Accepted Article

PROF. CONG LI (Orcid ID : 0000-0003-0020-4663)

Article type : Research Article

Removal of disinfection byproducts and their precursors

during drinking water treatment processes

Qiufeng Lin1, Feilong Dong1, Yunxia Miao1, Cong Li2*, Weicheng Fei1

1College of Civil Engineering and Architecture, Zhejiang University, Hangzhou 310027, China.
2School of Environment and Architecture, University of Shanghai for Science and Technology,
Shanghai, 200433, China
E-mail: congil@aliyun.com

*Corresponding author
Email addresses: congil@aliyun.com (C. Li)

This article has been accepted for publication and undergone full peer review but has not been through the
copyediting, typesetting, pagination and proofreading process, which may lead to differences between this
version and the Version of Record. Please cite this article as doi: 10.1002/WER.1263

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Accepted Article
Abstract
In this study, we investigated the control efficiency of a wide variety of disinfection
byproducts (DBPs) (including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitiles
(HANs), haloketones (HKs), haloaldehydes (HAs) and trihalonitromethanes (THNMs)) with
different drinking water treatment processes including pre-ozonation, coagulation-sedimentation,
sand filtration and ozone combined with biological activated carbon (O3-BAC) advanced
treatment processes. The assessment of the treatment efficiency regarding the removal of organic
matter was measured by the excitation emission matrix (EEM) spectra. There was a superior
efficiency in reducing the formation of DBPs and their precursors by different drinking water
treatment processes. Though some DBPs such as THMs could be promoted by ozonation, these
byproducts from ozonation could be degraded by the following BAC filtration process. In
addition, the organic matter from the aromaticity, fulvic acid-like, protein and soluble microbial
byproducts-like regions could be further degraded by the O3-BAC treatment.
Keywords: Disinfection byproducts (DBPs), Drinking water, Oxidation, Biological treatment

Research Highlights
 A wide variety of DBPs in different drinking water treatment processes was investigated.
 The treatment efficiency regarding the removal of organic matter was measured.
 Some DBPs such as THMs and HAAs could be increased by ozonation.
 The removal percentage of nitrogen precursors and organic carbon would be increased by
BAC filtration.

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Accepted Article

1. Introduction
Since the early 20th century, the disinfection of drinking water successfully protected public
health and it also reduced the morbidity of waterborne diseases including amoebic dysentery,
cholera and typhoid fever (Dong, Li, He, Chen, & Mao, 2017; Dong, Li, Lin, & Duan, 2018; Li et
al., 2018; Selma & Panagiotis, 2011). As we all know, chlorine is effective in deactivating
pathogens, however, it would lead to concern about the formation of disinfection byproducts
(DBPs) (Dong, Li, Crittenden, et al., 2018; Du et al., 2017; Li et al., 2018). The reactions between
natural organic matter (NOM) and oxidants would form the DBPs in drinking water (Jones,
Saglam, Song, & Karanfil, 2012). Currently, more than 600 DBPs have been identified in drinking
water (Richardson, 2003; Richardson, Plewa, Wagner, Schoeny, & DeMarini, 2007; M. Yang &
Zhang, 2016).
Trihalomethanes (THMs) including chloroform (TCM), bromodichloromethane (BDCM),
dibromochloromethane (DBCM) and bromoform (TBM), and haloacetic acids (HAAs) including
monochloroacetic acid (MCAA), monobromoacetic acid (MBAA), dichloroacetic acid (DCAA),
bromochloroacetic acid (BCAA), dibromoacetic acid (DBAA), trichloroacetic acid (TCAA),

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 bromodichloroacetic acid (BDCAA), dibromochloroacetic acid (DBCAA) and tribromoacetic acid
Accepted Article
(TBAA), are the two most prevalent groups of DBPs, which have obtained crucial quantities of
research efforts (Mao, Wang, Guo, Yang, & Xie, 2016; Tuqiao Zhang, Dong, Luo, & Li, 2018;
Tianyang Zhang et al., 2015; Zhi et al., 2018). According to their cytotoxicity and genotoxicity,
their concentration levels have been regulated in many countries. A maximum contaminant level
(MCL) of 80 μg/L for THMs and 60 μg/L for HAAs were established by the US Environmental
Protection Agency (USEPA) (USEPA, 2006; Ye et al., 2013). In China, the maximum
concentration level of TCM, BDCM, DBCM and TBM were set at 0.06 mg/L, 0.06 mg/L, 0.1
mg/L and 0.1 mg/L, respectively. For HAAs, it was only specified the MCL of 0.05 mg/L and 0.1
mg/L for DCAA and TCAA in China, respectively.
Currently, increasing amount of attention has been focused on non-regulated DBPs such as
haloaldehydes (HAs), haloketones (HKs), haloacetonitiles (HANs) and trihalonitromethanes
(THNMs), due to their more genotoxic and cytotoxic in mammalian cell assays than that of those
regulated DBPs such as THMs and HAAs (J. Hu et al., 2018; Mao et al., 2016; Plewa et al., 2008;
Richardson et al., 2008; Richardson et al., 2007). HAs also drew a lot of attention, followed by
HKs (X. Wang, Mao, Tang, Yang, & Xie, 2015). However, the MCL for HAs is only regulated by
few countries except 20 μg/L (in Australia) and 10 μg/L (in China) of chloral hydrate (CH),
respectively (Huang, Zhu, Gan, Chen, & Yang, 2017). Nitrogenous DBPs, especially halogenated
nitrogenous DBPs, such as HANs and THNMs, have also received increasing attention. Due to the
increasing algae blooms, their precursors were occurred more frequently in water sources (H. Hu
et al., 2016; X. Liu et al., 2013; F. Yang, Zhang, Chu, Yin, & Templeton, 2014; Yu, Lin, Chen, &
Tao, 2015).
According to the complex composition of DBPs’ precursors (mainly mixed by compounds
such as algae and bacteria products, amino acids and proteinaceous compounds), the conventional
treatments are difficult to completely remove the precursors of DBPs (Chu, Gao, Templeton, &
Yin, 2011). Hence, it is a relatively effective way to remove the precursors of DBPs by
pretreatment and advanced treatment technologies (Chu, Gao, Krasner, Templeton, & Yin, 2012;
Chu, Gao, Yin, Deng, & Templeton, 2012). Taking the environmental impact and low

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 consumption into account, pre-ozonation and ozone combined with biological activated carbon
Accepted Article
(O3-BAC) have been widely adopted in present drinking water treatment plants (DWTPs), which
promotes the removal rate of organic matter and ammonia nitrogen. According to Mao et al.’s
study (Mao et al., 2016), the total drinking water treatment capacity of O3-BAC process was at
approximately 20 million m3/d by 2013 in China. It is found that pre-ozonation process can
enhance the removal of algae, while algae is difficult to be removed by conventional coagulation
treatment (Widrig, Gray, & McAuliffe, 1996). Moreover, the precursors of THMs and HAAs can
be remarkably reduced by the O3-BAC process (Chu, Gao, Yin, et al., 2012; Chu, Li, Gao,
Templeton, & Zhang, 2015).
The water source of the DWTP in the experiment was taken from Taihu Lake (Zhejiang
Province, China). Algae blooms occur in Taihu Lake every year, mainly from May to November
(Cheng et al., 2014; Han et al., 2009). Nevertheless, little is known on the comprehensive
treatment efficiency of seasonal high algae water for the formation potentials (FPs) of regulated
and non-regulated DBPs during the advanced drinking water treatment processes. Therefore, the
aims of this study were as follows: (1) to research the formation and the removal of regulated and
non-regulated DBPs during different drinking water treatment processes (including pre-ozonation,
sand filtration, post-ozonation and BAC filtration); (2) to assess the effects of different drinking
water treatments on the removal precursors of DBPs, as well as the changes of physicochemical
properties of dissolved organic matter. It will be helpful to control DBPs and optimize drinking
water treatment processes.

2. Materials and methods

2.1 Chemicals and regents
For regulated DBPs, the four common THMs (TCM, BDCM, DBCM and TBM) and five
HAAs (MCAA, DCAA, TCAA, BCAA and DBAA) were measured. For non-regulated DBPs,
including CH, two HKs (1,1-dichloro-2-propanone (1,1-DCP) and 1,1,1-trichloro-2-propanone
(1,1,1-TCP)), four HANs (dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN),
dibromoacetonitrile (DBAN) and bromochloroacetonitrile (BCAN)) and trichloronitromethane
(TCNM) were analyzed.

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 All chemicals were at least of analytical grade except as noted. The standards of four THMs
Accepted Article
and five HAAs were purchased from Supelco (Supelco Park, PA, USA). The standards of four
HANs, two HKs, TCNM and CH were obtained from Aladdin (China). The free chlorine solution
was made by a 5% sodium hypochlorite solution (NaOCl, Aladdin, China). Methyl tert-butyl ether
(MTBE) was obtained from Sigma-Aldrich with chromatography grade for liquid-liquid
extraction. Other reagents, including sulfuric acid (H2SO4, analytical grade), bicarbonate
(NaHCO3, analytical grade), ascorbic acid ( ≥ 99%), methanol ( ≥ 95%) and sodium sulfate
( ≥ 95%) were obtained from Sinopharm Chemical Reagent (Shanghai, China).
2.2 Sampling and chlorination
The collection of water samples was from a modernized DWTP located in Zhejiang (China).
Fig.1 shows the flow chart of drinking water treatment processes. The DWTP operated at 200,000
m3/d. The treatment processes used in the DWTP contain pre-ozonation (O3 dosage: 0.5-1.5
mg/L), coagulation-sedimentation, sand filtration, post ozonation (O3 dosage: 0.5-3.0 mg/L), BAC
filtration and chlorination disinfection. From each sampling site, the samples were collected and
then stored in 5 L glass bottles and then stored in the dark at 4 ℃ in the laboratory. As the
samples were taken from DWTP, all experiments were completed within 24 hours.
In this DWTP, the water which treated by BAC filtration process was chlorinated for
approximately four hours before being transported to the pipe network. In addition, the maximum
chlorine dosage for the BAC filtered water was 3 mg/L during the disinfection process in this
DWTP. In order to simulate DBPs produced by each treatment processes, the chlorine dosage and
contact time were set at 3 mg/L and four hours, respectively.1 L water of each sample was taken
into 1 L brown bottle and the DBPs FP test was initiated at 3 mg/L as free Cl2. The sample was
kept in the dark at 25 ℃ for four hours. For sampling time, the experimental steps were as
follows: (1) 10 mL of sample was taken immediately for residual chlorine determination; (2) when
30 mL of sample was collected, excess ascorbic acid was added as a quenching agent to stop any
further reactions with chlorine for HAA determination; (3) when another 30 mL of sample was
collected, excess ascorbic acid was added to stop the reaction for the other DBPs determination.
The free chlorine concentration of each sample was shown in Table S1. The removal percentage of

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 these 17 DBPs by different treatment processes were calculated by Eq. (1):
Accepted Article Removal (%) =
𝐶𝐴 ― 𝐶𝐵
× 100%
𝐶𝐴

where CA is concentration detected in raw water after chlorination and CB is concentration detected
by each treatment process after chlorination.
[Fig. 1]
2.3 Analysis
The free residual chlorine was measured by DR2800 (HACH). The detection of pH uses pH
meter (PhS-3C, Shanghai Lei Magnetic Instrument Factory). The turbidity of water sample was
tested by portable turbidity meter (2100Q, HACH). The absorbance of UV254 was measured by
DR-6000 (HACH). The total organic carbon (TOC) was measured by a TOC analyzer
(TOC-VCPH, Shimadzu). The Chlorophyll a was measured by PHYTO-PAM (Zealquest
Scientific Technology Co., Ltd.). The detection of bromide ions was tested by using ICS-2000
(Dionex, USA), and their analysis conditions are shown in Table S2.
The extraction processes of five HAAs were as follows: (1) a 30 mL of water sample was
extracted by addition of 3 mL MTBE and 2.4 g anhydrous sodium sulfate; (2) the sample was
shaken in a mechanical shaker for 3 min and then was allowed to stand for 5 min; (3) 2 mL of the
upper MTBE layer of the sample was taken into a screw glass centrifuge tube and then was added
by addition of 3 mL methanol sulfate solution (10%); (4) the sample was heated in a 50 ℃ water
bath for 2 hours and then was placed in a 4 ℃ refrigerator for 10 minutes; (5) the sample was
added by addition of 5 mL sodium sulfate solution (150g/L) and then was shaken for 3 min and
was stood for 5 min; (6) the bottom aqueous layer of the sample was removed and 1 ml of
saturated sodium bicarbonate solution was added; (7) the sample was shaken and stood for 3 min
and 5 min, respectively. Five HAAs were detected by gas chromatography/mass spectrometry
(GCMS-QP2010 SE, Kyoto, Japan) with an Agilent HP-5 MS capillary column (30 m × 0.25 mm
× 0.25 µm, Agilent, Santa Clara, CA, U.S.). The operating parameters of GC-MS are shown in
Table S3.
The analysis of the other DBPs was conducted by liquid-liquid extraction (LLE) as a

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 pretreatment technology. The extraction processes of other DBPs were as follows: (1) a 30 mL of
Accepted Article
water sample was extracted by adding 2 mL MTBE and 8 g anhydrous sodium sulfate in order to
better stratification; (2) the sample was shaken in a mechanical shaker for 5 min and then was
standed for 30 min. The separation and identification of other DBPs were detected by gas
chromatography with electron capture detector (GC-ECD, Thermo Fisher) which was equipped
with an Agilent HP-5 capillary column (30 m × 0.25 mm ×0.25 μm, Agilent, Santa Clara, CA,
U.S.). The operating parameters of GC-ECD are shown in Table S4 and the limit of detection and
calibration curves is shown in Table S5.
Excitation emission matrix (EEM) spectra was carried out by using a Hitachi F-4600
fluoresence spectrophotometer (Hitachi, Japan). The operating parameters of EEM are shown in
Table S6.

3. Results and discussion

3.1 Water characteristics
Table 1 shows the water characteristics of each water sample. The pH of water sample
decreased from pH 8 to pH 7.5 by each process and the finished water was generally weakly
alkaline. The pre-ozonation process was unable to substantially reduce DOC level and its removal
efficiency only reached 7.12%. While after the conventional treatment
(coagulation-sedimentation-filtration), post ozonation and BAC filtration, the removal efficiency
reached 31.47%, 42.66% and 59.87%, respectively. In addition, it was shown that the removal
percentage of turbidity reached 42.11% (pre-ozone water), 99.55% (filtered water), 99.63%
(post-ozone water) and 99.74% (BAC filtered water), respectively. The turbidity of finished water
in this DWTP could be stably controlled below 0.1 NTU.
A similar tendency could be seen in the removal efficiencies of UV254 and their removal
percentages were 24.14% (pre-ozone water), 84.73% (filtered water), 91.13% (post-ozone water)
and 92.12% (BAC filtered water), respectively. As we all know, ozone could easily react with
carbonyl bonds or olefinic and damage benzene rings (J. Hu et al., 2018; Nishijima & Speitel,
2004). Hence, the aromatic organics, which contained the structures of the unsaturated carbon
bonds, could be strongly absorbed at 254 nm and removed with prominent efficiency. Relating to

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 the organic compounds' hydrophobicity and aromaticity, the SUVA was a quantitative indicator
Accepted Article
(Kikuchi et al., 2017). Some low UV254-absorbing compounds could be consumed by
microorganisms and it would leave other aromatic compounds with UV254 absorbance (Y. Chen,
Lin, & Chen, 2019). Moreover, a slight increase in SUVA could be found after BAC treatment,
which probably because of the lower DOC after BAC treatment.
Chlorophyll is one of the important components of algae organisms. All algae contain
chlorophyll a, so the level of chlorophyll a can reflect the type and quantity of algae in the water
(Ankarali, Demir, Kanik, & Keskýn, 2005; Kasprzak, Padisak, Koschel, Krienitz, & Gervais,
2008). The chlorophyll a of raw water was 9.25μg/L and it decreased to 1.32 μg/L after all
treatments, whose removal efficiency was 85.73%. It was indicated that the processes of this
DWTP were effective for eutrophic water treatment.
As shown in Table 1, the bromide ion concentration level of this DWTP was relatively high. It
was ineffective to remove the bromide by drinking water treatment processes, except that
pre-ozonation and conventional treatment processes. Although the bromide ion concentrations of
pre-ozone water and post-ozone water were similar, it increased dramatically after BAC filtration.
Maybe it is because the bromide ion desorption on the surface of activated carbon led to the
increase of bromide ion. On the whole, the results indicated that the water quality was
significantly improved by the O3-BAC process.
[Table 1.]
3.2 Removal of regulated DBPs
Fig. 2 shows the removal percentage of THM FPs. The removal percentages of THMs’
precursors reached 13.86% and 38.86%, respectively, using the pre-ozonation treatment and the
conventional treatment. After post ozonation treatment, the removal percentage of THM FPs
decreased to 16.83%. Nonetheless, the removal percentage of THM FPs could be further increased
to 60.62% by the O3-BAC advanced treatment. From Fig. 3, the removal percentage of HAA FPs
shows a similar trend with that of THM FPs. The removal efficiencies of each process were
-27.33% (pre-ozone water), 14.02% (filtered water), -30.86% (post-ozone water) and 36.64%
(BAC filtered water), respectively. In sum, with the basis of conventional treatment, the O3-BAC

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 advanced treatment significantly promoted the removal of THMs and HAAs in current drinking
Accepted Article
water treatment processes.
In addition, it was clear that the removal percentage of DOC was improved after ozonation
treatment although it had an adverse effect on DBP FPs. After pre-ozonation and main ozonation,
both the THM FPs and HAA FPs increased dramatically, especially for brominated HAAs. During
the conventional treatment, the removal percentages of TBM, BCAA and DCAA increased by
7.85%, 61.43% and 39.7%, respectively. Although the precursors of THMs and HAAs were able
to be reduced by sand filtration treatment, the removal percentages were much lower than that of
BAC filtration treatment. After post ozonation treatment, the removal percentages of TBM, BCAA
and DCAA decreased to -49.69%, -58.93% and -79.29%, respectively. It was indicated that the
amount of TBM, BCAA and DCAA produced by pre-ozonation chlorination was more than that
generated by chlorination of raw water, hence the removal efficiency became negative. Though
ozone has a strong power of oxidation, the organic matters could not be mineralized drastically by
ozonation. It was known that high-molecular weight organic matter could be transformed by ozone
into the low-molecular weight organic matter, which accounts for the formation of TBM, BCAA
and DCAA (Chu, Gao, Yin, Krasner, & Mitch, 2014; Dotson, Olya, Debbie, & Linden, 2010;
Wert, Rosario-Ortiz, Drury, & Snyder, 2007; Y. Zhang, Chu, Yao, & Yin, 2017). A previous study
showed that many compounds such as aldehydes, ketones, and alcohols which were confirmed to
be significant precursors of DBPs, were formed by pre-ozonation and main ozonation treatment
processes and these compounds would lead to a notable increase of the THM FPs and HAA FPs
(Zha, Ma, Wu, & Liu, 2016). Nonetheless, these byproducts from ozonation could be further
degraded by BAC filtration (Mao, Wang, Tang, Yang, & Xie, 2015). The synergistic function
between ozonation and BAC may contribute to the promotion of removal of DBPs’ precursors
(Chien, Kao, Dong, Chen, & Chen, 2007). To conclude, the performance of the combined
O3-BAC treatment was much better than the single ozonation process in controlling the formation
of DBPs.
[Fig. 2]
[Fig. 3]

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 3.3 Removal of non-regulated DBPs
Accepted Article
From Fig. 4, the removal percentage of the HAN FPs gradually increased by the following
treatment steps in DWTP except the post ozonation process. In this study, the pre-ozonation,
conventional treatment, post ozonation and BAC filtration processes removed 5.18%, 53.38%,
29.50% and 71.80% of the precursors of HANs, respectively. In summary, the formation of DBPs
could be well controlled by the conventional processes (coagulation, sedimentation and filtration)
(Tom, Jin, Templeton, & Graham, 2011). Of note, BAC filtration could further improve the
removal of HAN FPs, which was mainly because the dissolved organic nitrogen (DON) could be
better removed by the O3-BAC advanced treatment than DOC (Y. Zhang et al., 2017). Moreover,
the removal percentage of brominated HANs exhibited the same trend as brominated THMs and
brominated HAAs. However, the biodegradability of N-containing organic matters could be
promoted by ozonation and so they would be removed by subsequent BAC filtration (Y. Zhang et
al., 2017).
[Fig. 4]
As shown in Fig. 5, it shows the removal efficiencies of CH, TCNM, 1,1-DCP and
1,1,1-DCP. The pre-ozonation, conventional treatment, post ozonation and BAC filtration
processes removed 24.07%, 78.66%, 42.10% and 84.56% of the precursors of CH, respectively. It
was clear that ozonation could promote the formation of CH and this result was similar with Mao
et al.’s study (Mao et al., 2016). Ozone would react with dissolved organic matter to form the
compounds that contained the acetyl group, and these compounds had a higher potential to form
CH (Mcknight & Reckhow, 1992).
Moreover, ozonation also could promote the formation of TCNM. In this study, after
pre-ozonation and post ozonation treatment, the removal percentage of TCNM decreased to
-25.00% and -56.25%, respectively. It showed that the formation of TCNM generated by
pre-ozonation and post ozonation chlorination was more than that produced by the chlorination of
raw water. Some previous studies indicated that ozonation would dramatically increase the
formation of TCNM (Bond, Huang, Templeton, & Graham, 2011; J. Hu et al., 2018; Jiang,
Goodwill, Tobiason, & Reckhow, 2016). In Mao et al.’s study, the formation of TCNM increased

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 with the dosage of ozone increasing (Mao, Wang, Yang, Wang, & Xie, 2014). The dosage of
Accepted Article
ozone in post ozonation treatment was much larger than that of pre-ozonation, so the formation of
TCNM in main ozonation was higher. However, those TCNM and aldehydes could be further
removed with subsequent biofiltration (Chu, Gao, Yin, et al., 2012).
As for the HKs, 1,1-DCP and 1,1,1-TCP were the main species detected. The removal
percentages of the two HKs of each process were 9.32% (pre-ozone water), 61.35% (filtered
water), -30.59% (post-ozone water) and 70.55% (BAC filtered water), respectively. It was shown
that ozonation would increase the formation of HKs, especially 1,1,1-TCP. It was known that the
precursors of 1,1-DCP could be generated by ozonation and it could be further oxidized to
1,1,1-TCP rapidly by the chorine (F. Wang et al., 2014). Therefore, above results were expected.
[Fig. 5]
3.4 Changes of DBP precursors
The dissolved organic matter (DOM) was analyzed by EEM spectra in the raw water,
pre-ozonation, sand filtration, post ozonation and BAC filtration, as shown in Fig. 6. According to
Chen et al., (Wen, Westerhoff, Leenheer, & Booksh, 2015), the EEM spectra were divided into
five regions (Table 2). As shown, DOM in the raw water (Fig. 6a) and pre-ozonated water (Fig.
6b) both had several peaks in the aromatic protein (AP)-like region and fulvic acid-like region.
However, the fluorescence intensities of these peaks were remarkably reduced after the
conventional treatment and there is no significant peak of the AP-like region and fulvic acid-like
region was found in other treated water. It may attribute to the conventional treatment processes,
which could remove the most compounds of AP-like substances and fulvic acids (H. Liu, Hu, Zhao,

& Qu, 2009; Yan, Wang, You, Qu, & Tang, 2006).
As for the soluble microbial-like products (SMP), two obvious peaks were observed in Region
IV (one peak centering at 305 nm excitation and 340 emission wavelengths with an intensity of
454.00 a.u., and the other peak centering at 315 nm excitation and 355 nm emission wavelengths
with an intensity of 313.10 a.u.,). After pre-ozonation and conventional treatments, the intensities
of two peaks only decreased by 26.89% (Ex/Em: 305 nm/340 nm) and 22.10% (Ex/Em: 315
nm/355 nm), respectively. Previous study showed that SMP-like substances were the significant

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 precursors of nitrogenous DBPs (such as HANs and TCNM) (Chu, Gao, Deng, & Krasner, 2010).
Accepted Article
The intensities of two peaks decreased by 77.91% (Ex/Em: 305 nm/340 nm) and 78.31% (Ex/Em:
315 nm/355 nm) by O3-BAC process. It was shown that O3-BAC process was able to reduce the
precursors of HANs and TCNM, which was consistent with the results of earlier study (Chu, Gao,
Yin, et al., 2012).
In addition, a maximum fluorescence was occurred in Region V. In the raw water, a peak was
centered at 335 nm excitation and 380 nm emission wavelengths with an intensity of 209.90 a.u.,.
While after pre-ozonation treatment, the intensity of the similar center of peak (Ex/Em: 335
nm/380 nm) decreased to 190.70 a.u.. The intensity of this peak only decreased by 8.13% after the
conventional treatments, and it was showed that the pre-ozonation and the conventional treatments
were ineffective at removing the humic acid-like substances. However, after the O3-BAC
treatment, the intensity of this peak from influent to effluent was 175.20 a.u. to 48.30 a.u., with the
intensity reduction of 72.73%. It was indicated that the humic acid-like substances could be
significantly reduced by the O3-BAC process.
Overall, the treatment efficiencies concerning the removal of organic matter were represented
by the EEM spectra. The organic matters from the aromaticity, fulvic acid-like, protein and
soluble microbial byproducts-like regions could further reduced by the O3-BAC advanced
treatment.
[Fig. 6]
[Table 2.]

4. Conclusion
The conventional processes combined with the O3-BAC processes have the abilities of
removing DBP precursors’ indicators. The removal percentages of DOC, turbidity, UV254 and
chlorophyll a reached 59.87%, 99.74%, 92.12% and 85.73%, respectively, after pre-ozonation
treatment, conventional treatment and O3-BAC process. The formation of varieties of halogenated
DBPs could be reduced by the following treatment processes (including pre-ozonation treatment,
conventional treatment and O3-BAC process). The removal efficiencies of THMs, HAAs, HANs,
HKs, CH and TCNM were 60.62%, 36.64%, 71.80%, 70.55%, 84.36% and 93.75%, respectively.

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 The ozonation had an adverse effect on DBP FPs (e.g. THMs and HAAs), however these
Accepted Article
byproducts from ozonation could be further degraded through BAC filtration. Due to ozonation,
the high-molecular weight organic matter could be transformed into low-molecular weight organic
matters. Moreover, the removal percentage of nitrogen precursors and organic carbon would be
increased by BAC filtration. Therefore it would reduce the formation of chlorinated DBPs. The
results of EEM indicated that the synergistic function between ozonation and BAC could decrease
the substances from SMP-like and humic acid-like regions. To sum up, the performance of the
combined O3-BAC treatment was much better than the single ozonation process in controlling the
formation of DBPs. However, the removal percentage of HAAs was relatively low by these
multiple drinking water treatment processes. In the future, the effects of seasonal variation,
different raw water quality and operating parameters of O3-BAC process need to be assessed for
better controlling DBPs.

Acknowledgement
This work was supported by the National Major Projects for Water Pollution Control and
Treatment (Grant No. 2017ZX07201003) and the National Natural Science Foundation of China
(No. 51778565, 51578487).

Appendix A. Supplementary data

Supplementary data regarding this article could be found in the online version.

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Accepted Article
Table 1. The water characteristics of each water sample

DOC UV254 SUVA Chlorophyll a Br ―

Samples pH NTU
(mg/L) (cm-1) (L/mg.m) (μg/L) (μg/L)
Raw water 8.00 10.260 0.203 1.98 38.00 9.25 229.80

Pre-ozone water 7.90 9.530 0.154 1.62 22.00 7.22 141.72

Filtered water 7.70 7.031 0.031 0.44 0.17 2.01 82.72

Post-ozone water 7.70 5.883 0.018 0.31 0.14 1.40 139.76

BAC filtered water 7.50 4.117 0.016 0.39 0.10 1.32 171.20

Table 2. Excitation and emission matrix fluorescence spectroscopy partition

Region Ex (nm) Em (nm) Typical Substance

Region I 200 to 250 250 to 330 Aromatic proteins I
Region II 200 to 250 330 to 380 Aromatic proteins II
Region III 200 to 250 380 to 550 Fulvic acid-like
Region IV 250 to 400 250 to 380 Soluble microbial-like products
Region V 250 to 400 380 to 550 Humic acid-like

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 wer_1263_f1-6.docx

Accepted Article
Fig. 1. The flow chart of drinking water treatment processes

Fig. 2. Removal of the formation potentials of trihalomethanes (THMs) in the

multiple water treatment processes

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Accepted Article

Fig. 3. Removal of the formation potentials of haloacetic acids (HAAs) in the

multiple water treatment processes

Fig. 4. Removal of the formation potentials of haloacetonitriles (HANs) in the

multiple water treatment processes

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Accepted Article

Fig. 5. Removal of the formation potentials of other non-regulated DBPs in the

multiple water treatment processes

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Accepted Article

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Accepted Article

Fig. 6. Fluorescence EEM spectra of each water sample ((a) Raw water, (b)

Pre-ozone water, (c) Filtered water, (d) Post-ozone water and (e) BAC filtered

water)

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