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Removal of natural organic matter in full-scale conventional and

advanced water treatment plants: Assimilable organic carbon and its
precursors

Huan He , Tian Li , Chang He , Jiapei Chen , Huaqiang Chu ,

Bingzhi Dong

PII: S2666-8211(21)00098-3
DOI: https://doi.org/10.1016/j.ceja.2021.100183
Reference: CEJA 100183

To appear in: Chemical Engineering Journal Advances

Received date: 20 June 2021

Revised date: 3 September 2021
Accepted date: 14 September 2021

Please cite this article as: Huan He , Tian Li , Chang He , Jiapei Chen , Huaqiang Chu ,
Bingzhi Dong , Removal of natural organic matter in full-scale conventional and advanced water treat-
ment plants: Assimilable organic carbon and its precursors, Chemical Engineering Journal Advances
(2021), doi: https://doi.org/10.1016/j.ceja.2021.100183

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Highlights

 Fractions with high hydrophilicity and low MW contributed to the majority of AOC.

 BACF with long-time operation introduced large amounts of AOC precursors.

 Chlorination was responsible for the rebound of AOC.

 The presence of POM in pre-ozonation had slight impact on AOC formation rate.

 The formation rate of AOC showed a linear relationship with UV254 and TFI.

1
Removal of natural organic matter in full-scale conventional and advanced water

treatment plants: Assimilable organic carbon and its precursors

Huan Hea, b, Tian Lia, c, d, *, Chang Hea, Jiapei Chene, Huaqiang Chua, c, d, Bingzhi Donga, c, d

a
College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China

b
Department of Civil, Environmental, and Geo- Engineering, University of Minnesota - Twin Cities,

500 Pillsbury Dr. SE, Minneapolis, MN 55445, United States

c
State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai

200092, China

d
Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University,

Shanghai 200092, China

e
College of Architecture and Design Art, Shaoxing Vocational and Technical College, 526 Shanyin

Road, Yuecheng District, Shaoxing 312000, China

*Corresponding author

Tel/Fax: +86-21-65983869

Email: litian001@tongji.edu.cn

Address: College of Environmental Science and Engineering, Tongji University, Shanghai 200092,

China

2
Abstract

This study aimed to investigate the performance of three full-scale long-time water treatment

plants with influent from Taihu Lake for the removal of natural organic matter (NOM) and

assimilable organic carbon (AOC), emphasizing on the processes of pre- and post-ozonation and

biological activated carbon filtration (BACF). High-performance size exclusion chromatography

(HPSEC) separation, hydrophilicity/hydrophobicity resin fractionation and excitation-emission

matrix (EEM) fluorescence spectroscopy were applied to determine NOM fraction variation in

purification processes and their relationships with AOC. The results indicated that NOM fractions

with high hydrophilicity (NHPI) and lower molecular weight (1 kDa - 10 kDa) likely contributed to

the majority of AOC. The advanced water treatment processes behaved negative removals of AOC

since the BACF with long-time operation introduced large amounts of AOC precursors and could

cause drastic rebound of AOC upon chlorination disinfection. Finally, during exposure to ozone, the

formation rate of AOC showed a linear relationship with UV254 and total fluorescence intensity (TFI)

and each regional fluorescence intensity (RFI) with slight interference by the presence of particulate

organic matter (POM). This study provides useful information for variation of NOM and its

associated bio-availability during conventional and advanced processes in full-scale water treatment

plants.

Keywords: Natural organic matter; Assimilable organic carbon; Advanced water treatment;

Biological activated carbon; Ozonation

3
1. Introduction

Removal of natural organic matter (NOM) has become one of the major challenges in drinking

water treatment. It is acknowledged that NOM can cause many adverse effects, i.e. generation of

odors and tastes, formation of disinfection by-products and increase of chlorine demand in

purification processes, etc. Moreover, the biodegradable part of NOM can induce bacterial regrowth

in the distribution systems. Assimilable organic carbon (AOC), referring to the most readily

consumed fraction of NOM [1, 2], is regarded as the critical parameter for controlling bacterial

regrowth potential of drinking water.

To enhance NOM removal and promote biological stability of drinking water, advanced water

treatment processes are widely applied prior to the final process of disinfection. Because of high

reactivity in breakdown of complex NOM, ozone is added in pre-ozonation and post-ozonation as an

oxidant to enhance overall performance of the subsequent processes [3, 4]. Although considerable

efforts have been made to evaluate NOM removal by ozonation processes [5, 6], much remains

unclear about the differences between pre-ozonation and post-ozonation, particularly with respect to

their impact on AOC. Following post-ozonation, biological activated carbon filtrations (BACFs) are

commonly settled to remove NOM and limit AOC via multiple mechanisms including adsorption,

physical filtration, and biodegradation [7]. Previous studies have monitored NOM removal of BACF

over operation period ranging from several months to one year [7, 8], while have paid scarce

attention to filters under longer-time operation (over 2 or even 5 years) when regeneration cannot be

timely conducted out of economic limits in developing countries. For most long-term advanced

treatment plants in China, although the finished water can be guaranteed to satisfy Sanitary Standard

for Drinking Water (GB5749-2006) (i.e. chemical oxygen demand (CODMn) ≤ 3 mg/L), other
4
parameters of NOM, such as dissolved organic carbon (DOC), ultraviolet absorbance at 254 nm

(UV254), and AOC, remain unsure, and thus require urgent investigation.

Various fractionation methods have been adopted to describe the characteristics and treat-abilities

of NOM, including (i) the excitation-emission matrix (EEM) fluorescence spectroscopy, (ii)

membrane filtration and high-performance size exclusion chromatography (HPSEC) on the basis of

molecular weight (MW) distributions, and (iii) resin adsorption/desorption according to the degree of

hydrophobicity/hydrophilicity [9]. However, studies rarely combined these approaches to achieve a

more detailed and comprehensive understanding specific NOM fractions and their corresponding

removal rates by drinking water treatment processes; and even if some did, they only focused on one

specific unit rather than investigating the whole treatment processes of full-scale plants [10, 11].

Furthermore, studies are scant on coupling NOM constituents with AOC as well as its precursors in

terms of their fate during advanced drinking water treatment.

In light of the above, the targets of this work were intended to: (i) assess NOM removal in

full-scale long-term advanced treatment plants located in east-southern China with influent from

Taihu Lake through measurement of bulk parameters like DOC, UV254, and AOC, and compare

advanced treatment plants with traditional one in terms of their removal efficiencies; (ii) apply resin

adsorption/desorption, HPSEC-UV-TOC, and EEM measurement simultaneously to investigate the

fate of various NOM fractions throughout advanced treatment processes, especially emphasizing on

pre- and post-ozonation and the long-time operated BACF, and to explore relationships of NOM

fractions with AOC as well as its precursors; and (iii) evaluate dynamics of AOC formation during

pre- and post-ozonation processes and establish quantitative transformation model of AOC and its

precursors.

5
2. Materials and Methods

2.1 Preparation of AOC-free materials

Borosilicate glass bottles (250 and 100 mL) and vials (45 mL) were used for sampling and AOC

measurement, respectively. Carbon-free glassware was prepared as described in Clesceri et al. [12].

All glassware was first washed with detergent, then rinsed with hot water and 0.1 M hydrochloric

acid for two times and deionized water for three times. After air drying, the bottles and vials were

capped with foil and heated in a Muffel furnace at 550°C for 6 h. Screw caps (with Teflon-lined

silicone septa) for the glassware were soaked in a 10% sodium persulfate solution for 1 h at 60°C,

rinsed three times with carbon-free deionized water and finally air-dried.

2.2 Collection of samples from drinking water treatment plants

In the period of April to August 2013, water samples were taken from three drinking water

treatment plants, i.e. Xiang Cheng water treatment plant (XCWTP), Xu Jiang water treatment plant

(XJWTP), and Bai Yang Wan water treatment plant (BYWWTP) under the Suzhou Water Supply

Corporation (SWSC), located in Suzhou City, Jiangsu Province, China. All of the three plants take

source water from Taihu Lake, the third largest freshwater lake of China, which is severely plagued

by pollution and eutrophication due to rapid economic growth in the area of Yangtze River delta in

recent decades. XCWTP and XJWTP have introduced the ozone-biological activated carbon

(O3-BAC) advanced treatment process since 2008 and 2010, respectively, while BYWWTP still

adopts traditional treatment process. Table 1 presents the treatment processes and operation

parameters of the three full-scale water treatment plants.

6
 Table 1 Operation parameters of the three full-scale plants investigated in the study.

Treatment Treatment Plant

Operation parameter Unit
Process XCWTP/XJWTP BYWWTP
Pre-ozonation – CS – RSF
Processes - - – Post-ozonation – BACF CS – RSF – Chlorination
– Chlorination
Ozone dosage mg/L 0.4-0.8
Pre-ozonation N.A.
Contact time min 3
Capacity m3/d 7.5×104 (×4 units) 7.5×104 (×2 units)
Coagulant type - Aluminum sulfate Aluminum sulfate
Coagulation-
Hydraulic retention time h 2.5 2
Sedimentation
Horizontal velocity mm/s 15 12
3 2
Surface loading m /(m ·d) 27 34
3 5 4
Capacity m /d 1.5×10 (×2 units) 1.25×10 (×12 units)
Surface area per filter m2 139.8 68.89
Rapid sand Filtering velocity m/h 7.6 8
filtration Filtering material - Uniform quartz sand Uniform quartz sand
Effective grain size, d10 mm 0.95 0.95
Media depth m 1.35 1.30
Ozone Dosage mg/L 0.4-0.8
Post-ozonation N.A.
Total contact time min 12 (three stages)
Capacity m3/d 1.5×105 (×2 units)
Surface area per filter m2 121.1
Coal-based crushing
Biological Filtering material -
carbon
activated
Particle size mesh 12×40 N.A.
carbon
Media depth m 2
filtration
Empty bed retention time min 12
Filtering velocity m/h 10.4
Backwash cycle d 10-15
3
Storage capacity m 3.2×104 (×3 units) 7.5×103 (×2 units)
Effective depth m 4.2 4.0
Hydraulic retention time h 7.68 2.4
Chlorination
liquid chlorine (as sodium liquid chlorine (as sodium
Disinfectant type -
hypochlorite) hypochlorite)
Dosage mg/L as Cl2 1.0-2.0 1.0-2.0

The sampling ports for the two advanced treatment plants, XCWTP and XJWTP, included raw

water, after pre-ozonation, after coagulation-sedimentation (CS), after rapid sand filtration (RSF),
7
after post-ozonation, after BACF, and after chlorination; while the sampling ports for the

conventional treatment plant BYWWTP only contained raw water, after CS, after RSF, and after

chlorination. Samples of XCWTP were collected monthly from May to August 2013, and samples of

XJWTP and BYWWTP were collected only once, in May and July, 2013 respectively. Raw waters of

XCWTP were also collected for AOC measurements in winter (December 2012 to January 2013) to

investigate seasonal variation of AOC levels in source waters. All the samples were stored in 250 mL

AOC-free bottles prepared as described above, transported to the laboratory under refrigerated

conditions (4 °C in the dark), and processed within 6 h after sampling for determination of AOC, and

within 24 - 48 hours for measurements of other parameters (see below). In addition, water samples

collected on May 26th 2013 from one of the advanced treatment plants, XCWTP, were fractionated

with the use of XAD and IRA resin with each fraction analyzed in terms of DOC, UV 254, and MW

distribution. Details of all the analytical measurements are provided in Section 2.4.

2.3 Lab-scale ozone experiment

2.3.1 Ozone reactor system

Lab-scale ozone experiments were performed in a semi-continuous mode [13, 14]. The

cylindrical reactor (Ø40 mm × 600 mm) was made of glass, with a porous glass plate at the bottom.

Ozone was generated by an ozone generator (ANSEROS, COM-AD-01, Germany) using high purity

O2 as feed gas. The O2 flow rate was set constant as 0.5 L/min and the conversion rate of O3 to O2 as

10%.

8
2.3.2 Determination of concentration-time (c-t) curve

Prior to experimental operation, 500 mL water sample was added into the reactor, and then ozone

was continuously introduced into the reactor through a glass diffusor. At selected time intervals (10

sec -10 min), 10 mL samples were taken with the ozone concentration determined by the indigo

method [15]. The c-t curve indicated the concentration of ozone rapidly increased to equilibration

within 30 sec and could be approximately considered as constant during the whole reaction, thus the

contact time was used as the only determinant parameter for all experiments.

2.3.3 Lab-scale simulation of the pre-ozonation and post-ozonation processes

To investigate AOC formation during pre-ozonation and post-ozonation in the full-scale

treatment processes, lab-scale ozonation experiments were carried out using both the raw water

taking from XCWTP and its filtrate after a 0.45 µm membrane filter, respectively. Experimental

conditions and operations were kept identical as described in the determination of c-t curve. At

pre-determined intervals (30 sec -10 min), water samples were withdrawn into 100 mL AOC-free

bottles, with sodium nitrite (in molar excess of > 20-fold) pre-added to terminate further reaction.

The quenched samples were then analyzed for DOC, UV254, MW distribution, EEMs, and AOC.

After each run, the reactor was rinsed with 0.01 M sulfuric acid and Milli-Q water repeatedly. All

experiments (on raw water or its filtrate) were conducted at room temperature (22 ± 1 °C) in

triplicate.

9
2.4 Analytical methods

2.4.1 XAD and IRA resin fractionation

XAD-8, XAD-4, and IRA-958 (Amberlite, USA) was used to separate water samples into

hydrophobic (HPO), transphilic (TPI), charged hydrophilic (CHPI), and neutral hydrophilic (NHPI)

fractions [9, 16]. Recoveries of all fractionations were determined through measurements of DOC

and UV254, which turned out to be 101-107% and 81-102%, respectively. The presented data were

normalized to 100%.

2.4.2 Determination of DOC and UV254

DOC and UV254 were qualified using a total organic carbon analyzer (TOC-VCPH, Shimadzu) and

a UV spectrophotometer (Hach-5000), respectively.

2.4.3 Determination of AOC

AOC concentrations were measured according to a modified version of the Van der Kooij method

[17]. For each AOC assay, 40 mL water sample was filtered through 0.22 μm glass-fiber membranes

(pre-combusted at 550°C for 6 h) into the 45 mL AOC-free vial and then pasteurized in 70°C water

bath for 0.5 h. After cooling, these samples were inoculated with Pseudomonas fluorescens strain

P17 to a final concentration of 10,000 CFU/mL. After incubation at 25°C for 2 days, the

colony-forming units of P17 were counted by spread plating on LLA agar at 25°C until visible

colonies formed. At the end of P17 incubation (and after taking aliquots for spread plating), the same

water samples were pasteurized to kill P17 and then inoculated with Spirillums strain NOX, also to

10,000 CFU/mL. After incubation at 25°C for 3 days, the colony-forming units of NOX were

counted (also on LLA agar as above). AOC concentrations were calculated by using the
10
colony-forming unit numbers and yield coefficients of P17 and NOX, which in this study were

determined to be 4.68×106 CFU/μg acetate-C and 1.43×107 CFU/μg acetate-C, respectively. Total

AOC concentration was determined as the sum of both AOC-P17 and AOC-NOX. For each water

sample, AOC measurement was conducted in triplicate.

2.4.4 Molecular weight distribution

Molecular weight (MW) distributions were determined by the HPSEC-UV-TOC method, which

was achieved on a high-performance liquid chromatography system (Waters e2695, USA) equipped

with a size exclusion chromatography column (TSK-GEL G3000 PWXL, 7.8 mm × 30 mm),

followed by a UV/visible detector (Waters 2489, USA) plus an on-line TOC analyzer (Sievers 900

Turbo, USA, with detection limit of 1 μg C/L). The peak areas on the chromatographs were

calculated through integration with the use of Origin 8.5, and finally the percentage of each peak

over the total DOC was obtained.

2.4.5 Fluorescence spectroscopy

Measurements of Excitation Emission Matrix (EEM) were acquired with a fluorescence

spectrophotometer (model F-4500, Hitachi, Japan). The excitation and emission wavelengths were

incrementally increased from 250 nm to 400 nm, and from 250 nm to 550 nm, respectively, with a

step of 5 nm. Data were analyzed using Origin 8.5 and Surfer 8.0. The fluorescence responses were

separated into four regions, i.e. Zones T, B, C, and A, representing biological product of tryptophan,

tyrosine proteins, humic-like substances, and fulvic acid, respectively [18, 19]. Then the total

fluorescence intensity (TFI) and the regional fluorescence intensity (RFI) method were employed to

calculate the accumulated florescence intensity (Ф𝑖 ), the normalized accumulated florescence

intensity (Ф𝑖,𝑛 , Ф 𝑇,𝑛 ), and percent fluorescence response (𝑃𝑖,𝑛 ) based on the method described by

11
Chen et al. [20] as:

Ф𝑖 = ∑𝑒𝑥 ∑𝑒𝑚 𝐼(𝜆𝑒𝑥 𝜆𝑒𝑚 ) ∆𝜆𝑒𝑥 ∆𝜆𝑒𝑚 (1)

Ф𝑖,𝑛 = 𝑀𝐹𝑖Ф𝑖 (2)

Ф 𝑇,𝑛 = ∑𝑖 Ф𝑖,𝑛 (3)

Ф
𝑃𝑖,𝑛 = Ф 𝑖,𝑛 × 100% (4)
𝑇,𝑛

where ∆𝜆𝑒𝑥 and ∆𝜆𝑒𝑚 are the excitation and emission wavelengths, respectively; 𝐼(𝜆𝑒𝑥 , 𝜆𝑒𝑚 ) is

the fluorescence intensity at each excitation-emission wavelength pair.

3. Results and Discussion

3.1 Removal of DOC, UV254 and AOC in conventional and advanced treatment plants

Figs. 1(a), 1(b) and Fig. 2 present concentrations of DOC, UV254 and AOC, respectively, in the

effluent of each treatment processes of the three full-scale water treatment plants, with the

corresponding removal efficiencies listed in Table 2. Detailed removal efficiencies and performances

for each process of the three plants shall be discussed in the following sections.

Fig. 1 Concentrations of (a) DOC, and (b) UV254 in each treatment process effluent in the three

full-scale plants. Datasets of XCWTP are presented as average ± standard deviation (presented as

12
 error bars) of monthly measurements for samples collected in the period of May to August 2013

(sample number N = 4). There is no error bar for datasets of XJWTP and BYWWTP, where samples

were collected and analyzed only once in May and July, 2013, respectively (sample number N = 1

for each).

Fig. 2 Concentrations of AOC in each treatment process effluent in the three full-scale plants.

Datasets of XCWTP are presented as average ± standard deviation (shown as error bars) of monthly

measurements for samples collected in the period of May to August 2013 (sample number N = 4).

There is no error bar for datasets of XJWTP and BYWWTP, where samples were collected and

analyzed only once in May and July, 2013, respectively (sample number N = 1 for each).

13
3.1.1 XCWTP

Raw water

For XCWTP, the raw water had an average concentration of 3.87±0.61 mg/L for DOC and

0.062±0.005 cm-1 for UV254. Accordingly, SUVA of the raw water was 1.65±0.37 (< 2) L/(mg∙m),

indicating NOM in the raw water mostly was low molecular organic with weak hydrophobicity. The

average AOC concentration of the raw water (May to August, 2013) was 38±19 μg/L, much lower

than 125±26 μg/L in winter season (December 2012 to January 2013), which was consistent with the

phenomenon recognized by Ohkouchi et al. [21]. The lower concentrations of AOC in summer

season probably resulted from conversion of organic fractions from those easily consumable into

biomass or extracellular components, which could be ascribed to higher activity of heterotrophic

bacteria at higher water temperature [22].

Table 2 Average removal efficiencies of DOC, UV254 and AOC in the three full-scale plants as

measured over the period of May to August 2013. Datasets of XCWTP are presented as average ±

standard deviation of monthly results for samples collected in the period of May to August 2013

(sample number N = 4). Datasets of XJWTP and BYWWTP were results for samples collected only

once in May and July 2013, respectively (sample number N =1 for each).

Removal efficiency (%)

Treatment Process XCWTP XJWTP BYWWTP
DOC UV254 AOC DOC UV254 AOC DOC UV254 AOC
Raw water — — — — — — — — —
Pre-ozonation 3.9±3.7 20.5±4.6 -42.0±15.7 — — — — — —
Coagulation-
11.9±3.2 12.5±3.8 9.0±21.9 14.4 23.7 71.9 16.3 35.0 -72.2
Sedimentation
Rapid sand filtration 10.9±4.5 11.1±5.9 -16.9±30.2 7.8 4.1 - 56.5 -2.2 2.9 35.2

14
 Post-ozonation 4.3±3.5 37.4±6.6 -221.3±129.2 1.1 38.0 -412.9 — — —
BACF 7.4±1.7 -18.1±15.5 36.6±22.6 11.7 9.1 66.9 — — —
Chlorination 3.7±3.4 14.1±10.3 -65.2±73.7 -1.7 5.0 - 183.2 5.0 5.2 -28.8
Total removal efficiency 35.8±1.1 61.4±2.6 -300.3±108.7 30.0 60.8 - 111.4 18.8 40.2 -43.7

Pre-ozonation

After pre-ozonation, DOC was reduced by 3.9±3.7% and UV254 by 20.5±4.6%, whereas AOC

increased to 55±33 μg/L by 42.0±15.7%. Since ozonation could break the benzene ring and double

bonds of organic compounds and thus generate smaller compounds with carbonyl or carboxyl groups,

the content of NOM with high UV254 response in the raw water was significantly decreased and the

newly formed carboxylic acids constituted a large fraction of the AOC increment [23]. However, the

mild decrease of DOC revealed that the ozone exposure in pre-ozonation was insufficient for

complete mineralization [24].

Conventional treatment unit

Afterwards, CS-RSF was effective to remove both DOC and UV254, with removal rates of

11.9±3.2% and 12.5±3.8% respectively, by CS, and 10.9±4.5% and 11.1±5.9% respectively, by RSF.

The AOC concentration was not significantly changed by either CS or by RSF (55±48 μg/L and

54±26 μg/L in each effluent respectively). Though some previous studies recognized the good

effectiveness of RSF in AOC removal [21, 25], several others reported that the removal efficiency by

RSF depended on the influent AOC concentration, i.e. RSF performed effectively on removing AOC

through absorption or filtration with influents of high AOC concentrations; however, with influents

of low AOC concentrations, RSF even released AOC that was already absorbed on sand grains into

water [25, 26].

15
Advanced treatment unit

After post-ozonation, DOC was removed by 4.3±3.5% and UV254 by 37.4±6.6%, which was

similar to the trends in pre-ozonation. Meanwhile, AOC rose up dramatically to 151±31 μg/L with an

increasing fold (221.3±129.2%) much higher than that in pre-ozonation (42.0±15.7%). Such

difference between pre-ozonation and post-ozonation could be due to: (i) despite the same ozone

dosage around 0.6 mg/L in both processes, post-ozonation had a much longer contact time (12 min in

total) than pre-ozonation (3 min); and (ii) large amounts of particulate organic matters (POM), such

as algae, contained in the source water, might interfere AOC formation during pre-ozonation [27].

The impact of contact time and POM on AOC formation shall be further discussed in Section 3.3.

After the subsequent BACF, DOC was reduced by 7.4±1.7%, whereas UV254 was increased by

18.1±15.5%, which indicated that BACF of XCWTP preferentially removed NOM with weak

response to UV254 than those with high degree of aromatization and unsaturation, like humic acids

and fulvic acids. Although the AOC concentration decreased to 96±42 μg/L by 65.2±73.7% after

BACF (mostly likely through microbial consumption), it was still higher compared to the level of the

RSF effluent (54±26 μg/L), which means the O3-BAC advanced treatment unit behaved a negative

removal effect for AOC.

16
Chlorination

The final step, chlorination, reduced DOC by 3.7±3.4% and UV254 by 14.1±10.3%. However, the

drastic rebound of AOC (by 65.2±73.7%) implied that the effluent of BACF still contained abundant

AOC precursors, which could be readily transformed into AOC once upon chemical oxidation [21].

The whole processes of advanced treatment had better removal effect on UV254 (61.4±2.6%) than

DOC (35.8±1.1%), and a negative removal rate for AOC (-300.3±108.7%). In the finished water, the

concentration of AOC remained 142±48 μg/L, far exceeding the recommended criterion of

bio-stability in chlorinated distributions (100 μg/L) [28].

3.1.2 XJWTP

The other advanced treatment plant, XJWTP, had similar variation trends of NOM with XCWTP.

The total removal rate for UV254 (60.8%) was much higher than DOC (30.0%), and the whole

advanced treatment process also behaved negative for AOC removal (-111.4%).

Nevertheless, it is noticeable that although BACF of XJWTP reduced DOC by 11.7%, close to

XCWTP (7.4±1.7%), its removal rate for UV254 was 9.1%, positive and substantially different from

XCWTP (-8.1±15.5%). It suggested that with similar influent qualities, the BACF of the two plants

had different preference for NOM removal, which might have relation with the operation time of the

filters, 5 years for XCWTP and 2 years for XJWTP. As time progressed, the sorption sites of

activated carbons gradually became saturated and biodegradation arose as the principal mechanism

for NOM removal, thus leading to higher removal rates for fractions with lower weights and higher

biodegradability [29]; for those more resistant to bacterial degradation, such as humic acids and

biopolymers, BACF had less capacity to remove them and even released some through metabolism

of bacterial community on carbon surface [30], which resulted in UV254 increase by an older filter

17
(like XCWTP) rather than reduction by a younger one (like XJWTP).

However, the operation time seemed to have minimal influence on AOC removal (66.9% for

XJWTP and 36.6±22.6% for XCWTP). Even after long-time operation, BACF of both plants still

performed stable efficiencies to remove the biodegradable fractions, which should be attributed to

the mature and steady bacterial community evolved on the filters of both plants.

3.1.3 BYWWTP

BYWWTP, which takes traditional treatment processes, also behaved a better removal effect for

UV254 than DOC. While the total removal rate for both UV254 (40.2%) and DOC (18.8%) was

obviously lower than that of the advanced treatment plants.

After CS-RSF, the concentration of AOC was nearly unchanged from 35 μg/L in the raw water to

39 μg/L. After final chlorination, the AOC concentration rose up again, similarly to the cases of the

advanced treatment plants but with much less extent (only by 28.8%). This difference was probably

due to that the effluent of long-time RSF had a much lower content of AOC precursors than the

BACF and shorter hydraulic retention time of subsequent chlorination in the BYWWTP. In the

finished water, the AOC concentration was 50 μg/L, within the bio-stability standard proposed by

LeChevallier et al. [28].

3.2 Removal of NOM fractions in advanced treatment processes: fluorescence organics,

hydrophobicity/hydrophilicity, and MW distribution

3.2.1 Fractions of fluorescence organics (EEMs)

Fig. 3 shows the EEM results of the effluents of RSF, post-ozonation and BACF in two full-scale

advanced water treatment plants of XCWTP and XJWTP (full details of the raw waters and effluents

of each treatment process for the three treatment plants are provided in Figs. S1-S3). In general,

18
variations of EEMs were similar to that of UV254 during treatment processes of each plant. As

presented in Fig. 3 as examples, ozonation of RSF effluents in both advanced treatment plants

significantly decreased all the fluoresence peaks including both humic-like (peak A, C) and

protein-like (peak B, T) NOM. Combining with the results of UV254 decrease (Fig. 1(b)) and AOC

increase (Fig. 2) by ozonation treatment as discussed above, it is plausible to relate aromatic and

fluorescent organics (characterized by UV254 and EEMs, respectively) to AOC precursors, which

shall be further investigated below (see Section 3.3). Fluorescence intensity of the humic-like (peak

A, C) and protein-like (peak B, T) compounds increased by BACF of XCWTP, while decreased by

BACF of XJWTP, which is also consistent results of UV254 (Fig. 1(b)), again suggesting the age of

BAC filters might affect their preferential performance in removing NOM.

400 400 400
64 64 64
(a) 60 (b) 60 (c) 60
56 56 56
350 52 350 52 350 52
48 48 48
C 44 C 44 C 44
Ex(nm)

Ex(nm)

Ex(nm)

40 40 40
300 36 300 36 300 36
32 32 32
T 28 T 28 T 28

250 A 24
20 250 A 24
20 250
24
20

B
16
12 B 16
12 B A 16
12
8 8 8
200 4 200 4 200 4
250 300 350 400 450 500 550 250 300 350 400 450 500 550 250 300 350 400 450 500 550
Em(nm) Em(nm) Em(nm)
(a) RSF, XCWTP (b) Post-O 3 , XCWTP (c) BAC, XCWTP
400 400 400
30 30 30
(d) 27
(e) 27
(f) 27
350 24 350 24 350 24

C 21
C 21
C 21
Ex(nm)
Ex(nm)

Ex(nm)

18 18 18
300 15 300 15 300 15

T 12
9
T 12
9
T 12
9
250 A 6 250 A 6 250 A 6

B 3
0
B 3
0
B 3
0
200 -3 200 -3 200 -3
250 300 350 400 450 500 550 250 300 350 400 450 500 550 250 300 350 400 450 500 550
Em(nm) Em(nm) Em(nm)
(d) RSF, XJWTP (e) Post-O3 , XJWTP (f) BAC, XJWTP

Fig. 3 EEMs in the treatment process effluents of the two full-scale advanced water treatment plants:

(a) RSF, XCWTP; (b) post-ozonation, XCWTP; (c) BACF, XCWTP; (d) RSF, XJWTP; (e)

post-ozonation, XJWTP; and (f) BACF, XJWTP. Samples were collected for XCWTP monthly in the

period of May to August 2013 (with results of May 2013 shown here as examples), and collected for

19
 XJWTP once on July 9th, 2013.

3.2.2 Fractions of hydrophobicity/hydrophilicity in couple with MW distribution

(HPSEC-UV-TOC)
To further investigate removal of specific NOM fractions in advanced treatment processes, water

samples from XCWTP (May 26th, 2013) were isolated into fractions of HPO, TPI, NHPI and CHPI

according to their hydrophobicity/hydrophilicity, which were subsequently analyzed by

HPSEC-UV-TOC to resolve MW distributions. Fig. S4 shows an example of HPSEC chromatograms

for the four fractions isolated from the raw water in XCWTP. According to Fig. S4, three major

peaks were found in fractions of HPO and NHPI, i.e. high molecular weight (HMW, 1.00×107 -

1.20×104 Da), medium molecular weight (MMW, 1.20×104 - 1.41×103 Da), and low molecular

weight (LMW, 1.41×103 - 2.16×102 Da); while in fractions of TPI and CHPI only the latter two

peaks existed.

Fig. 4 presents percentage compositions of the four fractions in the raw water and each treatment

process effluent collected from XCWTP, along with their total DOC concentrations. In the raw water,

HPO and NHPI were the predominant fractions, accounting for 33.1% and 29.7% of the total DOC,

respectively, and then followed by CHPI (18.9%) and TPI (18.2%). For NHPI, MMW (16.6% of the

total DOC) was more significant than LMW and HMW. While for the other three fractions, LMW

(24.6%, 14.3%, and 16.4% for HPO, TPI, and CHPI, respectively) was the most prevalent. No matter

within HPO or NHPI, HMW was detected at a very low percentage (< 2% for both fractions).

20
 Fig. 4 DOC concentration (○) in the raw water and each treatment process effluent of XCWTP and

composition of DOC according to the fractions of HPO, TPI, NHPI and CHPI analyzed by HPSEC.

Despite effective removal of total DOC, composition of the four fractions did not differ much in

the finished water, in which HPO and NHPI were still the predominant fractions, followed by CHPI

and TPI, accounting for 36.0%, 27.2%, 19.2% and 17.5% of the total DOC, respectively. This

indicated that the whole advanced treatment processes had no absolute preference in removing the

four fractions, with the highest removal rate found for NHPI (42.4%) and lowest for HPO (31.9%).

From the perspective of MW distribution, the total removal rate for HMW (62.1%) was higher than

MMW (29.7%) and LMW (39.6%).

21
 Nevertheless, there were several noteworthy changes in the DOC composition by the individual

treatment processes: (i) after pre-ozonation, the proportion of CHPI increased from 18.9% to 20.1%,

with reduction of the other three fractions; (ii) after post-ozonation, both CHPI and NHPI increased,

from 18.6% to 19.9% and from 32.3% to 36.1%, respectively; and (iii) after BACF, the proportion of

hydrophobic fraction recovered, with HPO from 27.8% to 36.2% and TPI from 16.2% to 17.4%. To

illustrate the forementioned results in detail, the DOC concentration for each fraction in the major

three MW distributions was calculated for each treatment process effluent, which is presented along

with the corresponding AOC concentration in Fig. 5. All the subsequent data were “zeroed” by

subtracting values of the raw water to simplify a direct comparison.

Fig. 5 DOC concentration in each treatment process effluent of XCWTP and composition of DOC

according to the fractions of HPO, TPI, NHPI and CHPI analyzed by HPSEC. All the data were

22
“zeroed” by subtracting values of the raw water to simplify a direct comparison, thus here the y-axis

is labeled as Δ(carbon concentration) (µg/L).

As for the first two points (i) and (ii), it is known that ozonation could significantly improve

hydrophilicity of NOM [31, 32], and our results implied that different reaction conditions, such as

varying contact time and presence/absence of POM (as mentioned in Section 3.1), likely resulted in a

subtle but not negligible difference, in the hydrophilic products. Compared to pre-ozonation,

post-ozonation generated larger-amounts of MMW, especially NHPI-MMW (steeper slope); and it

effectively reduced all fractions of LMW, even including HPO-LMW, which was not removed but

enhanced by pre-ozonation. Consequently, the products of post-ozonation had a higher proportion of

NHPI, mainly in MMW. While beyond our expectation, a substantial increase of HMW (59.7% for

HPO and 65.8% for NHPI) was observed in post-ozonation but not in pre-ozonation. This

abnormality might be ascribed to that the emergence of HMW from POM, such as extracellular

organic matters (e.g. polysaccharides and biopolymers) on the surface of algae biomass could only

be observed at a high ozone exposure (pre-ozonation: ~1.8 mg/(L·min); post-ozonation: ~8

mg/(L·min)) [33, 34]. Higher exposure of ozone could further oxidize the HMW compounds usually

having high hydrophobicity to MMW or LMW with low hydrophobicity.

23
 With regards to (iii), after BACF, there was an obvious increase of HPO (83.8% for MMW and

122.4% for HMW) and a slight raise of TPI (8.93% for LMW), which implies BACF released large

amount of humic acids and aromatic compounds, together with certain amount of aliphatic

compounds, thus overall behaved a negative removal of UV254 (see Fig. 1(b) and Section 3.1.1).

Though Ramseier and co-workers reported that chlorine had a much lower molar yield factor for

AOC formation than ozone (0.07 and 0.16 as the ratio of μM AOC formed over μM oxidant

consumed, respectively) [35], our result showed that chlorination could increase AOC as drastically

as ozonation. Comparing the effluent of RSF (in reaction with ozone) and BACF (in reaction with

chlorine), we found that the BACF effluent possessed a much higher content of HPO in MMW and

HMW (Fig. 4) despite lower UV254 (Fig. 1(b)) than the RSF effluent. These high-content HPO

fractions in the BACF effluent, mainly biopolymers and humic substances, belonging to reactive

aromatic systems and likely important AOC precursors, would readily generate AOC even applied

with oxidants with relatively lower reactivity (like chlorine). This assumption might also be

supported by the fact that chlorination of XCWTP and XJWTP (in reaction with the BACF effluents)

caused much higher increase of AOC than that of BYWWTP (in reaction with the RSF effluent) (see

Section 3.1.3), although chlorine exposures at the full-scale plants (by considering both residual

chlorine concentrations and chlorination retention time) must be taken into account before making

such conclusion.

24
3.2.3 Relationship between NOM fractions and AOC

According to Fig. 6, it seemed that the variation trend of AOC concentration approximately

corresponded to the fractions of MMW except HPO, mainly for the effluents after advanced

treatment processes. Therefore, it is plausible to speculate the fractions of CHPI, NHPI, and TPI in

MMW contributed the majority of AOC. Labanowski and Feuillade indicated that in the surface

water, the hydrophilic fraction (HPI, including both CHPI and NHPI) was the most reactive toward

microorganisms, followed by TPI, and HPO had the lowest biodegradability (the order of AOC/DOC

was HPI > TPI > HPO) [36]. Our results also showed that HPO-MMW had a variation trend in

contradiction with AOC (for effluents of post-advanced treatment processes). The comparisons of

NOM fraction concentrations in major MW distributions versus AOC concentrations are provided in

Fig. S5 to emphasize the trends discussed above.

From the viewpoint of MW distribution, previous studies proved that about 70-90% of total AOC

was ascribed to NOM below 10 kDa (MMW and LMW) but over 50% came from NOM below 1

kDa (LMW) [37, 38], which did not seem to completely confirm with our results that MMW had

similar variation trend with AOC rather than LMW. This discrepancy may be due to these aspects: (i)

the MW identified by HPSEC differs from that by membrane filtration, and the key evidence was the

fact that acetate, a typical LMW compound, appeared at the retention time corresponding to the

MMW peak (data not shown); (ii) though LMW seemed not related much to AOC concentration, for

instance, LMW decreased while AOC increased after post-ozonation, the readily biodegradable part

of LMW might actually get a raise and could not be distinguished by HPSEC.

The only exception appeared in the last process of chlorination. After chlorination, the

hydrophilic proportion rose again (CHPI from 17.4% to 19.2%) together with AOC with the

25
increased fractions belonging to LMW instead of MMW. This might be related to that chlorination,

different from ozonation, primarily oxidized the MMW to LMW products (but without further

mineralization), which was beneficial for AOC formation.

3.3 Formation of AOC during pre- and post-ozonation

To elucidate the role of contact time and POM on AOC formation, we carried out ozonation

experiments on the filtered and unfiltered raw water of XCWTP. Fig. 6(a) illustrates degradation of

kinetics of NOM (characterized by DOC and UV254) during under pre-ozonation (using raw water

before filtration) and post-ozonation (using raw water after filtration). Correspondingly, Fig. 6(b)

depicts kinetics of AOC formation as a function of contact time, with AOC values of the raw water

subtracted from the subsequent data for each time point. Details of NOM degradation and AOC

formation during bench-scale pre- and post-ozonation of raw water (i.e. with and without presence of

POM) shall be discussed in the following section.

26
 Fig. 6 Ozonation of the raw water from XCWTP (as pre-ozonation) and its filtrate through 0.45 μm

membranes (as post-ozonation). (a) degradation of DOC and UV254 in pre- and post-ozonation, and

(b) concentrations of AOC as a function of contact time in pre- and post-ozonation. The raw water

had a pH of 8. All experiments were done at room temperature and the ozone concentration was 1.60

± 0.01 mg/L. The data in (b) were zeroed by subtraction of the AOC values measured before

ozonation and error bars indicate standard deviation of results obtained from triplicate experiments.

3.3.1 Post-ozonation

During post-ozonation, UV254 continuingly declined throughout the time range; while some

fluctuations in DOC were observed and probably attributed to the transformation from undetected
27
POC of the raw water into DOC upon exposure to ozone [39, 40]. At the end point of reaction (t = 10

min), UV254 decreased by 63.8% (from 0.058 to 0.021 cm-1) and DOC decreased by 5.3% (from 2.76

to 2.62 mg/L). The removal of UV254 was much higher than that of DOC, which is similar to the

situations in the full-scale treatment that both pre- and post-ozonation of XCWTP preferentially

removed UV254 (by 20.5±4.6% and 37.4±6.6%, respectively) than DOC (by 3.9±3.7% and 4.3±3.5%,

respectively) (see Table 2).

In the raw water, an AOC concentration of 54 μg/L was measured. Fig. 1(b) shows that within the

period of treatment (0-10 min contact time), the AOC concentration increased by about 6-fold to 373

μg/L. At the time point of 1.0 min (ozone concentration = 1.60 mg/L after reaching equilibrium at 30

sec, thus ozone exposure = ~1.2 mg/(L·min)), an AOC formation of 88 μg/L was achieved. When

normalized with the original DOC concentration of 2.76 mg/L, the AOC formation per amount of

DOC at O3 exposure of ~1.2 mg/(L·min) was 31.9 μg AOC/mg DOC, which is consistent with the

results of Hammes et al. [23] (for Zurich Lake water, 31.3 μg AOC/mg DOC at 1.5 mg/(L·min); for

Greifensee Lake water, 32.9 μg AOC/mg DOC at 1.6 mg/(L·min)) and Ramseier et al. [35] (for

Greifensee Lake water, 17.0 μg AOC/mg DOC at 1.0 mg/L·min). The generally good agreement

found amongst different studies support the hypothesis by Hammes et al. [23] that NOM quantity

and quality of different source water samples had little impact on AOC formation during ozonation,

probably because that natural lake water samples shared similar characteristics of NOM, mainly of

water-borne origin.

3.3.2 Pre-ozonation

The pre-ozonation experiment had identical conditions as post-ozonation except that the raw

water was not filtered through 0.45 μm membranes and retained the entire POM, including

28
suspensions, colloid substances, and microorganisms, in the raw water. From Fig. 6(a), the

degradation curve of UV254 obtained in pre-ozonation condition (i.e. with POM) almost overlapped

with that in post-ozonation condition (i.e. without POM). Difference was found by comparing DOC

degradation curves obtained under pre-ozonation and post-ozonation conditions that post-ozonation

resulted in stronger DOC degradation than pre-ozonation at longer contact time (t ≥ 5 min).

Differences were also found for AOC formation: (i) at first (t < 2 min), the formation rate of AOC

was slower than post-ozonation; (ii) then (2 min < t < 3 min) the formation rate remarkably increased

and surpassed that of post-ozonation; (iii) afterwards (t > 3 min), the formation rate slowed down and

the formation curve gradually became approximately parallel with that of post-ozonation, and the

final yields of AOC at the endpoint of reaction had no significant difference for pre- and

post-ozonation conditions.

Considering the other water property parameters (DOC, UV254, etc.) were identical in the pre-

and post-ozonation treatment, a reasonable explanation for such distinction was the presence of POM

in pre-ozonation, which was absent in post-ozonation. It is suspected that at the beginning stage of

ozonation, a large part of the available ozone reacted with POM (thus not with the DOC of the

source water) and generated considerably less bio-available compounds, therefore the starting rate of

AOC formation was slower; with more of these compounds (belonging to important AOC precursors)

released into water, the formation of AOC speeded up subsequently. Notably, the precursors released

in pre-ozonation did not influence on the degradation curve of UV254, but on that of DOC at higher

exposure (t ≥ 3 min), thereby it is highly possible that they belonged to NOM fractions with no

UV254 response (e.g. HPO and NHPI fractions in HMW). Such fractions (HPO and NHPI in HMW)

were also found increased by the full-scale process of post-ozonation but not in pre-ozonation (see

29
Section 3.2), which was possibly due to that the contact time of the full-scale pre-ozonation was

much shorter than that of the full-scale post-ozonation and the bench-scale experiments.

3.3.3 Kinetics and mechanisms of the formation of AOC during ozonation

Combining Fig. 6(a) and 6(b), we found that the formation of AOC could be related to the

consumption of UV254, in both scenarios of post-ozonation or pre-ozonation. To simplify discussion,

here we only focused on post-ozonation, in which reactions occurred without interference of POM.

The relationship between UV254 and the contact time t and AOC concentration were analyzed with

the results presented in Fig. 7. From Fig. 7(a), the degradation of UV254 as a function of contact time

obeyed pseudo second order kinetic, therefore,

𝑡 = 1/𝑘1 [(UVt′ )−1 − (UV0′ )−1 ] (5)

where U𝑉0 represents the UV254 of the raw water before ozonation, U𝑉𝑡 represents the UV254 at the

contact time of t in the process of ozonation, and 𝑘1, representing the observed reaction rate constant,

was determined as 17.2 from the slope of the linear regression line; from Fig. 8(b), the formation rate
UV′
of AOC presented a linear relationship with ln UV0′ , therefore,
t

UV′0
dAOC = 𝑘2 dln (6)
UV′t

where 𝑘2 was determined as 156; combining Eqs. (5) and (6), it can be deduced that,
dAOC 𝑘 dUV′t −𝑘
= − UV2′ = UV2′ [−𝑘1 (UVt′ )2 ] = 𝑘1 𝑘2 UVt′ (7)
d𝑡 t d𝑡 t

30
 200
(a)
180
y=17.189x
160
R2=0.9944
140
(UVt')-1-(UV0')-1

120
100
80
60
40
20
0
0 2 4 6 8 10
t (min)
350
Fig. 7 (b)
(a) Pseudo second order kinetic plot of UV254 degradation under ozonation, and (b) linear
300 y=156.09x
R2=0.9961
250 relationship between the AOC concentration and UV254.
AOC (g C/L)

200

150
In Eqs. (5) to (7), it can be obtained that UVt′ = U𝑉𝑡 − 0.016 and UV0′ = U𝑉0 − 0.016; the
100
value 0.016 indicates that 0.016 cm-1 of UV254 was undegradable by treatment of ozonation.
50

It 0is well known that UV254 is used to estimate the concentration of NOM with unsaturated
0.0 0.5 1.0 1.5 2.0 2.5

0 t ln(UV /UV )
' '
carbon-carbon bonds (>C=C<, including those on the benzene ring of aromatic compounds) in water

samples. Hence, to some extent it reflects the amount of >C=C<, which is very active upon exposure

to ozone. According to the formation mechanisms proposed in former study [35], breakdown

of >C=C< directly involved in the formation of carboxylic acids, an important fraction of

newly-formed AOC during ozonation, which can be directly consumed by microorganisms. Our

study quantizes the relationship between the two bulk parameters, i.e. summation of unsaturated

bonds and bioavailability of their ozonation products. Therefore, UV254 degradation could be used to

determine the formation rate of AOC and evaluate its formation potential.

3.3.4 The relationship of AOC formation rate to EEMs under ozonation

To further explore the relationship of AOC formation with various precursors in the pool of
31
DOM during ozonation, the relationship between the AOC formation rate and the fluorescence

characteristics in terms of TFI and RFI were analyzed with the results presented in Fig. 8. From Fig.

8(a) and 8(b), degradation of TFI as a function of contact time obeyed pseudo-third-order kinetic law.

For each region of EEMs, degradation of RFI for Region B, T agreed to pseudo-third-order kinetic

law, while that for Region A, C followed pseudo-second-order kinetic law, with further details

summarized in Table S1. The diversity in kinetic laws followed by various DOM groups likely come

from the difference in their molecular structures and reaction mechanisms toward ozone. Knapik et al.

[41] qualitatively evaluated the relationship between the particulate organic carbon (POC) and the

fluorescence substances in polluted rivers. They found that the biodegradable dissolved organic

carbon substance contained an average of 28% up to 95% of POC, which led to a decrease of

tryptophan-like and tyrosine-like fluorescence peak intensity during the incubation time. Our results,

for the first time, quantitatively analyzed the AOC formation rate and the degradation dynamics of

fluorescence characteristics of TFI and RFI during ozonation.

From Fig. 8(c) and 8(d), the formation rate of AOC also showed linear relationships with TFI and

each RFI similar to the case of UV254 (further detailed information of the linear regression lines in

Fig. 8 is summarized in Table S2). The quantitative transformation model extended from

“AOC&UV254” to “AOC&EEMs” has largely enriched characterization of AOC precursor types,

because EEMs can provide a more abundant description for NOM by associating various molecule

structures (bonds and functional groups) characterized with different regions. However, it should

also be noted that in Fig. 8 only one RFI in each single-variable model was considered, instead of

integrating all of them into a multi-variable one. Accordingly, it is still poorly understood how each

NOM family (represented by each RFI) made contribution to AOC formation, or whether RFIs

32
would compete with each other during NOM degradation by ozone. Therefore, future studies are

recommended to develop a multi-variable model.

Fig. 8 Ozonation of the raw water from XCWTP: kinetic plots for the degradation of (a) TFI, and (b)

RFIs; relationships of the AOC formation to (c) TFI, and (d) RFIs.

4. Conclusion

In this study, the performance of three full-scale long-time water treatment plants with influent

from Taihu Lake for the removal of NOM and AOC were examined, and the processes of pre- and

post-ozonation and BACF on the AOC precursor variation were investigated, with key findings listed

in the following.

33
 (1) The two advanced treatment plants performed better removal effect for UV254 than DOC, with

both yielding seriously negative removals for AOC. Chlorination is responsible for the rebound of

AOC.

(2) Comparing with the traditional treatment plant, the advanced treatment plants had higher

removal efficiency for NOM as characterized with DOC and UV254, while far more negative removal

efficiency for AOC, which was likely due to higher content of AOC precursors present in the BACF

effluent (mostly the HPO fraction of MMW and HMW), compared with the RSF effluent.

(3) For long-term BACF, although the saturated sorption of activated carbons led to low and even

negative removal for UV254, the mature bacterial community evolved on aged carbon filters always

guaranteed effective removal for AOC.

(4) Fractionation of NOM indicated that CHPI, NHPI, and TPI in MMW contributed the majority

of AOC formed during ozonation. Post-ozonation generated larger-amounts of MMW, mainly

belonging to NHPI, than pre-ozonation.

(5) The presence of POM in pre-ozonation seemed to have slight impact on AOC formation rate

(only slightly lower than that in post-ozonation at the beginning stage of treatment). The formation

rate of AOC showed a linear relationship with UV254, which could be used to determine the

formation rate of AOC and evaluate its formation potential.

(6) The kinetics relationship between the AOC formation rate and the fluorescence characteristics

during ozonation extended indicated that the degradation of TFI as a function of contact time obeyed

the pseudo-third-order kinetic law, while the degradation of RFI for Region B, T agreed to the

pseudo-third-order kinetic law and for Region A, C followed the pseudo-second-order kinetic law.

34
Declaration of interests

☒ 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.

☐The authors declare the following financial interests/personal relationships which may be considered as
potential competing interests:

Acknowledgements

This study was funded by the Major Science and Technology Program for Water Pollution

Control and Treatment (No. 2017ZX07201-001 and No. 2012ZX07403-001), the Natural Science

Foundation of Shanghai (No. 20ZR1460800) and the National Natural Science Foundation of China

(No. 51922078 and No. 52100012). The authors would like to thank all members of Suzhou Water

Supply Corp (SWSC) for continuous support with sampling and analyses. Associate Professor Lei Li

from Tongji University is gratefully acknowledged for patient guidance and fruitful discussions.

35
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