Science of the Total Environment 771 (2021) 145409

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Determining the leading sources of N-nitrosamines and dissolved organic

matter in four reservoirs in Southern China
Jiaxing Zhang a,b,c,1, Tahir Maqbool a,b,c,1, Yu Qiu c,1, Yanling Qin a,b,c, Muhammad Bilal Asif a,b,c,
Chao Chen c, Zhenghua Zhang a,b,c,⁎
a
Institute of Environmental Engineering & Nano-Technology, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, Guangdong, China
b
Guangdong Provincial Engineering Research Centre for Urban Water Recycling and Environmental Safety, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen
518055, Guangdong, China
c
State Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China

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

• Simultaneous occurrence of N-
nitrosamines and DOM in four reservoirs
was discussed.
• A total of 22 N-nitrosamines precursors
were identified by TOF-MS.
• Diverse distributions of 9 N-nitrosamines
in four reservoirs were assessed by LC-
MS.
• Anthropogenic DOM was dominant in
reservoirs shown by fluorescence spec-
troscopy.
• Sum of N-nitrosamines and NDMA-FP
showed a direct relationship with BIX.

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

Article history: The presence of carcinogenic N-nitrosamines and dissolved organic matter (DOM) in freshwater is a significant
Received 14 December 2020 concern from the perspective of public health and drinking water treatment plant operation. This study investi-
Received in revised form 13 January 2021 gated the N-nitrosamines concentration and their precursors' distributions, and DOM composition in four reser-
Accepted 20 January 2021
voirs located in a southern city of China. A total of 22 renowned precursors were identified. Precursors from
Available online 26 January 2021
industrial and pharmaceutical origins were found to be dominant in all reservoirs; however, traces of
Editor: Damia Barcelo pesticide-based precursors, i.e. pirimicarb and cycluron were also found. The distribution of nine N-nitrosamines
was substantially different among the reservoirs. N-Nitrosodibutylamine (NDBA), N-Nitrosopiperidine (NPIP), N-
Keywords: Nitrosodimethylamine (NDMA), and N-Nitrosopyrrolidine (NPYR) were abundantly present in all reservoirs.
N-nitrosamines Most of N-nitrosamines except NDMA and N-nitrosodiethylamine (NDEA) were far below the generally accepted
Time-of-flight mass spectroscopy cancer risk of 10−6, and NDMA/NDEA were found close to the risk level (10−6). Anthropogenic DOM was dom-
Dissolved organic matter inant in three reservoirs as depicted by a higher biological index (BIX) than the humification index (HIX). By the
Excitation-emission matrix principle component analysis, BIX appeared as an indicator of N-nitrosamines (except NDEA and NPIP). A strong
Spectroscopic index
and direct relationship was observed between the NDMA-formation potential (FP) and concentration of total N-
nitrosamines (∑NA), and BIX. These results confirmed that the anthropogenic activities were the leading source
of DOM and N-nitrosamines in this city based on land-use.
© 2021 Elsevier B.V. All rights reserved.

⁎ Corresponding author at: Institute of Environmental Engineering & Nano-Technology, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055,
Guangdong, China.
E-mail address: zhenghua.zhang@sz.tsinghua.edu.cn (Z. Zhang).
1
Co-first authors.

https://doi.org/10.1016/j.scitotenv.2021.145409
0048-9697/© 2021 Elsevier B.V. All rights reserved.
J. Zhang, T. Maqbool, Y. Qiu et al.
1. Introduction
Source water quality is of prime importance to obtain protected
drinking water; water treatment plants are optimized based on influent
characteristics (Pai et al., 2020; Xue et al., 2014). The disinfection by-
products (DBPs) and dissolved organic matter (DOM) precursors have
been recognized as indicators of source water quality from finished
water and treatment plant operation perspectives (MacKeown et al.,
2020). N-nitrosamines are non-regulated DBPs formed during chlorina-
tion, chloramination, and pre-oxidation of drinking water and wastewa-
ter (Piazzoli et al., 2018). Presence of the N-nitrosamines in drinking
water poses a serious threat to human health because of their higher
carcinogenicity as compared to trihalomethanes (THMs), halo-acetic
acids (HAAs) and haloacetonitrile (Kristiana et al., 2013; Li et al.,
2020). Along with DOM, pharmaceuticals and the ingredients of per-
sonal care products, as well as insecticides/pesticide, and industrial
chemicals/by-products can act as the precursors of N-nitrosamines
(Wang et al., 2011; West et al., 2016). N-nitrosamines and their precur-
sors are ubiquitously detected in freshwater due to the discharge of
wastewater treatment plant effluent, unregulated wastewater dis-
charge, and surface/agricultural runoff as well as the discharge of indus-
trial effluent (Chen et al., 2019). Owing to the ineffective removal of N-
nitrosamines and their precursors by conventional water treatment
plants, selecting an efficient and feasible unit process and its optimiza-
tion remains a challenge (Qiu et al., 2020).
DOM in source water could affect the water treatment plant opera-
tion by: (i) increasing the coagulant dose (Hussain et al., 2019); and
(ii) causing membrane fouling (Yu et al., 2018). Notably, available
DOM-based precursors could transform into carcinogenic DBPs (includ-
ing N-nitrosamines) following treatment, particularly during the
disinfection process (Farré et al., 2019; West et al., 2016). DOM compo-
sition and concentration in surface water quality is highly dependent on
several environmental factors that are influenced by surrounding land-
use and applications (Shi et al., 2020). Other factors include mixing ef-
fluent organic matter and other pollutants from industrial sewage into
freshwater (Bhattacharya and Osburn, 2020). The DOM in freshwater
originates from natural and anthropogenic sources (Lee et al., 2019).
The terrestrial and soil organic matter enriched with humic substances
form the allochthonous part of DOM, while microbial activity generating
large-sized macromolecules is classified as autochthonous DOM (Lee
et al., 2018). Along with DBPs formation, the composition of DOM
plays a significant role in metal-and micropollutant binding (Lee and
Hur, 2017). Besides, DOM in finished water (treated water) could con-
tribute to color formation, taste and odor (Krzeminski et al., 2019). In
a few previous studies, DOM was used as a surrogate for DBPs precur-
sors in fresh water bodies and water treatment plants (Yang et al.,
2015b). The role of DOM in instigating the formation of DBPs precursors
was also observed in a lab-scale experiment (Gan et al., 2019). There-
fore, efforts are required to systematically analyse the occurrence of
DOM and DBPs precursors in drinking water reservoirs for obtaining
deep insights.
Agricultural activities, residential areas, and industries are the pri-
mary examples of the land-use, directly impacting the DOM status and
abundence of DBPs precursors in surface water (Delpla and Rodriguez,
2016; Shi et al., 2020). A previous study reported the direct influence
of land-use patterns on the micropollutant in different Portuguese
rivers (Barbosa et al., 2018). Thus, analysis of only the bulk water quality
parameters (e.g., dissolved organic carbon) may not facilitate the
decision-making process related to the selection of water source.
Extensive urbanization and agricultural/industrial activities may dif-
ferently influence DOM composition and N-nitrosamine occurrence in
freshwater sources due to varying anthropogenic inputs (Bhattacharya
and Osburn, 2020). Agricultural practices can cause the release of soil
organic matter, while effluent organic matter containing macromole-
cules and pharmaceutical and personal care products (PPCPs) mainly
originate from domestic activities (Bhattacharya and Osburn, 2020;
2
Science of the Total Environment 771 (2021) 145409
Michael-Kordatou et al., 2015). The studied city, located in southern
China, is a new financial hub with several high-tech industries and
rising population density. Currently, drinking water reservoirs in the
city are being recharged by the water extracted from a river located
in the north of this city. In addition, these reservoirs also rely on
rainfall-runoff for recharge. The land surrounding the reservoirs is
not homogenously used; the distribution of industries and residen-
tial areas varies among the reservoirs catchments. Therefore, it was
hypothesized that DOM composition and N-nitrosamines concentration
would depend on the land-use in the catchment of these freshwater
reservoirs, and the leading sources of DOM and N-nitrosamines may
be different.
In this study, the leading sources of N-nitrosamines and DOM in four
main drinking water reservoirs were investigated using time-of-flight
mass spectrometer (TOF-MS), liquid chromatography-tandem mass
spectrometry (LC-MS/MS) and fluorescence spectroscopy. The specific
objectives of this study include: (i) identifying the leading precursors con-
tributing to N-nitrosamines formation quantified using solid-phase ex-
traction (SPE) and TOF-MS; (ii) comparing the distribution of nine N-
nitrosamines along with N-Nitrosodimethylamine (NDMA)-formation
potential (FP); (iii) characterizing DOM via excitation-emission matrix
(EEM) using fluorescence spectroscopy; (iv) distinguishing DOM status
by fluorescence-based indices such fluorescence index (FI), biological
index (BIX), and humification (HIX); and (v) elucidating the association
between DOM composition/concentration and N-nitrosamines using
multivariate analysis.
2. Material and methods
2.1. Water sampling and bulk water quality measurement
The water samples were collected from four different drinking water
reservoirs (DR-A, DR-B, DR-C, and DR-D) located in a southern city of
China. Reservoirs location and catchment characteristics are presented
in Fig. 1 and Table S1. The catchment area of each reservoir was deter-
mined through delineating on a digital elevation model (DEM) of
90 m × 90 m resolution using the shuttle radar terrain task (STRM,
V4.1). The land-use type was determined using the data of China's
land-use status monitoring database (2018). The land-use within the
catchment is categorized into forest, agriculture, water, city, roads, and
factory areas. The area associated with roads is extracted and processed
in a unified way, using OpenStreetMap. The three reservoirs DR-A
(213 km2), DR-B (219 km2), and DR-C (207 km2) have comparable
catchment areas, while the DR-D reservoir is the largest with a catch-
ment area of 386 km2. The forest cover was calculated to be higher in
DR-A (42.6%) and DR-B (34.4%) than DR-C (21.2%) and DR-D (31.3%).
The agricultural land was found to be the largest in DR-D (14.3%),
followed by DR-A (12.1%), DR-C (10.3%), and DR-B (9.2%). The city
areas (%) were 1.95, 0.29, 0.49, and 1.30% in the catchments of DR-
A, DR-B, DR-C, and DR-D, respectively. Two water supply systems re-
charge these reservoirs: one emerges from the eastern tributary of
Dongjiang River recharging DR-B and DR-C (termed as the Eastern
Water Supply System); and the second emerges from the western
end of the river recharging DR-A and DR-D (termed as Dongshen
Water Supply System). The layouts of these water supply lines are
presented in Fig. S1.
The depth of these reservoirs ranged between 10 and 20 m. For an
effective representation of water quality, samples were collected from
the surface, middle (5 m), and bottom (10 m) of the reservoirs. The
averages of water quality parameters were calculated based on the sam-
ples collected from three different depths. After transferring the sam-
ples to the laboratory located in the same city, water samples were
immediately filtered using a 0.45 μm cellulose triacetate membrane fil-
ter. All the experiments were conducted within 48 h of sampling. Dis-
solved organic carbon (DOC) and total bound nitrogen (TNb) were
measured using the TOC-V analyzer (Shimadzu, Japan). An ultra-violet
J. Zhang, T. Maqbool, Y. Qiu et al.
Fig. 1. Location of four reservoirs and their respective catchment boundaries as well as land-use.
(UV) spectroscopy-based method was adopted for the measurement of
− −
ammonium (NH+ 4 ), nitrite (NO2 ), and nitrate (NO3 ) as outlined in the
Standard Examination Methods for Drinking Water - Nonmetal
Parameters, China, GB/T 5750.5–2006.
2.2. NDMA formation potential (NDMA-FP) test
For the determination of NDMA-FP, a monochloramine-based
method was adopted with a few modifications (Wang et al., 2013).
Briefly, the test was performed in a 20 mL amber glass bottle. After
the addition of monochloramine (2 mM), the solution was held for
24 h at room temperature. Phosphorus buffer solution containing
KH2PO4 and Na2HPO4.2H2O was used to maintain the pH of the solution
at 7.0. Sodium thiosulfate solution (2 g/L) was added to quench the re-
maining chlorine, followed by filtration through 0.22 μm nylon filters.
The NDMA measurement was performed using LC-MS (Model 8050,
Shimadzu, Japan) (Zou et al., 2020).
2.3. N-nitrosamines measurement
The N-nitrosamines concentration in water samples collected from
reservoirs and NDMA generated through the NDMA-FP test were mea-
sured using the SPE-LC-MS method. The SPE cartridges (CNW Technol-
ogies Shanghai, China) containing coconut charcoal media were used to
extract N-nitrosamines from water samples. Steps for the extraction
procedure are as follows: loading water sample (1 L) with a speed of
10 mL/min; vacuum drying of SPE cartridge; elution using dichloro-
methane (12 mL); sparging N2 gas to reduce the volume to 0.2 mL; ad-
dition of Milli-Q water to make volume up to 1 mL (Fig. S2). The SPE
extraction and LC-MS method were adopted from Maqbool et al.
(2020b). The LC-MS parameters (Table S2), as well as N-nitrosamines
recoveries (Fig.S3, and Table S3) following SPE, are provided in
supporting information. The chromatographs of blank and standard so-
lutions are also presented in Fig. S4 and the calibration curves of the
3
Science of the Total Environment 771 (2021) 145409
selected nine N-nitrosamines (R2 > 0.99) are shown in Tables S4 and
S5. Precision and accuracy were determined using three levels of con-
centrations (i.e., 5, 10, 20, ng/L) with six replicates (Table S6). The RSD
% and method detection limits (MDLs) were also calculated (Table S5)
as described and adopted in previous studies (Bei et al., 2016b; Chen
et al., 2019). Detailed information were presented in Sections 1–6 of
the supplementary information.
2.4. Screening of N-nitrosamine precursors
The N-nitrosamine precursors screening method developed by Bei
et al. (2016b) was adopted to obtain the leading precursors in reser-
voirs. Following is the brief procedure: (i) concentrating the N-nitrosa-
mine precursors using reverse osmosis, (ii) extraction through two
types of SPE cartridges, viz SCX and C18, and (iii) eluting the adsorbed
organic content and N-nitrosamine precursors using CH3OH/NH3.H2O
(90%/10%, v/v) and CH3OH, respectively. The sample volume and the
flow rate during analysis were 10 μL and 300 μL/min, respectively.
The pre-concentrated N-nitrosamine precursors were analyzed
using LC (ACQUITY UPLC, Water, USA) with a C8 analytical column
(C8 BEH 2.1 × 100 mm 1.7 mm, Waters, U.K.) coupled with time-of-
flight mass spectrometry (TOF-MS) (Xevo G2-XS QTof, Water, USA).
N-nitrosamine precursors were relatively determined before and after
chloramination. We firstly narrowed the scope of possible N-
nitrosamine precursors by picking out the chromatographic peaks that
decreased drastically after chloramination in non-target mode. Then,
we made a list of 68 N-nitorsamine precursors reported in literature
(Le Roux et al., 2011; Mitch and Sedlak, 2004; Schmidt and Brauch,
2008; Selbes et al., 2013; Shen and Andrews, 2011), imported their
structure information to form a library, and tried to screen the N-
nitrosamine precursors in target mode. We set the screening criteria
with mz tolerance of ±5 mDa. Through the match in terms of accurate
molecular weight, primary fragments, secondary fragments, isotope
peak clusters with the library, speculated N-nitrosamine precursors
J. Zhang, T. Maqbool, Y. Qiu et al.
could be identified. Moreover, we purchased the speculated chemicals,
injected them into the instrument, and confirmed their presence by
comparing the retention time with those of the standard chemicals.
2.5. Fluorescence spectroscopy
Fluorescence spectra, in the form of a three-dimensional excitation-
emission matrix (EEM), were collected using a fluorescence spectrome-
ter (F-7000, Hitachi, Japan). A four-sided 1 cm quartz cuvette cell was
used to collect the fluorescence spectra. The UV–Vis (UV, Shimadzu,
Japan) spectra were collected to confirm the absorption value of less
than 0.05 cm−1 at 254 nm to avoid any inner filter effect in fluorescence
spectra as well as the sample dilution requirement (Yang et al., 2015a).
The fluorescence spectra were collected with the following adjusted pa-
rameters: excitation and emission wavelengths ranges were set at
220–450 nm and 280–600 nm with wavelength steps of 5 nm and
1 nm, respectively. The scan speed was 30,000 nm/min, and excita-
tion/emission slits were fixed to 5 nm. The EEM of Milli-Q water was
also measured and subtracted from that of the collected water samples.
Raman area integration was used to normalize the obtained EEMs
(Lawaetz and Stedmon, 2009). The fluorescence index (FI), humifica-
tion index (HIX), and biological index (BIX) were calculated from
EEM. The FI was calculated as a ratio of emission wavelengths at
470 nm and 520 nm, obtained at excitation of 370 nm. The calculation
of HIX was based on the emission spectrum areas under the wave-
lengths of 435–480 nm to 300–345 nm at Ex of 255 nm (Hansen et al.,
2016; Ohno, 2002). The BIX was estimated using a ratio of Em intensity
at 380 nm to 430 nm at an Ex of 310 nm (Hansen et al., 2016).
3. Results and discussion
3.1. Nitrosamine precursors
The TOF-MS analysis confirmed the occurrence of a total of 22 re-
nowned chemicals as N-nitrosamine precursors in the SPE extracts of
samples collected from four reservoirs. Depending on the sources re-
ported in the current literature (Chen et al., 2019; Shen and Andrews,
2011), these precursors are categorized into three classes: industrial;
agricultural; and pharmaceuticals and ingredients of personal care
products as well as their metabolites (Table S7). In a study by Hanigan
et al. (2017), the occurrence of N-nitrosamine precursors in water sup-
plied was analyzed using LC/TOF-MS fragmentation. They developed a
database consisting of 66 known and/or suspected precursors of
NDMA. Several are common chemicals found in our study.
Among the four reservoirs, DR-A and DR-C have shown the most
common compounds: diphenylamine, betain, and morpholine while
DR-D with significant agricultural land (14.3%) showed most distin-
guished precursors (Table 1). Such heterogeneous sources of precursors
in reservoirs indicated different activities (land-use) in four different
catchments. For example, morpholine and diphenylamine are abun-
dantly formed in industries producing/using rubber or emulsifiers
(Wang et al., 2011), while piperidine originates from food processing in-
dustries (Sallan et al., 2019). Similarly, a few other precursors originat-
ing from paper and pulp industries, paint, and dye manufacturing could
play a role in forming different N-nitrosamines (Table 1) (Chen et al.,
2019). In this study, diphenylamine is the only precursor found in
all reservoirs, and 5-(dimethylaminomethyl)-2-furanmethanol was
found in three reservoirs except for DR-B that has a small residential
area (0.29%). Diphenylamine was abundantly detected as an envi-
ronmental pollutant in surface water and groundwater (Alizadeh
and Farokhcheh, 2014). Several studies from China also reported
diphenylamine occurrence in drinking water sources with a concen-
tration ranging from 0.2 to 1.0 μg/L in a country-wide survey (Wang
et al., 2011). The surface runoff over the roads, parking lots, roofs, and
pavements are sources of the precursors that may lead to the formation
of NDPhA. Importantly, 5-(dimethylaminomethyl)-2-furanmethanol
4
Science of the Total Environment 771 (2021) 145409
was reported to be a pharmaceutical intermediate (Shen and Andrews,
2013), and could be found in the list of precursors provided by Hanigan
et al. (2017).
Based on the available literature, the chemicals found in this study
have a N-nitrosamine molar conversion ranging between <1%
and > 90%. For instance, ranitidine has been reported to have the highest
molar conversion (89.9–94.2%), followed by 5-(dimethylaminomethyl)-
2-furamethanol (81.8%), doxylamine (8.0–9.7%), sumatriptan (6.1%). No-
tably, N,N-diethyl-3-methylbenzamide (DEET) and lidocaine have the
lowest molar conversion (Selbes et al., 2013; Shen and Andrews, 2011;
Zhou et al., 2014). Among the identified precursors, a few pharmaceuti-
cals such as ranitidine, 5-(dimethylaminomethyl)-2-furanmethanol, and
sumatriptan have been reported to have higher molar conversion than
other industrial or agricultural-related compounds. The chemicals with
the highest N-nitrosamine yield mostly have a dimethyleamine (DMA)
group attached to electron-rich moieties (Shen and Andrews, 2011).
Few precursors with a low molar conversion (e.g., DEET) have a
diethylamine (DEA) group attached to the electron-withdrawing car-
bonyl functional group, and thus showed low NDEA yield (Shen and
Andrews, 2011). Although the city's reservoirs mostly received precur-
sors from industrial and pharmaceuticals origins (Table 1 and Table S7),
a few traces of pesticides such as the insecticide pirimicarb (DR-D), and
the herbicide cycluron (DR-A) indicated the influx of precursors from
urban agriculture/horticulture (Fujioka et al., 2020; Li et al., 2018).
These precursors were only detected in DR-A and DR-D, which have the
highest agricultural areas, i.e., 12.1%, and 14.3%, respectively.
The precursors remaining (%) in Table 1 indicates the decrease in
their peak areas obtained from the TOF-MS spectra after chloramination,
and it represents the consumption of chemical compounds through
chloramination. However, it could not help in the exact estimation of
N-nitrosamines formation unless the molar conversion is taken into ac-
count. This approach was reported to be useful for estimating the poten-
tial of each precursor to form N-nitrosamines (Bei et al., 2016a; Hanigan
et al., 2017). The extent of reduction in precursor concentration was
different in the samples collected from different reservoirs. It could
be attributed to the difference in initial concentrations as well as
competition between different precursors or their affinity with
DOM during chloraminationas reported previously (Hinneh et al.,
2019). Indeed, in this study, diphenylamine (% remaining) was
found to be ranged between 4.3% (DR-A) to 12.7% (DR-D). The % re-
maining for morpholine was 4.3% (DR-A) and 43.5% (DR-C). Simi-
larly, 5-(Dimethylaminomethyl)-2-furanmethanol was consumed
entirely (0% remaining) in DR-C, while it was consumed by up to
70% and 14.8% in DR-A and DR-D, respectively. The % remaining of
triethylamine was up to 43.4% and 3.0% in DR-C and DR-D, respectively.
Notably, the consumption of betaine in the samples of DR-B and DR-C
was comparable. Among all the precursors, ranitidine, DEET, and
gramine showed complete degradation during chloramination. The re-
sults of this study inferred that consumption of N-nitrosamine precur-
sors during chrloramination is dependent on the type of precursors,
and also might be affected by the presence of DOM.
The above results present a qualitative overview of different re-
nowned precursors in different reservoirs of the city. This approach
highlighted that the precursors were abundantly present. However,
inter-reservoir comparison and absolute share of these precursors
in N-nitrosamines are the limitation of this study and will be focused
in our future studies. Based on the classification, the distribution of
these precursors in four reservoirs is presented in Fig. S5 that the
precursors from industrial origin (or industrial products) were
dominant in all the reservoirs, followed by pharmaceuticals and
their metabolites. Although a diverse composition of N-nitrosamine
precursors was found in the selected reservoirs, land-use industrial
processing/manufacturing, pharmaceutical and personal care prod-
ucts affected the occurrence of these precursors. Due to extensive ur-
banization, rising industrial and modern agricultural activities in the
city, the occurrence of these precursors could also be ascribed to the
J. Zhang, T. Maqbool, Y. Qiu et al. Science of the Total Environment 771 (2021) 145409

Table 1
Isolated and confirmed N-nitrosamine precursors in four reservoirs.

Chemical Name Structure Uses/Sources Remaining after Molar

chloramination (%) conversion

DR-A DR-B DR-C DR-D

<1% (Shen
Industrial: Chemical raw materials, catalysts and analytical
Diphenylamine (DPhA) 4.3% 6.2% 7.0% 12.7% and Andrews,
reagents; used in the manufacture of rubber, dyes, plastics, etc.
2011)
Drugs: Intermediate for pain killing (an anti-inflammatory 25% (Selbes
2-Dimethylaminomethylpyrrole – 3.6% – –
analgesic). et al., 2013)
Industrial: Organic synthetic raw materials for the production of
petroleum additives, rubber vulcanization accelerators, mineral 0.32% (Zhou
Dibutylamine (DBA) – 15.4% – –
flotation agents, corrosion inhibitors, emulsifiers, insecticides, et al., 2014)
polymerization inhibitors and dyes.
Industrial: New high-efficiency catalyst widely used in chemical 2.32% (Zhou
4-Dimethylaminopyridine – 11.0% – –
synthesis et al., 2014)
Industrial: Production of surfactants and detergents, feed 12% (Kemper
Betaine – 5.4% 1.7% –
additives, drugs et al., 2010)
6.1% (Shen
Sumatriptan Drugs: An analgesic – 19.6% – and Andrews,
2011)
<1.0% (Shen
N,N-diethyl-3-methylbenzamide (DEET) Drugs: Mosquito repellent, insecticide – – 0% – and Andrews,
2011)

Gramine Drugs: Pharmaceutical intermediates – 0% – – NA

<1.0% (Shen
Lidocaine Drugs: Local anesthesia and antiarrhythmic drugs – – – – and Andrews,
2011)
(8.0–9.7%)
(Shen and
Doxylamine Drugs: Sedative drugs – – – –
Andrews,
2011)
Industrial: It is mainly used for the production of rubber
vulcanization accelerators, but also for the synthesis of
0.47% (Zhou
Morpholine surfactants, textile printing and dyeing aids, medicines and 4.3% – 43.5% –
et al., 2014)
pesticides. Also used as metal corrosion inhibitor, rust inhibitor
and solvent

Cycluron Agricultural: herbicide 29.0% – – – NA

81.8 ± 1.6%
5-(Dimethylaminomethyl)-2-furanmethanol Drugs: Used as pharmaceutical intermediate 29.6% – 0% 85.2% (Selbes et al.,
2013)
0.2 ± 0.03%
Industrial: Used in dye intermediates, latex accelerators,
N,N-Diethylaniline 18.8% – – – (Selbes et al.,
pharmaceuticals, pesticides, etc.
2013)

Tapentadol Drugs: Analgesics 0% – – – NA

0.37% (Selbes
2-Dimethylaminopyridine Industrial: New high-efficiency catalyst for chemical synthesis – – 16.6% –
et al., 2013)
Industrial: It is mainly used as a solvent, curing agent, catalyst, <1% (Mitch
Triethylamine polymerization inhibitor, preservative, and synthetic dye in – – 43.4% 3.0% and Sedlak,
industry 2004)
Industrial: Food flavors, solvents in organic synthesis, 1.56% (Zhou
Piperidine (PIP) – – – 18.2%
intermediates for synthetic drugs et al., 2014)
Drugs: Used as an intermediate for the drug neostigmine bromide 1.0% (Selbes
3-Dimethylaminophenol – – – 9.1%
and anthrone dye et al., 2013)
89.9–94.2%
(Shen and
Ranitidine Drugs: Stomach medicine – – – 0.0%
Andrews,
2011)
Industrial: Chemical synthesis additives, catalysts, used in resin, 0.59% (Zhou
Dimethylethanolamine – – – 0.0%
medicine, textile and other manufacturing et al., 2014)
Agricultural: It is mainly used as a solvent, curing agent, catalyst,
0.06% (Li
Pirimicarb polymerization inhibitor, preservative, and synthetic dye in – – – 21.6%
et al., 2018)
industry

NA = Not available.

heterogeneous sources. The fewer common chemicals in the reser- concentration in reservoirs and their distributions in different reser-
voirs of the city indicated a significant role of diverse local activities voirs, as well as their association with DOM and with the land-use in
in different catchment areas, although all the reservoirs received the surroundings of the reservoirs, are discussed in the following
recharged water from Dongjiang River. Overall N-nitrosamine sections.

5
J. Zhang, T. Maqbool, Y. Qiu et al.
3.2. Occurrence of N-nitrosamines in reservoirs
Although most of the N-nitrosamines are formed during the disin-
fection process at drinking water plants, several studies have reported
the occurrence of N-nitrosamines in freshwater reservoirs (Chen et al.,
2019; Ma et al., 2012). In this study, nine N-nitrosamines were found
in the water samples collected from different reservoirs. Their concen-
trations are presented in Table S8. None of the N-nitrosamines was
found to be above 7 ng/L. The sequence of the abundances (Fig. 2) was
found to be different among the reservoirs, and a comparison with
other studies of China is provided in Table 2. The sum of N-
nitrosamines (and NDMA-FP) in DR-A, DR-B, DR-C, and DR-D was
30.93 ± 0.26 (29.49 ± 0.93), 24.64 ± 0.20 (25.45 ± 2.73), 29.92 ±
0.78 (30.82 ± 1.28), and 36.06 ± 0.85 (33.94 ± 0.23) ng/L, respectively.
Surprisingly, instead of NDMA, the contribution of NPIP was the highest
in two reservoirs (i.e., DR-A and DR-B), while NDBA was the most abun-
dant in the other two reservoirs, namely DR-C and DR-D. The concentra-
tion sequence of N-nitrosamines in DR-A and DR-B was found to be in
the following order: NPIP>NDBA>NPYR>NDMA. However, sequences
were NDBA>NPYR>NDMA>NMOR and NDBA>NMOR>NDMA>NPYR
in DR-C and DR-D, respectively (Fig. 2). Notably, major N-nitrosamines
in DR-A and DR-B were similar, dominant N-nitrosamines in DR-C and
DR-D were comparable. The occurrence of these N-nitrosamines has
been reported in previous studies related to the drinking water in
China. For instance, Chen et al. (2019) found NDBA as a leading
N-nitrosamine in one of the rivers in southern China, while NDPA
was detected in the freshwater as reported by Zhao et al. (2019). Gener-
ally, NDMA has been reported as a major N-nitrosamine in the freshwa-
ter sources of China (Luo et al., 2020; Qiu et al., 2020; Wang et al., 2016a,
2016b). In a recent study, the occurrences of N-nitrosamines in different
branches of the Pearl River delta were investigated. N-nitrosamines
were regarded to be associated with sewage discharge from industries
including textile printing, electroplating, and food processing, NDMA
was detected with the highest concentration followed by NDEA, NPYR,
NMOR, and NDBA (Chen et al., 2019).
8.75%
NDMA 13.79%
NMOR
NPYR
NMEA
18.04% 8.49%
NDEA
NPIP
NDPA
NDBA
NDPHA
13.8%
7.22%
2.81%
4.8%
22.31%
9.3%
15.45%
18.98%
15.27%
6.7%
10.01% 18.74%
3.01%
2.54%
Fig. 2. Distribution of the selected nine N-nitrosamines in four reservoirs. Total N-nitrosamines (∑NAs) in DR-A, DR-B, DR-C, and DR-D were 30.93 ± 0.26, 24.64 ± 0.20, 29.92 ± 0.78, and
36.06 ± 0.85 ng/L, respectively.
Science of the Total Environment 771 (2021) 145409
Among the reservoirs, DR-B had the lowest sum of N-nitrosamines
(∑NAs) and NDMA-FP, which could be due to the relatively low resi-
dential (city, 0.29%) activity in its catchment area (Tables S1 and S8).
Most of the detected N-nitrosamines (except NPIP) in DR-B were re-
corded to be the lowest among the four reservoirs. The DR-D reservoir
with a reasonable residential area (city, 1.30%) and the highest agricul-
tural land (14.28%) showed the highest ∑NAs and NDMA-FP. It is es-
sential to mention that the DR-A and DR-D are located in the
commercial hub of the city, which is also reflected by their ∑NAs.
The results of this study inferred that the commercial/residential activ-
ities could directly impact the concentration and distribution of N-nitro-
samines in freshwater. The catchments with the lowest residential
activities may not receive abundant quantities of N-nitrosamines
(Table S1).
Removal efficiency for N-nitrosamines by drinking water treatment
plants has been reported to be 10–20% (Krasner et al., 2013; Maqbool
et al., 2020b). Currently, the drinking water treatment systems in the
city of interest are using NaOCl as the disinfectant, which could cause
a slight increase in N-nitrosamines concentration. In this context, poten-
tial cancer (Table S9) risk was calculated based on the N-nitrosamines
concentration in the water samples collected from the reservoirs; and
an average removal of 20% by full-scale water treatment plants. The av-
erage cancer risk of N-nitrosamines was found to be in the range of
2.98 × 10−10 (for NDPhA) to 5.50 × 10−6 (for NDMA). Values for
seven out of the nine selected N-nitrosamines were far below the gener-
ally accepted risk of 10−6, while the values for NDMA/NDEA were found
to be closed to the risk level (10−6) (US EPA, 2015) (Table S9). These
cancer risk assessment indicated that these reservoirs contain water of
reasonable quality with less public health concerns.
3.3. Comparison of DOM characteristics among different reservoirs
The DOC levels were 3.67 ± 0.09, 4.04 ± 0.67, 4.82 ± 0.10, and
3.91 ± 0.41 mgC/L in DR-A, DR-B, DR-C, and DR-D, respectively
(Table 3) with lowest in DR-A and highest in DR-C (t-test, p < 0.01,
(a) DR-A (b) DR-B
8.98% 14.04%
16.18%
8.72%
7.44% 14.05%
3.01%
5.01%
22.59%
(c) DR-C 8.18% (d) DR-D
18.03%
19.17%
18.65%
5.85%
8.82%
2.55%
2.13% 16.63%
6
J. Zhang, T. Maqbool, Y. Qiu et al. Science of the Total Environment 771 (2021) 145409

Table 2
The dominant N-nitrosamines and ranges of fluorescence indices in freshwater across China.

Source water Location Sampling date Predominant References

Nitrosamines

Hanjiang River Central China January 2016 to December 2016 NDMA>NDEA> NPIP (Luo et al., 2020)
Hongze Lake East China March and October 2017 NDPA> NDBA> NPYR (Zhao et al., 2019)
Source water of 54 drinking water plants Overall China March and May 2010 NDMA>NDEA>NDBA (Wang et al., 2016b)
Pearl River South China July 2016, December 2016, June 2017 and January 2018 NDMA>NDEA>NPYR (Chen et al., 2019)
Songhua River North China September and November 2014 NDMA>NDBA>NDEA (Wang et al., 2016a)
Jialu river Central China November 2010, January 2011, and March 2011, NDMA>NDEA>NPIP (Ma et al., 2012)

Fluorescence indices
Nanfei River Central China April and August 2018 FI = 1.64–2.49 (Zhang et al., 2020)
BIX = 0.84–1.15
HIX = 1.37–2.51
Changshou Lake Southwest China January, April, July, and November 2014 FI = 1.60 ± 0.01 (Jiang et al., 2018)
BIX = 0.75–0.90
HIX = 3.10–6.47
Artificial reservoirs Northwest China April 2019 FI = 2.2–2.5 (Wang et al., 2017)
BIX = 0.8–1.0
HIX = 0.2–0.8
Xiaoqing River Eastern China April 2014 FI = 1.0–2.2 (Jiang et al., 2017)
BIX = 0.9–1.2
HIX = 0.61–2.67
17 lakes Central and south China – FI = 1.9 ± 0.3 (Zhou et al., 2017)
BIX = 1.1 ± 0.5
HIX = 1.3 ± 0.8

Table 3). These DOC levels in all reservoirs were relatively higher than
those reported in the reservoirs located in the southern part of the coun-
try (Hong et al., 2008). This could be attributed to the extensive human
activities in the catchment areas of the selected reservoirs. For example,
the DOC level in the Hongjiadu reservoir was reported to be ranged
from 0.68 to 1.73 mg/L (Yu et al., 2020). The TNb concentration was
found to be the highest (1.92 ± 0.11 mg/L) in DR-A and was the lowest
in DR-D (0.47 ± 0.03 mg/L). In reservoirs DR-A, DR-B, and DR-C, TNb
was mostly detected in the form of NO− 3 (85.1% to 89.9%), while its con-
tribution to TNb was marginal (21.89 ± 0.04%) in the samples collected
from DR-D. The TNb distribution shows higher organic nitrogen in DR-D
than three reservoirs (DR-A, DR-B, and DR-C). Relatively higher nutrient
levels in three reservoirs (i.e., DR-A, B, and C) could be linked to the
land-use. A previous study reported a positive correlation between agri-
cultural land and TNb concentration, while a strongly negative correla-
tion between developed areas and TNb concentration was observed
(Lacher et al., 2019). Notably, in this study, no specific relationship be-
tween land-use and TNb concentration was found. However, NH+ 4 was
found to be higher in DR-A and DR-D with extensive agriculture areas,
and at the same time, these catchments also have the largest residential
areas. Meanwhile, the point of Dongjiang River recharging DR-A and
DR-D had higher TNb concentrations as compared to the eastern tribu-
tary recharging DR-B and DR-C (Fig. S6).
All the reservoirs showed high FI that ranged from 2.58 (average,
DR-C) to 3.17 (average, DR-D), suggesting the effects of microbial-
derived DOM (Hansen et al., 2016) (Table 3). This index has been re-
ported as a potential indicator describing the relative contribution of
terrestrial and microbial-derived DOM (Hansen et al., 2016; McKnight
et al., 2001). The biological- and humification index (BIX and HIX) are
the proxies of biological contributions (i.e., autochthonous source),
and the extent of humification in DOM, respectively (Huguet et al.,
2009; Ohno, 2002). Ranges of both indices in the selected reservoirs
presented a higher contribution of biological DOM in DR-A, DR-C, and
DR-D (BIX > 1.10, HIX ≤1.0). On the other hand, HIX and BIX of DR-B
were significantly (P < 0.05) different from the rest of the reservoirs
with an average ± SD of 2.91 ± 0.16 and 0.93 ± 0.05, respectively
(Table 3). The higher BIX and organic nitrogen in DR-D could ascribe
to the abundance of biological derived DOM. Previous studies have
found a direct association between organic nitrogen and protein con-
tent in water and wastewater-related research (Huber et al., 2011;
Jacquin et al., 2017). Generally, these indices indicated a higher share
of biological DOM as compared to terrestrial DOM in all reservoirs ex-
cept for DR-B that seems to originate from terrestrial DOM mainly.
The biological sources of DOM in these reservoirs include: effluent or-
ganic matter, algal growth (eutrophication), and in-situ produced
DOM by microbial activity. The higher BIX also represents the role of an-
thropogenic activities in the surroundings of aquatic systems. Consis-
tent with the results of this study, values of fluorescence indices have
been reported in several other drinking water reservoirs (or rivers) of
China, such as Nanfei River (HIX = 1.32–2.51, BIX = 0.84–1.15, Zhang

Table 3
Basic quality parameters, EEMs peaks, and fluorescence indices in water from four reservoirs.

Parameters DR-A DR-B DR-C DR-D

DOC (mgC/L) 3.67 ± 0.09 4.04 ± 0.67 4.28 ± 0.10 3.91 ± 0.41
TNb (mg/L) 1.92 ± 0.11 0.91 ± 0.05 0.79 ± 0.02 0.48 ± 0.04
NH+4 (mg/L) 0.12 ± 0.01 0.10 ± 0.01 0.08 ± 0.00 0.14 ± 0.00
NO−3 (mg/L) 1.67 ± ±0.13 0.77 ± 0.04 0.68 ± 0.02 0.10 ± 0.02
HIX 0.89 ± 0.02 2.91 ± 0.14 1.04 ± 0.31 0.99 ± 0.02
BIX 1.21 ± 0.07 0.93 ± 0.06 1.15 ± 0.05 1.31 ± 0.03
FI 2.60 ± 0.01 2.91 ± 0.16 2.58 ± 0.06 3.17 ± 0.19
Peak T1 (230/340 nm) (R.U.) 0.42 ± 0.02 0.21 ± 0.03 0.55 ± 0.07 0.49 ± 0.05
Peak T2 (275/316 nm) (R.U.) 0.27 ± 0.01 0.13 ± 0.01 0.20 ± 0.03 0.32 ± 0.01
Peak C1 (310/396 nm) (R.U.) 0.14 ± 0.01 0.16 ± 0.00 0.11 ± 0.02 0.14 ± 0.01
Peak C2 (235/408 nm) (R.U.) 0.27 ± 0.02 0.29 ± 0.01 0.24 ± 0.03 0.24 ± 0.00

7
J. Zhang, T. Maqbool, Y. Qiu et al. Science of the Total Environment 771 (2021) 145409

et al., 2020) and Changshou Lake (HIX = 3.10–6.47, BIX = 0.75–0.90,
Jiang et al., 2018). It is important to note that land-use was found to
have a direct influence on these fluorescence indices. For instance, DR-
B and DR-C with lower residential areas and commercial activities
could be the reason for limited autochthonous DOM. On the other
hand, a higher HIX value shows a substantial share of allochthonous
DOM in DR-B than the other three reservoirs. Importantly, the associ-
ated Eastern Water Supply System for DR-B and DR-C originates from
the tributary of Dongjiang River with relatively low anthropogenically
affected watershed compared to the western end of Dongjiang River
(for DR-A and DR-D).
The relationship between DOC/TNb and fluorescence indices was not
observed in this study, which illustrates that DOM composition in the
water samples collected from the selected reservoirs was different. For
the pseudo-quantitative comparison of FDOM, the EEMs of water sam-
ples from different reservoirs are presented in Fig. 3, and the fluores-
cence intensities are presented in Table 3. The fluorescence spectra of
reservoirs shared four characteristic peaks. Similar peaks were abun-
dantly reported in the literature on drinking water sources. Peak T1 rep-
resents protein-like moieties, specifically tryptophan-like, while Peak
T2 is associated with soluble microbial products (Bieroza et al., 2009;
Hua et al., 2018; Rosario-Ortiz et al., 2007). These two peaks can indicate
synchronized changes in these peaks and are stemmed from similar
sources and attributed to the similar protein-like moieties (Han et al.,
2020; Wang et al., 2019; Zhang et al., 2019). Our results also presented
a similar difference between both peaks, as shown by the EEMs of the
water samples collected from different reservoirs. The variation in
peak T1 intensity between DR-B vs. DR-C was ~39.0% (based on the
mean values), and, on the other hand, ~63.0% was the difference in the
intensity of peak T2. Unlike the fluorescence indices, these intensities
could be used for the pseudo-quantitative comparison (Maqbool et al.,
2020a). The fluorescence peak below 380 nm (Peak T1 and Peak T2)
represents DOM mainly originating from a microbial source and could
be linked with bio-labile fractions (Maqbool et al., 2020a). Several stud-
ies have linked the existence of such peaks with the potential release of
effluent in the drinking water reservoirs as well as algal bloom in
nutrient-rich reservoirs (Derrien et al., 2017; Li et al., 2020). The fluo-
rescence indices with higher BIX already indicated toward a major
share of anthropogenic activities in the reservoirs and fluorescence
intensities also showed higher intensities in this region. Among the
selected four reservoirs in this study, DR-B is least affected by an-
thropogenic activities.
The intensities of the peaks above 380 nm (Peak C1 and Peak C2)
among the four reservoirs did not show any significant difference. The
highest difference (32%) in peak C1 was found between DR-B and DR-
C, while Peak C2 showed a 18% difference between DR-B and DR-C.
The results of this study inferred that the city's reservoirs are receiving
an equal share of allochthonous DOM with the concentration of those
less affected throughout the city. This comparison shows relatively
higher human activities in the catchment of three reservoirs (except
for DR-B), clear from the extensive urbanization and increasing com-
mercial activities in the city.
3.4. Correlation between N-nitrosamines and DOM
Existence and relationship between N-nitrosamines and DOM
have been studied previously (Farré et al., 2019). Few correlations
have already been reported, which linked the sources of DOM com-
position with N-nitrosamines abundances. Most studies focused on
NDMA-FP; while a few reported a strong association with DOM con-
stituents, an insignificant relationship has also been reported (Uzun
et al., 2015; Yang et al., 2015b). Keeping aside the DOM as the

440 440

DR-A DR-B

400 400

360 360
Ex (nm)

Ex (nm)

320
C2
320
C2

280
T2
280
T2
240
T1 C1 240
T1 C1
240 280 320 360 400 440 480 520 560 600 240 280 320 360 400 440 480 520 560 600
Em (nm) Em (nm)
440 440
DR-C DR-D
400 400

360 360
Ex (nm)

Ex (nm)

320 320
C2 C2
280
T2 280 T2

T1 C1 C1
240 240
T1
240 280 320 360 400 440 480 520 560 600 240 280 320 360 400 440 480 520 560 600
Em (nm) Em (nm)

Fig. 3. Excitation-emission matrix (EEM) of the samples collected from four reservoirs.

8
J. Zhang, T. Maqbool, Y. Qiu et al.
precursors of N-nitrosamines, hydrological parameters could also af-
fect them simultaneously and cause mutual variations in natural
aquatic systems. For instance, higher rainfall causes leaching of ter-
restrial DOM from deep soil, while washing off the road, roof, and
run-off over the dumped waste extract the N-nitrosamine precursors
and lead them to aquatic systems.
The correlation among the basic quality parameters, N-nitrosamines,
and fluorescence indices was revealed using principal component anal-
ysis (PCA), as shown in Fig. 4. The principal component 1 (PC1) accounts
for 56.47%, while the PC2 represents 26.81% of the total variances. The
majority of DR-C and DR-D samples fell on the positive side of PC1,
which seems to be governed by BIX. On the contrary, HIX and DR-B
were on the negative side of PC1 and PC2, representing actively alloch-
thonous DOM in the reservoir. The concentration and abundances of the
N-nitrosamines (except for NDEA and NPIP) in reservoirs across the city
were mainly associated with the BIX and protein-like fluorescence
peaks T1 and T2, highlighting the role of anthropogenic activities in
the watersheds. The PCA also indicated an insignificant role of DOC in
determining the N-nitrosamine composition. When samples from dif-
ferent reservoirs were compared, a negligible contribution of DOM orig-
inating from allochthonous sources was found. The association between
NDEA (and NPIP) and TNb (NO− 3 ) indicated a fundamental difference in
Fig. 4. (a) Principal component analysis (PCA) biplot for N-nitrosamines, fluorescence in-
dices, and basic quality parameters, and (b) correlation between BIX and NDMA-FP/∑NA.
9
Science of the Total Environment 771 (2021) 145409
the existence and the possible formation of N-nitrosamines. These N-
nitrosamines are possibly formed within the environment of reservoirs
rather than carried along with the DOM-enriched run-off. The correla-
tion between the total N-nitrosamines and NDMA-FP/BIX was
reconfirmed (Fig. 4b). The DR-D with the highest BIX showed the
highest abundance of N-nitrosamines (and NDMA-FP) and vice-versa
(in the case of DR-B). Based on the discussion above, it could be deduced
that DOM origin plays an important role and could be used as a surro-
gate of N-nitrosamine concentrations in the reservoirs. Consistent
with the findings of this study, in a recent study by Bei et al. (2020),
amino acids secreted by microbes were found to be directly related to
NDMA-FP. The laboratory-based aerobic and anaerobic incubation
with surface water collected from multiple rivers accounted for 38%
(maximum) or 27% (average) of the median NDMA-FP in the freshwa-
ter of China. As compared to the natural sources, the anthropogenic ac-
tivities seem to have a dominant influence on the occurrence of the
precursors; and/or the already formed nitrosamines originating from
residential or commercial areas. One of the reasons is ever-increasing
industrial activities and extensive urbanization in the city.
4. Conclusion
This study investigated the occurrence of N-nitrosamines and their
precursors in four drinking water reservoirs in a southern city of
China. The major sources of N-nitrosamines and DOM were traced,
and the association between them was determined based on TOF-MS,
LC-MS, and fluorescence spectroscopy. Followings are the main conclu-
sions drawn from the results:
• A total of 22 N-nitrosamine precursors of different origins were iden-
tified. Among the identified precursors, two were of agriculture origin,
while eleven and nine were of industrial and pharmaceuticals (and
their metabolites) origin, respectively.
• TOF-MS analysis demonstrated that pharmaceuticals had a
higher potential for N-nitrosamine formation vs. the agricultural
or industrial compounds due to higher molar conversion ratios. A
few precursors such as ranitidine, gramine, DEET, tapentdol, and
dimethylethanolamine were fully depleted upon chloramination.
However, pirimicarb and cycluorn showed a high residual con-
tent up to 78.4% and 71.0%, respectively.
• The total N-nitrosamines (∑NA) and NDMA-FP were found to be in the
range of 20–35 ng/L and 15–25 ng/L in all the reservoirs, respectively.
However, the distribution of N-nitrosamines was found to be substan-
tially different in the reservoirs. NDBA, NDMA, NMOR, and NPYR were
the main N-nitrosamines in this study.
• Cancer risk analysis demonstrated that most of N-nitrosamines are
under the generally accepted limit of 10−6. However, NDMA and
NDEA are found near the threshold limit.
• Fluorescence spectroscopy indicated a higher contribution of
biologically-derived DOM, (as represented by BIX and protein-like fluo-
rescence) in three reservoirs, indicating that the contamination was
caused by effluent organic matter. However, one of the reservoirs (i.e.,
DR-B) received DOM with limited protein-like fluorescence moieties.
• A linear relationship (R2 > 0.92; p < 0.001) was recorded between
∑NA (and NDMA-FP), and BIX. Based on the PCA analysis, BIX was
found to be a proxy of a few N-nitrosamines (except NMOR, NMEA,
and NPYR) concentrations in freshwater. Overall, the catchment com-
prising urban areas caused a higher release of N-nitrosamines and
more autochthonous DOM in the reservoirs.
CRediT authorship contribution statement
Jiaxing Zhang: Writing – original draft, Conceptualization, Method-
ology, Visualization, Investigation. Tahir Maqbool: Writing – original
draft, Conceptualization, Methodology, Visualization, Investigation. Yu
J. Zhang, T. Maqbool, Y. Qiu et al.
Qiu: Conceptualization, Methodology, Visualization, Investigation.
Yanling Qin: Investigation. Muhammad Bilal Asif: Validation. Chao
Chen: Validation. Zhenghua Zhang: Supervision, Validation, Writing –
review & editing, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgment
This research was supported by the National Natural Science
Foundation of China (51708325), Tsinghua University Start-
up Funding (QN20180001), and the Committee of Science
and Technology Innovation of Shenzhen (JCYJ20170817161942307;
JCYJ20190813163401660).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2021.145409.
References
Alizadeh, N., Farokhcheh, A., 2014. Simultaneous determination of diphenylamine and
nitrosodiphenylamine by photochemically induced fluorescence and synchronous
fluorimetry using double scans method. Talanta 121, 239–246. https://doi.org/
10.1016/j.talanta.2013.11.054.
Barbosa, M.O., Ribeiro, A.R., Ratola, N., Hain, E., Homem, V., Pereira, M.F.R., Blaney, L., Silva,
A.M.T., 2018. Spatial and seasonal occurrence of micropollutants in four Portuguese
rivers and a case study for fluorescence excitation-emission matrices. Sci. Total Envi-
ron. 644, 1128–1140. https://doi.org/10.1016/j.scitotenv.2018.06.355.
Bei, E., Liao, X., Meng, X., Li, S., Wang, J., Sheng, D., Chao, M., Chen, Z., Zhang, X., Chen, C.,
2016a. Identification of nitrosamine precursors from urban drainage during storm
events: a case study in southern China. Chemosphere 160, 323–331. https://doi.
org/10.1016/j.chemosphere.2016.06.081.
Bei, E., Shu, Y., Li, S., Liao, X., Wang, J., Zhang, X., Chen, C., Krasner, S., 2016b. Occurrence of
nitrosamines and their precursors in drinking water systems around mainland China.
Water Res. 98, 168–175. https://doi.org/10.1016/j.watres.2016.04.013.
Bei, E., Li, X., Wu, F., Li, S., He, X., Wang, Yufang, Qiu, Y., Wang, Yu, Wang, C., Wang, J.,
Zhang, X., Chen, C., 2020. Formation of N-nitrosodimethylamine precursors through
the microbiological metabolism of nitrogenous substrates in water. Water Res. 183,
116055. doi:https://doi.org/10.1016/j.watres.2020.116055.
Bhattacharya, R., Osburn, C.L., 2020. Spatial patterns in dissolved organic matter composition
controlled by watershed characteristics in a coastal river network: the Neuse River Basin.
USA. Water Res. 169, 115248. https://doi.org/10.1016/j.watres.2019.115248.
Bieroza, M., Baker, A., Bridgeman, J., 2009. Relating freshwater organic matter fluores-
cence to organic carbon removal efficiency in drinking water treatment. Sci. Total En-
viron. 407, 1765–1774. https://doi.org/10.1016/j.scitotenv.2008.11.013.
Chen, W., Chen, Y., Huang, H., Lu, Y., Khorram, M.S., Zhao, W., Wang, D., Qi, S., Jin, B.,
Zhang, G., 2019. Occurrence of N-nitrosamines in the Pearl River delta of China: char-
acterization and evaluation of different sources. Water Res. 164, 114896. https://doi.
org/10.1016/j.watres.2019.114896.
Delpla, I., Rodriguez, M.J., 2016. Experimental disinfection by-product formation potential
following rainfall events. Water Res. 104, 340–348. https://doi.org/10.1016/j.
watres.2016.08.031.
Derrien, M., Yang, L., Hur, J., 2017. Lipid biomarkers and spectroscopic indices for identi-
fying organic matter sources in aquatic environments: a review. Water Res. https://
doi.org/10.1016/j.watres.2017.01.023.
Farré, M.J., Jaén-Gil, A., Hawkes, J., Petrovic, M., Catalán, N., 2019. Orbitrap molecular fin-
gerprint of dissolved organic matter in natural waters and its relationship with
NDMA formation potential. Sci. Total Environ. 670, 1019–1027. https://doi.org/
10.1016/j.scitotenv.2019.03.280.
Fujioka, T., Kodamatani, H., Yujue, W., Yu, K.D., Wanjaya, E.R., Yuan, H., Fang, M., Snyder,
S.A., 2020. Assessing the passage of small pesticides through reverse osmosis mem-
branes. J. Memb. Sci. 595, 117577. https://doi.org/10.1016/j.memsci.2019.117577.
Gan, W., Huang, S., Ge, Y., Bond, T., Westerhoff, P., Zhai, J., Yang, X., 2019. Chlorite forma-
tion during ClO2 oxidation of model compounds having various functional groups
and humic substances. Water Res. https://doi.org/10.1016/j.watres.2019.05.020.
Han, X., Ji, X., Ma, X., Liu, J.-L., He, Z.-Y., Chang, W., Tang, F., Liu, A.-L., 2020. An investiga-
tion of changes in water quality throughout the drinking water production/distribu-
tion chain using toxicological and fluorescence analyses. J. Environ. Sci. 87, 310–318.
https://doi.org/10.1016/j.jes.2019.07.015.
Hanigan, D., Ferrer, I., Thurman, E.M., Herckes, P., Westerhoff, P., 2017. LC/QTOF-MS frag-
mentation of N-nitrosodimethylamine precursors in drinking water supplies is
10
Science of the Total Environment 771 (2021) 145409
predictable and aids their identification. J. Hazard. Mater. 323, 18–25. https://doi.
org/10.1016/j.jhazmat.2016.04.023.
Hansen, A.M., Kraus, T.E.C., Pellerin, B.A., Fleck, J.A., Downing, B.D., Bergamaschi, B.A.,
2016. Optical properties of dissolved organic matter (DOM): effects of biological
and photolytic degradation. Limnol. Oceanogr. 61, 1015–1032. https://doi.org/
10.1002/lno.10270.
Hinneh, K.D.C., El Hanafi, A., He, K., Kosaka, K., Echigo, S., Asada, Y., Itoh, S., 2019. Forma-
tion of N-nitrosodimethylamine by chloramination of anthropogenic nitrogenous
compounds with dimethylamine monitored by Japanese water authorities.
J. Hazard. Mater. 367, 620–628. https://doi.org/10.1016/j.jhazmat.2018.12.102.
Hong, H.C., Wong, M.H., Mazumder, A., Liang, Y., 2008. Trophic state, natural organic mat-
ter content, and disinfection by-product formation potential of six drinking water
reservoirs in the Pearl River Delta. China. J. Hydrol. 359, 164–173. https://doi.org/
10.1016/j.jhydrol.2008.06.024.
Hua, B., Yang, J., Liu, F., Zhu, G., Deng, B., Mao, J., 2018. Characterization of dissolved or-
ganic matter/nitrogen by fluorescence excitation-emission matrix spectroscopy and
X-ray photoelectron spectroscopy for watershed management. Chemosphere 201,
708–715. https://doi.org/10.1016/j.chemosphere.2018.03.043.
Huber, S.A., Balz, A., Abert, M., Pronk, W., 2011. Characterisation of aquatic humic and
non-humic matter with size-exclusion chromatography - organic carbon detection
- organic nitrogen detection (LC-OCD-OND). Water Res. 45, 879–885. https://doi.
org/10.1016/j.watres.2010.09.023.
Huguet, A., Vacher, L., Relexans, S., Saubusse, S., Froidefond, J.M., Parlanti, E., 2009. Prop-
erties of fluorescent dissolved organic matter in the Gironde Estuary. Org. Geochem.
40, 706–719. https://doi.org/10.1016/j.orggeochem.2009.03.002.
Hussain, S., Awad, J., Sarkar, B., Chow, C.W.K., Duan, J., van Leeuwen, J., 2019. Coagulation
of dissolved organic matter in surface water by novel titanium (III) chloride: mecha-
nistic surface chemical and spectroscopic characterisation. Sep. Purif. Technol. 213,
213–223. https://doi.org/10.1016/j.seppur.2018.12.038.
Jacquin, C., Lesage, G., Traber, J., Pronk, W., Heran, M., 2017. Three-dimensional excitation
and emission matrix fluorescence (3DEEM) for quick and pseudo-quantitative deter-
mination of protein- and humic-like substances in full-scale membrane bioreactor
(MBR). Water Res. 118, 82–92. https://doi.org/10.1016/j.watres.2017.04.009.
Jiang, T., Skyllberg, U., Björn, E., Green, N.W., Tang, J., Wang, D., Gao, J., Li, C., 2017. Char-
acteristics of dissolved organic matter (DOM) and relationship with dissolved mer-
cury in Xiaoqing River-Laizhou Bay estuary, Bohai Sea. China. Environ. Pollut. 223,
19–30. https://doi.org/10.1016/j.envpol.2016.12.006.
Jiang, T., Chen, X., Wang, D., Liang, J., Bai, W., Zhang, C., Wang, Q., Wei, S., 2018. Dynamics
of dissolved organic matter (DOM) in a typical inland lake of the Three Gorges Reser-
voir area: fluorescent properties and their implications for dissolved mercury species.
J. Environ. Manag. 206, 418–429. https://doi.org/10.1016/j.jenvman.2017.10.048.
Kemper, J.M., Walse, S.S., Mitch, W.A., 2010. Quaternary amines as nitrosamine precur-
sors: a role for consumer products? Environ. Sci. Technol. 44, 1224–1231. https://
doi.org/10.1021/es902840h.
Krasner, S.W., Mitch, W.A., McCurry, D.L., Hanigan, D., Westerhoff, P., 2013. Formation,
precursors, control, and occurrence of nitrosamines in drinking water: a review.
Water Res. 47, 4433–4450. https://doi.org/10.1016/j.watres.2013.04.050.
Kristiana, I., Tan, J., Joll, C.A., Heitz, A., von Gunten, U., Charrois, J.W.A., 2013. Formation of
N-nitrosamines from chlorination and chloramination of molecular weight fractions
of natural organic matter. Water Res. 47, 535–546. https://doi.org/10.1016/j.
watres.2012.10.014.
Krzeminski, P., Vogelsang, C., Meyn, T., Köhler, S.J., Poutanen, H., de Wit, H.A., Uhl, W.,
2019. Natural organic matter fractions and their removal in full-scale drinking
water treatment under cold climate conditions in Nordic capitals. J. Environ.
Manag. 241, 427–438. https://doi.org/10.1016/j.jenvman.2019.02.024.
Lacher, I.L., Ahmadisharaf, E., Fergus, C., Akre, T., Mcshea, W.J., Benham, B.L., Kline, K.S.,
2019. Scale-dependent impacts of urban and agricultural land use on nutrients, sed-
iment, and runoff. Sci. Total Environ. 652, 611–622. https://doi.org/10.1016/j.
scitotenv.2018.09.370.
Lawaetz, A.J., Stedmon, C.A., 2009. Fluorescence intensity calibration using the Raman
scatter peak of water. Appl. Spectrosc. 63, 936–940. https://doi.org/10.1366/
000370209788964548.
Le Roux, J., Gallard, H., Croué, J.-P., 2011. Chloramination of nitrogenous contaminants
(pharmaceuticals and pesticides): NDMA and halogenated DBPs formation. Water
Res. 45, 3164–3174. https://doi.org/10.1016/j.watres.2011.03.035.
Lee, Y.-K., Hur, J., 2017. Using two-dimensional correlation size exclusion chromatogra-
phy (2D-CoSEC) to explore the size-dependent heterogeneity of humic substances
for copper binding. Environ. Pollut. 227, 490–497. https://doi.org/10.1016/j.
envpol.2017.04.099.
Lee, M.-H., Osburn, C.L., Shin, K.-H., Hur, J., 2018. New insight into the applicability of spec-
troscopic indices for dissolved organic matter (DOM) source discrimination in
aquatic systems affected by biogeochemical processes. Water Res. 147, 164–176.
https://doi.org/10.1016/j.watres.2018.09.048.
Lee, M.-H., Lee, Y.K., Derrien, M., Choi, K., Shin, K.H., Jang, K.-S., Hur, J., 2019. Evaluating the
contributions of different organic matter sources to urban river water during a storm
event via optical indices and molecular composition. Water Res. 165, 115006. https://
doi.org/10.1016/j.watres.2019.115006.
Li, S., Shu, Y., Tang, X., Lin, P., Wang, J., Zhang, X., Chen, C., 2018. Reaction patterns of
NDMA precursors during the sequential chlorination process of short-term free chlo-
rination and monochloramination. Sep. Purif. Technol. 204, 196–204. https://doi.org/
10.1016/j.seppur.2018.04.055.
Li, L., Wang, Y., Zhang, W., Yu, S., Wang, X., Gao, N., 2020. New advances in fluorescence
excitation-emission matrix spectroscopy for the characterization of dissolved organic
matter in drinking water treatment: a review. Chem. Eng. J. 381, 122676. https://doi.
org/10.1016/j.cej.2019.122676.
J. Zhang, T. Maqbool, Y. Qiu et al.
Luo, Q., Bei, E., Liu, C., Deng, Y.-L., Miao, Y., Qiu, Y., Lu, W.-Q., Chen, C., Zeng, Q., 2020. Spa-
tial, temporal variability and carcinogenic health risk assessment of nitrosamines in a
drinking water system in China. Sci. Total Environ. 736, 139695. https://doi.org/
10.1016/j.scitotenv.2020.139695.
Ma, F., Wan, Y., Yuan, G., Meng, L., Dong, Z., Hu, J., 2012. Occurrence and source of nitro-
samines and secondary amines in groundwater and its adjacent Jialu River basin.
China. Environ. Sci. Technol. 46, 3236–3243. https://doi.org/10.1021/es204520b.
MacKeown, H., Adusei Gyamfi, J., Schoutteten, K.V.K.M., Dumoulin, D., Verdickt, L.,
Ouddane, B., Criquet, J., 2020. Formation and removal of disinfection by-products in
a full scale drinking water treatment plant. Sci. Total Environ. 704, 135280. https://
doi.org/10.1016/j.scitotenv.2019.135280.
Maqbool, T., Ly, Q.V., Asif, M.B., Ng, H.Y., Zhang, Z., 2020a. Fate and role of fluorescence
moieties in extracellular polymeric substances during biological wastewater treat-
ment: a review. Sci. Total Environ. 718, 137291. https://doi.org/10.1016/j.
scitotenv.2020.137291.
Maqbool, T., Zhang, J., Qin, Y., Ly, Q.V., Asif, M.B., Zhang, X., Zhang, Z., 2020b. Seasonal oc-
currence of N-nitrosamines and their association with dissolved organic matter in
full-scale drinking water systems: Determination by LC-MS and EEM-PARAFAC.
Water Res., 116096 https://doi.org/10.1016/j.watres.2020.116096.
McKnight, D.M., Boyer, E.W., Westerhoff, P.K., Doran, P.T., Kulbe, T., Andersen, D.T., 2001.
Spectrofluorometric characterization of dissolved organic matter for indication of
precursor organic material and aromaticity. Limnol. Oceanogr. 46, 38–48. https://
doi.org/10.4319/lo.2001.46.1.0038.
Michael-Kordatou, I., Michael, C., Duan, X., He, X., Dionysiou, D.D., Mills, M.A., Fatta-
Kassinos, D., 2015. Dissolved effluent organic matter: characteristics and potential
implications in wastewater treatment and reuse applications. Water Res. 77,
213–248. https://doi.org/10.1016/j.watres.2015.03.011.
Mitch, W.A., Sedlak, D.L., 2004. Characterization and fate of N-nitrosodimethylamine pre-
cursors in municipal wastewater treatment plants. Environ. Sci. Technol. https://doi.
org/10.1021/es035025n.
Ohno, T., 2002. Fluorescence inner-filtering correction for determining the humification
index of dissolved organic matter. Environ. Sci. Technol. 36, 742–746. https://doi.
org/10.1021/es0155276.
Pai, C.-W., Leong, D., Chen, C.-Y., Wang, G.-S., 2020. Occurrences of pharmaceuticals and
personal care products in the drinking water of Taiwan and their removal in conven-
tional water treatment processes. Chemosphere 127002. https://doi.org/10.1016/j.
chemosphere.2020.127002.
Piazzoli, A., Breider, F., Aquillon, C.G., Antonelli, M., von Gunten, U., 2018. Specific
and total N-nitrosamines formation potentials of nitrogenous micropollutants
during chloramination. Water Res. 135, 311–321. https://doi.org/10.1016/j.
watres.2018.02.019.
Qiu, Y., Bei, E., Wang, Y., Wang, J., Zhang, X., Chen, C., 2020. One representative water sup-
ply system in China with nitrosamine concern: challenges and treatment strategies.
J. Environ. Sci. 88, 12–20. https://doi.org/10.1016/j.jes.2019.08.005.
Rosario-Ortiz, F.L., Snyder, S.A., Suffet, I.H. (Mel), 2007. Characterization of dissolved or-
ganic matter in drinking water sources impacted by multiple tributaries. Water Res.
41, 4115–4128. doi:https://doi.org/10.1016/j.watres.2007.05.045.
Sallan, S., Kaban, G., Kaya, M., 2019. Nitrosamines in sucuk: effects of black pepper, so-
dium ascorbate and cooking level. Food Chem. 288, 341–346. https://doi.org/
10.1016/j.foodchem.2019.02.129.
Schmidt, C.K., Brauch, H.J., 2008. N,N-dimethylsulfamide as precursor for N-
nitrosodimethylamine (NDMA) formation upon ozonation and its fate during drink-
ing water treatment. Environ. Sci. Technol. doi:https://doi.org/10.1021/es7030467.
Selbes, M., Kim, D., Ates, N., Karanfil, T., 2013. The roles of tertiary amine structure, back-
ground organic matter and chloramine species on NDMA formation. Water Res. 47,
945–953. https://doi.org/10.1016/j.watres.2012.11.014.
Shen, R., Andrews, S.A., 2011. Demonstration of 20 pharmaceuticals and personal care
products (PPCPs) as nitrosamine precursors during chloramine disinfection. Water
Res. 45, 944–952. https://doi.org/10.1016/j.watres.2010.09.036.
Shen, R., Andrews, S.A., 2013. NDMA formation from amine-based pharmaceuticals – im-
pact from prechlorination and water matrix. Water Res. 47, 2446–2457. https://doi.
org/10.1016/j.watres.2013.02.017.
Shi, Y., Zhang, L., Li, Y., Zhou, L., Zhou, Y., Zhang, Y., Huang, C., Li, H., Zhu, G., 2020. Influence
of land use and rainfall on the optical properties of dissolved organic matter in a key
drinking water reservoir in China. Sci. Total Environ. 699, 134301. https://doi.org/
10.1016/j.scitotenv.2019.134301.
US EPA, 2015. US EPA Integrated Risk Information System (IRIS). United States Environ.
Prot. Agency.
11
Science of the Total Environment 771 (2021) 145409
Uzun, H., Kim, D., Karanfil, T., 2015. Seasonal and temporal patterns of NDMA formation
potentials in surface waters. Water Res. https://doi.org/10.1016/j.watres.2014.11.017.
Wang, W., Ren, S., Zhang, H., Yu, J., An, W., Hu, J., Yang, M., 2011. Occurrence of nine nitro-
samines and secondary amines in source water and drinking water: potential of sec-
ondary amines as nitrosamine precursors. Water Res. 45, 4930–4938. https://doi.org/
10.1016/j.watres.2011.06.041.
Wang, C., Zhang, X., Wang, J., Chen, C., 2013. Characterization of dissolved organic matter
as N-nitrosamine precursors based on hydrophobicity, molecular weight and fluores-
cence. J. Environ. Sci. 25, 85–95. https://doi.org/10.1016/S1001-0742(12)60029-1.
Wang, X., Liu, Z., Wang, C., Ying, Z., Fan, W., Yang, W., 2016a. Occurrence and formation
potential of nitrosamines in river water and ground water along the Songhua River.
China. J. Environ. Sci. 50, 65–71. https://doi.org/10.1016/j.jes.2016.05.021.
Wang, W., Yu, J., An, W., Yang, M., 2016b. Occurrence and profiling of multiple nitrosa-
mines in source water and drinking water of China. Sci. Total Environ. 551–552,
489–495. https://doi.org/10.1016/j.scitotenv.2016.01.175.
Wang, X., Zhang, F., Kung, H., Ghulam, A., Trumbo, A.L., Yang, J., Ren, Y., Jing, Y., 2017. Eval-
uation and estimation of surface water quality in an arid region based on EEM-
PARAFAC and 3D fluorescence spectral index: a case study of the Ebinur Lake Water-
shed, China. CATENA 155, 62–74. https://doi.org/10.1016/j.catena.2017.03.006.
Wang, Y., Hu, Y., Yang, C., Wang, Q., Jiang, D., 2019. Variations of DOM quantity and
compositions along WWTPs-river-lake continuum: implications for watershed envi-
ronmental management. Chemosphere 218, 468–476. https://doi.org/10.1016/j.
chemosphere.2018.11.037.
West, D.M., Wu, Q., Donovan, A., Shi, H., Ma, Y., Jiang, H., Wang, J., 2016. N-nitrosamine
formation by monochloramine, free chlorine, and peracetic acid disinfection with
presence of amine precursors in drinking water system. Chemosphere 153,
521–527. https://doi.org/10.1016/j.chemosphere.2016.03.035.
Xue, C., Wang, Q., Chu, W., Templeton, M.R., 2014. The impact of changes in source water
quality on trihalomethane and haloacetonitrile formation in chlorinated drinking
water. Chemosphere 117, 251–255. https://doi.org/10.1016/j.chemosphere.2014.06.083.
Yang, L., Han, D.H., Lee, B.-M., Hur, J., 2015a. Characterizing treated wastewaters of differ-
ent industries using clustered fluorescence EEM-PARAFAC and FT-IR spectroscopy:
implications for downstream impact and source identification. Chemosphere 127,
222–228. https://doi.org/10.1016/j.chemosphere.2015.02.028.
Yang, L., Kim, D., Uzun, H., Karanfil, T., Hur, J., 2015b. Assessing trihalomethanes (THMs) and
N-nitrosodimethylamine (NDMA) formation potentials in drinking water treatment
plants using fluorescence spectroscopy and parallel factor analysis. Chemosphere
121, 84–91. https://doi.org/10.1016/j.chemosphere.2014.11.033.
Yu, W., Liu, Teng, Crawshaw, J., Liu, Ting, Graham, N., 2018. Ultrafiltration and
nanofiltration membrane fouling by natural organic matter: mechanisms and mitiga-
tion by pre-ozonation and pH. Water Res. 139, 353–362. https://doi.org/10.1016/j.
watres.2018.04.025.
Yu, J., Chen, J., Zeng, Y., Lu, Y., Chen, Q., 2020. Carbon and phosphorus transformation dur-
ing the deposition of particulate matter in the large deep reservoir. J. Environ. Manag.
265, 110514. https://doi.org/10.1016/j.jenvman.2020.110514.
Zhang, Y., Zhang, B., He, Y., Lev, O., Yu, G., Shen, G., Hu, S., 2019. DOM as an indicator of
occurrence and risks of antibiotics in a city-river-reservoir system with multiple pol-
lution sources. Sci. Total Environ. 686, 276–289. https://doi.org/10.1016/j.
scitotenv.2019.05.439.
Zhang, H., Cui, K., Guo, Z., Li, X., Chen, J., Qi, Z., Xu, S., 2020. Spatiotemporal variations of
spectral characteristics of dissolved organic matter in river flowing into a key drink-
ing water source in China. Sci. Total Environ. 700, 134360. https://doi.org/10.1016/j.
scitotenv.2019.134360.
Zhao, C., Lu, Q., Gu, Y., Pan, E., Sun, Z., Zhang, H., Zhou, J., Du, Y., Zhang, Y., Feng, Y., Liu, R.,
Pu, Y., Yin, L., 2019. Distribution of N-nitrosamines in drinking water and human uri-
nary excretions in high incidence area of esophageal cancer in Huai’an, China.
Chemosphere 235, 288–296. https://doi.org/10.1016/j.chemosphere.2019.06.124.
Zhou, W., Chen, C., Lou, L., Yang, Q., Zhu, L., 2014. Formation potential of nine nitrosa-
mines from corresponding secondary amines by chloramination. Chemosphere 95,
81–87. https://doi.org/10.1016/j.chemosphere.2013.08.020.
Zhou, Y., Shi, K., Zhang, Y., Jeppesen, E., Liu, X., Zhou, Q., Wu, H., Tang, X., Zhu, G., 2017.
Fluorescence peak integration ratio IC:IT as a new potential indicator tracing the
compositional changes in chromophoric dissolved organic matter. Sci. Total Environ.
574, 1588–1598. https://doi.org/10.1016/j.scitotenv.2016.08.196.
Zou, X., Zhang, J., Zhao, X., Zhang, Z., 2020. MoS2/RGO composites for photocatalytic deg-
radation of ranitidine and elimination of NDMA formation potential under visible
light. Chem. Eng. J. 383, 123084. https://doi.org/10.1016/j.cej.2019.123084.