carbon adsorption has been noticed as more suitable
for low molecular weight DOM removal compared to high molec-
ular weight DOM (Matilainen et al., 2006). Activated carbon
adsorption that follows the alum coagulation process reduced DOC
again by 51.87% and the SUVA254 value fall below 3 which indicates
the removal of hydrophobic and hydrophilic DOM.
Table 1
Peat water characteristics.
Parameters Mean SD
DOC (mg.C/L) 25.9 1.47
UV254 (1/cm) 1.52 0.02
SUVA254 (L/mg.m) 5.9 0.24
pH 5.0 0.3
Chloride (mg/L) 85 2.5
Bromide (mg/L) 67 2.2
M. Qadafi, S. Notodarmojo and Y. Zevi
3.2.1. Effects of coagulation and activated carbon adsorption on
DOM fractions characteristics
Fig. 1 shows the effect of alum coagulation and activated carbon
adsorption on DOM fraction in peat water. Approximately 50.9% of
the DOM content is dominated by HPOA fractions followed by TPH,
HPIC, and HPIN with concentrations of 26.4%, 14.1%, and 8.3%
respectively. Since HPOA fraction dominates the raw peat water,
alum coagulation standalone tends to significantly reduce the DOC
concentration (Fig. 1a). However, the coagulation process did not
give any further effect on the other three fractions except only
slightly decreasing the TPH fraction. This is consistent with
Edzwald and Tobiason (1999) and Hudori et al. (2020) which stated
that the coagulation process only reduced the concentration of the
hydrophobic fraction containing humic-like compound, and had no
significant effect on the hydrophilic fraction. Activated carbon
standalone has greater TPH, HPIC, and HPIN fraction removal than
coagulation standalone, but lower for HPOA fraction. This may
happen due to activated carbon adsorption was more amenable for
low molecular weight DOM (Matilainen et al., 2006). The combi-
nation process of alum coagulation followed by activated carbon
adsorption has a significant impact on DOM fraction removal.
Coagulation followed by adsorption of activated carbon also
decreased the SUVA254 value of each DOM fraction (Fig. 1b), which
when above 4 indicates high aromaticity of DOM with strong hy-
drophobic, while between 2 and 4 indicates the mixture of hy-
drophobic and hydrophilic fraction in water (Edzwald and
Tobiason, 1999; Matilainen et al., 2010). The coagulation process
could decrease the concentration of DOC of HPOA fraction
dramatically, but the SUVA254 value slightly decreased and still
above 4. This may happen because the isolated sample was only
contained by the HPOA fraction since the other fractions were
Fig. 1. Effects of alum coagulation (Al), activated carbon adsorption (AC), and coagu-
lation followed by powdered activated carbon adsorption (Al þ AC) on the peat waters’
DOM fractions characteristics: (a) DOC, and (b) SUVA254.
4
Chemosphere 279 (2021) 130642
separated by the resins. The coagulation process could not remove
all the HPOA fractions containing humic acid that has high
aromaticity and molar mass, conjugated double bond, and phenolic
structure (Matilainen et al., 2010).
As a continuation of the coagulation process, activated carbon
adsorption has a significant impact on reducing the DOC concen-
tration of all DOM fractions. Furthermore, the remaining HPOA
fraction tends to be completely removed by the activated carbon
adsorption process, while the TPH drops to 20%. A quite significant
decrease also occurred in the hydrophilic fraction where the HPIC
decreased by 50% and the HPIN by up to 40%. This result is
consistent with previous research (Park et al., 2019) which stated
that adsorption of activated carbon reduced the hydrophilic frac-
tion concentration in water, although this decrease is selective to-
wards the DOM molecular weight in water. The decrease in DOC
concentration of each fraction also contributes to that which
occurred in SUVA values.
3.2.2. Effects of coagulation and activated carbon adsorption on
THM4 and HAA5 formation
Fig. 2 shows the coagulation effect accompanied by adsorption
of activated carbon on the THM4 and HAA5 formation after chlorine
disinfection. Raw tropical peat water originating from Indonesian
peatlands has a very high THM4 formation (Fig. 2a), which the total
after chlorination reached 1545.80 ± 8.49 mg/L exceeding the USEPA
standard of 80 mg/L. Similar to our previous study (Qadafi et al.,
2020a), BDCM formation was slightly greater than that of TCM
due to the high concentration of bromide in tropical peat water.
Concerning THM4, HAA5 formation in raw peat water chlorination
was dominated by C-HAA5 (DCAA and TCAA), followed by MBAA
and DBAA respectively (Fig. 2b). Furthermore, MCAA is the least
Fig. 2. Effects of alum coagulation (Al), activated carbon adsorption (AC), and coagu-
lation followed by powdered activated carbon adsorption (Al þ AC) on the peat water’
DBPs formation: (a) THM4, and (b) HAA5.
M. Qadafi, S. Notodarmojo and Y. Zevi
formed HAA5 after the chlorination of raw tropical peat water.
Previous researches (Stuart et al., 2001; Sururi et al., 2019) states
that C-THM dominates the chlorination of raw water containing
hydrophobic DOM. The high concentration of B-DBPs in peat water
is triggered by that of bromide due to the introduction of seawater
(Ged and Boyer, 2014; Qadafi et al., 2020b). The presence of bro-
mide ions triggers the formation of bromate and hypobromous acid
that is more reactive than chlorine during the chlorination process
(von Gunten, 2003b; Teksoy et al., 2008).
The coagulation process using alum succeeded in reducing the
THM4 formation significantly to 80.58 ± 2.32 mg/L, but this value
was still the same or above the USEPA standard. Also, the activated
carbon adsorption standalone has slighter THM4 removal than the
coagulation process. But, the adsorption of activated carbon from
coagulated water was able to reduce the total THM4 by 36.3% that
lead to the total THM4 (t-THM4) formation below USEPA standard.
Adsorption of activated carbon reduced the DBPs formation after
the chlorination process (Utku et al., 2020) because the carbon
absorbed the hydrophilic DBPs precursor that cannot be removed
through the coagulation (Abouleish and Wells, 2015). Based on
these results, only coagulation-filtration and adsorption of acti-
vated carbon are needed to reduce THM4 formation in peat water
treatment after chlorination. Additional treatment is possibly
required when the peat water condition has a higher DOM
concentration.
The total HAA5 formed after chlorination of raw peat water
reached 727.52 ± 32.10 mg/L, much higher than the USEPA standard
of 60 mg/L. The alum coagulation process succeeded in reducing the
total HAA5 (t-HAA5) concentration significantly (74.3%), especially
DCAA and TCAA. Since alum coagulation reduced hydrophobic
DOM (Edzwald and Tobiason, 1999) that is the main precursor of C-
DBPs, the removal of C-HAA formation using this same process has
been quite successful. A quite significant decrease also happened in
the MBAA formation of B-HAA5, while the formation of MCAA and
DBAA was not significant.
Activated carbon adsorption standalone has better HAA5 for-
mation removal, especially DCAA and DBAA compared to alum
coagulation. This result was agreed by Park et al. (2019) that report
the powdered activated carbon could remove the DBPs formation
consistently. The combination process of alum coagulation fol-
lowed by the activated carbon adsorption has better performance
than the standalone processes. Although it succeeded in reducing
the HAA5 formation significantly (88.9%), the process of alum
coagulation followed by activated carbon adsorption has not been
able to reduce the t-HAA5 below the USEPA standard. Hence, the
next process is required to reduce the total formation of HAA5.
3.3. Microbubble ozonation
Microbubble ozonation did not have a significant effect on
changes in DOC concentration but affected UV254 absorbance
(Table S2). Note, the ozonation did not significantly remove the
DOM content in water, but it changed the DOM characteristics
(Sadrnourmohammadi et al., 2020; Siddiqui et al., 1997), but the
process significantly reduced UV254 (Sadrnourmohammadi et al.,
2020). This transforms from a high into low molecular DOM (Qi
et al., 2018; Zhong et al., 2017a, 2017b) that is potentially biode-
gradable (Siddiqui et al., 1997). The ozonation effect on DOM
€
transformation is pH-dependent (Onnby et al., 2018).
The ozone consumption in microbubble ozonation at alkaline
conditions happens quite quickly, followed by neutral. This infer-
able from the decrease in dissolved ozone residues during micro-
bubble ozonation (Fig. S2). At acidic conditions, ozone consumption
appears to be quite stable because of O3 reaction selectivity on high
5
Chemosphere 279 (2021) 130642
molecular weight DOM (Zhong et al., 2017a) under these condi-
tions. On the other hand, high reactivity occurs at alkaline condi-
€
tions due to the formation of OH$ (Hu et al., 2020; Onnby et al.,
2018) that not has selectively reacted with DOM.
3.3.1. Effects of microbubble ozonation on DOM fractions
characteristics
Microbubble ozonation standalone has a significant effect on the
DOM fractions composition of peat water (Fig. S3). Microbubble
ozonation could lead to the degradation of the HPOA fraction at all
pH conditions (5.5, 7, and 8.5) (Fig. S3a) and the TPH fraction at pH 7
and 8.5 (Fig. S3b). On the other hand, the hydrophilic fraction was
increased (Fig. S3c,d). Alkaline condition (pH 8.5) has better per-
formance on the HPOA and TPH fractions removal by 55.0% and
59.2% respectively than the other conditions. In the same condition,
the greater formation of HPIC and HPIN fraction has been achieved.
The microbubble ozonation of peat water could only achieve the
higher DOC concentration removal by 19.5% at the neutral condi-
tions. This could happen due to the formation of volatile DOM
(Zhong et al., 2017a). High pH conditions could increase ozone
reactivity and decomposition into hydroxyl radical (OH$) (von
€
Gunten 2003b; Onnby et al., 2018). Ozonation can transform the
hydrophobic DOM into the hydrophilic (Zhong et al., 2017a, 2017b),
but could not remove it significantly from water (Matilainen et al.,
2006). Since the DOM removal was insignificant, ozonation
standalone could not be used in the peat water treatment process.
Fig. 3 shows the effect of microbubble ozonation of treated peat
water (alum coagulation followed by activated carbon adsorption)
pH conditions on the DOM fractions composition. Ozonation has an
important role in the DOM hydrophobicity in tropical peat water
treatment. Furthermore, the TPH fraction was degraded during the
microbubble ozonation process (Fig. 3a). The TPH fraction is a DOM
fraction that has intermediate polarity between hydrophobic and
hydrophilic DOM and has low aromatic and phenolic carbon
compared to HPOA fraction (Croue  et al., 2003). The TPH fraction is
also defined as a low hydrophobic DOM fraction (Shi et al., 2018).
The pH condition played a significant role in the degradation of the
TPH where alkaline conditions have a faster degradation rate fol-
lowed by acidic and neutral. Conversely, HPIC and HPIN fractions
increased during the microbubble ozonation process as shown in
Fig. 3b and c respectively. HPIN fraction formation is faster than
HPIC, especially at alkaline conditions.
At acidic conditions, ozone reacts slowly and selectively with
DOM, whereas ozone decomposition to OH$ occurs when the pH
€
was increasing (Ozbelge and Erol, 2009; Sadrnourmohammadi
et al., 2020). The acidic condition also caused the DOMs contain-
ing carboxylic and phenolic groups to become less negatively
charged as the effect of protonation (Sadrnourmohamadi et al.,
€
2015) that has lower reactivity to ozone (Onnby et al., 2018; von
Sonntag and von Gunten, 2012). The high decomposition of
ozone to OH at alkaline conditions increases the ozonation effec-
€
tiveness (Onnby et al., 2018), therefore the TPH degradation process
and formation of hydrophilic fractions take place faster.
Each DOM fraction has a different reactivity to ozone (von
Gunten, 2003b). Therefore, the increase in the concentration of
hydrophilic fractions happens due to the reaction between ozone in
two pathways (ozone and OH$) and organic compounds with a
large molecular weight (HMW) to form a lower molecular weight
(LMW) DOMs (von Gunten, 2003b; Onnby € et al., 2018;
Phattarapattamawong et al., 2016). The O3 and OH$ can quickly
react with double bonds and aromatic compounds forming the
hydrophilic DOM such as carboxylic acid, aldehyde alcohols, and
aliphatic (Phattarapattamawong et al., 2016; Zhong et al., 2017a).
M. Qadafi, S. Notodarmojo and Y. Zevi
Fig. 3. Effects of microbubble ozonation on DOM fractions formation in peat water treatment process: (a) TPH, (b) HPIC, and (c) HPIN.
The O3 and DOM reactions happened more selectively by the
electron-rich functional groups such as unsaturated hydrocarbon
bonds and activated aromatic structures (De Vera et al., 2015; Qi
et al., 2018), while OH$ is more reactive and tend to react with all
DOM fractions (Hu et al., 2017; Ratpukdi et al., 2010). In this case,
the LMW formation happened due to degradation of the TPH
fraction that generally had an aromatic carbon (Croue  et al., 2003)
and also changed in the weight between the hydrophilic fractions
themselves. This was because the HPOA fraction has been
completely removed in the process of alum coagulation and acti-
vated carbon adsorption.
3.3.2. Effects of microbubble ozonation on THM4 formation
The effect of microbubbles ozonation on coagulated and
adsorbed peat water using activated carbon on the THM4 formation
can be seen in Fig. 4. Similar to the pre-ozonation process in the
previous research (Qadafi et al., 2020a), chlorinated THM4 (C-
THM4) experienced a decrease in formation during the micro-
bubble process. Ozonation under alkaline conditions (pH 8.5)
reduced TCM formation better, followed by neutral (pH 7) and
acidic (pH 8.5) conditions respectively (Fig. 4a). The pattern of TCM
reduction at alkaline was faster than the other two conditions
where the formation decreased significantly after 20 min of
microbubble ozonation before finally stabilizing. This could happen
6
Chemosphere 279 (2021) 130642
due to high ozone reactivity and decomposition to OH$ at the
€
alkaline condition that more reactive to the phenolic group (Onnby
et al., 2018). Since the phenolic and aromatic group was a precursor
to TCM (Zhang et al., 2017), the degradation could perform faster.
Similar to TCM, BDCM experienced a significant decrease at
alkaline conditions followed by acidic and neutral respectively
(Fig. 4b). In reducing BDCM formation, ozonation under acidic
conditions was slightly better than in the neutral ones. It was re-
ported that ozonation has the ability to reduce C-THM4 formation,
especially TCM (Qadafi et al., 2020a; Sadrnourmohammadi et al.,
2020). The high ozone reactivity at alkaline conditions led to a
high decrease in the C-THM formation. Contrarily, the low ozone
reactivation under acidic conditions causes small changes in chlo-
rinated THM4 precursors (Ӧnnby et al., 2018). The decrease in C-
THM4 formation during microbubble ozonation under acidic con-
ditions was slow due to the small ozone reactivity, therefore the
precursor removal cycle happened (Hansen et al., 2016; von
Gunten, 2003b).
In contrast to C-THM4, the formation of brominated THM4 (B-
THM4) has increased significantly during the microbubble ozona-
tion. CDBM formation was increased by up to 130% and 140% under
neutral and acidic conditions, respectively (Fig. 4c). Meanwhile, it
fluctuates at alkaline during the microbubbles ozonation where the
M. Qadafi, S. Notodarmojo and Y. Zevi
Fig. 4. Effects of microbubble ozonation on THM4 formation in peat water treatment process: (a) trichloromethane (TCM), (b) bromodichloromethane (BDCM), (c) chlorodi-
bromomethane (CDBM), and (d) tribromomethane (TBM).
formation dropped to the lowest point (25% decrease) after 40 min
and rose to the highest (110% increase) at the end of the process
(60 min). The fluctuation could happen due to the formation of B-
DBPs precursor shifted into the bromate as the increase of the
ozone dose in alkaline condition (Siddiqui et al., 1995). The for-
mation of CDBM was influenced by the presence of bromide ions
since it is a high brominated DBPs (Petronijevic et al., 2019). Higher
bromide-to chlorine ratios in the water result in more bromine
incorporation (Hua and Reckhow, 2012). The change of NOM hy-
drophobicity into more hydrophilic that more reactive with
bromine than chlorine also contribute to the formation of B-DBPs
(Petronijevi c et al., 2019) such as CDBM. The increase in the TBM
formation happened quite significantly compared to BCDM and
occurred more rapidly in the microbubbles ozonation under acidic
conditions than at neutral (Fig. 4d). Also, there was a fluctuation in
the TBM formation at alkaline conditions that decreased after
30 min of the process. The increase in B-THM formation in water
ozonation of coagulated tropical peat and activated carbon
adsorption is not much different from the pre-ozonation in the
previous research (Qadafi et al., 2020a).
The increase of B-THM4 formation, especially TBM happened
due to the formation of hydrophilic NOM during the ozonation,
which is the main precursor of B-THM4 (Hua and Reckhow, 2013).
7
Chemosphere 279 (2021) 130642
The increase of THM4 formation under ozonation at acidic condi-
tions was following Galapate et al. (2001). The high bromide con-
centration in peat water triggered hypobromous acid in the
ozonation process (Zhang et al., 2005; Teksoy et al., 2008; Hua and
Reckhow, 2013; Verma et al., 2016) which react with natural
organic compounds in water and form brominated THM4 (von
Gunten, 2003b; Teksoy et al., 2008). The reduction in TBM forma-
tion after an increase of 30 min microbubble ozonation under
alkaline conditions followed Siddiqui et al. (1997). Increasing the
ozone dose at alkaline tends to reduce the formation of hypobro-
mous acid that reacted with DOM to form B-DBPs, but increases
bromate formation (Siddiqui et al., 1997). The fluctuation of TBM
formation at alkaline happened due to the high decomposition of
ozone to OH$ (Jacangelo et al., 1989; Sun et al., 2018).
Since ozonation is only able to decrease C-THM and increase B-
THM formation, then the reduction in t-THM4 concentration only
happened for 10e20 min under neutral and alkaline conditions. At
acidic conditions, tTHM4 increased during the ozonation process.
Mao et al. (2014) stated that the TCM, BDCM, and CBDM concen-
tration decreased with increasing ozone dose. The increase in total
THM4 formation in post-ozonation at neutral conditions corre-
sponds to Hansen et al. (2016), Verma et al. (2016), and Sun et al.
(2018) but in contrast to Chang et al. (2002) and Zhang et al.
M. Qadafi, S. Notodarmojo and Y. Zevi
(2017) which stated that ozonation potentially reduced the tTHM
concentration.
3.3.3. Effects of microbubble ozonation on HAA5 formation
The effect of microbubble ozonation on HAA5 formation in peat
water treatment can be seen in Fig. 5. Similar to THM4, the for-
mation of chlorinated HAA5 (C-HAA5) decreased for 60 min of
microbubble ozonation, and that of MCAA reduced more rapidly
under neutral conditions, followed by acidic and alkaline (Fig. 5a).
After 60 min, the reduction efficiency of MCAA formation was not
significantly different at all pH conditions. Jacangelo et al. (1989)
stated that ozonation significantly reduced the concentration of
DCAA and TCAA precursors. In contrast to MCAA, DCAA decreased
more rapidly under ozonation at acidic but insignificantly under
alkaline conditions (Fig. 5b). The existence of HAA5 which has 2
halogen ions (D-HAA) is often in the spotlight because of its high
formation during the chlorination process in water treatment,
especially DCAA (Farre  et al., 2011). Furthermore, different results
were obtained again on the decrease in TCAA formation (Fig. 5c)
where the pH condition did not have a significant effect even
though there was still a faster decrease in the formation under
neutral conditions. The efficiency for the removal of TCAA is smaller
than the removal of DCAA. Hua and Reckhow (2007) stated that the
formation of HAA5 which has 3 halogen ions (T-HAA) is more
dependent on the presence of hydrophobic NOM than transphilic
and hydrophilic, meanwhile, D-HAA5 depends more on a hydro-
philic NOM (Hua and Reckhow, 2007; Hong et al., 2013).
Similar to B-THM4, brominated HAA5 (B-HAA5) increased dur-
ing microbubble ozonation and MBAA formation elevated signifi-
cantly (Fig. 5d). Furthermore, similar to monohalogenated C-HAA
(MCAA) but in the opposite direction, the formation of MBAA is
faster at alkaline (409%) conditions followed by acidic (330%) and
neutral (194%), which also decreased after 30 min of microbubble
ozonation. A significant increase also occurred in the formation of
DBAA under acidic and neutral conditions (Fig. 5e). At alkaline
conditions, similar to the MBAA and TBM, there was a change in the
pattern of DBAA formation during the microbubble ozonation
process where the increase experienced was faster than in acid and
neutral conditions which reached 439% in just 20 min. However, it
decreased after 30 min until the microbubble process was com-
plete. This occurred due to the high formation of bromate on
ozonation under alkaline conditions (Siddiqui et al., 1997). The
increasing of ozone dose under alkaline conditions could lead to the
increase of bromate formation that minimizes the formation of
hypobromous acid (Siddiqui et al., 1995) that could lead to the
formation of B-DBPs (von Gunten, 2003a). The reduction in DBAA
formation on microbubble ozonation at alkaline conditions at
60 min is still high compared to when ozonation is not involved.
The formation of B-HAA5 shows a significant effect on t-HAA5
formation. Hua and Reckhow (2013) and Jacangelo et al. (1989)
stated that ozonation can increase brominated DBPs (B-DBPs),
and this process can be carried out at low pH to control the for-
mation of bromate (Siddiqui et al., 1997) which can react with DOM
to form B-DBPs. The high level of B-HAA5 formation tends to be
influenced by the presence of HAA5 precursors which are similar to
amino acids and the dicarboxylic group in the form of 3-
oxopentanedioic acid, hydrophilic NOM formed during the ozona-
tion process (Dickenson et al., 2008; Dotson et al., 2009; Bond et al.,
2012). The formation of B-DBPs has a close relationship with the
presence of hydrophilic NOM during the chlorination process (Hua
and Reckhow 2007). Therefore, because ozonation degrades highly
aromatic HMW NOMs to hydrophilic carboxylic-rich LMW (Zhong,
2007a), the formation of B-DBPs is increased (Hua and Reckhow
2013).
8
Chemosphere 279 (2021) 130642
3.4. THM4 and HAA5 precursor formation mechanism
Fig. 6 shows the suggested mechanism of THM4 and HAA5
precursors formation in proposed peat water treatment systems.
The coagulation process can easily remove the HPOA fraction and
few TPH. Meanwhile, alum coagulation cannot remove the hydro-
philic (HPIC and HPIN) fractions. Since HPOA in the form of humic
acid has a higher contribution to THM4 and HAA5 formation in
tropical peat water, the coagulation process significantly reduced
the formation. The activated carbon adsorption has a different role
in the proposed peat water treatment process compared to coag-
ulation. It was selective through molecular weight, while the
coagulation process was through hydrophobic fractions. The
remaining HPOA that has higher molecular weight was easily
removed by the activated carbon adsorption, but still selective to a
hydrophilic fraction. This process led to the removal of THM4 and
HAA5 except for the TBM that slightly increased due to the high
hydrophilic content of activated carbon adsorbed water.
Because the HPOA has been removed by the alum coagulation
and activated carbon adsorption process, the presence of TPH, HPIC
and HPIN fraction is important in the formation of DBPs. The ex-
istence of TPH and HPI NOM played an important role in the for-
mation of DBPs in low humic substance water (Hua and Reckhow
2007). Since the ozonation process was carried out in two mech-
anisms, namely direct O3 and decomposition to OH$, the ozonation
by-product tends to vary based on O3 and OH$ selectivity (von
Gunten, 2003). The direct reaction was highly selective to aromatic
compounds when the indirect mechanism occurred in fast and
non-selective oxidation (Zhong et al., 2017b). The TPH fraction that
contained more aromatic-acid-like compounds (Wang et al., 2016)
tends to be easily oxidized, directly and indirectly, producing more
hydrophilic fractions. Furthermore, the hydrophilic fractions
potentially passed through indirect reactions giving intermediate
product, peroxide, acids, and aldehydes (Zhong et al., 2007a; Hua
and Reckhow, 2013).
The reduction of TPH fraction in the microbubble ozonation
process tends to reduce the formation of C-THM4 and C-HAA5.
Furthermore, the formation of a hydrophilic fraction (HPIC and
HPIN) increased the amount of B-THM4 and B-HAA5 after the final
chlorination process especially in acid and neutral conditions.
Higher ozone doses at alkaline conditions have the ability to reduce
the B-DBPs formation. This occurred due to the high ozone
decomposition in the alkaline condition that led to the formation of
bromate instead of hypobromous acid, the precursor of B-DBPs
(Siddiqui et al., 1997). Since the formation of C-DBPs was still
dominant in the coagulated and activated carbon adsorbed tropical
peat water, the ozonation process had a significant impact on the
reduction of tTHM4 and tHAA5 formation. Based on this treatment
process, it is concludable that the microbubbles ozonation process
can be used to reduce the formation of THM4 and HAA5 in a certain
time and pH condition to maintain the formation of B-DBPs under
control.
3.5. Effect of microbubble ozonation on USEPA regulation standards
achievement
Microbubble ozonation standalone could reduce THM4 and HAA
formation (Fig. S4), but the formations still extremely exceed the
USEPA standards. Microbubble ozonation could only reduce THM4
formation by 3.86% at the acidic condition when neutral and
alkaline conditions increase the formation (Fig. S4a). The HAA5
formation of raw peat water was reduced by 9.93% and 6.07% at
acidic and neutral conditions respectively, but alkaline conditions
uplift the formation (Fig. S4b). Since the ozonation process could
not reduce the DOC concentration significantly (Matilainen et al.,
M. Qadafi, S. Notodarmojo and Y. Zevi Chemosphere 279 (2021) 130642

Fig. 5. Effects of microbubble ozonation on HAA5 formation in peat water treatment process: (a) chloroacetic acid (MCAA), (b) dichloroacetic acid (DCAA), (c) trichloroacetic acid
(TCAA), (d) bromoacetic acid (MBAA), and (e) dibromoacetic acid (DBAA).

2006), the DBPs formation still shows high formation. Ozonation could not be removed efficiently by the ozone standalone (Qadafi
could transform high molecular weight NOMs to low molecular et al., 2020a).
weight NOMs that are relatively volatile (Zhong et al., 2017a). On The microbubble ozonation as an additional treatment after
the other hand, the high presence of DOC in natural peat water coagulation and activated carbon adsorption has successfully

9
M. Qadafi, S. Notodarmojo and Y. Zevi
Fig. 6. Proposed mechanism of THM4 and HAA5 precursors formation on peat water treatment processes based on DOM fractions hydrophobicity.
reduced the formation of total THM4 and HAA5 under USEPA
standards (Fig. S5). The optimum condition of microbubble ozon-
ation was achieved at acidic conditions (pH 5.5) after 20 min.
Although was increased in the optimum condition compared to
without microbubble ozonation, the t-THM4 formation was still
below the USEPA standard (Fig. S5a). On the other hand, t-HAA5
formation decreased below USEPA standard (Fig. S5b). The pattern
of t-THM4 formation only shows a reduction in alkaline conditions.
Conversely, the t-HAA5 shows the fluctuation at all pH conditions
since a different pattern of C-HAA5 and B-HAA5 formations.
Ozonation in low to medium pH conditions could reduce the
formation of C-DBPs (Zhong et al., 2017a; Qadafi et al., 2020a). The
ozone residue was more stable under low pH conditions (Siddiqui
et al., 1995), but B-DBPS can form (Siddiqui et al., 1997).
Conversely, ozonation at At higher pH condition, ozonation at high
dose could lead to the formation of bromate (Siddiqui et al., 1997)
so that the fluctuation could happen. The pH condition plays a
significant role in controlling DBPs precursor formation during
ozonation (von Gunten, 2003a).
3.6. Effect of inorganic salts on peat water ozonation
Inorganic salt has a significant role in the ozone oxidation pro-
cess (Boncz et al., 2005) and disinfection by-product removal
(Deeudomwongsa et al., 2017), and its speciation (Fang et al., 2018).
10
Chemosphere 279 (2021) 130642
The presence of inorganic salts could affect the ozone solubility and
bubble size distribution that contribute to the mass transfer effi-
ciency (Boncz et al., 2005). Since inorganic salt has a radical-
scavenging effect, the presence of inorganic salts also could affect
ozone selectivity on NOM (Boncz et al., 2005; Lam et al., 2019). The
presence of inorganic salt could also carry the halogen ion such as
bromide, chloride, and iodide into the water that affects the DBPs
speciation during the disinfection process (Fang et al., 2018;
Manasfi et al., 2017; Pantelaki and Voutsa, 2018). Considering the
fact that most of the peat river is located in the coastal and sub-
coastal area and a buffer between the salt and fresh water (Page
et al., 2006). The research regarding the effect of inorganic salts
on ozone microbubble mass transfer and DBPs speciation in peat
water treatments should be done in future studies.
4. Conclusions
The microbubble ozonation process of peat water which has
experienced alum coagulation and activated carbon adsorption
process has significantly reduced the total formation of THM4 and
HAA5 below the USEPA standards. The alum coagulation and acti-
vated carbon adsorption process removed the whole HPOA fraction
but still left other fractions. Due to the absence of the HPOA frac-
tion, the TPH fraction which had hydrophobic properties became
the main precursor for C-THM4 and C-HAA5. Furthermore, the
M. Qadafi, S. Notodarmojo and Y. Zevi
hydrophilic fractions (HPIC and HPIN) were more liable to be pre-
cursors of B-THM4 and B-HAA5. The microbubble ozonation pro-
cess succeeded in reducing the concentration of TPH fraction in
peat water which led to a decrease in the formation of C-THM4 and
C-HAA5. Meanwhile, the opening of an aromatic ring from TPH
fraction in the ozonation process increased the concentration of
HPIC and HPIN which triggered the formation of B-THM4 and B-
HAA5, especially at acidic and neutral conditions. The B-DBPS de-
creases after 20e30 min microbubble ozonation at alkaline con-
ditions. Because C-DBPS dominates the formation of THM4 and
HAA5 in peat water, ozonation at low doses tends to reduce t-THM4
and HAA5, while their overall formation is potentially increased by
a high dose.
Credit author statement
Muammar Qadafi: Conceptualization, Methodology, Investiga-
tion, Formal analysis, Writing e original draft, Project administra-
tion, Suprihanto Notodarmojo: Supervision, Conceptualization,
Yuniati Zevi: Supervision, Validation, Investigation
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This research was funded by The Indonesia Endowment Fund
for Education (Lembaga Pengelola Dana Pendidikan/LPDP), Minis-
try of Finance Indonesia, Grant No. 201705210110920. The authors
express gratitude to the Integrated Laboratory, Poltekkes Kemenkes
Bandung, for providing a laboratory analysis facility.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2021.130642.
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