Water Research 183 (2020) 116096

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Water Research
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Seasonal occurrence of N-nitrosamines and their association with

dissolved organic matter in full-scale drinking water systems:
Determination by LC-MS and EEM-PARAFAC
Tahir Maqbool a, b, c, 1, Jiaxing Zhang a, b, c, 1, Yanling Qin a, b, c, Quang Viet Ly d,
Muhammad Bilal Asif a, b, c, Xihui Zhang a, b, 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
School of Environment, Tsinghua University, Beijing, 100084, China
d
Institute of Research and Development, Duy Tan University, Danang, 550000, Viet Nam

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

Article history: N-nitrosamines have been identified as emerging contaminants with tremendous carcinogenic potential
Received 29 March 2020 for human beings. This study examined the seasonal changes in the occurrence of N-nitrosamines and N-
Received in revised form nitrosodimethylamine formation potential (NDMA-FP) in drinking water resources and potable water
23 May 2020
from 10 drinking water treatment plants in a southern city of China. The changes in N-nitrosamines are
Accepted 20 June 2020
Available online 22 June 2020
well correlated with dissolved organic matter (DOM), particularly fluorophores, which were measured
and compared between traditional fluorescence indices and excitation-emission matrix coupled with
parallel factor analysis (EEM-PARAFAC). Four of N-nitrosamine species including N-nitrosodimethyl-
Keywords:
N-nitrosamines
amine (NDMA), N-Nitrosodibutylamine (NDBA), N-Nitrosopyrrolidine (NPYR), and N-Nitrosodiphenyl-
Dissolved organic matter amine (NDPhA) are found to be abundant compounds with an average of 29.5% (26.7%), 20.0% (25.2%),
Fluorescence spectroscopy 18.9% (16.0%), and 9.0% (9.9%) in the source (and treated) water, respectively. The sum of N-nitrosamines
Full-scale drinking water systems concentration is recorded to be low in the wet season (JulyeSeptember), whereas the dry season
EEM-PARAFAC (OctobereDecember) provided opposite impacts. EEM-PARAFAC modeling indicated the predominance
of humic-like component (C1) in the wet season while in the dry season the water was dominant in
protein-like component (C2). All the N-nitrosamines excluding NDPhA and N-Nitrosomorpholine
(NMOR) showed a strong association with protein-like component (C2). In contrast, humic-like C1, which
was directly influenced by rainfall, was found to be a suitable proxy for NMOR and NDPhA. The results of
this study are valuable to understand the correlation between different N-nitrosamines and DOM
through adopting fluorescence signatures.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction 2016). N-nitrosamines are classified as potentially carcinogenic

Environmental contamination of aquatic systems by N-Nitro-
sodimethylamine (NDMA) and other N-nitrosamines is a subject of
active research during the last decade (Chen et al., 2019; Dai and
Mitch, 2013; Fan and Lin, 2018; Hebert et al., 2010; Wang et al.,
* Corresponding author. School of Environment, Tsinghua University, Beijing,
100084, China.
E-mail address: zhenghua.zhang@sz.tsinghua.edu.cn (Z. Zhang).
1
Co-first authors with equal contribution.
and mutagenic disinfection by-products (DBPs) with far more
severity than the regulated DBPs (US EPA, 2015). Depending on
different countries, various guidelines for N-nitrosamines have
been adopted in drinking water, ranging from 9 to 100 ng/L
(Kristiana et al., 2013). The release of these compounds or their
precursors in natural water systems poses serious health concerns
due to the limited removal in drinking water plants and even the
increase during the disinfection processes (Wang et al., 2016; West
et al., 2016). Sources of N-nitrosamines in surface water include by-
products from drinking water and wastewater treatment systems,
and unintentional formation during a few industrial processing

https://doi.org/10.1016/j.watres.2020.116096
0043-1354/© 2020 Elsevier Ltd. All rights reserved.
2 T. Maqbool et al. / Water Research 183 (2020) 116096
(Chen et al., 2019; Fan and Lin, 2018). For example, food and
beverage industries employing the fermentation process remain an
important source of N-nitrosamines (Fan and Lin, 2018). Numerous
surveys from different countries (e.g., USA, China, Spain, and
Australia) have been conducted to examine the abundance of
different N-nitrosamines and available precursors in water bodies
including surface water, groundwater, and wastewater (Chen et al.,
2019; Dai and Mitch, 2013; Farre  et al., 2020; Kristiana et al., 2017;
Ma et al., 2012). A previous study has presented an excellent picture
of N-nitrosamines around China, and found N-nitrosodimethyl-
amine (NDMA) in a range of 0e189 ng/L and generally with the
highest concentration among others (Bei et al., 2016). Most of the
studies reported NDMA (or NDMA-formation potential (FP)) as the
most dominant compound among N-nitrosamines irrespective of
sources and seasonal variations (Bei et al., 2016; Chen et al., 2016;
Krasner et al., 2013; Woods et al., 2015). However, few exceptions
are also documented for other N-nitrosamines i.e. N-Nitro-
somorpholine (NMOR) (Krasner et al. (2013). Chen et al. (2019)
observed the total highest concentration of N-nitrosamines up
to ~ 1100 ng/L in the southeastern Pearl River delta of China with
the sequence of N-nitrosodibutylamine (NDBA) > NDMA > N-
nitrosodiethylamine (NDEA) > N-nitrossopyrrolidine (NPYR).
In addition to the anthropogenic sources, dissolved organic
matter (DOM) are well-recognized as the catastrophic precursors
for the formation of N-nitrosamines. Wang et al. (2013a) system-
atically studied the NDMA-FP by different fractions of DOM and
noticed that hydrophilic fraction has 1.3e3.5 times higher extent of
causing NDMA-FP than the hydrophobic fraction. In terms of mo-
lecular size, lower molecular weight (<1 kDa) fraction of DOM was
found to be more responsible for the formation of NDMA, NPYR,
NMOR, and N-nitrospiperidine (NPIP) compared to the large-sized
molecular fraction (Wang et al., 2013b). A recent study used high
resolution mass spectrometry (HRMS, Orbitrap analysis) for
investigating the relationship between DOM and NDMA-FP (Farre
et al., 2019). They concluded that DOM constituents with H/
C
1.5 correlated positively with NDMA-FP. These DOM constitu-
ents present bioavailable fraction of DOM containing higher het-
eroatoms (such as nitrogen) and can be used as a marker for
potential wastewater inputs or algal bloom in aquatic body
 et al., 2019).
(D’Andrilli et al., 2015; Farre
Although few studies successfully explored the association and
role of different DOM fractions on basis of molecular size and hy-
drophobicity/hydrophilicity in the formation of N-nitrosamines
(Wang et al., 2013a, 2013b), DOM-N-nitrosamines relationship
employing spectroscopic-based tools for quality monitoring as-
pects is still mostly unknown. The successful application could help
in drafting a strategy for controlling water quality and under-
standing the association of DOM constituents with the abundance
of N-nitrosamines.
Fluorescence spectra of water and wastewater present fluores-
cent dissolved organic matter (FDOM) associated with protein-like
and humic-like contents, which was found to be helpful in
describing the overall changes in DOM up to some extent (Li et al.,
2020; Maqbool et al., 2020). Fluorescence spectra in the form of an
excitation-emission matrix (EEM) of DOM are complex with several
overlying FDOM peaks requiring additional interpretation
approach. A mathematical tool, parallel factor analysis (PARAFAC),
developed by Stedmon and Bro (2008) is a multi-way parallel data
analysis technique that is recognized for distinguishing FDOM on
the basis of fluorescence features. Given that, the EEM-PARAFAC
approach has previously explored the occurrence of FDOM and
micropollutants (Sgroi et al., 2017). In a recent study, fluorescence
based monitoring of an advanced wastewater treatment process
provided a strong correlation between the removal of protein-like
fluorescence and NDMA-FP and its precursors (Roccaro et al.,
2020). Yang and coworkers assessed the correlation between the
EEM-PARAFAC components and NDMA-FP in nine different drink-
ing water systems. A direct correlation was reported between
NDMA-FP and protein-like component (Yang et al., 2015). In these
studies, only NDMA/NDMA-FP were tried to correlate with FDOM.
The association between different N-nitrosamines and FDOM are
not discussed yet.
In the current study, the correlation between N-nitrosamines
and DOM are explored to develop seasonal monitoring tool for
source and treated water in different drinking water treatment
plants in a southern city of China. Specific objectives include; (i)
determining the relationship between the fluorescence compo-
nents and N-nitrosamines or NDMA-FP (ii) measuring dependence
of N-nitrosamines and FDOM on the seasonal variation, and (iii)
impacts of treatment on fluorescence components and N-nitrosa-
mines as well as NDMA-FP. This report is first in providing simul-
taneous monitoring of FDOM through EEM-PARAFAC and N-
nitrosamines to find the relationship between the different fluo-
rophores, N-nitrosamines and NDMA-FP.
2. Material and methods
2.1. Water samples collected
Source and treated water (effluent) samples from 10 different
drinking water treatment plants were collected monthly from July
to December (2018), which covers the seasonal changes in a
southern city of China that has high rainfall in JulyeSeptember and
has the dry season in OctobereDecember. The samples were kept in
5 L mild-cleaned plastic bottles. These water samples were
immediately transferred to the laboratory and stored at below 4  C
before further treatment. Pretreatment includes filtration through
0.45 mm cellulose triacetate membrane filter. All of the analytical
 characterizations were performed within 24 h after sampling.
2.2. Analytical characterization
Turbidity and pH of both source and treated water samples were
on-site measured using portable meters (HACH 2100Q and HQ40d,
Japan). Total organic carbon (TOC) and total nitrogen (TN) of filtered
samples were measured using TOC/TN analyzer (TOC-V, Shimadzu,
Japan). The ammonium (NHþ  
4 ), nitrite (NO2 ) and nitrate (NO3 )
concentrations were determined using the ultra-violet (UV) spec-
troscopy method based on Standard Examination Methods for
Drinking Water - Nonmetal Parameters, China (GB/T 5750.5e2006).
2.3. N-nitrosamine analysis
The nine N-nitrosamines (NDMA, NMOR, NDBA, NDEA, N-
Nitrosopyrrolidine (NPRY), NPIP, NDPhA, N-Nitrosomethylethyl-
amine (NMEA) and N-Nitrosodipropylamine (NDPA)) in source and
treated water were measured using the solid-phase extraction
(SPE)-LC-MS (Liquid Chromatography/Tandem Mass Spectrometry)
(8050, Shimadzu, Japan) method. SPE cartridge (CNW Technologies
GmbH, Shanghai, China) containing coconut charcoal was used to
extract N-nitrosamines from samples. The detailed extraction
procedure is presented in Supplementary Information and Fig. S1.
The LC-MS parameters are included in Table S1. The recoveries of N-
nitrosamines through SPE at different concentrations were found in
the range of 60.3e98.4% for the blank matrix (Milli-Q) and
58.9e98.6% for the real matrix (Fig. S2, Tables S2 and S3). The
chromatographs of blank and standard solutions are also presented
(Fig. S3) and the calibration curves of nine N-nitrosamines
(R2 > 0.99) are shown in Tables S4 and S5. For the precision and
accuracy, three levels of concentration (5, 10, and 20 ng/L) with
 T. Maqbool et al. / Water Research 183 (2020) 116096
replicates (n ¼ 6) were prepared and measured (Table S6). The RSD
% of retention time (RT) and area (A) was 0.04e0.43% and
0.98e6.2%, respectively. The method detection limits (MDLs) were
also calculated (Table S5) as described and adopted in previous
studies (Bei et al., 2016; Chen et al., 2019). The estimated lifetime
average daily dose (LADD) and cancer risk were calculated on the
basis of the approach provided by US EPA (1992), details are pro-
vided in Supplementary Information and Table S7.
2.4. NDMA formation potential
For the determination of NDMA-FP, samples were collected in
2 L amber glass bottles and then they were disinfected using freshly
prepared monochloramine (Wang et al., 2013a). The NDMA-FP test
was carried out at ambient temperature and held for 24 h in 20 mL
amber bottles. Phosphate buffer solution (KH2PO4 and Na2H-
PO4$2H2O) was used to stabilize the pH of 7.0 during the reaction.
After the reaction, the remaining chloramine was quenched with
sodium thiosulfate (2 g/L) (Zou et al., 2020). Before the measure-
ment of NDMA, samples were filtered through 0.22 mm nylon
filters.
2.5. UVevis and fluorescence spectroscopy
The UVevis and fluorescence spectra of filtered samples were
collected using UVevis spectroscopy (UV-2600, Shimadzu, Japan)
and fluorescence spectrophotometer (F-7000, Hitachi, Japan),
respectively. The 1 cm four-sided quartz cell was used to collect
broad UVevis spectra (200e800 nm) with 1 nm step of all water
samples and the same cuvette was used for fluorescence spectra.
UVevis spectra were obtained to ensure the DOM concentration in
the sample, the UV absorbance (at 254 nm) was confirmed to less
than 0.05 cm1 to avoid any inner filter effects (Ly et al., 2018).
Following are the adjustments of fluorescence spectrometer for
collection of three-dimensional EEMs; excitation (Ex) and emission
(Em) ranges were set at 220e450 nm and 280e600 nm with scan
steps of 5 nm and 1 nm, respectively; scans were gathered with a
speed of 30,000 nm/min; both of the slits (Ex and Em) were fixed at
5 nm of each. The EEMs of Milli-Q water (18 Um) as blank was
subtracted from the EEMs of all water samples using built-in soft-
ware (FL Solutions 4.2, Japan) to remove Raman scatterings. The
blank sample used without any subsequent filtration, was collected
from a Milli-Q® apparatus (Millipore, USA) which produces excel-
lent quality reference water (TOC < 5 ppb).
The humification index (HIX) and biological index (BIX) were
based on the Em spectrum areas under the wavelengths of
435e480 nm to 300e345 nm at Ex of 255 nm (Hansen et al., 2016;
Ohno, 2002). The BIX was estimated using a ratio of Em intensities
at 380 nme430 nm at an Ex of 310 nm (Hansen et al., 2016).
2.6. PARAFAC modeling
The PARAFAC modeling was applied to EEMs datasets of cu-
mulative samples of source and treated water from all 10 different
drinking water treatment plants. Total samples used for combined
modeling are 120 with 20 samples collected each month. The
modeling was performed using the DOMFlour toolbox in Matlab
13.0 (MathWorks Inc. USA) by following the tutorial of Stedmon
and Bro (2008). The PARAFAC analysis comprises the following
steps: (i) remove scattering by cutting few wavelengths; (ii) non-
negativity constraints; (iii) loading leverage; (iv) identify and
removal of outliers (if any); and (v) validation for a suitable number
of components through split-half analysis. The Fmax represents the
maximum fluorescence intensity for an individual component (e.g.,
humic-like and protein-like). This fluorescence intensity was also
3
normalized by using the Raman integration method (Lawaetz and
Stedmon, 2009).
2.7. Statistical analysis
The principal component analysis (PCA) and Pearson correlation
were conducted to select suitable fluorescence indices to represent
the seasonal changes in N-nitrosamines of source and treated water
in 10 drinking water plants. The selected parameters are sum of N-
P
nitrosamines ( NA), NDMA-FP, nine N-nitrosamines, EEM-
PARAFAC components, and fluorescence indices (HIX and BIX). A
PCA biplot was developed which showed loading and scores for the
selected components. The PCA was performed on three months
averages parameters during wet (WS) and dry (DS) seasons in 10
drinking water plants. The data points of different drinking water
plants were arrange as WS-DWP1 to WS-DWP10 and DS-DWP1 to
DS-DWP10 for the wet and dry seasons, respectively. The Pearson
correlation among different parameters was also analyzed on
monthly values of selected parameters and presented in the form of
heat-map. All the statistical analysis were performed using Origin
software.
3. Results and discussion
3.1. Characterization of N-nitrosamines in source and treated water
The general occurrence of N-nitrosamines in water samples
collected from 10 different drinking water plants is shown in Fig. 1
and Table S8. Among the N-nitrosamines, NDMA and NDPhA were
present in all of water samples, i.e. 100%, followed by NMOR, NPYR,
NDEA, NPIP, NMEA, NDBA and NDPA with detection frequency of
97% (98%), 93% (93%), 85% (97%), 70% (78%), 72% (67%), 63% (65%),
52% (52%) and 48% (48%) for source (treated) water, respectively.
The detection frequency is based on the MDL (Table S5) and pre-
sented in Table S8. The frequencies of N-nitrosamine species in this
study are reported to be slightly different from those obtained from
the previous surveys for other Chinese water sources. For example,
Ma et al. (2012) observed the highest frequency (i.e., 100%) of NDEA
relative to other N-nitrosamine counterparts in Jialu River basin
while NDMA was also frequently detected (98%). Another excellent
N-nitrosamines detection campaign found NMOR (77%) superior in
Fig. 1. General occurrence of N-nitrosamines in source and treated water in 10
drinking water treatment systems (n ¼ 60).
4 T. Maqbool et al. / Water Research 183 (2020) 116096
the frequency sequence followed by NDBA (68%) while the NDMA
has presented only 38% (Bei et al., 2016). The above reports, how-
ever, have also shown that NDMA, NDEA, and NDBA are among the
commonly found N-nitrosamines in surface water (Bei et al., 2016;
Ma et al., 2012), and are in good agreement with our study. It is
noteworthy that the water source properties could play a vital role
in N-nitrosamines formation. For example, as compared to surface
water, wastewater effluent has shown the consistent presence of
NDMA and NMOR with 100% frequency (Chen et al., 2019). Mean-
while, NDEA has shown a substantial frequency of 67% along with
NDMA (77%) in groundwater (Ma et al., 2012).
The four abundant N-nitrosamines found in source (and treated)
water are; NDMA, NDBA, NPYR, and NDPhA with average compo-
sition of 29.5% (26.7%), 20.0% (25.2%), 18.9% (16.0%), and 9.0% (9.9%)
(Fig. 1), at concentrations of 4.2 ± 2.0 (3.4 ± 2.1), 2.8 ± 3.4 (3.2 ± 4.1),
2.7 ± 1.9 (2.1 ± 1.6), and 1.3 ± 1.1 (1.3 ± 1.2) ng/L, respectively
(Table S8). Such diverse N-nitrosamines in the source could ascribe
to heterogeneous contaminant sources due to extensive urbaniza-
tion, rising industrial and modern agricultural activities in the city.
The main industries in the city include pharmaceutical, electronics,
electroplating, leather, textile, and printing and paper factories (Wu
et al., 2020). Rare studies are available in the literature reporting
nine nitrosamines in source or drinking water. For instance, N-ni-
trosamines campaigns in 11 Spanish drinking water plants showed
the absence of NPYR, NPIP, NDPA and NMEA (reporting limit of
0.1 ng/L) (Farre  et al., 2020). A study on a drinking water plant in
North America found only NDMA above the minimum reporting
limit of 1.5 ng/L (Woods et al., 2015). A recent study traced the
leading sources of N-nitrosamines in a river delta and found five N-
nitrosamines (NDMA, NDEA, NPYR, NMOR, and NDBA) abundant in
industrial effluent. However, NDMA, NDEA, and NMOR were
abundant in domestic wastewater leading to the river delta (Chen
et al., 2019). Krauss and coworkers observed higher share of in-
dustrial effluent in N-nitrosamines pollution than domestic
discharge in different sewage treatment plants of Switzerland,
NDMA and NMOR were found to be likely candidates for contam-
ination in drinking water (Krauss et al., 2009). The average distri-
bution of N-nitrosamines in source and treated water is presented
in Fig. S4. Unlike other Chinese regions, NDMA in drinking water
systems of this southern city was not at a higher concentration. For
instance, the NDMA concentration in surface waters (i.e., rivers and
reservoirs) in other works was 53.6 ng/L (Wang et al., 2016), and
28.5 ng/L (Bei et al., 2016), significantly higher than that in the
current study. Meanwhile, other N-nitrosamines are comparable
(Bei et al., 2016; Wang et al., 2016).
It should be underlined the slight difference in the N-nitrosa-
mines concentration between the source and treated water
(p ¼ 0.24, One Way ANOVA), implying neither inadequate removal
of N-nitrosamines nor any noticeable production of N-nitrosamines
upon drinking treatment practices (Fig. 1). The performances of
these drinking water plants in terms of basic quality parameters are
reasonable (Table S9). The limited removal of all N-nitrosamine are
frequently reported in studies and are challenging to achieve safe
drinking water levels (Luo et al., 2012; Wang et al., 2016). These
concentrations in treated water meet the standard for potable
water and would not pose any severe human health risk (WHO,
2011). None of the N-nitrosamines in treated water has shown
discrimination (source vs. treated) in detected frequencies implying
the dependence of treated water on source quality. Strong re-
lationships (R2 ¼ 0.36e0.91, and p < 0.001) between the concen-
tration of N-nitrosamines in source and treated water are found, as
illustrated in Fig. S5. It is essential to note all of the treatment fa-
cilities continuously dosed NaOCl for disinfection.
For the estimation of the available precursors in source and
treated water, the results of NDMA-FP for source and treated
samples collected are presented in Fig. 2. The NDMA formation po-
tential was found in the range of 14.7e38.8 ng/L and 11.4e34.4 ng/L
with an average (median) of 26.3 ± 6.2 (25.3) ng/L and 19.2 ± 5.7
(18.1) ng/L for source and treated water, respectively. The average
decrease, 27.1 ± 10.6%, in NDMA-FP presented a slight reduction of
precursors (ANOVA, p < 0.05) during the treatment units.
The correlation among N-nitrosamines (or NDMA-FP) and bulk
parameters such as DOC, TN, NHþ  
4 , NO2 , NO3 , and turbidity were
also conducted for source and treated water. There was no any
strong linear relationship found with DOC but TN, and NO 3 have
shown up to a few extents, illustrated in Tables S10 and S11. Our
results aligned with few other studies, which did not find any
significant relationship between the basic water quality parameters
and N-nitrosamines in drinking water (or NDMA-FP) (Bei et al.,
2016; Wang et al., 2016). Nevertheless, some opposite observa-
tions were devised. For example, Yang et al. (2015) reported a linear
correlation between DOC and NDMA-FP (r ¼ 0.53, p < 0.001).
From the above results, it infers that all drinking water plants in
the southern city of China are receiving the source water with a
moderate concentration of N-nitrosamines and current operating
conditions are providing treated water meeting all the guidelines
for drinking water. The average cancer risk of N-nitrosamines was
found to be in the range of 1.79  1010 (NDPhA) to 5.01  106
(NDMA). Eight N-nitrosamines except NDMA were far below the
generally accepted risk of 106, and NDMA was found close to the
risk level (106) (US EPA, 2015) (Table S7).
3.2. Seasonal impacts in N-nitrosamines
The average temperature and the rainfall were 28.87 ± 0.44 and
22.03 ± 2.78  C, and 456.90 ± 106.85 and 30.54 ± 20.24 mm for the
wet season (July to September) and the dry season (October to
December), respectively. In this territory, there is no major
discrepancy in temperature, but the rainfall does significantly
change between the two seasons. No any noticeable impacts of
season changes were recorded on basis quality parameters in
source and treated water between wet and dry seasons (Table S9).
The results indicated that the general occurrence of N-nitrosa-
mines was profoundly affected by the seasonal variation; the higher
rainfall in the wet season likely caused less release or generation of
N-nitrosamines in source water (Fig. 3). Similarly, so did it for the N-
nitrosamine concentrations in treated water.
P
Fig. 2. The total concentration of N-nitrosamines ( NA) and NDMA-FP in source
(black) and treated (red) water of drinking water plants, n ¼ 60. (For interpretation of
the references to colour in this figure legend, the reader is referred to the Web version
of this article.)
 T. Maqbool et al. / Water Research 183 (2020) 116096
P
Fig. 3. Impact of seasonal changes on total N-nitrosamines ( NA) in (a) source and (b)
treated water of 10 drinking water plants.
The highest difference in N-nitrosamines concentration can be
found between August and December (ANOVA, p < 0.001), the
average concentrations during these months were recorded to be
6.12 ± 1.63 and 22.34 ± 4.76 ng/L in source water, and 6.38 ± 1.38
and 21.97 ± 3.15 ng/L in treated water, respectively (Tables S12 and
S13). The range of total N-nitrosamines during August and
December was found to be, 2.79e9.32 and 13.75e31.06 ng/L in
source water, 3.59e8.28 and 18.36e28.83 in treated water,
respectively. Such a matching concentration of N-nitrosamines in
source and treated water of different treatment systems during
both of the seasons illustrated the identical activities around
different reservoirs or matching seasonal influence on these water
compartments. A previous study by Jurado-Sa nchez et al. (2012)
had witnessed the insignificant effects of temperature and rainfall
on N-nitrosamines in source water but effluent showed an increase
in the pollutants’ concentration when the season changed from
summer to winter. Unlike the current study, chloramine was
employed in their study (Jurado-Sanchez et al., 2012). There was no
any matching trend or correlation of any basic water quality pa-
rameters with N-nitrosamines during the varying seasons in the
current area under investigation (Tables S10 and S11), which urged
to investigate further the behavior of all nine N-nitrosamines in
different treatment facilities.
In addition to already present N-nitrosamines, the extent of
available precursors during varying seasons estimated through
measuring the NDMA-FP are illustrated in Fig. 4. Interestingly, there
was a strong correlation between NDMA-FP with N-nitrosamines,
regardless of the sources and the treated water (R2
0.77),
5
Fig. 4. Relationship between the N-nitrosamines and NDMA-FP in (a) source and (b)
treated water.
highlighting the importance of precursor substances in the water
source, which varied upon the climate change. Previous studies
have also compared the NDMA-FP during different seasons and
found the dilution effects in high rainfall events up to some extent.
For instance, Uzun et al. (2015) investigated the impacts of seasonal
parameters (precipitation) on NDMA-FP in 12 different water
sources including rivers and lakes/reservoirs. They concluded that
not all the water sources were affected by precipitation in terms of
water quality, all the rivers and mostly reservoirs showed higher
NDMA-FP during flood season and vice-verse results were reported
for remaining reservoirs. Their work ascribed such variability in
different rivers and reservoirs to the land-use which possibly
impacted the NOM along influx to the water bodies. On the con-
trary to the previous study, which reported that NDMA-FP in water
bodies is location-dependent rather than being affected by seasonal
variation (Aydin et al., 2012), our study has shown the higher in-
fluence of rainfall with matching concentration in source and
treated water of drinking water plants. The results are in line with a
nationwide NDMA campaign in Japan presenting higher NDMA
concentration in the raw water and effluent during the winter
season than that during summer and results were pronounced in
the East and West parts of the country (Asami et al., 2009).
The further exploration of N-nitrosamines in drinking water
involves understanding the dynamics of each N-nitrosamine, as
illustrated in Fig. 5, S6 and S7. Most of the N-nitrosamines share a
similar trend with total N-nitrosamines, except for NDPhA and
NMOR, which have lower concentration during the wet season and
6 T. Maqbool et al. / Water Research 183 (2020) 116096
higher concentration in the dry season. It is interesting to note that
NDPhA and NMOR behaved significantly (p < 0.001) different from
the rest, which infers that weather conditions have a pronounced
influence on the main sources of NMOR and NDPHA (e.g., roads,
streets, roofs, pavements, and parking lots) and/or precursors
availability and ultimately determine the composition of overall N-
nitrosamines. The cluster of NDMA and NDPhA in source and
treated water of all drinking water treatment plants are shown in
Fig. 5, and trends of remaining N-nitrosamines are presented in
Figs. S6 and S7. On opposite of others N-nitrosamines, NMOR and
NDPhA have shown positive association with rainfall. Compare to
the increase of NDMA with changes in season, the variation in
NDPhA was more severe with the average reduction of more than
seven times in both source and treated water. The uniform changes
in each N-nitrosamine in source and treated water of all drinking
water treatment plants indicated that environmental conditions or
the aquatic biogeochemistry had played a critical role rather than
rainfall dilution and anthropogenic activities. Previous studies re-
ported substantial changes in allochthonous and autochthonous
activity upon changes in season (Shi et al., 2020), which could
change the occurrence of precursors and their links to such unusual
behavior of different N-nitrosamines. It infers that not only one
Fig. 5. The impact of seasonal change on the NDMA and NDPhA concentration in source (a and c) and treated (b and d) water.
factor controls the N-nitrosamines concentration in aquatic bodies,
biogeochemistry, land-use, and industrial activities play a com-
posite role. The following discussion is comprised of the impact of
changing season on DOM composition, which associates with
different sources of activities in the source water.
3.3. Seasonal impacts on FDOM
For FDOM, a two-component EEM-PARAFAC model was vali-
dated and provided a component 1 (C1) with Ex/Em of 245/414 nm
and component 2 (C2) located at Ex/Em 230 (280)/328 nm (Fig. 6).
The selection criteria for determining the reasonable number of
components is based on the split-half validation. According to
previous available studies, C1 is traditionally termed as a humic-
like component, while C2 resembles free and or bound protein-
like component (Cory and McKnight, 2005; Vera et al., 2017).
Multiple sources of fluorescence have been reported in studies such
as the terrestrial DOM, algal bloom, and effluent organic matter,
microbial humification (Singh et al., 2010; Williams et al., 2019).
Generally, the components located beyond emission of 380 nm are
assigned to humic-like fluorescence with origins of microbial hu-
mification or terrestrial humic substances (Li et al., 2014; Yamashita
 T. Maqbool et al. / Water Research 183 (2020) 116096
Fig. 6. Fluorescence components obtained through EEM-PARAFAC. C1 and C2 represent the humic-like and protein-like FDOM, respectively.
and Jaffe, 2008). The peaks located <380 nm are assigned to
different protein-like fluorescence moieties. Tryptophan- and
tyrosine-like amino acids are the main sources of such fluorescence
signatures, the former located at longer emission than the later
(Baghoth et al., 2011). Also, the traditional indices such as HIX and
BIX were of use to compare with EEM-PARAFAC regarding the
seasonal changes in source and treated water. The extent of these
indices in source and treated water of all drinking water plants did
not present any clear tendency with the change of the weather
conditions including the rainfall (Fig. S8). Most notably, the EEM-
PARAFAC components illustrated the direct impact of rainfall on
the DOM changes, showing linear relationships between the fluo-
rescence components with the extent of rainfall with C1 and C2
being R2 of 0.62 and 0.41, respectively (Fig. S9).
Fig. 7 represents the changing fluorescence components in
source and treated water over the six months of sampling period in
all drinking water plants. It is noteworthy that both components
have shown different trends (p < 0.05, one way ANOVA), which
infers that seasonal changes in the city substantially influence the
DOM composition in the aquatic system. The average of fluores-
cence components in source water has a relatively linear increase
and decrease in Fmax of C1 and C2, respectively. The fluorescence
component with maximum (0.32 ± 0.05 R.U.) and minimum
(0.18 ± 0.024 R.U.) intensities of C1 were recorded during
September and December, respectively. On the other hand, DOM
were enriched (0.38 ± 0.05 R.U.) with C2 in November and it
showed the lowest abundance (0.25 ± 0.04 R.U.) in July. It infers
7
that the wet season with hot summer conditions favors the release
of the humic-like FDOM in reservoirs providing the source water to
the different treatment plants, which was ascribed to the washout
of diverse soil-/leaf-derived organic substances from upstream
catchments into water supplies (mostly, rivers and lakes) (Ly et al.,
2015). This finding is in line with a few previous studies presenting
the higher release of humic substances during the rainfall events
and vice-versa for the protein-like component. Higher rainfall
caused the release of DOM from the deep soil with more erosion
heading toward the surface water (Liu et al., 2019; Zhou et al.,
2016). On the other hand, mild flow rate during dry season pro-
vides a perfect niche to thrive microorganisms release autochtho-
nous DOM mostly having the feature like protein contents (Ly et al.,
2017). To compare the relative changes in DOM, C1/C2 was deter-
mined on the average basis of the wet season (July to September)
and dry season (October to December) (Fig. 8). A significant dif-
ference in FDOM composition (ANOVA, P < 0.001) was recorded in
source and treated water between wet and dry seasons with
dominant humic-like and protein-like constituents, respectively.
The composition of FDOM (C1/C2) also corresponds to the relative
abundance of C1 and C2 in the source water. Numerous studies
have found protein-like components as dominant fluorescence
features than the humic-like in soluble microbial products and
effluent organic matter (Ly et al., 2018; Shen et al., 2012). Current
results also provide evidence of substantial concentration of solu-
ble microbial products or effluent organic matter in source water by
presenting a lower C1/C2 ratio during dry season. Several studies
8 T. Maqbool et al. / Water Research 183 (2020) 116096

Fig. 7. The changes in EEM-PARAFAC components during wet and dry seasons in source and treated water of 10 drinking water plants (n ¼ 10).

all these techniques bioploymers with large molcular weight, with

fluorescence featues of protein-like, and molecular composition
with O-poor aromatics were found to be abundant in dry season
showing the presence of bioavialable DOM (Liu et al., 2020; Shi
et al., 2020; So et al., 2017). It is speculated that such prominent
changes in DOM composition could be linked with abundances of
precursors in drinking water systems, especially in the source
water. Effluent organic matter have been observed to be the leading
sources of precursors for NDMA and other N-nitrosamines (Ma
et al., 2012; Wang et al., 2011). Few of the N-nitrosamines (specif-
ically, NDMA/NDM-FP) have shown direct association with FDOM
composition and concentration in water and wastewater treatment
systems (Roccaro et al., 2020; Yang et al., 2015). On the other hand,
a few studies have reported terrestrial humic substances as the
origins for N-nitrosamines after releasing amine precursors under
photochemical irradiation (Bushaw-Newton and Moran, 1999;
Mitch and Sedlak, 2002). Below are the correlations presented for
the different fluorescence components and indicators to obtain any
proxies for these season-dependent N-nitrosamines in source and
treated water.
Fig. 8. The average of C1/C2 during water season (July to September) and dry seasons
(October to December) in source and treated water of drinking water plants (n ¼ 60).
3.4. Correlation between N-nitrosamines and spectroscopic
indicators

have proved compositional variations in DOM upon changing sea- The aforementioned results proved that seasonal changes
son through application of fluorescence spectroscopy, size exclu- influenced N-nitrosamines and FDOM in water sources, rainfall was
sion chromatography, and high resolution mass spectrometry. By found to be mostly responsible for the patterns obtained. In a bid to
 T. Maqbool et al. / Water Research 183 (2020) 116096
untangle the complex relationship between a variety of parame-
ters, PCA was applied to compile all the given data together with
heat-map for Pearson correlation (Figs. 9 and S10). The principal
component 1 (PC1) explained for 50.82% of the total variances,
while the PC2 was responsible for 16.48% of the variations (Fig. 9).
These correlations imply that the protein-like component C2
possibly derived from the microbial activity (and effluent organic
matter) in the reservoir is mostly responsible for the N-nitrosa-
mines, excluding NMOR and NDPhA, or it also potentially forms
these compounds as measured in terms of NDMA-FP. The concen-
trations of NMOR and NDPhA have been determined by humic-like
component and the ratio of C1/C2 which presented the overall
composition change in DOM. A similar correlation can be found in
treated water (Fig. S10) and the above results already proved that
the abundance of the N-nitrosamines or the NDMA-FP solely de-
pends on the influent quality and also mirrors the N-nitrosamines
composition. The extent of correlation determined through heat-
map also clearly distinguished the occurrence of NDPhA and
NMOR from the rest of N-nitrosamines and provided fluorescence
components C1/C2 as a fluorescence proxy. These correlations
indicated that organic matter from autochthonous activities in the
surface water are directly linked with the N-nitrosamines
Fig. 9. Principal component analysis (PCA) biplot (a) and heat-map for Pearson cor-
P cence. The calculated C1/C2 ratio was double fold, 1.05 ± 0.12
relation for total N-nitrosamines ( NA), each N-nitrosamine and fluorescence in-
dicators (b).
9
formation; however, terrestrial DOM could act as proxy for a few of
them (e.g., NMOR and NDPhA). Such a noticeable difference in the
concentration of these N-nitrosamines (NMOR and NDPhA) with
the rainfall and concurrent changes in humic-like fluorescence
indicated the dual effects of rainfall on source water chemistry. First
is the leaching of these particular N-nitrosamines from the roads,
streets, roofs, pavements, and parking lots. Meanwhile, the soil
erosion, DOM extraction from deep soil, and dried leaf/vegetation
are second effect. The rainfall could also leach N-nitrosamines from
improperly disposed waste and dumping sites and transport them
into source water reservoirs. The binding property of humic-
substances could also assist in the mobility of N-nitrosamines. It
concludes from the discussion that humic substances could be an
appropriate proxy for the NMOR and NDPhA in source water rather
than a source for their generation.
Results from this work demonstrate that seasonal dependent
DOM composition in source water could affect the occurrence of N-
nitrosamines and also provide precursors for the formation of these
compounds. Unlike the basic water quality parameters and tradi-
tional fluorescence indices, the general occurrence of N-nitrosa-
mines in source and treated water of drinking water plants could
sufficiently be explained by EEM-PARAFAC modeling. The treated
water quality is found to depend on source water unless operating
parameters are regulated and tuned under seasonal variations. The
important implication of the study is to monitor the water quality
through the fluorescence spectroscopy method and to obtain in-
formation related to carcinogenic pollutants. A future broader
study comprising of sampling from different climate regions is
mandatory to develop a reliable relationship between these con-
stituents. This approach could also be proved as a source tracking
tool to monitor the different discharges to the drinking water re-
sources i.e. surface water and penetration of the groundwater.
Furthermore, such studies help to adjust the parameters of the
water treatment plants with changes in seasonal to limit such
compounds in treated water.
4. Conclusions
This study investigated the occurrence of N-nitrosamines in
source and treated water from 10 different drinking water systems
in a southern city of China. The impacts of seasonal change and the
presence of different DOM on the abundance of N-nitrosamines and
NDMA-FP are comprehensively investigated. Following are the
conclusions drawn from the results;
 All N-nitrosamines in source and treated water are found to be
well below the guidelines. The maximum levels recorded for
total N-nitrosamines and NDMA-FP in the source (and treated)
water are 31.60 (28.84) and 38.86 (34.41) ng/L, respectively. The
strong linear relationship (R2 > 0.77, P < 0.001) between the
total N-nitrosamines and NDMA-FP in source and drinking
water has also been found.
 The general concentration of N-nitrosamines was recorded to be
low (Max ¼ 9.3 ng/L) in the wet season
(rainfall ¼ 456.90 ± 106.85 mm); however, it increased more
than two folds (Max ¼ 31.6 ng/L) in the dry season with an
average rainfall of 30.54 ± 20.24 mm. NDMA-FP also followed a
similar trend. Meanwhile, two N-nitrosamines (NDPhA and
NMOR) have shown vice-versa trends.
 The EEM-PARAFAC modeling provides unique trends of different
fluorescence components and their relative contributions; wet
season was found to be favorable for humic-like component and
dry season released DOM enriched with protein-like fluores-
and 1.10 ± 0.25, in wet season than dry season with a ratio of
10 T. Maqbool et al. / Water Research 183 (2020) 116096
0.55 ± 0.11 and 0.52 ± 0.13 in source and drinking water,
respectively.
 The statistical analysis provided a correlation and insights into
changes in N-nitrosamines and DOM. Among the N-nitrosa-
mines, seven of these were correlated with protein-like (C2)
fluorescence presenting their association with autochthonous
DOM or contamination by effluent organic matter. Meanwhile,
the dynamics of NMOR and NDPhA were well explained by
humic-like (C1) fluorescence and abundance could also be
determined by the ratio of humic-like to protein-like fluores-
cence (C1/C2).
 The results of the study provided a coherence among the
different N-nitrosamines concentration, NDMA-FP, and fluo-
rescence components. These findings are useful in presenting
the overall water quality in drinking water i.e., fluorescence
proxies could be an useful tool for the rough estimation of N-
nitrosamines and precursors available to form N-nitrosamines.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgement
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 Tech-
nology 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.watres.2020.116096.
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